Fuels and Lubricants Handbook Technology, Properties, Performance, and Testing - 0803120966 - ASTM International PDF

Fuels and
Lubricants
Handbook:
Technology,
Properties,
Performance,
and Testing
George E. Totten, Editor

Section Editors
Steven R. Westbrook
Rajesh J. Shah
ASTM Manual Series: MNL37WCD
ASTM International
100 Barr Harbor Drive
# PO Box C700
iMTBttmrmtM. West Conshohocken, PA 19428-2959
Printed in the U. S. A.
Library of Congress Cataloging-in-Publication Data
Fuels and lubricants handbook: technology, properties,

performance, and testing/George E. Totten, editor;
section editors, Steven R. Westbrook, Rajesh J. Shah,
p. cm.—(ASTM manual series; MNL 37)
Includes bibliographical references and index.
ISBN 0-8031-2096-6
1. Fuel—Testing—Methodology. 2. Fuel—Analysis.
3. Lubrication and lubricants—Analysis. I. Totten,
George E. II. Westbrook, Steven R., 1956-III. Shah,
Rajesh J., 1969-IV. Series.
TP321.F84 2003
662',6—dc21 2003049604
Copyright © 2003 ASTM International, West Conshohocken,

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June 2003
Foreword
This publication, Fuels and Lubricants Handbook: Technology, Properties, Performance,
and Testing, was sponsored by ASTM Committee D02 on Petroleum Fuels and Lubri-
cants and edited by George E. Totten, G. E. Totten & Associates, LLC, Seattle, Wash-
ington. The section editors were Steven R. Westbrook, Southwest Research Institute,
San Antonio, Texas; and Rajesh J. Shah, Koehler Instrument Company, Bohemia, New
York. This publication is Manual 37 of ASTM's manual series.
Contents
Preface—George E. Totten, Steven R. Westbropk, and Rajesh J. Shah ix
I. PETROLEUM REFINING PROCESSES FOR FUELS

AND LUBRICANT BASESTOCKS—ô/esfe / . Shah, Section Editor
Chapter 1—Petroleum Oil Refining 3

Marvin S. Rakow
II. FUELS: PROPERTIES AND PERFORMANCE—

Steven R. Westbrook, Section Editor
Chapter 2—Liquefied Petroleiun Gas 31

Roberts. Falkiner
Chapter 3—Motor Gasoline 61

B. Hamilton and Robert J. Falkiner
Chapter 4—Aviation Fuels 89

Kurt H. Strauss
Chapter 5—Âutomotive Diesel and Non-Aviation Gas Turbine Fuels 115

Steven R. Westbrook and Richard he Cren
Chapter 6—Introduction to Marine Petroleum Fuels 145

Matthew F. Winkler
III. HYDROCARBONS AND SYNTHETIC LUBRICANTS:

PROPERTIES AND PERFORMANCE—/?a;es/i/. Shah, Section Editor
Chapter 7—Hydrocarbon Base Oil Chemistry 169

Arthur J. Stipanovic
Chapter 8—Hydrocarbons for Chemical and Specialty Uses 185

Dennis W. Brunett, George E. Totten, and Paul M. Matlock
Chapter 9—Additives and Additive Chemistry 199

Syed Q. A. Rizvi
Chapter 10—Synthetic Lubricants: Nonaqueous 249

Thomas F. Buenemann, Steve Boyde, Steve Randies,
and Ian Thompson
Chapter 11—Environmentally Friendly Oils 267

Hubertus Murrenhoff and Andreas Remmelmann
Chapter 12—Turbine Lubricating Oils and Hydraulic Fluids 297

W. David Phillips
vi CONTENTS
Chapter 13—Hydraulic Fliiids 353

Willie A. Givens and Paul W. Michael
Chapter 14—Compressor Lubricants 383

Desh Garg, George E. Totten, and Glenn M. Webster
Chapter 15—Refrigeration Lubricants—Properties and Applications 413

H. Harvey Michels and Tobias H. Sienel
Chapter 16—Gear Lubricants 431

Vasudevan Bala
Chapter 17—Automotive Lubricants 465

Shirley E. Schwartz, Simon C. Tung, and Michael L. McMillan
Chapter 18—Metalworking and Machining Fluids 497

Syed Q. A. Rizvi
Chapter 19—Petroleum Waxes 525

G. Ali Mansoori, H. Lindsey Barnes, and Glenn M. Webster
Chapter 20—Lubricating Greases 557

Thomas M. Verdura, Glen Brunette, and Rajesh Shah
Chapter 21—Mineral Oil Heat Transfer Fluids 573

John Fuhr, Jim Oetinger, George E. Totten, and Glenn M. Webster
Chapter 22—Non-Lubricating Process Fluids: Steel

Quenching Technology 587
Bozidar Liscic, Hans M. Tensi, George E. Totten,
and Glenn M. Webster
rv. PERFORMANCE/PROPERTY TESTING PROCEDURES—

Steven R. Westbrook and Rajesh J. Shah, Section Editors
Chapter 23—Static Petroleum Measurement 635

Lee Oppenheim
Chapter 24—Hydrocarbon Analysis 649

James C. Fitch and Mark Barnes
Chapter 25—Volatility 675

Rey G. Montemayor
Chapter 26—Elemental Analysis 707

R. Kishore Nadkami
Chapter 27—Diesel Fuel Combustion Characteristics 717

Thomas W. Ryan HI
Chapter 28—Engineering Sciences of Aerospace Fuels 729

Eric M. Goodger
Chapter 29—Properties of Fuels, Petroleum Pitch, Petroleum Coke,

and Carbon Materials 757
Semih Eser and John M. Andresen
CONTENTS vii
Chapter 30—Oxidation of Lubricants and Fuels 787

Gerald J. Cochrac and Syed Q. A. Rizvi
Chapter 31—Corrosion 825

Maureen E. Hunter and Robert F. Baker
Chapter 32—Flow Properties and Shear StabiUty 833

Robert E. Manning and M. Richard Hoover
Chapter 33—Cold Flow Properties 879

Robert E. Manning and M. Richard Hoover
Chapter 34—Environmental Characteristics of Fuels

and Lubricants 885
Mark L. Hinman
Chapter 35—Lubrication and Tribology Fundamentals 909

Hong Liang, George E. Totten, and Glenn M. Webster
Chapter 36—Bench Test Modeling 963

Lavem D. Wedeven
Chapter 37—Lubricant Friction and Wear Testing 1017

Michael Anderson and Frederick E. Schmidt
Chapter 38—Statistical Quality Assurance of Measurement Processes

for Petroleiun and Petroleum Products 1043
Alex T. C. Lau
Index 1061
Preface
There are many books on various aspects of fuels and lubricant chemistry, applications,
and testing. However, few focus on testing and none provide extensive, in-depth cover-
age on fluid properties and testing methodologies together. And while there are nu-
merous national and international standards that deal with specific testing procedures
appropriate for fuels and lubricants, it is generally beyond the scope of these proce-
dures to provide an extensive discussion of the principles behind the tests and their re-
lationship to the properties themselves. Therefore, there is a strong need to address
these informational shortcomings in the Fuels and Lubricants industry, which is one of
the most significant tasks undertaken in this work.
The ASTM Fuels and Lubricants Handbook: Technology, Properties, Perfor-
mance, and Testing is an extensive, in-depth, well-referenced handbook that provides
a detailed overview of various testing methodologies and also provides a thorough
overview of the applications-related properties being tested. Since this manual provides
an overview of all of the ASTM and important non-ASTM test procedures relating to the
application areas addressed, it is an excellent companion text to the Annual Book of
ASTM Book of Standards, or it is an invaluable reference manual on its own.
The organization of the ASTM Fuels and Lubricants Handbook: Technology, Prop-
erties, Performance, and Testing is based approximately on the committee structure
of the ASTM D.02 Petroleum Fuels and Lubricants Committee and the standards for
which each committee is responsible. The information in this text is subdivided into
four sections: I-Petroleum Refining Processes for Fuels and Lubricant Basestocks;
II-Fuels; Ill-Hydrocarbons and Synthetic Lubricants; and IV-Performance/Property
Testing Procedures.
This manual contains thirty-eight chapters covering the following topics:
• An overview of petroleum oil refining processes
• Liquified petroleum gas (LPG)
• Aviation, automotive diesel, non-aviation gas turbine, and marine fuels
• Gasoline and oxygenated fuel blends
• Petroleum hydrocarbon base oil chemistry
• Synthetic hydrocarbons
• Environmentally friendly fluids including those formulated from vegetable oil and
synthetic ester basestocks
• Lubricating oils for turbines, compressors (industrial and refrigeration), gears, and
automotive applications
• Metalworking fluids
• Petroleum waxes
• Lubricating greases
• Oils used in non-lubricating applications: heat transfer fluids and metal quenchants
• Detailed discussion on: static petroleum measurement, volatility, elemental analysis,
fuel combustion characteristics, oxidation, corrosion and viscosity
• Properties of coke, petroleum pitch, and carbon materials
• Hydrocarbon structural analysis procedures
• An extensive discussion of lubrication and wear
• Environmental and toxicity testing
• Statistical quality assurance testing procedures
Essentially, all of the numerous important applications and test methods involved
in the Fuels and Lubricants industry are discussed and referenced here. We strongly
believe that this book will be an invaluable resource for anyone working in this
industry, especially since this information is not available in any other single source.
ix
X PREFACE
The preparation of a text of this scope was an enormous task involving many people.
The editors are deeply indebted to the authors for their h a r d work and incredible pa-
tience. Specicd thanks go to Monica Siperko and Kathy Demoga at ASTM for their con-
tinued support and encouragement throughout the development of this text. The edi-
tors are especially indebted to their families for many evenings and weekends lost to
this project. We Eilso acknowledge the vital support of Southwest Research Institute and
the Koehler Instrument Corporation.
George E. Totten
General Editor
G.E. Totten & Associates, LLC.
Seattle, WA, USA
Steven R. Westbrook
Section Editor-Fuels
Southwest Research Institute
San Antonio, TX, USA
Rajesh J. Shah
Section Editor-Lubricants
Koehler Instrument Company
Bohemia, NY, USA
Section I: Petroleum Refining Processes for Fuels and
Lubricant Basestocks
Rajesh J. Shah, Section Editor
MNL37-EB/Jun. 2003
Petroleum Oil Refining

Marvin S. Rakow^
THIS CHAPTER PRESENTS AN OVERVIEW of t h e m o d e m , integrated pie, in the United States, one hundred volumes of crude oil
oil refinery, a n d how it separates a n d processes crude oil and are converted into about fifty volumes of gasoline (the ratio
other hydrocarbon feedstocks into the required array of liq- is about 42% o n a weight basis). Yet, crude oil typically has
uid fuels a n d other products. A description of an overall, sim- only 15 to 20% of its hydrocarbons in the gasoline boiling
plified refinery flow plan serves to introduce the subject and ramge. The fluid cataljrtic cracking unit (FCCU) is the main
terminology unique to the industry. process that provides the additional "gasoline" and is thus a
I m p o r t a n t crude oil properties a n d test methods, along key process unit in the U.S. refinery flowsheet. The gasoline
with a perspective on past, current, a n d likely future fuel to crude oil ratio is substantially lower in all other parts of the
product quality and demand, is presented. Each important world; thus FCCU, while in place worldwide, plays a signifi-
refinery process is described in sufficient detail to appreciate cantly lesser role in non-U.S. refineries. Similar comparisons
its purpose, operating characteristics, yield a n d quality pa- are summarized for other refinery processes in Table 2.
rameters, a n d current and future utilization in light of antic- In order of increasing boiling range, description and uti-
ipated fuels product trends. lization of the distillation fractions are as follows:
• CI to C4 gases—The crude oil gases, along with gases cre-
ated by the downstream process chemistry, cuê separated
GENERIC REFINERY FLOW PLAN by carbon n u m b e r and hydrocarbon type in one o r more
light ends plants (also called vapor recovery units, o r "sats"
Figure 1 is a simplified block flow diagram of a fully inte- and "unsats" gas plants). Impurities, the main one being
grated refinery utilizing the major process options in genereJ H2S, a r e removed, with final separation providing t h e
use. Each actual plant will incorporate those options that product disposition shown in Table 3.
meet crude throughput and quality, as well as product de- • LSR—The light (straight run) gasolines, in most refineries,
m a n d and quality, while striving for m i n i m u m capital and are blended directly t o t h e gasoline pool. If a refiner is
operating cost. Since most refineries reach their current con- squeezed for octane number, o r if LSR octane quality di-
figuration by periodic revamp and expansion, it is both likely minishes d u e t o refiner response to changing gasoline
and economically feasible for two refineries with similar feed specifications, the octane n u m b e r of this stream cem be in-
and product slates to have a different mix of processes to sat- creased by the isomerization process.
isfy all technical a n d economic parameters.
• HSR—The heavy (straight r u n ) naphtha, whether from
Crude oil first undergoes physical separation by distillation crude oil or other process units, is too low in octane num-
(ASTM Test Method for Distillation of Petroleum Products, ber to be economically blended in gasoline. Thus, all HSR
D 86-99a) to yield various boiling range streams as dictated by is processed through the catalytic reforming unit (CRU)
the chemical processing to follow (Table 1). The atmospheric wherein the hydrocarbon composition is changed or "re-
distillation unit usually separates about one-half of the crude formed" to a higher octane n u m b e r stream.
oil into the indicated cuts ranging from the low boiling gases • Kerosine—This fraction, after appropriate cleanup (treat-
through a gas oil. The final boiling point of the atmospheric ing), is directly sold to the kerosine and jet fuel markets
gas oil can range from as low as 340°C t o as high as 410°C.
and is also used as a blending component for the lighter
Vacuum distillation of the atmospheric distillation unit bot-
fuel oils and diesel fuels. Since the jet fuel market now ex-
toms (ASTM Test Method for Distillation of Petroleum Prod-
ceeds the kerosine market in parts of the world, many re-
ucts at Reduced Pressure, D 1160-95) usually separates an-
finers now label this stream the "jet" cut.
other 30% of the crude oil as vacuum gas oils having a fined
• Atmospheric Gas Oil (AGO)—The gas oils are generally
boiling point ranging from 500-575°C.
those distillable streams heavier than kerosine. The name
Selection of downstream processing units is greatly dic- was derived in the early industry days when these oils were
tated by demand and specifications of the different products, thermcJly cracked to produce olefin-containing "illuminat-
and, particularly, increasing sulfur removal requirements. ing" gases for street lighting, for example. Depending on
One of the key considerations is gasoline demand. For exam- the final boiling point of the AGO a n d the downstream pro-
cess options, t h e atmospheric distillation unit m a y jdeld
one AGO c u t o r two. The lighter portion m a y b e hy-
' President, Edu-Tech Management Resources, 73 Yorktown Road, drotreated to produce low sulfur diesel, while the heavier
East Brunswick, NJ 08816-3329. cut, hytrotreated or not, is typically processed in the FCCU.
Copyright' 2003 by A S I M International www.astm.org

4 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK
C, + C,
REF. FUEL
•LPG
GASES PROPANE
•LPG •ALKYLATE
CRUDE BUTANES -MTBE
•GASOLINE
LSR ISOMERIZATION -GASOLINE

A
T NAPH CAT
M HYDROTREATING
REFORMING
•GASOLINE
D KERO
I HYDROTREATING •JET FUEL
S
T GAS OIL
• HYDROTREATING — No. 2 FO/DIESEL
MTBE
ATM V RESID
GASES
Q ALKYLATION
L GASOLINE
V GASOLINE
A
C LVGO FLUID LCO
No. 2 FO
CATALYTIC
D HCO
No. 6 FO
I HVGO CRACKING
s DO
•CARBON BLACK
T
H, PLANT
HYDROCRACKING •REFORMER FEED

— No. 6 FO •JET FUEL
— ASPHALT •VISBREAKING
•DEASPHALTING
VAC RESID •COKING
•HYDROCRACKING
FIG. 1—Refinery block flow diagram.
Vacuum Gas Oils (LVGO and HVGO)—i:\iese cuts are usu- The need for sulfur removal is on an ever-increasing path
ally processed in the FCCU. They can be processed in a hy- as average crude oil sulfur content continues to increase and
drocracking unit (HCU) wherein they can be converted product sulfur is forced to lower levels by environmental leg-
into catalytic reformer feed, jet and diesel fuel, and for pro- islation. Sulfur removal, today, is accomplished in "hy-
duction of lubricating oil base stocks. droprocessing" units. Hydrotreating, wherein the goal is to
Vacuum Resid—The residuum portion of crude oil is the remove sulfur (and other heteroatoms) with minimum con-
non-distillable cut, boiling above, say, 575°C. It cannot be version of the hydrocarbon feed stream to lower boiling
distilled without causing substantial thermEd destruction molecules, is the most widely utilized. Alternatively, hydroc-
of its hydrocarbons. This cut is sold to the asphalt and racking is utilized to remove heteroatoms and concurrently
heavy fuel oil markets, or processed by the options shown convert varying amounts of "high boilers" to lower boiling
in Fig. 1. streams.
CHAPTER 1: PETROLEUM OIL REFINING 5
TABLE 1—Crude section cuts. the maximum possible hydrogen. To compUcate matters, in
Carbon Approximate crude oil some carbon atoms are also bonded to sulfur, ni-
Name/Other Names Number Boiling Range, "C trogen, oxygen and metals, as well as trace amounts of other
Gases C1-C4 -160-0 elements.
Light straight run gasohne C5-C6 25-90 The four hydrocarbon types, based on the above character-
light n a p h t h a istics, are:
LSR
gas condensate Name Chain/Ring Saturated/Unsaturated Example
Heavy straight run naphtha C6-C10 85-190 Paraffin Chain Saturated Hexane
Heavy naphtha Olefin Chain Unsaturated Hexene
Naphtha Naphthene Ring Saturated Cyclohexane
Reformer feed Aromatic Ring Unsaturated Benzene
Kerosine or kerosine C9-C15 160-275
jet The four types are listed in the order shown after chemi-
Light atmospheric gas oil C13-C18 250-340 cal analysis, and are usually referred to by the term PONA
furnace oil
diesel
analysis (ASTM Test Method for Hydrocarbon Types in Liq-
Heavy atmospheric gas oil C16-C25 315^10 uid Petroleum Products by Fluorescent Indicator Adsorp-
AGO tion, D 1319-98). In chain hydrocarbons, all carbon atoms
gas oil can be linked in a straight row; these are the "normal" ver-
Light and heavy vacuum gas oils C22-C45 370-575 sions, such as the example of a six-carbon hydrocarbon,
LVGO and HVGO
Vacuum resid" C40+ 500+-565 +
normal hexane (n-hexane). "Isomers" of n-hexane exist as
vacuum bottoms branched-chain versions; as a group, these are labeled
short resid isoparaffins, for example i-hexanes. They are commonly
vacuum reduced crude connotated as nC6 and iC6s. When a hydrocarbon type
asphalt analysis is made that includes a normal/isoparaffin split, the
"The corresponding bottoms from the Atmospheric Crude Tower is called: normals keep the letter P, the isos take the letter I, and the
Atmospheric Resid Reduced Crude olefin/aromatic order is reversed, resulting in the acronym
Atmospheric Bottoms Topped Crude
Long Resid PIANO. This same split is not attempted for the normal and
branched-chain olefins because of the greater number of
potential olefin structures and the lesser impact on refinery
process options.
HYDROCARBON TERMINOLOGY
There cire four basic tjrpes of hydrocarbon chemical struc-
tures. Their differences relate to the bonding between carbon
TABLE 3—Disposition of refinery C1-C4 gases.
atoms and whether the carbon bonds create a chain- or ring-
shaped molecule. The number of electrons in the outer shell Carbon Chemical
Number Name End Uses
of a carbon atom requires each atom to have four bonds to be
stable. This four-bond requirement can be peirtially met by a CI Methane Refinery Fuel Gas (RFG)
C2 Ethane RFG
carbon atom forming single or multiple bonds with adjacent Ethylene RFG, PetrochemicEils
carbon atoms. Nearly all hydrocarbon molecules encoun- C3 Propane Liquefied Petroleum Gas (LPG)
tered in refining chemistry consist of all singly bonded car- Propylene Petrochemicals, Alkylation Unit,
bons, or contain pairs of doubly bonded adjacent carbons; Polygas or Dimerization Unit
the remaining bonds cu-e satisfied with hydrogen. When eill C4 n-Butane LPG, Isomerization Unit, Gasoline
Blending
carbon-carbon bonds in a molecule are single, it is called sat- i-Butane Alkylation Unit
urated, because it contains the maximum possible amount of Butylenes Alkylation Unit, MTBE, Polygas or
bonded hydrogen. When there cire double bonds present, the Dimerization Unit, Petrochemicals,
hydrocarbon is labeled unsaturated, since it holds less than Isooctane Unit
TABLE 2—^Worldwide refining capacity as percent of crude.

Weight Percent on Crude Capacity
Crude Oil
Distillation, Vacuum Hyd retreating
Region Million mt/year Distillation FCCU CRU + Hydrocracking Coke
Asia/Pacific 1020 23 13 9 41 0.4
Western Europe 740 36 15 13 58 0.5
Eastern Europe/FSU 540 35 8 12 38 0.8
Middle East 300 34 5 9 37 0.3
Africa 160 15 6 11 25 0.2
North America 1010 46 33 19 68 4.5
So. America/Caribbean 340 43 19 5 29 1.8
4110
Source: Oil & Gas Journal Worldwide Refining Report for January, 2001.
6 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK
By chemical naming convention, all saturated hydrocar- almost always less dense than water, which has a specific
bons, the paraffins and naphthenes, end in the letters "ane," gravity of 1.0. Worldwide, average API Gravity is about 31
while all unsaturated hydrocEirbons, the olefins and aromat- (sp. gr. = 0.87) and ranges from a high of about 45 for "light"
ics, end in the letters "ene." Each of the four species has dif- crudes to a low of 8-15 for the "heavy" crudes, tar sand oils,
ferent properties and reactivity, and this plays a major role in and the like. Aromatics are the densest of the hydrocarbon
refinery unit selection and operation. The amount of the var- types and are therefore lowest in API, while peiraffins Eire gen-
ious heteroatoms and the m a n n e r in which they are bound to erally highest in API gravity. As boiling point of the crude oil
carbon also is critical to refinery operation. These factors will increases, a r o m a t i c s content increases. Thus, high API
be apparent throughout the remainder of this chapter as well crudes likely have lower concentrations of high boilers and
as in other parts of this manual. most likely less aromatics, while low API crudes are generally
higher in aromatics and in high boilers.
C R U D E OIL
Sulfur
Hydrocarbon Composition Worldwide, weight average crude oil sulfur content is about
1.25% with commercial production ranging from 0.1-6%.
Crude oil is composed of aromatic, paraffin and naphthene
Crudes low in sulfur are labeled "sweet" while those higher in
hydrocarbons. Minor amounts of olefins may be present. Av-
sulfur £ure designated "sour." The terms derive mainly from
erage aromatics content is about 50%; however, it can range
the foul, or sour, odor of one of the sulfur species, the mer-
from as low as 2 5 % in light paraffinic crudes to as m u c h as
captans, as well as the corrosiveness of hydrogen sulfide and
75% in heavy oils, such as those recovered from Canadian tar
the mercaptans. The split between sweet and sour was at
sands. The paraffin/naphthene ratio is widely ranging and is
0.5% when average sulfur was m u c h lower than today; now,
qualitatively identified via the labeling of many crudes as
the crossover is more likely in the 0.5-1.5% range and is usu-
"paraffinic" or "naphthenic." Hydrocarbon composition af-
ally designated by each refinery depending on its history and
fects many considerations in selecting processing options, or
capability to process higher sulfur crudes. Barring the dis-
meeting product specifications, as shown by the following ex-
covery of major low sulfur crude oil pools, it is expected that
amples:
average sulfur will continue to modestly increase.
Aromatics
Because of their inherent molecular stability, they are the Nitrogen
bane of refining. Aromatics are the most difficult compounds
to thermally crack, hydrogenate, and desulfurize. They are Generally, nitrogen content is about 5-20% of sulfur content
increasingly "unwanted" species in fuel products because in most crudes. This is a helpful circumstance because nitro-
they are the hardest to completely combust, thus contribut- gen removal requires greater process severity than sulfur re-
ing more to pollution and equipment maintenance. As prod- moval since nitrogen is mostly bound in ring form while a
uct aromatics content is regulated to lower levels, refinery greater percent of sulfur is bound in chain form. Heteroatom
removal from rings is more difficult than from chains. Many
process severity and costs will increase. Aromatics do have
California crude oils are high in nitrogen content, often
value in the refinery flow plan as a high-octane gasoline
equaling sulfur content, and thus require greater process
blending component from the catalytic reforming unit and in
severity than other crudes of equal sulfur content.
the recovery of chemical grade aromatic feedstocks for the
petrochemical industry.
Metals
Paraffins and Naphthenes
These constituents are more readily processed in the refinery. Organometallic compounds are predomineintly found in the
Each offers "positive" and "negative" features, but the effects vacuum resid. Important metals are nickel, vanadium, cop-
of these species are not as severe as for the aromatics. As an per and iron, with nickel (Ni) and vanadium (V) usually in
example, paraffins crack cleanly and thus yield m i n i m u m highest concentration. Ni + V levels in resid range from a few
coke, but, in fuel blends, they raise pour point and are more p p m to as m u c h as 1000 ppm. The metals, particularly Ni,
difficult to octane-upgrade in the CRU. have an adverse effect on catalyst performance and have
specified maximum limits in products such as heavy fuel oil
and petroleum coke. This can affect crude selection options
Density for many refinery process configurations and product slates,
The density of chemiceJ compounds is expressed as specific as well as in process selection for future refinery revamp/ex-
gravity (sp. gr.). In the petroleum industry, this weight/vol- pansion projects.
u m e relation is expressed worldwide as "API (American
Petroleum Institute), or commonly as "API Gravity", per the Oxygen
formula "API = (141.5/sp.gr.) - 131.5 (ASTM Test Method
for API Gravity of Crude Petroleum and Petroleum Products, Acids, particularly naphthenic acids, and phenols constitute
D287-92). The formula was adapted from the Baume density the main organic oxygen compounds in crude oil. A substan-
equation used for sulfuric acid. Its value is the creation of a tial portion are in the naphtha, kerosine, and gas oil boiling
whole n u m b e r scale to more readily discern one crude oil ranges. These compounds are readily eliminated via hydro-
from another, rather than using decimals, since crude oils are genation, and will pose less concern as more hydrotreating is
added to the flow plan to achieve greater sulfur removal. If process technology such as catalytic reforming and alkyla-
these streams are not hydrotreated, the acids are usucJly re- tion. However, the industry also introduced organic oxy-
moved by many variations of caustic treating. genates to gasoline blends, initially alcohols and then ethers,
since such compounds have high octane quality (Table 4).
Of the three utilized alcohols, the only surviving member is
PRODUCTS ethanol, which is used in the U.S. through the help of gov-
ernment price subsidy. Concern for water solubility, corro-
The main refinery products, except for the gas streams shown sion, and emissions problems from the alcohols, verified or
in Table 3, are automotive gasoline, kerosine/jet fuel. No. 2 not, drove the U.S. refining industry to the ethers. The first,
and No. 6 fuel oils, and No. 2 diesel fuel. Changes to the re- a n d still dominant, ether was methyl tertiarybutyl ether
finery flow plan have mainly been driven by changes in crude (MTBE), which was initially provided by ARCO Chemical
oil quality, and in specifications and demand for these prod- converting tertiarybutyl alcohol, a by-product from their
ucts. It should be noted that all industry fuels and lubricants propylene oxide process, to the isobutylene feed needed to
are presented in this manual including a complete presenta- make the ether.
tion and discussion of test methodology and properties. Volatility requirements can be described as the control of
the boiling range of the gasoline to assure that the automo-
bile operates properly during startup, warm-up, and hot op-
Gasoline eration. Gasoline specifications assure that there is a proper
balance among the C5 through C l l hydrocarbons that con-
The first meaningful specifications evolved in the 1920s.
stitute the gasoline boiling reuige, and that the final boiling
From this beginning until 1990, the two key control proper-
point is limited. Volatility control also includes the need to
ties have been "octane number" and "volatility." Octcine num-
add liquefied n-butane to provide sufficient vapor pressure
ber, the measure of the engine to resist the rapid "pinging"
(ASTM Test Method for Vapor Pressure of Petroleum Prod-
noise, called "knock," due to improper combustion, steadily
ucts (Reid Method), D 323-99a) to ensure cold engine startup.
increased as engines became larger and more powerful, peak-
This results in "seasonal" volatility grades wherein butane
ing in the eeirly 1970s. The refinery met the required octane
content and boiling range Eire varied to match expected am-
appetite of the car population by instcJling processes that
bient temperature.
produce high octane streams, such as the FCCU, CRU, and
alkylation and isomerization. In addition, organolead com- As industry used the oxygenates to meet octane number re-
pounds, mainly tetraethyllead (TEL), were used to add about quirements, data showed oxygenates can reduce pollutants
eight octane numbers to the gasoline pool. such as carbon monoxide (CO) and nitrogen oxides (NO^).
And, as analysis of the effect of various gasoline constituents
Two laboratory octane n u m b e r test methods are used to
on tailpipe emissions became better defined, it became ap-
measure and control this gasoline quality parameter, the Re-
parent that other compositional changes would be beneficial.
search Octane N u m b e r (RON) and Motor Octane N u m b e r
This was addressed by passage of the U.S. Clean Air Act
(MON), per ASTM Test Methods for Research Octane Num-
Amendments in 1990. This legislation, and subsequent regu-
b e r a n d Motor Octane N u m b e r of Spark-Ignition Engine
lations such as those enacted in Ccdifomia, has substantively
Fuel, D 2699-97a and 2700-97, respectively. Their different
changed the entire composition of gasoline (Table 5), per
operating conditions, detailed in this manual, act to delineate
ASTM Specification for Automotive Spark-Ignition Engine
and bracket the potential for knock in the automobile popu-
Fuel, D 4814-99. As a result, the refinery has undergone con-
lation. In most of the world, RON is the value the consumer
tinuous change to meet the cleaner fuel product require-
sees at the "pump," while in the United States and Canada,
ments. These changes, initiated in the U.S., are being adopted
the average of both the RON and MON is the guiding specifi-
throughout most of the world; in some instances, legislation
cation.
in other locales is resulting in even more severe specifications
The first significant response to pollution from vehicular (Table 6).
emissions came with the passage of the U.S. Clean Air Act in
1973. This legislation stipulated that the m a i n pollutants
emitted from the automobile tailpipe; namely, u n b u m e d hy-
drocarbons, carbon monoxide and nitrogen oxides, had to be TABLE 4—The oxygenates.
reduced by 90%. The automotive industry chose to use a cat-
Blending
alyst to comply with this regulation. This "catalytic con- Actual
verter" requires platinum, or other noble metal such as palla- Name Source RVP, kPa RON MON
dium, to effect the desired emissions reduction chemistry. Alcohols
Platinum's activity, however, is adversely affected by lead. As Methanol Natural Gas 32 133 99
a result the oil industry had to remove lead from gasoline and Ethanol Crops 16 130 96
would have lost the eight octane numbers from the addition t-butyl alcohol Propylene Oxide By-Product 12 109 93
of TEL. The Act also required an increase in fuel economy Alcohol Olefin
from 12.5 mpg (5.35km/l) to 27.5 mpg (11.77km/l). This led Ethers
to a reduction in vehicle weight and power, which in turn re- MTBE Methanol Isobutylene 54 118 100
duced octane appetite by about four numbers. Thus, the net TAME Methanol Isoamylene 27 111 98
ETBE Ethanol Isobutylene 17 118 102
effect on the U.S. oil industry from 1974 through the mid- TAEE Ethanol Isoamylene 6
eighties was to add about four octane numbers to the base DIPE (Propylene + Water) 104"
gasoline pool. This was achieved mainly by the addition of "Average of RON and MON.
TABLE 5—History of U.S. gasoline specifications. Jet Fuel

Pre-1974 1974-1991 1992-1994 1995+
Today's military and commercial aircraft use jet fuels that are
Regular Grade produced almost exclusively from the kerosine fraction of
RON 94 Remove Pb, 91 91
MON 86 Increase Fuel 83 83
crude oil or similar boiling range cuts from certain refineiy
Pb, g/1 0.8 Economy 0.1 0 processes (Table 7). Key requirements focus on sulfur and
Premium Grade aromatics contents, clean burning characteristics, and stor-
RON 100 " 98 98 age stability (ASTM Specification for Aviation Turbine Fuels,
MON 90 88 88 D 1655-99). Increasingly, refineries use hydrotreating tech-
PB, g/1 0.9 0.1 0
RVP, kPa 62-103 50-90
nology, as well as crude slate selection, to meet specifications
Oxygen, %w 0 0.3-1.0" 2.7* 2.0-2.7* and aircraft power demand. Legislative reduction in sulfur
Benzene, %w, max 0.8-1.0 and aromatics is not currently anticipated.
90% Dist., °C, max 185-190 165-180
Aromatics, %w 30-45 20-35
Olefins, %w 8-15 4-10 F u e l Oil
Sulfur, p p m w 300-500 30-150
The various fuel oil grades are shown in Table 8 (ASTM
'Ôptional use for octane number improvement.
'Mandatory in locales requiring "oxy fuel" or reformulated gasoline. Specification for Fuel Oils, D 396-98). The major products
are No. 2 and No. 6 fuel oils. No. 2 fuel oil, commonly called
furnace oil or home heating oil, is the fuel used for residen-
tial and small commercial oil heating systems. No. 6 fuel oil
is commonly called industrial or heavy industrial fuel oil
TABLE 6—Gasoline specifications in U.S. and Europe. when used by utilities for electricity and steam generation.
United States California Europe
It is called Bunker, or Bunker C, fuel when used by the ma-
rine industry for those ships powered by "furnaces." Nos. 1,
Locale Year 1998-2000 2004 1996 2000 2005
4, and 5 are specialty products. For example, No. 1, also
Oxygen, %w 2.0-2.7 0.0-2.7 2.0 2.7 2.7 known as stove oil, is a kerosine-type blend for small stove-
MTBE, %w 11.0-14.8 Unknown 11.0" 14.8 14.8
1.0
like non-atomizing b u r n e r s a n d some farm equipment,
Benzene, %w 0.95-1.0 0.8-1.0 0.8-1.0 1.0
Sulfur, p p m w 150-350 30-150 30 150 10-30 while Nos. 4 and 5 are lower viscosity industrial fuel oils for
Aromatics, %v 25-32 20-30 25 35 30-35 smaller commercial furnaces such as those used by schools
Olefins, %v 6-12 4-9 4-6 14 12-14 and hospitcds.
''MTBE banned by 2003, but enforcement is currently on hold. Sulfur content is an important quality parameter. While
most No. 2 fuel oil is specified at 0.5%, maximum, (ASTM
Test Methods for Sulfur in Petroleum Products, D 129-95,
D 1266-98, and D 2622-98, for example) m u c h product has
considerably lower sulfur because of the n e w low sulfur
TABLE 7—Jet fuel specifications. diesel requirement. Many refiners have found that the added
Density, kg/m^ 775-840 cost to desulfurize No. 2 fuel oil to match diesel specifica-
10% Dist, °C, max 204 tions may be offset by reducing the n u m b e r of separate prod-
Final Boiling Point, °C, max 288-300 ucts, providing increased product blending options and re-
Flash Point, °C, min 38-60
Aromatics, %v, max 20-25 ducing storage and distribution costs. No. 6 fuel oil sulfur
Sulfur, %w, max 0.3-0.4 ranges from 0.25-3.5% depending on end use and locale. It is
MercaptEin Sulfur, %w, max 0.002 anticipated that average "six-oil" sulfur content will decrease
Freeze Point °C, max - 4 0 to -47 over time.
TABLE 8—Fuel oil specifications.

Grade No. 1 No. 2 No. 4 No. 5 No. 6
Stove Home Light Medium Heavy Ind'l
Uses and Farm Heating Industrial Industrial & Marine
Density, kg/m^, max 850 876
90% Dist, °C, max 288 338
Flash Point, °C, min 38 38-55 55 55 60
Pour Point, °C, max -18 -6 -6
Sulfur, %w, max 0.3-0.5 0.3-0.5 0.25-3.5
Viscosity
mm^/s @ 40°C
min 1.3 1.9 5.5
max 2.1 3.4 24.0
mm^/s @ 100°C
min 5-9 15
max 9-15 50
TABLE 9—Diesel fuel specifications. a n d v a c u u m towers/columns/crude u n i t s to provide the

Grades No. 1 No. 2 No. 4 streams in Table 1. Many refineries incorporate a preflash
Automobile Railroad, column before the atmospheric tower to remove a portion of
Farm, Truck, Marine, the lower boiling components. This improves subsequent cut
Uses City Bus Railroad Stationary Engine point control and flexibility in the atmospheric tower, and
90% Dist, °C, max 288 338 can increase m a i n c o l u m n capacity. A complex heat ex-
Sulfur, ppmw, max 10-5000 10-5000 20 000 change network is used to warm the crude to desalter tem-
Cetane No., m i n 40-55 40-55 30 perature and then to furnace inlet temperature.
Flash Point, °C, min 38-55 52-55 55
Aromatics, %w, max 10-35 10-35 Desalting is accomplished by mixing 100 parts of crude oil
with about 3-10 parts of water at about 120-140°C. Emulsi-
fier or demulsifier additives may be used to aid either the
mixing of crude and water or separation of the two after mix-
Diesel Fuel ing. Electrically charged plates may also be used to coalesce
water to aid in separation. The desalted water is then sent to
Key diesel fuel specifications and major uses eire shown in
wastewater treatment and, if necessary, for stripping of un-
Table 9 (ASTM Specification for Diesel Fuel Oils, D975-98b).
desired contaminants such as benzene.
The U.S. Clean Air Act Amendments also required the reduc-
tion of sulfur to 0.05% (500 ppmw), maximum, for over-the- After further heat exchange, usually to 210-240°C, the
road usage; namely, buses, trucks, and automobiles. The leg- crude is sent through multi-pass furnaces to attain atmo-
islation did not require lower sulfur for other use such as the spheric column inlet temperature in the range of 340-410°C.
railroad and marine industry. Again, as with the fuel oils, Then, by control of top column reflux a m o u n t and tempera-
m u c h No. 1 and 2 diesel is made "low sulfur" for all markets ture, reboil, and p u m p a r o u n d / p u m p d o w n parameters, the
to minimize product distribution costs. Driven initially by desired cuts are obtained.
European and California legislation, diesel fuel sulfur is be- Atmospheric column bottoms are usually sent to the vac-
ing further reduced toward 10-50 ppmw, requiring more se- u u m tower to recover the vacuum gas oils to a final boiling
vere hydrotreating. point (FBP) as high as 575°C, although 540-565°C may be
more common. The ability to reach desired FBP depends on
While the U.S. law did not substantially constrain aromat-
m a x i m u m furnace outlet temperature a n d its concomitant
ics content, California law did, requiring reduction of aro-
coke laydown on the furnace coils vs. economic run length,
matics to as low as 10%. Worldwide adoption of this level of
and attainable vacuum. Vacuums in the range of 7-25mm Hg
dearomatization will be difficult to achieve near-term, but a
absolute are usually achieved using steam ejector systems or
trend toward lower aromatic content diesel is occurring. This
vacuum p u m p s .
is being affected in part by requiring higher Cetane N u m b e r
diesel fuel (ASTM Test Method for Cetzuie Number of Diesel
Fuel Oils, D613-95). Aromatics decrease "cetane rating."
PROCESSES FOR GASOLINE AND
P o u r point (ASTM Test Method for Pour Point of
DISTILLATE YIELD A N D QUALITY
Petroleum Products, D97-96a) and cloud point (ASTM Test
Method for Cloud Point of Petroleum Products, D5771-95)
Fluid Catalytic Cracking
are importctnt parameters to assure proper flow of fuel oils
and diesel fuels under all anticipated ambient temperatures. This is the predominant process for converting high boiling
Pour point must be low enough to prevent solidification of gas oils a n d resid into lower boiling streams, mostly gases, a
the entire fuel while cloud point must be low enough to as- gasoline blending component and a light gas oil for No. 2 fuel
sure that normal paraffins will not solidify and block fuel oil blending, fts place in the refinery is mainly driven by the
flow in piping or through nozzles. yields and compositions of the product components, the abil-
ity of the process to vary product yield/composition, a n d
lower capital investment cind operating costs compared to al-
CRUDE OIL PREPARATION ternative process options.
AND SEPARATION Figure 3 depicts the process operating principles. Many
equipment configurations and catalysts are employed, but
A refinery may process just one crude oil or u p to as many as the essence of the process is reactor and regenerator "ves-
a few dozen, depending on factors such as captive crude sup- sels," vapor phase fluidization of the catalyst in each vessel,
ply, access to ocean and river delivery, and pipeline supply lo- flow of catalyst between the two vessels, thermal cracking of
gistics. At a refinery handling multiple crudes, individucil the feed in the reactor and removal of coke from the catalyst
crude oils are usually fed sequentially over variable lengths of in the regenerator. Much of the design variations cire related
time. Some of the crude oils may first be blended in interme- to engineering improvements and the increased processing
diate crude storage tanks to reduce the effects of substcintial of poorer quality feed, which in t u r n has been enabled by
changes in crude oil quality on the process units. greatly increased activity of today's catalysts.
In almost all refineries, the crude oil slate is processed as in Fresh feed and, if desired, heavy product recycle, are intro-
Fig. 2. Crude oil is first "descJted" to reduce entrained and duced into the reactor. The feed vaporizes and thermally
dissolved salts, mainly sodium, m a g n e s i u m and calcium cracks in about 1-3 s at about 525-550°C, to yield a potential
chlorides, to a n acceptable level a n d to remove "debris" such variety of product s t r e a m s exemplified in Table 10. Coke
as mineral matter resulting from transportation. The crude forms in the reactor section due to rapid polymerization of
oil is then physiccJly separated by distillation in atmospheric olefins a n d aromatics as cracking chemistry occurs. This
Condenser
Atmospheric —•0—iS^S—I I *•'Wet Gas

Distillation
•*LPG
Reflux "B-' Water • • Light

xr
r'stabifeation'l Straight Run
-*• and.
^ L.SpJtttinjtJ_*
~ ) P Stripper Naphth:
Kerosene
Crude t Stripper
Steam * Diesel
-Water
Preheat
Desaiteri
Steam "Gas Oil
Brim
Preheat L f i j J Furnace^»i=J
Preflash Steam -••Topped Crude

Drum
Vacuum Pre-
Non-condensat)les Condenser
Distillation
and steam
High Pressure
Steam
Non-
C.W. condensables
O P T -
QHot Wbll Accumulator [) » Naphtha
^ Heavy
Sour Water
Gas Oil
Topped
Crude
Q Ejectors
Coil
Steam Stripping
> Vacuum Resid
Steam
FIG. 2—Atmospheric and vacuum distillation units.
coke "lays down on" the fluidized catcJyst particles, dimin- CO, a pollutant, must be removed from the regenerator flue
ishing their activity. The "coked-up" catalyst is continuously gas. Even if CO emissions were not an issue, economics of
removed from the reactor section and transported with air to maximizing heat recovery would dictate oxidation of CO to
the regenerator wherein controlled combustion converts the CO2. This is accomplished by the use of combustion additives
coke into a "flue gas" consisting mainly of carbon monoxide in the regenerator, improved regenerator design and opera-
(CO), carbon dioxide (CO2), water (H2O), and sulfur and nition, and external secondary combustion in a CO or waste
trogen oxides (SOx and NOx) resulting from the presence of heat boiler. SOx and NOx pollutants face refinery emission
sulfur and nitrogen in the feed. This combustion raises the limits. Acceptable levels in the flue gas can be achieved with
catalyst temperature to 680-760°C which, in turn, supplies regenerator additives, various flue gas scrubbing processes,
most or all of the heat to raise fresh feed to its reactor tem- or by installing "cat feed hydrotreaters" to reduce the sulfur
perature as the "hot" regenerated catalyst is continuously re- and nitrogen content in the FCCU feed.
moved from the regenerator and re-mixed with fresh feed. In Run length between scheduled turnarounds for inspection
fact, many FCC units operate in heat balance, meaning that and maintenance is 3-5 years. Longer runs have resulted
all heat to raise the feed to reactor temperature is supplied by from ongoing improvements to the overall design that in-
the regenerated catalyst. clude multistage regeneration, improved cyclones and feed
nozzles, and taking advantage of favorable FCCU process TABLE 10—FCCU yields.
economics. Factors favoring economics include the ability to Operating Mode Gasoline Gas Distillate
produce high yields of high-value gas and gasoline from low Reactor Products, %w
value feed, substantial yield flexibility resulting from catalyst C1-C2 3 6 2
selection and variable operating parameters, operation at es- C3s 6 22 4
sentially atmospheric pressure, and no addition of hydrogen C4s 11-12 20 8
as is required in the hydr©cracking process. Gasoline 46-52 27 38
Light Cycle Oil 15-19 12 35
The cyclone systems in both the reactor and regenerator are Heavy Cycle Oil 7-8 5 9
mechanical devices to collect the catalyst carried out of the Coke on Catalyst 6 8 4
dense phase fluidized beds by the respective cracked product
and flue gas vapors. Although thousands of tons of catalyst
circulate each day, cyclone efficiency is so close to 100% that light products without the overproduction of coke. Catalyst
losses are kept in the 1-10 ton-per-day range. The losses from formulations can be chosen to maximize gasoline yield and
the reactor are returned via the downstream product recovery octane number, gas yield and olefin content; tolerate resid
train. Losses from the regenerator are collected and then dis- metals; and resist higher regenerator temperature resulting
posed, thus creating the need for daily catalyst replacement. from additional coke p r o d u c t i o n from the higher carbon
Early catalysts were silica-alumina "clays" incapable of residue level in the resid portion of the feed.
processing resid and limited in activity. Today's catalysts Reactor effluent is taken to the "cat main fractionator"
contain various highly active zeolites, combined with appro- wherein the main separation occurs to yield the olefin con-
priate silica-alumina bases, which permit the processing of taining gases, gasoline blending streams, a light gas (cycle) oil,
heavier, dirtier feed, as well as provide increased yields of and a heavy gas (cycle) oil. If the heavy gas oil has the right
properties, it, or a heavier portion of it, may be sold as feed to
produce carbon black for the manufacture of tires and print-
Reactor Vapor ing inks. If so, it will be labeled carbon black oil, decant oil,
slurry oil, or clarified oil. It is the heavy gas oil that is used as
the "washing" stream at the b o t t o m of the fractionator to re-
move the catalyst to the settler and then back to the reactor.
The gases undergo further absorption and distillation to
achieve the desired separation for various end uses. Some re-
finers select feed, catalyst and operating conditions to maxi-
Reactor
mize olefin gas yield at the expense of gasoline and/or light
cycle oil yield. This has been done to meet growing demand
for propylene as a petrochemical feedstock and to provide
Reactor Riso'
butylenes for MTBE and alkylation feed.
The "cat" gasoline, a major gasoline blending component
used throughout the world, is treated for mercaptan sulfer re-
Regenerator moval prior to product blending for odor and corrosion con-
Spent-Catalyst trol. Removal of other sulfer compounds, or just the sulfur
/ / Stripper atoms themselves, will be required to meet future demand for
Combustor low sulfer gasoline. While desulfurization via hydrotreating
Riser
will r e m a i n a d o m i n a n t technology for some time, other
sulfer removal technologies, for example utilizing extraction
Catalyst or oxidation, are in various stages of commercicdization.
Cooler
(Future) The light cycle oil is mainly blended to No. 2 fuel oil. As
feeds to the "cat" unit get dirtier, and as demand for cleaner
Spent-Catalyst fuels grows, the refiner will be faced with an increasing need
Combustor Standpipe to reduce the sulfur, nitrogen, and aromatics content of this
stream, if for n o other reason than to provide blending flexi-
Recirculated- Regenerated- bility into the diesel fuel markets. Heavy cycle oil yield is very
Catalyst Catalyst
Standpipe Standpipe low in today's operation; most refiners blend this cut to No. 6
fuel oil, while some recycle it to extinction in the reactor. It
was this recycle of the FCCU gas oil in the early days of this
Cooled- process that gave rise to labeling them light and heavy cycle
Cataiyst Chargestock
Standpipe oil in addition to light and heavy gas oil.
(Future)
Key fluid catalytic cracking process variables include:
t • Catalyst circulation rate, commonly called the "cat-to-oil
ratio"
Combustion Air • Reactor temperature
UitGas • Catalyst activity
• Feed residence time
FIG. 3—Fluid catalytic cracking unit.
\
The cat to oil ratio, in the weight range of 4 to 15, can be case, the sensitivity of the catalysts to coke, and to deactiva-
varied within the Umits of maintaining the necessary pres- tion from heteroatoms such as sulfur and nitrogen, requires
sure balances and vessel vapor velocities so that catalyst flow that the naphthas first be hydrotreated.
and bed fluidization are properly maintained. Reactor tem- Fresh hydrotreated naphtha feed plus recycle hydrogen is
perature will vary with cat-to-oil ratio, regenerator tempera- heated to reactor temperature of about 500-530°C in a fur-
ture and catcdyst cooling, and from feed preheat for those nace and fed to the first reactor. The over-riding chemistry is
units having feed furnaces. Process severity is mainly defined endothermic dehydrogenation of naphthenes to aromatics.
in terms of conversion of the heavy feed into gas and gaso- Thus, as the feed progresses down through the catalyst, as
line, and is expressed as 100 minus the product streams boil- m u c h as 60°C cooling occurs from top to bottom in the first
ing above gasoline. Conversion typically ranges from reactor, reducing activity and hence aromatics yield. The net
50-85%. Lower conversion is desired to meiximize light cycle effect is that octane n u m b e r gcdn in one reactor is not enough
oil yield for blending No. 2 fuel oil during the oil heating sea- to make the process attractive. Therefore, the reactor effluent
son, while higher conversion is set to meet gasoline a n d is reheated in a second furnace, or in a second coil within the
olefin gas deniEmd. same furnace, back to 500-530°C and fed to a second reactor,
and so on, until desired octane product is attained. Cat re-
formers usually consist of three reactors although as many as
Catalytic R e f o r m i n g five are utilized.
This process is an essential part of every refinery that desires Typical yields at two product RON levels are shown in
to use the heavy straight run naphtha fraction from crude, or Table 11. The net hydrogen produced from aromatics forma-
similar boiling range material from a n o t h e r process unit tion is the m a i n source of hydrogen in the refinery for its
such as the hydrocracker, as a gasoline component. The feed, desulfurization and related needs. Refineries are in "hydro-
usually a C6-C10 cut, is too low in octane n u m b e r to be eco- gen balance" if all such hydrogen can be provided by the re-
nomiccdly blended to the gasoline pool. The "cat reformer" formers. If not, refiners purchase hydrogen or build their
converts low octane n u m b e r peiraffins and naphthenes in the own hydrogen plants.
feed into "high octane" aromatics in the product. Typical feed Figure 5 depicts the main process parameters of catalytic
unleaded RON is 40-65 while product is 94-103. reforming; namely, the "yield-octane" relationship. Higher
There Eire three main reactor configurations, two of which octane n u m b e r d e m a n d requires higher reactor temperature
are shown in Fig. 4; all accomplish essentially the same and/or longer residence time. Both will cause more of the
chemistry. naphtha feed to crack into gas and thus reduce gasoline 3rield.
• Semiregenerative—Fixed bed reactors, all operating in se- "Reformer severity" is uniquely defined as the unleaded RON
ries. of the C5 + liquid product, the second major gasoline blend-
• Cyclic—Fixed bed reactors in series; one out of service on ing component. In fact, the gasoline streams from the fluid
rotating basis for catalyst regeneration. cat cracker emd cat reformer make u p about two-thirds of the
• Continuous—Moving bed reactors in series with "continu- world's gasoline.
ous" catalyst regeneration. Significant changes in feed composition to the reformer
The evolution from the original semiregenerative reformer a n d in downstream utilization of the reformate are occur-
to today's continuous unit was driven by "competing chem- ring, related to the move toward cleEmer fuels. The major
istry" within the process and by the need for higher octane source of benzene in gasoline is catal3îc reformate. The
n u m b e r product to help replace the lost octanes from lead. trend is to reduce benzene to a m a x i m u m of 1%, with the po-
Hydrogen must be added with the naphtha feed to minimize tential for even lower limits being legislated in parts of the
coke formation and laydown on the catcdyst and achieve eco- world. When the p u s h for lower benzene content began,
nomic run length, since catalyst performance is readily di- worldwide benzene levels ranged from as low as 1.6% in the
minished by coke. Higher operating pressure aids in reduc- U.S. to as high as 5% in pEirts of Europe and Asia. Refiners
ing coke formation chemistry. However, the goal is to can reduce benzene concentration as follows:
maximize the conversion of naphthenes to aromatics since 1. Remove benzene precursors from the feed. This is accom-
higher eiromatics content translates into higher octane num- plished by increasing the initial boiling point of the heavy
ber reformate. Lower operating pressure increases aromatics naphtha feed, or, in essence, raising the cut point between
yield since it makes it easier for hydrogen to "escape" from light and heavy straight run naphtha. This results in less
the naphthene. The continuous process is thus able to oper- feed available to the reformer and lower octane quality in
ate at lower pressure because the resulting higher coke make the resultant higher boiling range light straight r u n
can be removed "continuously." In actuality, a catalyst parti- stream.
cle tcikes about five days to migrate from the top of the first 2. Leave the benzene precursors in the feed. In this case, re-
reactor to the bottom of the last; such r u n length in the fixed finers can then distill the C6 cut from the reformate. Ben-
bed "semi-regen" reformer would be unacceptable. zene can be extracted from this cut for chemical sale, or the
The original catalyst that enabled this chemistry consisted benzene can be reacted with olefins to produce alkylben-
of an alumina base promoted with 0.25-0.75% platinum. To- zenes. The C6 cut can also be hydrotreated to convert ben-
day's catalysts may contain just the platinum promoter; may zene to cyclohexEine with a resultant loss in octane number.
be bi- or tri-metallic using additional metals such as rhenium Clcciner gasoline also mcindates lower final boiling point
and tin; may have the alumina base converted to the more and lower total aromatics. This requires the refiner to elimi-
acidic chloride form by treatment with chlorine or chloro- nate a substantial portion of high boiling fraction from the
i
form, for example; or may utilize appropriate zeolites. In any naphtha feed and, in some cases, to r u n the reformer at lower
Semiregenerative Catalytic
Reforming Unit
Net hydrogen
Compressor
Recycle hydrogen
Off Gas
C3s&C4s
^^-^cÔ
Heavy
Naphtha
Separator
Reformate
Continuous Catalytic
Reforming Unit
Spent Catalysi
Product
'Separatiofi
Naphtha &
Recycle Gas
FIG. A—Semiregenerative and continuous catalytic reforming units.

severity to yield less total aromatics. Beside the loss of octane of their widely different freeze points, or by adsorption with
number and yield, these changes likely yield less by-product molecular sieves, which takes advantage of their different
hydrogen, a costly ingredient needed for desulfurization molecular diameters.
chemistry.
Catalytic reformate also plays an important role in the Isomerization
petrochemical industry by being a major source of benzene,
para-xylene, ortho-xylene, and toluene primary feedstocks. This process mainly converts normal paraffins into isoparaf-
The recovery of these aromatics is illustrated in Fig. 6. Total fins. The technology is employed to increase the octane qual-
reformate, or a narrower C6-C8 cut, is fed to a liquid-liquid ity of light straight run gasoline/naphtha by converting n-
extraction column where it is contacted countercurrently pentane and n-hexane into mixed C5-C6 isoparaffins. The
with a solvent with known selective solubility for aromatics. process is also used to convert n-butane into isobutane to ei-
The main solvents are sulfolane or di- to tetra-ethylene gly- ther provide feed to the alkylation process or as a step in the
cols. The aromatics, called the extract, are then distilled from process to make MTBE when isobutylene is not available.
the reusable solvent. The rejected paraffins and naphthenes, A simplified process flow diagram is shown in Fig. 7. Fresh
called raffinate, must find a new home which can include the feed, along with recycle hydrogen, is heated to reactor tem-
solvent/spirits market or as feed to ethylene plants running perature of 180-260°C by heat exchange or a furnace. The
on naphtha; recycling the raffinate to a high severity catalytic feed then flows down through a fixed bed of catalyst that is
reformer is usually not economically attractive. The "pure" similar to reforming catalyst. Operation may be once-
aromatics in the extract are then separated in a series of dis- through, or with peirtial or total recycle of unconverted n-
tillation columns, except for meta- and para-xylene, which paraffin. The recycle can be recovered using distillation to
have virtually identical boiling points. Their separation is ac- separate lower boiling isoparaffin product from the normals,
complished either by crystallization, which takes advantage or adsorption with molecular sieves to separate smaller di-
ameter n-paraffins from isoparaffins. Recycle yields a greater
octane number increase at the expense of higher capital in-
TABLE 11—Catalytic reforming unit yields. vestment and operating cost. Octane improvement generally
Reformer Severity 102 94 ranges from 5-25 numbers depending on feed composition
Yield, %w and process configuration.
Hydrogen 3.0 1.7 Because of the low reactor temperature, thermal cracking
CI + C2 3.7 1.0 of the feed is very low, in the order of 1-2% compared to
C3 3.5 1.8
iC4 1.8 1.4 12-20% in the CRU. However, the sensitivity of the catalyst to
nC4 2.5 2.1 coke laydown still requires the presence of hydrogen to min-
C5+ Reformate 85.5 92.0 imize coke formation and hence provide satisfactory activity
and run length.
96
High Aromatics Feed
2
g>
+ Low Aromatics Feed
O
76
94 96 98 100 102 104
RON without Pb
FIG. 5—CRU yield/octane relationship.

'^Raffinue
Bxtfictio
^Tnadngind
Fnctiamtioii
Feed
LSGBflD
E«EXTRACTOR
S'STRlPfCR
RC - RECOVERY COLUMN
SR - SOLVB^TREOENERATOR
FIG. 6—Solvent extraction unit for btx recovery.
Alkylation availability, cost t o separate into chemical grade compo-

nents, and high octane quality of the alkylate. However, as
The reaction of an olefin with an aromatic or isoparaffin is la-
the light olefin content of gasoline diminishes due to evolving
beled alkylation. Benzene is alkylated with ethylene to even-
legislation, refiners may also find it economically attractive
tually produce styrene, and with propylene to eventually pro-
to use amylenes as alky feed, instead of converting them to
duce phenol. These "petrochemical" technologies are found
lower octane pentanes in a hydrotreater.
in some refineries. But the "alky" process that is part of the
typical refinery flow plan (Fig. 1) is the reaction of C3-C5 In many refineries, there is insufficient isobutane to match
olefins with the paraffin isobutane. the availability of olefins from the FCCU and cokers. The
The process requires that the paraffin be branched to pro- missing iC4 can be produced by isomerizing available nC4,
vide a reactive tertiary carbon atom, bonded to only one hy- by purchase from the natural gas condensate pool, or from
drogen. Normal paraffins, having only primary or secondary nearby refineries lacking an alky plant.
carbon atoms, are not sufficiently reactive. Isopentane could The catalysts that are commercially employed are 98-99%
be used, but it is already a clean, high-octane liquid con- sulfuric acid (H2SO4), or concentrated hydrofluoric acid
tained in the C5 part of the gasoline pool. Thus, the gas isobu- (HF) because the chemistry requires a very strong acid. Com-
tane becomes the obvious choice since it is reactive, not part mercialization of solid-type catalyst is in progress. The pro-
of the gasoline pool, and reasonably available in the refinery cess in concept is simple: pressurize the system to liquefy the
as a crude oil component, as well as in the C4 product from hydrocarbon feeds, mix them with the strong liquid acid, and
processes s u c h as the FCCU, CRU, a n d hydroprocessing separate the alkylate from the catalyst. The process in reality
units. is complex because of acid carryover into the alkylate; for-
The chemistry can be accomplished with any olefin. Ethy- mation of acid-hydrocarbon molecules; significant exother-
lene is not used because it is expensive to recover, operating mic heat of reaction; the need for substantial excess isobu-
pressure would have to be considerable since the process is tane to suppress olefin polymerization; high catalyst
carried out in the liquid phase, and the resulting alkylate oc- consumption and utility cost in the case of H2SO4; and safety
tane quality is poor compared to processing higher molecu- considerations, especially with hydrofluoric acid.
lar weight olefins. Propylene is a n "alky" feed in many units, Sulfuric acid alkylation m u s t r u n at low temperature,
but its use competes against its value as a petrochemical feed namely, about 5-10°C, in order to minimize olefin polymer-
for polypropylene, propylene oxide, and linear alpha olefins. ization, acid consumption, and by-product yield. This re-
The butylenes are the predominant alky feed because of their quires refrigeration of the catalyst and feed, and substantial
4—Mafenp
£ Hydiogra
• • [ ^ ri
c:^ OM
a ?
iall:^^ sr
X
LEGEMD
D-DRYER
C5-C
.J^ FIG. 7—Isomerization unit.
booMnli
R-REACrOR
ST • STABILIZER
mixing energy because of the acid's high viscosity. Most alky alkylate, cooling of recycle acid, recovery and recycle of isobu-
units used sulfuric acid from the commercialization of the tane, cleanup of alkylate, and separation of products. Typical
process in the 1940s until the 1970s, the period when energy product yields, quality, and disposition are shown in Table 12.
cost was low. In addition, H2SO4 consumption is substantial
at about 0.1 kg per kg alkylate. Since the early 1970s, most
new units have been H F alky plants to counteract higher en- MTBE
ergy cost. H F alkylation operates at about 25-50°C negating Oxygenates were introduced into the gasoline pool in the
refrigeration, acid viscosity is so much closer to that of the 1970s to help replace the lost octanes from lead additives.
hydrocarbons that designs can accomplish the chemistry in Their use has now been mandated in many parts of the world
piping or in simpler mixing vessels, and acid consumption is based on data showing their ability to reduce harmful vehicle
only about 0.001 kg per kg alkylate. However, the use of H F emissions. The majority of worldwide use of MTBE is by
poses a more serious safety concern than H2SO4 in the event commodity chemical p u r c h a s e . However, a substantial
of a n acid release. A sulfuric acid spill will cause soil and a m o u n t is made within the refinery gate, in particular in the
g r o u n d w a t e r contamination; however, hydrofluoric acid, United States. Typically, the MTBE unit is installed in front
which boils at 20°C, will release a vapor cloud of H F as it es- of a n alkylation unit. The C4 cut from the FCCU is first fed to
capes emd depressurizes. Releases of H F at a n u m b e r of U.S. the MTBE unit where the isobutylene is reacted with pur-
refineries in the 1980s led to significant re-engineering to as- chased methanol. The effluent C4 paraffin and olefin stream,
sure process safety and "save" the process from legislative ex- minus isobutylene, is then sent to the alky plant.
tinction.
MTBE has helped the refiner meet gasoline d e m a n d and
A simplified flow diagram is shown in Fig. 8 for an H F alky- octane, and is being adapted for blending worldwide. In fact,
lation unit. Key highlights include separation of the acid from during the 1980s and much of the 1990s, it was the fastest
FEED REACTION
PRElKEATMEm- SECTION BOSIRIFFER DEFKOPANIZER HFSnUFPER
Mixed
Batane*
OUfin
Feed DiyingAnd
Diokfin
"j » Saianlioa
FIG. 8—HP alkylation unit.
TABLE 12—HF alkylation unit yield and quality. banned, it is likely that TAME will suffer the same fate.
Olefin Feed C3 + C4 C4 Ethanol continues to be used, particularly in the United
Yields, %w
States and Canada, and some refiners are substituting
Propane 4-10 ethanol for the ethers.
n-Butane 2-5 3-6 Other technologies utilizing isobutylene, beside alkylation,
Alkylate 76-90 80-93 are being added to the refinery flowsheet. One example is the
Alky Bottoms" 3-8 3-8 dimerization of isobutylene to isooctene, followed by its con-
Alky Tar* 1 1
Alkylate Dist, °C version to isooctane via hydrogenation.
Initial BP 40 40
10% 70 75
30% 90 100 PROCESSES FOR HETEROATOM REMOVAL
50% 100 105
70% 105 110 AND AROMATIC/OLEFIN SATURATION
90% 120 125
Final BP 190 195 The main technology for removing unwanted heteroatoms
RON, without Lead 93 96 such as sulfur and nitrogen, and for reducing aromatics euid
MON, without Lead 92 94 olefin concentration in refinery liquid streams, is by contact-
^Too high boiling for gasoline. Usually blended to diesel and fuel ing the stream with hydrogen in the presence of a catalyst,
oil.
' A "waste" stream of high molecular weight. May be processed in and at appropriate temperature and pressure. The vocabu-
cracking units, burned as fuel, or disposed. Iciry to identify the numerous applications is extensive and
not universally consistent. The most common generic name
is hydroprocessing. This has been further divided into three
growing "chemical," with usage now surpassing 20 million categories; hydrotreating, hydrorefining, and hydrocracking,
mt per year. However, the use of this ether and perhaps other to delineate process severity for desired product cleanliness,
ethers could be reduced or banned because of concern for as well as feed and product boiling range. Currently, hy-
contamination of drinking water from gasoline storage tank drotreating and hydrocracking are the two most widely used
leakage, as detected in parts of the U.S. Should this happen, names for this technology, with the trend to place hydrore-
refiners will again have to find substitute streams to replace fining within the hydrotreating category.
lost octane and "barrels." This issue could become economi- Process severity, with respect to the above vocabulary, is de-
cally critical to the refiner and consumer as the industry si- fined by percent conversion (Table 13), or how much of the
multaneously reduces gasoline and diesel fuel sulfur, as well feed is thermcdly cracked into lower molecular weight, lower
as gasoline aromatics and olefins. boiling product. Conversion is usually defined as 100 minus
TAME, the ether produced by reacting isoamylene with the amount of product in the same boiling range as the feed.
methanol, has entered the refinery picture because it can pro- The vocabulary also expands to include the word desulfuriza-
vide an opportunity to reduce the C5 olefin content of gaso- tion, since sulfur reduction has been and remains the key need
line. A number of MTBE plants have been revamped to han- for hydroprocessing, in addition to denitrogenation and
dle the higher boiling olefins. However, if MTBE use is dearomatization. Some of the myriad names and abbrevia-
TABLE 13—Hydroprocessing terminology.

Conversion, %w Objectives
Hydrotreating (HT) "0" Cleanup without conversion
Hydrorefining (HR) As little as possible Cleanup of higher boiling streams
with minimum conversion
Hydrocracking (HC) 25 + Cleanup + Conversion
Additional Terminology
HDS Hydrodesulfurization
HDT Hydrotreating
HDN Hydrodenitrogenation
HDA Hydrodearomatization (HDA is also used for Hydrodealkylation
of Toluene to Benzene)
NHT Naphtha Hydrotreater
DDS Distillate Desulfurizer
MHC Mild Hydrocracking
ARDS Atmospheric Resid Desulfurization
VRDS Vacuum Resid Desulfurization
tions for this technology are also listed in Table 13. The refin- cess of hydrogen to minimize coke production, this runaway
ery streams that can/must undergo hydroprocessing, and the can increase reactor temperature by u p to 60°C per minute,
reasons for the process selection are summarized in Table 14. creating an unsafe operating condition. Refineries therefore
An example of a simplified process flow diagram is shown usually cap furnace outlet temperature at about 435-440°C.
in Fig. 9. Fresh feed, with hydrogen recycle and make-up hy- Thus, processing heavier, dirtier feed at higher severity,
drogen for the a m o u n t c o n s u m e d by the hydrogenation which requires higher start-of-run temperature, results in
chemistry, are heated to reaction temperature in a furnace shorter r u n length and/or multiple reactors.
and then fed downflow through one or more fixed catalyst The metal promoters on the alumina base end up in their
bed reactors in series. After the desired reactions have oc- oxide form from the drying of the finished catalyst. After be-
curred, the remainder of the process involves the recovery of ing in the reactor for a short time the metal oxides will con-
a high purity hydrogen recycle stream, separation of any vert to sulfides from the hydrogen reducing atmosphere,
cracked hydrocarbon gases from the desulfurized liquid combined with the production of hydrogen sulfide. The oxide
product, as well as distillation of the liquid into appropriate form is overactive and can cause temperature excursion, in-
cuts. Start-of-run r e a c t o r t e m p e r a t u r e ranges from 2 8 5 - creased coking, and partial catalyst deactivation from
400°C a n d pressure from 900-20 000 kPa; generally, the changes in the alumina and metal promoter structure. Thus,
higher the boiling range axid "dirtiness" of the feed and the cobalt-moly and nickel-moly catalysts must be "presulfided"
greater the desired cracking severity and dearomatization, or "presulfurized" prior to the start-of-run. This can be done
the greater is the required temperature, pressure and n u m b e r in-situ by adding compounds such as dimethyldisulfide to a
of reactors, as well as chemical hydrogen consumption. Ex- feed to condition the catalyst, for about one to two days, or it
cess hydrogen via the recycle is needed to minimize coke for- can be done ex-situ wherein the catalyst is pretreated by the
mation and laydown on the catalyst; this recycle is about 3-5 manufacturer, and then shipped and loaded to assure that
times the expected hydrogen consumption. the metals remain in the sulfide form.
The catalysts comprise the widest selection among all the re- At the end of a run, burning the coke off can regenerate the
finery processes because this technology is used to "clean" all "coked up" catalyst. This also is accomplished in-situ or ex-
refinery streams from light straight r u n gasoline through vac- situ. Ex-situ removal more efficiently removes the coke, but
u u m resid. The two most common formulations consist of at increased cost. If performed in-situ, the catalyst will usu-
combinations of cobalt and molybdenum or nickel and molyb- ally remain in the reactor for 2-4 runs, after which refiners
d e n u m promoters on an alumina base. The "cobalt-moly" cat- will d u m p the spent catalyst and replace it with fresh mate-
alyst, as it is typically called, is preferred for sulfur removal rial. Spent catalyst is usually then taken to hazardous waste
while the "nickel-moly" combination is active for nitrogen re- disposal. If the catalyst has been used to process resid, it may
moval and some aromatics saturation. Some catalysts also uti- be sent for nickel and vanadium recovery or to a process that
lize nickel-tungsten. Noble metal catalysts such as platinum as can remove enough of the feed metals to reactivate the cata-
well as zeolites are now employed, in particular for deep lyst and allow its reuse.
deciromatization. Cobalt-moly and nickel-moly catalysts con- Hydrogen consumption and throughput rate, often called
tain in the range of 3-25% promoter metals depending on feed "space velocity," are two of the key process and economic
properties and planned hydroprocessing severity. variables. As the boiling range of the feed, and thus its het-
Hydroprocessing is exothermic and increases with hydro- eroatom and aromatics content, increases, it can be expected
genation severity. Reactor outlet temperature in a fixed bed that hydrogen consumption will increase a n d throughput
reactor can be as m u c h as 35°C greater than inlet tempera- will need to decrease to increase residence time. A similar re-
ture when processing vacuum gas oils and resid. Further, as sponse occurs for a given feed as conversion increases. Ex-
the run proceeds, slow b u t inevitable loss of catalyst activity amples of yield, hydrogen consumption and residence time
due to coke and metals laydown occurs and is compensated for different feeds are shown in Table 15.
by raising furnace outlet temperature. Hydrogenation reac- Hydroprocessing will continue to play a n ever-increasing
tion rate increases with temperature and at about 470°C, can role in worldwide refining. The factors driving this conclu-
result in a "runaway" reaction. Since there is always an ex- sion are:
TABLE 14—Hydroprocessing options.

For the Reduction of
Stream B.P.° Sulfur Nitrog. Arom. Diolef. Acids End Use
Lt Str Run Gasoline Isomerization Unit Feed
Hvy Str Run Naphtha X Cat Reformer Feed
Coker Naphtha X Gasoline Blending, Cat
Reformer Feed
FCCU GasoHne Low Sulfur Gasoline
Catalytic Reformate Low Benzene Gasoline
Kerosine/Jet X Jet Fuel, Low Sulfur Diesel
Lt Attn Gas Oil Low Sulfur Diesel
Atm Gas Oil Gasoline Blending, Cat
Coker Gas Oil Reformer Feed, Jet Fuel,
Diesel Fuel
Vac Gas Oil FCCU Feed
Vac Gas Oil Gasoline Blending, Cat
Reformer Feed, Jet Fuel,
Diesel Fuel, Lube Oil
Base Stocks
Resid Cat Reformer Feed,
Jet Fuel, Diesel Fuel,
FCCU Feed, Coker Feed,
No. 6 Fuel Oil
"Boiling Point Range
HEATER IffTSTQ. REACTOR lEAlER 9 0 STTO. REACTOR STABIUZER HlACnONATOR
LightEmli
FIG. 9—Fixed bed hydroprocessing unit.
The sulfur content of crude oil has been increasing over 3. The aromatics content of fuel products has been decreas-
the years and is expected to continue that trend, barring ing and this trend should continue and expand worldwide.
major discoveries of low sulfur crudes. The technology and catalysts to achieve these results are
The sulfur content of fuel products, as we know them to- available; the only missing ingredient is money. If gasoline,
day, has been decreasing and this trend is expected to ac- jet fuel, and diesel fuel continue as the major sources of
celerate as the world seeks cleaner fuels. transportation fuels, then the industry will be forced to uti-
TABLE 15—Hydroprocessing unit yields. upgrading processes in commercicd operation; however, six
FCCU Crude FCCU LCO + have established a prominent position, as follows:
Feed LCO VGO Coker Gas Oil Carbon Rejection Hydrogen Addition
Density, kg/m^ 940 935 980 Visbreaking Fixed Bed Hydrocracking
Sulfur, p p m w 22 400 28 000 8600 Solvent Deasphalting Fluidized Bed Hydrocracking
Nitrogen, p p m w 940 1 000 Delayed Coking
Initial Boiling Ft., °C 220 365 215 Fluid Coking/Flexicoking
50% Distilled 275 470 280
Final Boiling Ft. 375 575 385 Table 16 shows a regional s u m m a r y of the worldwide in-
Products stallations for these technologies.
Naphtha
Yield, %w 5 24 27
Density 730 770 Visbreaking
Sulfur <1 <1
Nitrogen <1 This is a thermEtl cracking process using heat alone to par-
Jet/Diesel tially crack the resid feed to lower boiling products. Most
Yield 94" 35 68 commercial units operate in the 20-30% conversion range,
Density 900 810 865 thus, 70-80% of the product r e m a i n s in the resid boiling
Sulfur 500 <20 <20
Nitrogen 120 1
range. The attractiveness of the process is alluded to in its
Atm Gas Oil name; although most of the product is in the same boiling
Yield 38 reinge as the feed, this material is significantly lower in vis-
Density 825 cosity than the feed. Hence, the heat treatment reduces or
Sulfur <20 "breciks" the viscosity of the remaining resid, leading to the
Nitrogen <2
Hydrogen Consumption,
process name. The value of visbreciking is in utilizing the un-
%w of Feed 1.4 2.8 3.1 converted resid to blend No. 6 fuel oil. This product is made
by blending lower boiling, higher VEJUC streams, commonly
"Includes AGO
named cutter stocks, to reduce or cut the high viscosity of the
resid in order to meet product specifications. By lowering
resid viscosity, less cutter stock is required.
lize hydroprocessing for virtually every such product, world-
wide. There are very few visbreakers in North America since this
area has substantial gas production and is oriented toward
lighter fuels. The opposite pattern exists in Europe, for ex-
ample, where there are over 60 million metric tons of vis-
PROCESSES FOR RESID CONVERSION AND breaking capacity to meet that region's greater utilization of
UPGRADING heavier fuels, in general. Furthermore, until recently, Europe
has been a gas-poor region.
Processing of resid has its unique pEirameters and constraints There are two m a i n vEtriations t o the visbreaking flowsheet:
because of its composition. It, among the crude oil cuts, is: one is the soEiker coil visbreaker, the other the soaker drum
• the highest in carbon residue resulting in high rates of coke visbreaker, as in Fig. 10. Both subject the resid feed to heat-
production or laydown on catalyst. ing in a furnace; in the soaker coil unit, all thermal cracking
• the highest in sulfur, contaminEtnt metals, aromatics and tcikes place in the furnace coil, while in the soaker d r u m unit,
usually nitrogen, resulting in high operating severity the feed is partially cracked in the furnace at about 30°C
and/or hydrogen consumption. lower temperature and the cracking is completed by provid-
The easiest way for the refiner to handle resid is to sell it. ing increased residence time in the drum, as follows:
Its two m a i n markets Eire asphalt for road paving, roofing, Residence Time, min. Temperature, "C
and the like, and No. 6 fuel oil for utility and marine energy. Soaker Coil 1-2 465^85
To a lesser extent, resid is used by some refiners as a feed for Soaker Drum 4-8 435^55
the production of hydrogen. The asphalt market is finite, and
the "six oil" market is limited to the a m o u n t that can be sold The original driving force for the sociker drum process was
economically to compete with other fuels such as cocJ and to minimize coking in the furnace coil and thus increase run
gas. The net result is that the average refiner cannot dispose length. However, improvements in furnace design have nar-
of Eill of its resid via the above scenarios. In addition, the con- rowed the differences in process severity so that either pro-
cern for air pollution is driving the world toward the use of cess may be selected.
lighter, cleaner fuels. In response, a group of technologies
have established their place in the refineiy flowsheet to clean TABLE 16—Resid process capacity.
resid and convert it into lower boiling streams. These pro-
Capacity, Million mt/year
cesses yield products of a higher hydrogen to carbon ratio
North Western Asia-
than that of the resid feed, essentially the result of the crack- Process Worldwide America Europe Pacific
ing and/or saturation of its aromatics, which have the lowest
Visbreaking 159 11 62 21
hydrogen to carbon ratio among the hydrocairbon types cind Delayed Coking 155 96 13 16
crude oil fractions. The industry has categorized these tech- Fluid Coking 24 8 1 3
nologies as accomplishing this desired chemistry by carbon Fixed and Fluid Bed
rejection or by hydrogen addition. There Eire dozens of resid Hydrocracking 110 35 10 48
FRACTIONATION pentane. The "cleaner" resid components dissolve in the

TOWER paraffin while the dirtier asphaltenic ones do not. Thus the
HEATER
process yields "clean resid feed" that can be economically
processed in another unit, typically the FCCU. In fact, the
START
^>-4vvv1- ••ftd • process is oft-times defined as being used to provide incre-
I i
mentally clean "cat feed."
As the molecular weight of the paraffin increases, more of
the resid dissolves in the solvent. The part that dissolves in
the solvent is most commonly labeled deasphalted oil (DAO)
QUENCH f
RESID since the solvent has rejected the asphaltenes. The reject raf-
finate, mostly asphaltenic, is labeled pitch, tar, or simply as-
phaltenes. Figure 11 depicts the typical separation of het-
eroatoms between the DAO and pitch. The effect is usually
most pronounced for the metals, with lesser benefit for ni-
FRACTIONATION trogen and less yet for sulfur. Percentages of recovered DAO
SOAKER
X- TOWER
for the chosen paraffin solvents are:
Solvent Percent DAO
HEATER
C3 25-40
TT
C4 50-65
START
(§)--^^-^ C5 80-95
The process consists of a mixing vessel or column running

at sufficient pressure to liquefy the solvent and dissolve the
QUENCH DAO, separation of the DAO/solvent from the pitch, and re-
RESID covery of the recyclable solvent from the DAO by distillation
and stripping. The process can also be designed with two
FIG. 10—Visbreaking unit.
contact vessels operating at different temperatures to yield a
third, intermediate-cleanliness cut, usually labeled resin.
This may be done to give the refinery a more flexible scheme
TABLE 17—Visbreaking unit yields. for selling and further upgrading the various resid cuts. An
Resid Resid engineering feature that has played a role in reducing solvent
Feed Product Feed Product recovery cost sets the solvent recovery at temperature and
Initial Boiling Pt., °C 345 345 540 540 pressure such that the solvent is at or near its critical condi-
Yield, %w 78 72 tions. This significantly reduces solvent heat of vaporization
Density, kg/m^ 970 990 1015 1035 as well as its solubility in the DAO.
Sulfur, %w 4.1 4.3
Viscosity, m^/s @ SOX 720 250 100 000 45 000 Today's fluid cataljrtic cracking cateJysts, if chosen for high
metals tolerance, can accept cat feed with as much as 30 ppm
Ni 4- V. A resid at 300 ppm metals permits the addition of
10% resid as incremental cat fee, ignoring the effects of car-
Typical product yields are shown in Table 17. The ther- bon residue, nitrogen, and sulfur. However, based on typical
mally cracked gases contain olefins, but less than FCCU data (Fig. 11), the deasphalter can yield up to 75% "cleaner"
gases, and provide an added source of petrochemiccd and resid feed, at least from the constraint of metals that could
alkylation unit feeds. Visbroken light naphtha can be blended poison the catalyst. It is such performance that leads to the
into gasoline after removal of diolefins and mercaptan sulfur, incorporation of the deasphalting process into the refinery
and the heavy naphtha can be sent to the cat reformer hy- flowsheet.
drotreater (often called the naphtha hydrotreater) for olefin
saturation and sulfur/nitrogen removal, followed by octane
number upgrading in the reformer. The visbroken gas oils
will usually be blended to the fuel oil pool, but can be hydro- Delayed Coking
cracked for diesel and jet fuel blending, or hydrotreated to This is the dominant resid upgrading process in the U.S. and
yield additional FCCU feed. is showing growth in Europe and, in particular. South Amer-
ica. Like visbreaking, this is also a thermal cracking process.
Solvent Deasphalting Unlike visbreaking, this process runs at essentially 100% con-
version; all of the resid feed is converted into other products;
This is the only process of the six in which no chemical namely, cracked gases, coker naphthas and gas oils, and
changes to the molecules occur. The process is based on the coke. While the cracked gases and liquids are assumed to
low solubility of asphaltene-type residuum oil molecules in have higher market value than the resid feed, it is the market
low molecular weight paraffins. Asphaltenes are highly aro- utilization and pricing of some of the coke that further helps
matic, difficult to crack, and contain the majority of the sul- to drive favorable economics.
fur, nitrogen, and metals heteroatoms that are found in resid. A schematic of the process is shown in Fig. 12. The crack-
In the deasphalting process, feedstock, usually vacuum resid, ing chemistry takes place in pairs of "drums." Cracked gases
is mixed with a paraffin solvent, either propane, butane or and liquids leave the top of each drum, while the product
100
80
o
< 60
40
/y f. I
o
20
^C ^ ^ i^^Â—
C^C^^ , ^'^^""
20 40 60 80 100
DEASPHALTED-OIL YIELD, WT. %

FIG. 11—Resid solvent deasphalting unit: DAO quality.
Quench
XZ ^r^^ (nh
/ 'Gas
L5^ 'Gasoline
Stripper
J L— ^ Steam
—* Light Gas Oil
Rc ••Heavy Gas Oil
I
Coke Drums
^ ^
Fumace Steam
^
\ ^
Main
Column
Fresh Feed
^^ ~ ^''^^'^ recycle
FIG. 12—Delayed coking unit.

coke r e m a i n s in the d r u m s . At start-up, both d r u m s are unstable and subject to polymerization and gum formation
empty. The resid is fed to one d r u m for u p to a day while the even during storage at ambient conditions. Because of its in-
other drum remains idle. On the second day, feed is cracked herent instability, it is often call wild naphtha. The coker gas
in the other d r u m while the coke that has filled the first d r u m oils may be blended to fuel oil or hydrotreated for unsatu-
is removed (decoked). This back and forth coke removal cre- rates and sulfur reduction.
ates the continuous process. Drums have t3rpically been sized Removal of the sponge coke from a full drum involves the
to hold 24 h of coke make, since it required that amount of following steps:
time to decoke early units. Improvements to the decoking op- • Switch and Steam-out—Feed flow is switched from one
eration have enabled many units to r u n in 12-18 h cycles. d r u m to the other. The coke is then stripped with steam to
This has led to increased capacity revamps in existing units remove entrained vapor and liquid product. The stripping
or the opportunity to build smaller drums in new plants. steam-hydrocarbon mix is also fed to the main fractiona-
In a typical design, the resid fresh feed enters the bottom tor. The coke typically contains 4-10% liquids after strip-
section of the coker product m a i n fractionator. This provides ping. This "green" or raw coke may require further "dry-
for heat balance in the distillation column bottom, the picking" to below 0.5% liquids, via calcining, to meet market
u p of coke fines carried from the drums with the cracked needs.
products, and the removal of a heavy coker gas oil product • Cooling—The d r u m is next filled with water to cool the
for recycle to improve lighter product yield. Some fractiona- coke to about 90-95°C. This is required to prevent sponta-
tor designs also recover a lower boiling gas oil recycle. The neous combustion of hot coke and allow for safe handling
feed/recycle is then heated to cracking temperature, about when the drum is opened. The resultant steam production
490-510°C, in the coker furnace. Steam is usually added to is recovered either in the main fractionator when hot, or in
the feed to increase furnace coil velocity and thus minimize a unit called a blowdown system when it is at lower tem-
coke laydown on the furnace tubes as the feed reaches crack- perature.
ing conditions. The purpose is to delay coking as much as
• Coke Removal—In most designs, the d r u m heads are re-
possible until the feed enters the bottom of the drum, hence
moved, a hole is drilled through the center of the coke, and
the process name.
then high pressure water jets are used to break up the coke.
The time-temperature parameters in the drum cause com- The drilling/jet equipment in most existing units operates
plete conversion of the resid. As coke is produced, steirting at from drilling rigs placed on top of the drums. Large capac-
the bottom, the feed, which is part vapor-part liquid, contin- ity coker drums can be as much as 8 m in diameter and
ues to crack. As coke forms, it provides surface-induced 30-38 m in height. The drilling equipment would add Ein-
cracking as the feed passes through it. This operation suc- other 38 m to the elevation, making this unit easily recog-
ceeds because most of the coke that is produced is amor- nized. In early units, the coke was dumped into railroad
phous and spongy and is actually named sponge coke; thus, hopper cars directly below the elevated drums. In today's
the fresh feed is able to pass through. units, coke is dumped into pits and the coke is then moved
The cracked p r o d u c t s are recovered and separated in by front-end loader or conveyor system to the transport
equipment similar to other processes. An example of 5rields cars. Most of the engineering improvements in today's de-
and quality is shown in Table 18. Unlike the FCCU, changes signs focus on reducing the time and complexity in this
in operating parameters, in this case temperature, pressure step of the process.
and recycle ratio, have only a minor effect on product yields, • Rehead—The heads are rebolted to the drum, the system is
to the point that yields can be approximated based solely on pressure tested, and then hot gas such as cracked product
resid feed properties, in particular aromatics content, by us- vapors from the operating drum, or flue gas from the coker
ing either carbon residue (ASTM Test Method for Conradson furnace, is passed through the empty d r u m to warm the
Carbon Residue of Petroleum Products, D189-97) or API steel shell sufficiently to avoid thermal shock when fresh
gravity as the predictor. Coker n a p h t h a has lower octane hot feed is reintroduced.
quality compared to cat gasoline. In addition, it must be se-
Three types of coke can be m a d e . In usual operation,
lectively hydrogenated because non-catalytic cracked naph-
80-98% of the coke will be sponge coke. The others are shot
tha has a m u c h higher diolefin content, making it thermally
coke and needle coke. Shot coke, which is hard and pellet-
like, has no value other than as fuel and its yield must be min-
imized. Needle coke, which consists mainly of crystalline
elongated "needles," is highly valued and some cokers can be
TABLE 18—Delayed coking unit yields.
run, if given the proper resid feed properties and unit operat-
Carbon
Density, Sulfur, Nitrogen, Residue, Ni + V ,
ing parameters, to produce mostly needle coke.
kg/m' %w ppmw %w ppmw About one-third of delayed coker sponge coke, after calcin-
Resid Feed 1025 2.9 3000 22 250 ing, is sold to the aluminum industry to form the "carbon"
anode to produce the pure metal from aluminum oxide by
Yield,
Products %w electrolysis. Depending on its electrical conductivity,
strength, and contaminant levels of sulfur and resid metals
H2S 1.1
C1-C4 11.1 (Ni + V), calcined sponge coke c o m m a n d s a selling price
Naphtha 10.4 740 0.5 70 about 2-5 times its fuel value. Needle coke may be sold to the
Atm Gas Oil 32.4 850 0.95 600 steel industry for operation in arc furnaces to yield high qual-
Vac Gas Oil 12.0 960 1.9 2200 2.5 2 ity metallurgical steels. This coke may sell for as m u c h as
Coke 33.0 3.7 750 5-12 times its fuel value.
Fluid Coking/Flexicoking an equilibrium catalyst activity can be maintained. This elim-

inates the need to raise feed inlet temperature as run length
These technologies also convert all of the resid feed into progresses, as required in fixed bed units. In addition, the
cracked products and coke. The chemistry takes place, how- a m o u n t of recirculating liquid product required for proper
ever, in a reactor containing vapor phase fluidized coke par- catalyst bed operation is usually sufficient to provide a com-
ticles. The heated feed is sprayed onto the coke through feed plete heat sink for the exothermic heat of reaction; thus, the
nozzles around the reactor circumference. The product coke reactor essentially operates isothermally. This permits start-
deposits on the fluidized coke, which is continuously re- of-run temperature as high as 435°C, which is not technically
moved from the reactor. In the fluid coking process, suffi- or economically feasible in fixed bed reactors. This tempera-
cient coke is burned in a separate "burner" vessel to raise its ture, in turn, provides enough thermal energy to substantially
temperature so that this hot coke will maintain heat balance crack vacuum resid, and, from the presence of hydrogen at
upon its recirculation to the reactor. In the Flexicoking pro- high pressure, typically 15000-18000 kPa, enough hydro-
cess, essentially all of the coke is converted to a low heat con- genation reactivity to yield substantially desulfurized lower
tent gas in a third "gasifier" vessel, the hot gas then reheats boiling products.
the circulating coke via heat transfer in what was the fluid
coker burner vessel. As an example, if the chemistry yields
30% coke in the reactor, net coke from the fluid coker will be
a b o u t 20-24%, b u t will only be a b o u t 0.5%, as a p u r g e TABLE 19—ARDS unit yields.
stream, from the Flexicoker. Products
The net coke from the fluid coker is in the form of shot coke Vac
Feed Naphtha LGO HGO Resid
and can only be used as fuel. Because the delayed coking pro-
cess yields a higher average value of coke, it accounts for Boiling Range, °C 405 + 30-175 175-345 345-550 550-1-
Yield, %w 1.1 8.8 52.7 34.i
about 85% of worldwide coking capacity. The Flexicoking Density, kg/m^ 990 740 865 910 980
process provides the refiner the option of generating a fuel Sulfur, ppmw 44 000 200 300 1300 11000
gas that can be scrubbed of H2S, instead of coke laden with Nitrogen, ppmw 2800 20 200 400 2800
sulfur, nitrogen and metals. Because the gasifier operates on Viscosity, 105 10 2700
steam and air, rather than steam and oxygen, the resulting m2/s @ 100°C
gas heat content is in the range of 3000 to 4500 kJ/m^.
Cracked gas and liquids yields from the fluid coking pro-
cess are similar to yields from the delayed coking process. A
washing section is installed above the reactor to prevent car-
ryover of coke fines to the coker main fractionator, produce
a coker gas oil recycle and, as a result, control coker gas oil
final boiling point.
Fixed Bed Hydrocracking

Any boiling range material from crude oil can be hydro-
genated. As the boiling range increases, required operating
severity increases. In order to desulfurize, dearomatize, and
crack resid-containing feed, multiple fixed bed reactors in se-
ries are required. Commercial installations have utilized
from 2-6 reactors to attain desired process severity. How-
ever, most commercial units are usually designed to operate
on feeds no dirtier than atmospheric resid, based on capital
investment and operating cost, since running on v a c u u m
resid substantially increases severity. Existing atmospheric
resid hydrocrackers, oft times labeled ARDS units (Table 13),
produce clean products as exemplified in Table 19.
Fluidized B e d Hydrocracking
This is a liquid phase, fluidized catalyst bed process and is
more commonly called expanded or ebullated bed hydro-
cracking. In this process, depicted in Fig. 13, fresh resid feed,
along with hydrogen, is introduced into the bottom of the re-
actor. Liquid product is also recycled to the reactor bottom to
provide needed hydraulic lift to expand the catalyst bed by
about one-third. When this occurs, the catalyst goes into ran-
dom motion to create fluid bed behavior. This allows "spent"
Recycle Oil
catalyst to be withdrawn from the reactor each day and re-
placed with fresh material. Therefore, unlike fixed bed units. FIG. 13—Fluidized bed resid hydrocracking reactor.
TABLE 20—Fluidized bed resid hydrocracking unit yields.

Products @ 66% Conversion Products @ 80% Conversion
Feed Naph LGO HGO Vac Res Naph LGO HGO Vac Res
Boiling Range, °C 565 + C5-175 175-345 345-565 565 + C5-175 175-345 345-565 565 +
Yield, %w 9 18 32 34 12 23 38 20
Density, kg/m' 1037 710 860 920 1010 710 860 930 1060
Sulfur, p p m w 54 000 300 800 2500 12 400 900 2700 11800 27 800
Nitrogen, p p m w 4000 85 480 1900 5200 630 2500 7000
Conversion levels of 50-90% have been commercially at- use of the n-paraffins as wax product. The two largest mar-
tained. And, the unit can process any quality feed, recogniz- kets for this wax are the maJcing of candles and the coating of
ing that heavier, dirtier feeds will require lower throughput cardboard cartons for the preservation of fruits and vegeta-
rate (space velocity), and increased hydrogen consumption bles from farm to table. Separation of the solid paraffin crys-
and catalyst replacement rate. Examples of yields and quality tals from the mother liquor is aided by solvents such as
for a representative resid feed are shown in Table 20. methyl ethyl ketone and urea.
The refiner usually supplies some 4 to 9 lube base oils, that
vary mainly in viscosity, to lube plants that blend, package,
PROCESSES FOR LUBE OIL BASE and ship finished product. The largest single market for lube
STOCK PRODUCTION oil base stocks is for the production of motor oils. Hundreds
of other products, including greases, are also prepared for a
Lubricating oil base stocks are produced from the vacuum myriad of industrial needs. Overall, this is still a specialty
gas oils. While lube oil quality requirements are extensive, area of refining, accounting for only 1% of crude oil capacity.
process requirements are mainly driven by base oil viscosity
index, "cleanliness," and pour point. With respect to hydro-
carbon composition, the overall requirements are that fin- OTHER REFINERY PROCESSES
ished base stocks cannot contain aromatics, and are limited
in normal paraffin content. Aromatics must be removed or while the refinery cannot run without the processes included
converted to naphthenes because of their adverse effect on in this section, they are usually placed in the "other" category
oxidation stability and hot lube performance. Viscosity index since they do not contribute directly to the production of hy-
(VI) is the measure of the change in viscosity with tempera- drocarbon streams for fuel product blending.
ture. High VI, which equates to the least change of viscosity,
is most desired. Normal paraffins provide the highest VI Hydrogen Production
among the hydrocarbon types. However, n-paraffins are also
highest in pour point; hence, their concentration in finished Petroleum refineries, industry wide, long ago lost their abil-
lubes must be limited to avoid solidification. ity to satisfy the need for hydrogen via recovery from the cat-
alytic reforming process. The hydrogen shortfall can be sat-
There are two main process routes to produce the base oils. isfied either by buying hydrogen "across the fence," or by
The original, and still predominant, scheme incorporates building a refiner-owned plant inside the gate. Worldwide,
three process steps: first, aromatics are removed by solvent refinery hydrogen plant capacity has surpassed 300 million
extraction; secondly, normeJ paraffin content is reduced via m^/day.
crystallization (dewaxing), and, thirdly, the remaining iso- There are two process routes to hydrogen: the catalytic re-
paraffins and naphthenes are hydrotreated to remove other action of low molecular weight hydrocarbons with steam,
components such as organic acids, sulfur compounds and and the non-catalytic gasification of heavier hydrocarbons
the like that would adversely affect long term "cleanliness." with oxygen. The former is known as steam reforming or
A newer process utilizes one-step high severity hydrocrack- steam-methane reforming, while the latter is oft-times called
ing at about 18000 kPa. Under such high pressure, and with partial oxidation.
the proper catalyst, the aromatics are completely saturated to
naphthenes, the other heteroatom-containing components Steam Reforming
are hydrotreated as above, and a reasonable amount of the This process basically utilizes two-step or three-step chem-
normal paraffins are isomerized to isoparaffins, via the abil- istry, depending on when the plant was built. Older units typ-
ity of the catalyst to effect isomerization activity as well as hy- ically involve three separate catalytic reactions, while process
drogenation chemistry, to meet pour point requirements. If innovation has reduced many of today's flowsheets to two
the refiner is running a highly paraffinic crude slate, it may catalytic steps, followed by physical separation of product
still be necessary to dewax the hydrocracked product. components.
Aromatic extraction of vacuum gas oil is similar in concept The first reaction, which gives rise to the process name,
to extraction of catcJytic reformate, except the solvents are "reforms" the hydrocarbon feed into a hydrogen-rich synthe-
different. The most widely used solvent had been phenol, but sis gas, per the following theoreticeJ equation:
it has been banned because of its carcinogenicity. Solvents
used today include furfural and n-methylpjrrolidone. CH4 + H2O = 3H2 + CO
Dewaxing is accomplished by chilling the gas oil until the The reforming takes place at about 800°C over a nickel cat-
n-paraffins solidify. The process name derives from the end alyst placed inside tubes within a furnace. This design is re-
quired due to the high endothermicity of the reaction. The Partial Oxidation (POX)
high temperature also results in coke formation, but the coke The advantage of this process is that the chemistry requires no
reacts with excess steam to yield additional synthesis gas. catalyst, and zmy hydrocarbon can be used as feed including
With methane as the feed, the coke usucJly reacts as fast as it heavy gas oils, resid, coke and coal. Its disadvantages are the
forms to keep the catalyst and tubes clean. Heavier feed- need for oxygen, high reactor temperature, and more complex
stocks such as LPG, refinery fuel gas particularly containing gas cleaning. On balance, most hydrogen plants are steam re-
C3 +, or light naphtha, can cause coke buildup and limit r u n formers; partial oxidation will be chosen when there is no ac-
length. A n a p h t h a hydrocarbon feed may also require hy- cess to natural gas or other low moleculeir weight feeds, or
dro treating to remove heteroatoms, such as sulfur and chlo- when sale or utilization of high molecular weight refinery
rine, to protect the reforming catalyst. streams Eind coke is not feasible or economically attractive.
The second reaction, called "water gas shift," catalytically The POX process reacts hydrocarbon and oxygen at about
converts or shifts the CO to CO2, per the following equation: 1300-1550°C to yield a H2/CO synthesis gas. The oxygen is
usually p u r c h a s e d over-the-fence. The "syngas" is next
CO + H2O = CO2 + H2 treated for removal of sulfur compounds, which will include
This exothermic reaction takes place at about 350°C over a carbonyl sulfide in addition to H2S. The scrubbed syngas is
fixed bed of iron oxide catalyst. Some plants employ a lower then sent to catalytic shift conversion and hydrogen purifica-
temperature second catalytic shift using a copper-zinc cata- tion in similar manner to steam reforming.
lyst to convert any remaining CO. The product gas is then
treated for CO2 removed; the carbon dioxide is then vented or Sulfur Recovery
recovered.
Unfortunately, the hydrogen product gas may still contain Hydrogen sulfide is removed from refinery gas and liquid
u p to 1-3% CO/CO2 which will adversely affect catalyst in a streams via contact with liquid or solid absorbents and ad-
hydrotreater. Thus, a third reaction, called methanation, may sorbents. Among the dozen or so choices, the ones most
be employed to reduce impurities to acceptable levels. This widely used in refineries are the ethanolamine liquid ab-
step is carried out in a fixed bed using a nickel catalyst and sorbents. As a result, this step on the sulfur recovery flow-
uses a small amount of the product hydrogen, per the follow- sheet is commonly ccilled "amine treating." After the H2S has
ing chemistry: been separated from the hydrocarbons, it is converted into el-
emental sulfur in the sulfur recovery unit (SRU) by the Claus
CO/CO2 + H2 = CH4 + H2O process and its m3rriad variations. Recovery of sulfur from re-
fineries and from natural gas production now accounts for
Most of the newer steam reformers substitute adsorption the majority of sulfur supply to its end users.
for third-step chemistry to remove impurities from the hy- The most commonly used amine treating absorbents, or
drogen. The gases from the shift reactor pass through beds of solvents as they are normally called, are the primary amine,
molecular sieve that alternately adsorb and desorb uncon- monoethanolamine (MEA); the secondary amine, diethanol-
verted CO and the CO2, as well as other impurities such as ni- amine (DEA), and the tertiary amine, methyldiethanolamine
trogen and methEine, but not the hydrogen. The product hy- (MDEA). Selection is based on concentration of H2S in the
drogen gas usually exits the beds at 99.9% purity. The beds hydrocarbon gas stream, a m o u n t of other acid gas compo-
are most commonly desorbed by reducing pressure; hence, nents such as carbonyl sulfide and carbon dioxide, and the
the process name pressure swing adsorption. The desorbed relative solvent activity compared with useable concentra-
material is usueilly then blended as part of the fuel required tion of amine in water.
for the reformer furnace. Other sieve beds can be used to sep- The hydrocarbon feed stream is contacted countercurrent
arate CO2 for product sale. to a "lean" solvent, free of H2S, in absorbers (Fig 14). The sol-
Acid
Sweet Gas
'Gas
Lean
Amine
-^M—Q-J'
Mal<eup
-Water ^Ll
Amine
Stripper
Sour Gas Amine Flash

Contactor tank
Rich Amine
—CKl ^
Lean Amine
FIG. 14—Âmine treating unit.

vent picks u p the acid gases and exits the absorber as a "rich" chemical. Other outlets include its use as a cross linking
solvent. This stream is then sent to a regenerator where sol- agent for the manufacture of tires via the vulcanization pro-
vent reboil provides the heat to strip the H2S from the sol- cess for synthetic rubber, and as a blending component in the
vent. The solvent is t h e n cleaned a n d recycled to the ab- manufacture of road asphalt. However, the increasing pro-
sorber. The solvent may be filtered at one or more places in duction of sulfur from refinery hydrotreating and from the
the flowsheet to remove impurities, such as iron sulfides, that cleanup of natural gas has helped depress sulfur prices and
can cause equipment fouling and loss of solvent efficiency in not every refinery is able to sell all of its production.
the absorber.
The conversion of H2S to sulfur involves two chemical re-
actions; namely: REFINERY POLLUTION CONTROL
H2S + 3/2O2 = SO2 + H2O
Many parts of the world have imposed very strict control on
2H2S + SO2 = 3S + 2H2O
refinery pollutants. The three categories are air, wastewater,
Thus, Claus plants consist of a b u r n e r to convert about and particulates. Air pollution has mainly concentrated on
one-third of the H2S to SO2, followed by multiple fixed bed sulfur oxides and nitrogen oxides and refineries will have a
catalytic reactors to react the SO2 with the remaining hydro- limit on allowable emission levels, established over some time
gen sulfide to produce elemental sulfur, as in Fig. 15. Older frame, with higher levels cJlowed for short periods due to unit
Claus plants leave enough H2S in the vent gas that a second upsets. Three of the key emissions "points" during normal op-
catalytic process is needed to convert this dilute H2S stream. erations are furnaces, boilers, and the FCCU; flare systems be-
This added step is commonly labeled "tail gas cleanup." come part of the formula when unit upsets take process gases
Some of the newer Claus plant catalysts and designs claim no and liquids to flare from the opening of relief valves.
need for this last cleanup step. Wastewater treatment involves many process steps and
The Claus plant sulfur is a vapor as it leaves the reactors. It parts of its complexity are related to refinery unit selection
is cooled to produce liquid or molten sulfur and can be taken and operations. Many waste streams will first be sent to set-
to market in that form via tank trucks or railroad cars, or it is tling ponds and API separators to allow solids and various hy-
further cooled to yield a solid yellow powder. This powder drocarbon liquids to be separated from the water. The water
can be sold or stored in this form, or converted to prills or will then undergo some n u m b e r of biological treatment steps
into blocks, depending on end use. until "clean" water is produced. Some of the wastewaters are
Sulfur has many markets; the largest is for the production recycled back to parts of the refinery while the rest is sent to
of sulfuric acid, which in turn is the world's largest selling disposal via deep wells, for example.
AIR THERMAL SULFUR SULFUR

COMPRESSOR REACTOR CONVERTER CONDENSER REHEATERS
R«cycle HydfOKWi SIMMB CM
AeUQu
Fran Ajidiit
RMNnnlioQ
AddOM
From Sour Water Stripper
Com.
FIG. 15—Claus unit.
Particulate emissions can result from improper operation Based on historic data and recent findings, it is not likely that
of the catalyst recovery section on the cat cracker regenera- enough sweet, light crudes can be b r o u g h t to market to
tor. This Ccin occur from loss of cyclone efficiency that in turn counter the expected declining trend. Another factor is crude
will overload the flue gas solids removal system, or from mal- pricing. When higher prices, say, $145/metric ton ($20/bar-
function in the solids removal system itself. Obviously, any rel) and above, prevail, the economics of producing heavier,
furnaces and boilers running on coke or coal require control higher sulfur crude obviously improves and, if sufficient
of particulate emissions. price spread between heavy and light crude results, then the
refiner has a greater economic incentive to process poorer
qucJity crude. In addition, as the industry adds desulfuriza-
COGENERATION tion capacity to meet future low sulfur fuels demand, some of
this process capacity can be designed or revamped to handle
Refineries continue to add "cogen" plants to the flow sheet. dirtier crude. If the demand for today's fuel products contin-
They offer the opportunity to convert various low value fuels ues to increase, then more and more refiners will have no
or blend components into electricity. The electricity, in turn, choice but to process poorer quality crude oils.
can be used to supply part or all of the refinery's needs, or the Gasoline and No. 2 diesel will be the products that face the
plant can be large enough to permit the refiner to sell elec- near term drive to cleaner fuels. The key changes to gasoline
tricity to nearby utilities. With the advent of utility supply specifications, and their impact on refining, are:
and price deregulation, this option can take on added attrac- • Boiling Point—Continuing reduction to the E50, E70, E80
tiveness. Cogen feeds range from gases to heavy fuel oils to and E90, (the maximum temperature when 50, 70, 80, or
delayed and Quid coke. 90% of the gasoline has evaporated by distillation), for ex-
ample, will diminish product supply at existing refinery
crude capacity and flow sheet configuration. To meet gaso-
PRODUCT BLENDING line demand, refining capacity and/or cracking units will
have to be expanded just to replace the higher boiling cuts
Blending equations have been developed over the decades to being removed from the blending pool.
allow the refiner to optimally blend the fuel products with a • Aromatics—Reduction in total aromatics and, in particu-
high degree of accuracy. The equations may be relatively sim- lar, the higher boiling aromatics, can only effectively come
ple for properties such as viscosity, or relatively complex for from removal of the heavy portion of straight r u n naphtha
predicting blended gasoline octane number. These equations feed to catalytic reformers, and from lower severity re-
have been built into the refinery computer models with the former operation. Incorporation of b o t h options m a y
goal that each batch of product will be blended correctly and maintain gasoline yield, but will result in less hydrogen by-
will meet specifications at m i n i m u m cost. While the com-
product. Dearomatization of heavy reformate is not ex-
puter models and test methods continue to improve, most
pected to be economically attractive.
product is still blended by mixing the computer-indicated
• Benzene—Âmong the benzene reduction options presented
components in a product storage tank, sampling the tank,
earlier, it is expected that extraction for petrochemical Scile
and then waiting for appropriate laboratory data to certify
or removal of the C6 cut from reformer feed will prevail.
that the blend meets specifications. Some refineries do on-
line product blending, meaning that components are mixed The latter will increasingly require isomerization of the
directly into a product pipeline, for example, with key tests deeper-cut, lower octane number, light straight run gaso-
being performed using on-line instrumental analysis. On-line line.
octane analyzers are being used for gasoline blending, and • Olefins—The olefins in the C5-C6 fraction of cat gasoline
newer test methods such as near and mid-infrared are begin- will be reduced. Likely process options are to install "light
ning to replace m o r e complex or time-consuming older cat gasoline" hydrotreaters, which will reduce octane num-
methods. ber followed by isom units to octane-upgrade, to take at
least the C5 cut to alkylation units, or to convert the
isoamylenes to TAME, provided ethers are not banned.
• Sulfur—Cat gasoline provides 85-100% of gasoline sulfur
REFINING OPTIONS FOR THE FUTURE and most of this sulfur is concentrated in the higher boil-
ing fraction. Refiners will have the choice of hydrotreating
The key issues facing the refiner will be mainly driven by:
some portion or all of the cat gasoline, or deeply desulfur-
• Crude oil quality izing cat feed. Process selection will eJso depend on final
• Clean fuels legislation realized gasoline sulfur specifications. Capitcd and operat-
• Product demand and mix ing costs to remove sulfur from "cat feed" are so m u c h
• Alternative transportation options higher that, on the surface, the only apparent choice is to
• Crude oil and product pricing treat the cat gasoline. However, cat gasoline hydrotreating
Crude oil quality is expected to slowly worsen. The most reduces octane while cat feed h5ftrotreating can improve
critical parameter continues to be sulfur, but any increase in FCCU conversion without increasing coke on catalyst. Cat-
the percentage of resid from increased use of heavier crude alyst manufacturers and petroleum refiners continue to de-
oils will also play an important role as the world moves to- velop improved catalysts that will desulfurize cat gasoline
wEird a lighter fuel product mix. The rate of change is obvi- with m i n i m u m octane loss. The overall effect is that either
ously related to the crude oil assay quality of new discoveries. process option, or both, may be selected, based in part on
the refinery's crude slate and overall fuel product demand sweet/light crudes and sour/heavy crudes. On the product
balance. It is also euiticipated that some of the new sulfur side, refiners have not always been able to obtain a reason-
removal processes will gain substantial commercial accep- able return on investment for the legislated changes in fuels
tance, offering a n opportunity to meet future gasoline sul- specifications. The net effect in the late 1990s resulted in low
fur specifications with p e r h a p s less octane n u m b e r loss refining margins. This, in turn, has led to a sustained period
and less hydrogen consumption. of unusually high refinery utilization rates—^where 80-90%
• Oxygenates—As worldwide legislation for cleaner fuels had been considered the norm, rates have recently ranged
spreads, every region or country appears to be requiring between 93-98%. Thus, refineries have opted for longer r u n
the use of oxygenates for pollution abatement, with the length, which, in turn, has pushed many of the process units
concomitant octane benefit. It is not possible to know if the to their limit. It is expected that this mode of operation will
expected b a n on MTBE in California and the consideration continue until the cleaner fuels program is in place, refinery
of a countrywide ban by the U.S. Congress will cause a sim- capacity is in better balance with demand, and crude prices
ilar worldwide response. Removal of MTBE will likely stabilize.
place a b a n on TAME, increase interest in ethanol, require
an increase in cat reforming, cat cracking and edkylation
capacity, increase the need for isomerization of light
straight r u n gasoline and introduce the chemical conver- ASTM STANDARDS
sion of isobutylene to isooctane.
Number Title
The quality of No. 2 diesel fuel will mainly focus on sulfur
and aromatics. As the world likely adopts a m a x i m u m sulfur D 86-99a Method for Distillation, of Petroleum Products
specification in the 10-50 p p m w range and some reduction D 1160-95 Method for Distillation of Petroleum Products
in aromatics concentration, refiners will in turn install or re- at Reduced Pressure
vamp middle distillate hydrotreaters that have the flexibility D 1319-98 Method for H y d r o c a r b o n Types in liquid
to achieve deeper aromatics saturation with perhaps only the Petroleum Products by FIA
need for a catalyst changeout. D 287-92 Method for API Gravity of Crude Petroleum
Future product demand may be virtually impossible to pre- and Petroleum Products
dict. For example, in the U.S., the rapid acceptance of the van D 2699-97a Method for Research Octane Number
and sport utility vehicle in place of the standard car led to a D 2700-97 Method for Motor Octane Number
decrease in overEiU vehicle fuel economy because of lack of D 323-99a Method for Vapor Pressure of Petroleum Prod-
regulation for such vehicle tjrpes. This is in the process of be- ucts (Reid Method)
ing corrected but, meanwhile, gasoline demand in the U.S. is D 4814-99 Specification for Automotive Spark-Ignition
increasing at rates exceeding earlier estimates. Engine Fuel
Alternative sources of vehicle power create a long-term D1655-99 Specification for Aviation Turbine Fuels
uncertainty for the refiner. Natural gas and LPG are avail- D 396-98 Specification for Fuel Oils
able in varying degree in m a n y parts of the world; LPG is a D 975-98b Specification for Diesel Fuel Oils
readily available automotive fuel in European countries, for D 129-95 1
example. Ignoring availability, the main detriment to rapid D 1266-98 f Methods for Sulfur in Petroleum Products
expansion of these fuels is the needed supply and distribu- D 2622-98 J
tion infrastructure. Electricity-driven vehicles, via the bat- D 613-95 Method for Cetane Number of Diesel Fuel Oils
tery, are not likely to play any substantive role unless a ma- D 97-96a Method for Pour Point of Petroleum Products
jor b r e a k t h r o u g h in energy efficiency is found. Vehicles D 5771-95 Method for Cloud Point of Petroleum Products
powered o n externally-supplied hydrogen have little hope of D 189-97 Method for Conradson Carbon Residue of
p e n e t r a t i n g the marketplace because of high p r o d u c t i o n Petroleum Products
cost, delivery infrastructure, and safety. However, hybrid NOTE: The above are listed in order of appearance in text.
battery/gasoline powered vehicles will be available shortly.
The fuel cell may have an impact on future refineries. This
would be intriguing if it becomes technically and economi-
cally feasible t o produce a hydrogen/CO synthesis gas by
BIBLIOGRAPHY
steam reforming of naphtha "under the hood," since this liq- [1] Wauquier, J.-P., Crude Oil. Petroleum Products. Process Flow-
uid can take the place of gasoline or diesel fuel without any sheets, 1st edition. Editions Technip, Paris, 1995.
changes at the "pump." Should this occur, octane n u m b e r [2] Wauquier, J.-P., Separation Processes, 1st edition, Editions Tech-
becomes a non-issue, the value of cataljîc reforming, fluid nip, Paris, 2000.
catalytic cracking and, hence, alkylation would diminish, [3] Leprince, P., Conversion Processes, 1st edition. Editions Tech-
and hydrotreating and hydrocracking to supply additional nip, Paris, 2000.
"clean" n a p h t h a would increase, also requiring a major in- [4] Gary, J. H. and Handwerk, G. E., Petroleum Refining Technology
crease in refinery hydrogen. and Economics, 4th Edition, Marcel Dekker, Inc., NY, 2001.
[5] Kaes, G. L., Refinery Process Modeling, 1st edition, The Athens
Crude a n d product pricing has become a substantive un- Printing Co., Athens, GA, 2000.
known for the refiner. On the crude oil side, the difficulty [6] Meyers, R. A., Ed., Handbook of Petroleum Refining Processes,
has been unexpected changes in price, as well as the inabil- 1st and 2nd editions, McGraw-Hill Book Co., NY, 1986 and 1997,
ity to predict future prices or the price spread between respectively.
[7] Maples, R. E., Petroleum Refinery Process Economics, 2nd edi- Pretreating Methods to Remove Sulfur," Hydrocarbon Process-
tion, PennWell Books, Tulsa, OK, 2000. ing, Vol. 78, No. 11, November 1999, pp. 43-51.
[8] Chang, T., "Worldwide Refining Report," Oil & Gas Journal, Vol. [12] Swaty, T. E., Nocca, J. L., and Ross, J., "What are the Options to
98.51, December 2000, pp. 56-120. Meet Tier 11 Sulfur Requirements?," Hydrocarbon Processing,
[9] "Refining Processes 2000," Hydrocarbon Processing, Vol. 79, No. Vol. 80, No. 2, February 2001, pp. 62-70.
11, November 2000, pp. 85-142. [13] Law, D. v . , "Hydrocracking: Past, Present and Future,"
[10] Tromeur, P., Guibard, I., Harle, V., and Pike, M., "Hydropro- Petroleum Technology Quarterly, Vol. 5, No. 4, Winter 2000/2001,
cessing Atmospheric and Vacuum Residues," Petroleum Tech- pp. 55-63.
nology Quarterly, Vol. 5, No. 1, Spring 2000, pp. 21-27. [14] Chang, T., "Worldwide Catalyst Report," Oil & Gas Journal, Vol.
[11] Shorey, S. W., Lomas, D. A., and Keesom, W. H., "Use FCC Feed 97, No. 39, September 1999, pp. 45-68.
Section II: Fuels: Properties and Performance
Steven R. Westbrook, Section Editor

MNL37-EB/Jun. 2003
Liquefied Petroleum Gas

Robert J. Falkiner^
LIQUEFIED PETROLEUM GAS ( L P G ) IS A GENERIC TERM FOR utilize the butane. Temperate climates with large seasonal
ETHANE (C2) TO BUTANE (C4) h y d r o c a r b o n mixtures t h a t temperature changes could use propane in the winter and B-
can exist as liquids u n d e r modest pressures at a m b i e n t P mixtures in the summer. However, the logistics of seasonal
temperatures. distribution and air/fuel calibration changes, coupled with a
Methane (CI, natural gas) must be refrigerated to less more than adequate propane supply, generally favors the use
than —259°F to be condensed by compression to Liquefied of propane throughout the year.
N a t u r a l Gas (LNG). Pentane a n d heavier hydrocarbons The same properties that make LPG so useful contribute to
(C5 + , condensate) are liquids at ambient temperature and some of the unique challenges in using it safely. Water/ice/hy-
pressure, and are used in the manufacture of gasoline, drate properties are unique. Pressurized systems are more
n a p h t h a fuels, and solvents. Ethame, propane, and butane prone to leaks, even when the equipment is idle. The heavier
are gases at standard temperature and pressure, but can be than air vapor density allows accumulation in low points and
liquefied by compression and condensation of the vapor at cavities in the absence of ventilating air flow. When mixed
ambient temperature. Propane (C3), Butane (C4), and bu- with air in the right ratio in the narrow range, it has the
tane/propane mixtures (C3/C4 or B-P mix) have ideal prop- potential for high destructive power in the event of a n
erties for a fuel, widely used throughout the world in an ignition source that results in an explosion or fire. Conse-
amazing variety of applications. They are stable, high-en- quently, persons handling LPG and installing equipment are
ergy content, relatively low sulfur, clean burning fuels that tjrpically required to be trained and licensed. A variety of
can be transported economically as a liquid, and be used ei- safety devices and procedures are used, and LPG is odorized
ther as a liquid or a gas. Pure component properties are to help detect potentially dangerous leaks.
given in Figs. 1-4. Propane can be used from about -40°C
to 45°C, and butane from 0°C to about l l O X (about 0-250
psig vapor pressure) or higher depending upon equipment HISTORY
pressure ratings. The LPG tank is always under pressure at
normal operating temperatures above the normal boiling The LPG industry did not start until about 1904, more than
point of about — 42°C, so there is no need for a fuel p u m p 40 years after the start of North American crude oil and nat-
or electrical components for most applications. This maJses ural gas production a r o u n d 1860. Natural gas (methane)
LPG ideally suited to a wide variety of portable, mobile or cooking and lighting appliances were commonplace by 1900,
remote applications, using mechanically reliable and simple but it was difficult to make the gaseous fuel portable. It was
equipment. Propane applications tend to be robust and reli- not feasible to transport and store compressed natural gas
able as a result. (CNG) in the bulky pressure vessels of the day.
LPG is the ideal fuel for mobile and remote gas applica-
This chapter deals mostly with ASTM D1835 "Commercial tions. It is a high BTU content liquid at typical ambient tem-
Propane" and "Special Duty Propane" grades. The same dis- peratures and modest (<250 psig) pressures, that is practical
tribution equipment, rail/truck tanks and storage vessels can for storage and transportation. It can be used like natural gas
be used for propane or B-P mixtures so it is not outwardly once vaporized, in natural gas appliances adapted to gaseous
apparent what grade of LPG is being used in any region or LPG mixtures with small adjustment for air/fuel ratio.
application. The t e r m s "propane," "LPG," and "HD5" are The early years of the industry were cheiracterized by the
c o m m o n l y used interchangeably (although this is not need to solve the immediate problems of the day, without any
technically correct). ASTM D 1835 and GPA 2140 specifica- standardization or regulatory controls. LPG was one of the
tions exist for "Commercial B-P Mixtures," but this is rarely first c o n s u m e r goods transported and sold in pressure
used for consumer applications in North America. There is vessels. There were many economic and technical challenges
n o current Canadian (CGSB) specification for B-P Mixtures, to produce, transport, and t h e n sell it to the public. The
as the winter temperatures are too cold, and winter butane industry was at the forefront of many areas of research and
d e m a n d is high for winter gasoline production. Polar development, ranging from processes, equipment and
climates must use propane year round for low temperature appliances for m a n u f a c t u r e and use, to analytical test
operability. Tropical climates (no winter temperatures, no methods for composition a n d properties. The results (in
w i n t e r gasoline) tend to use B-P mixtures year r o u n d to retrospect) were predicable, a n d excesses abounded. How-
ever, in a short n u m b e r of years, the emerging industry was
' Imperial Oil Ltd., Quality Assurance Operations and Development,
Toronto, Ontario M5W 1K3, Canada. compelled by marketing a n d regulatory forces to develop
31
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products and practices that were acceptable to the pubhc. large scale commercial application was the piping of gas to
Most of the standards and regulations that were developed in Pittsburgh in 1883, about 20 yeEirs after the discovery of oil in
the early years endure today. Pennsylvania. By the early 1900s, a 20 in. pipeline 165 miles
long, was being used for natural gas production [3], and
longer pipelines soon followed.
History of t h e LPG Industry
The use of petroleum pitch from surface "seeps" date back
LPG was originally derived from both natural gas or crude oil to recorded time [4], and these were the first source of North
production, so the industry has two related historical roots. American crude production around the Lake Erie basin, at
Refining a n d various petroleum conversion processes Enniskillen township in Southern Ontario a n d Titusville,
became additional sources later. Pennsylvania in 1859/60. Early cable "drilling" consisted of
The Chinese first transported natural gas, as well as brine "punching a hole in the earth by repeatedly lifting and drop-
and oil, during the Shu Han dynasty (AD 221) from shallow ping a heavy cutting tool hung from the end of a cable," and
wells and seepages, through simple pipelines made of hol- collecting the crude in a wooden crib [5]. It produced virtu-
lowed b a m b o o logs [1]. The m a i n sources of early North ally no associated gas or LPG, these having weathered off
American gas were from numerous surface "seeps" and "gas from the shallow formation. Advances in drilling technology
springs" in Ontario, Pennsylvania and Southern California. quickly allowed deeper wells that hit shallow high-pressure
The "burning spring" at Niagara Falls, below the cataract, oil and gas bearing formations, at first with near disastrous
was described early in the 1800s, and was due to a flow of gas consequences. The first "gusher," in the spring 1862, "spewed
from the Niagara shales, which underlie the limestone of the oil above the treetops and covered 50 acres with oil 1-3 feet
Falls [2]. The first small scale commercial distribution in deep, and p o u r e d enough oil into Black Creek to blacken
North America was probably in Fredonia, New York in 1820 Lake St. Clair"[6]. The flow disappeared after several months
using small bore lead pipe distributing gas from a purpose- as suddenly as it began, after m o r e t h a n a n estimated 5
built shallow well. There are records of oilfield gas being million barrels "floated off the waters of Black Creek"[7].
supplied to several Pennsylvania towns by 1872. The first Additional discoveries were made in rapid succession all over
CHAPTER 2: LIQUEFIED PETROLEUM GAS 33
s
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n-Butane
Rsfsrenes Stales:
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Enthalpy, Btu/lb
FIG. 3—n-Butane P-H diagram. Reprinted with permission from the Gas Processors Association.
100 200 300 400 500 600 700

10000 10000
Propane
Rstorence Slates:
H(sat. llq.HOO Btu/lb « T(trp)
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Enthalpy, Btu/lb
FIG. 4—Propan P-H diagram. Reprinted with permission from the Gas Processors Association.
34
the United States, in virtually every state from the Appalacha duction, where imported LPG is vaporized centrally, and
to the Pacific. The industry remained regionalized around distributed locally in gas pipelines.
these local sources, until the legendary Spindletop East A balanced North American C3/C4 supply and demand was
Texas, Panhandle and Oklahoma discoveries, and the post- achieved about 1950. This was mostly due to increased in-
1900 development of crude oil and gas pipelines. dustrial or "chemicals" demand rather than the more modest
The discovery of large oil and gas fields in the early 1900s growth of consumer fuels markets. The alkylation process
resulted in an immediate excess production of LPG and light converted C3/C4 into gasoline, and large-scale seasonal stor-
naphtha hydrocarbons, far beyond the capability of devel- age in underground salt caverns, natural formations and
oping markets to consume them. The ratio of gas to liquid large storage spheres balanced out the seasonal swings in
and the quality of production varied widely between different heating demand. Later, LPG became a preferred feedstock
production formations. At one extreme was low sulfur for gas cracking and plastics manufacturing.
content "dry" or "non-associated" gas, essentially pure The LPG fuels industry has always been in excess supply.
methane with little or no condensable liquid in the under- The "chemicals" market is now more than twice the size of the
ground formation. This was ideal for distribution by gas LPG fuels market. This tends to make LPG fuels economically
pipeline, especially in areas such as southern California and attractive in a wide variety of niche markets, wherever the
the central United States where the gas wells were close to properties of LPG offer an advantage, and/or the economic re-
cities, and the terrain allowed easy pipeline excavation. At the turn is higher than alternate BTU or chemicals value.
other extreme was "sour" and "wet" gas that contained both
high sulfur and high propane and heavier content that con-
densed to a hydrocarbon liquid with even modest compres- History of LPG
sion. "Wet" gas was generally "associated" with an underlying The first uses of LPG mixtures were for heating, cooking, and
crude reservoir, either as a gas cap or dissolved in the crude lighting in remote or mobile applications that could not be
at high underground temperature and pressure. Wet gas serviced by natural gas or manufactured gases (town gas,
from either crude or gas wells produced a liquid condensate coal gas, water gas, etc.). Natural gas distribution was limited
(NGL, natural gas liquid) when the gas was compressed for to mainly urban markets, that were supplied by relatively
distribution. Condensate had few uses, and for more than short low pressure pipelines from regional gas wells or "town
50 years was burned or vented as a byproduct of crude and gas" plants. Mobile applications included railway coach
natural gas production. lighting and heating, where high BTU liquid storage was a
The wasteful practice of flaring enormous quantities of gas great advantage over compressed gas (Pinsch gas) or carbide
from oil wells was eventually realized to be extremely detri- gas (acetylene). Remote applications included smaller cities
mental to the amount of oil that could be recovered (see ret- and suburban areas, where underground pipelines were not
rograde condensation). The gas pressure in a formation economically or technically feasible. In fact, "Rockgas" was
helped force the oil to the surface. Excessive venting and de- an early reference to the alternative to pipeline gas in areas
pressurization left large portions of the crude unrecovered. where buried pipelines were not feasible due to bedrock or
Moreover, the practices of one gas or crude producer affected rocky terrain [9].
the yield of others in the same formation, since the crude and The earliest consumer use of LPG was "Blaugas" in Ger-
gas could flow underground between producers whose many about 1904. Several plants were established in the
ownership rights were determined by surface surveys. This United States afterward [10]. This was a foul mixture obtained
resulted in several decades of litigation and regulatory devel- by thermal cracking of hydrocarbon fuel oils, similar to town
opment to establish fair and equitable means to balance the gas production, but at lower temperatures that favored
often-conflicting social and economic goals [8]. greater condensable liquid yield. Composition was essentially
The regulated recovery of liquids from ever increasing gas uncontrolled, and the mixture contained a large amount of
and crude production resulted in a steadily increasing NGL dissolved hydrogen, methane, LPG, gasoline range hydrocar-
and LPG production, without adequate markets to consume bons and heavy ends, with a vapor pressure of up to 750-1800
them. This was aggravated by increasing production of psi at ambient temperature [11]. The first steel tanks imported
deeper and higher pressure crude and gas reservoirs with from Germany were called "bottles," a term still used today in
higher liquid condensable content. Whole industries ap- the "bottle gas" market. The early high-pressure cylinders
peared (and disappeared) based on the chronically depressed were bulky and extremely heavy. Up to 7 lbs. of steel was
price of LPGs and NGLs, and seasonal demand of natural transported for every pound of relatively low BTU fuel.
gasoline. Gas liquids were transported long distances to The earliest "Blaugas" sets used in United States had two
find new outlets, with even some marine exports in large replaceable liquid cylinders and a third permanent gas cylin-
drums from California. In the 1930s almost all of the world's der that fed the appliance through a low-pressure gas regula-
carbon black was manufactured from cheap Texas panhan- tor. The sets were expensive, since three "bottles," valves and
dle gas and gas liquids (eventually replaced by various regulators were required instead of one. Liquid flowed via a
"coking" processes). dip tube in the liquid cylinders through a valve or a "wet"
Hundreds of butane/air, propane/air, and LP-gas distribu- pressure regulator, where it vaporized into the third cylinder.
tion plants were built to distribute gas to smaller towns and This maintained a relatively constant composition of gas and
cities. Most were gradually replaced by expansion of natural avoided the problems associated with "weathering" or multi-
gas pipeline distribution system, but a few remain in isolated component distillation with the broad cut liquid being used
or remote areas of North America. This is commonplace in (although this process was not well understood at the time).
some areas of the world with low domestic natural gas pro- It was common in 1912 for such sets to lose many pounds of
gas daily. Stoves leaked too [12]. Even so, the industry was needed" [14]. As late as 1921, there were more than 100 dif-
modestly successful. Some "Blaugas" plants remained in op- ferent specifications for casinghead gasoline, most of them
eration into the 1920s b u t were all gradually displaced by meaningless and many based on what a producer may have
LPG recovered from crude/natural gas production a n d been producing on a particular day [15].
refining. Small regional businesses were built up around in- In April 1921, representatives from 31 companies formed
dividual supply sources and different gas mixtures and gas the Association of Natural Gasoline Manufacturers (ANGM),
sets. While the sets were relatively successful, they did expe- following upon two previous efforts to organize gas proces-
rience problems from residues and ice causing regulators to sors. This Association later became the Natural Gasoline As-
malfunction. Gasoline and heavier hydrocarbons collected in sociation of America (NGAA), and now the Gas Processors
the gas bottle, and had to be periodically drained out. Success Association (GPA). Its purpose was to impose both business
depended more on the ability of the equipment to tolerate the a n d technical controls on the unruly new industry. They
mixture than anything else. There were no specifications to created a new, m o r e acceptable product, called "natural
control dryness, icing, residues, or composition. gasoline" to replace "casinghead gasoline." The ANGM
The first commercial use of LPG produced from crude oil moved quickly to develop technical standards and related tar-
or natural gas was in 1912, indirectly as result of a burgeon- iff agreements, a n d to improve operations. Within three
ing demand for gasoline due to mass production of automo- months, the first specifications were written for seven grades
biles after 1908. Condensable liquids were reported as early of natural gasoline A-G, and four grades of blended natural
as 1893 in natural gas (methane) cryogenic drying processes gasoline m o t o r fuel. The Natural Gasoline specifications
for natural gas distribution. There are indications of a low- were based on density (API gravity) and percent recovered
pressure condensate from crude oil p r o d u c t i o n being (by evaporation). The lower gravity grades were preferred for
distributed in wooden barrels in the 1900-04 era, but it was gasoline blending a n d c o m m a n d e d a higher price. The
the automobile that changed everything. Automotive gaso- blended gasoline grades were defined by a wider set of spec-
line had to be liquid in atmospherically vented tanks, but ifications, including gravity, end point, initial boiling point,
volatile enough to evaporate when mixed with air in a carbu- vapor tension, color, and an important new concept, percent
retor. The automobile created an i m m e d i a t e d e m a n d for recovery in a standard distillation test. Boiling point criteria
naphtha from crude oil as well as condensate from natural and the distillation test marked significant advances in the
gas or crude p r o d u c t i o n . Customers w h o b o u g h t a quart development of m o d e r n specifications [16]. The blended
of l a m p oil now w a n t e d gallons of gasoline. The liquid gasoline specifications were intended to eliminate practices
condensate from gas production, called "casinghead gaso- such as "dumbbell" blending of kerosene with "wild" casing-
line," became a preferred product for sale to early refiners for head gas to give a blend with a naphtha range gravity that did
blending into gasoline, and a new industry was b o m . LPG not work well in automobiles. The blended gasoline specifi-
was displaced in importance by the frantic scramble to pro- cations were eliminated two years later, deferring to specifi-
duce casinghead gasoline, which was m o r e profitable, at cations developed elsewhere by the refining industry. The
least in the wintertime, when there was a strong demand. Ini- natural gasoline specifications were modified several times
ticdly, a high-pressure condensate was allowed to "weather" both for definition for the grades and for test methods as they
in standing tanks, until enough boiled off that it was "accept- were developed, and are still published today by the GPA.
able" for use in gasoline. The limits of acceptability were only
In 1910, a Pittsburgh motorcar owner walked into U.S. Bu-
loosely defined at the time, but these fundamental require-
reau of Mines chemist Dr. Walter Snelling's office, complain-
ments eventually led to the "weathering test" and "vapor
ing that the gallon of gasoline he had purchased was only half
tension" specification requirements many years later.
a gallon by the time he got home. He thought the government
Propane a n d b u t a n e continued to be problematic by- should look into why consumers were being cheated because
products from both crude and gas production. Propane was the gasoline was evaporating at a rapid and costly rate. Dr.
too volatile to be a significant portion of gasoline, and not Snelling took u p the challenge and discovered that the evap-
volatile enough for even moderately pressurized natural gas orating gases were propane, butane, and other hydrocarbons.
distribution networks pipelines. It was essentially worthless, Using coils from an old hot water heater and other miscella-
so there was a large economic incentive for producers to in- neous pieces of laboratory equipment. Dr. Snelling built a
clude as m u c h of the volatile propane/butane as possible into still that could separate natural gasoline into its liquid and
casinghead gasoline. While m a n y of the blends provided gaseous components [17]. This resulted in a 1913 patent for
good fuels for the engines of the day, "a frantic scramble to a continuous process "to obtain the most volatile ingredient
meet demands, coupled with not a little ignorance, began to or mixture in the form of a liquid gas under pressure" by frac-
create significant problems" [13]. Many serious incidents oc- tional condensation of compressed heated vapors of natural
curred due to excessive volatility and evaporative losses that gasoline [18,19]. This virtually eliminated b o t h excessive
sometimes exceeded 40%, and from boiling and over pres- pressure and residue problems, and became the keystone of
suring rail cEirs. In 1915, a rail car explosion killed 47 per- the m o d e m LPG industry. The first m o d e m LP business ven-
sons, injured more than 500, and virtually destroyed the town ture, American Gasol Co., was founded by Snelling, and three
of Ardmore, Oklahoma. Casinghead gasoline was almost uni- prominant "gas men" of the time, Frank Peterson and two
versally condemned, and developed such a poor reputation cousins, C. L. a n d A. N. Kerr. The products were called
that one major refiner stopped using it in gasoline a n d "Gasol" (propane) a n d "Gasolite" (butane). The company
advertised it as a consumer benefit. By 1919, the last major failed for lack of markets and the burden of cylinder and dis-
refiner announced that it was n o longer in the market for cas- tribution costs, and was sold two years later. Snelling went
inghead gasoline, and declared, "specifications were urgently back to the U.S. Bureau of Mines explosives research, and the
three "gas men" went into the casinghead gasohne business, Oberfell and Richard C. Alden, co-authors of the then classic
which was more profitable at the time. reference book "Natural Gasoline," were recruited by Phillips
The three "gas men" returned to the LPG business after to defend against the Carbide patent infringement litigation
WWI. A. N. Kerr became president of the Casinghead Gaso- on the pipestill "stabilization" process. The company also
hne Association about 1915, one of the failed predecessors of benefited from the close proximity and association with the
the ANGM (GPA). The Kerrs founded the Rockgas Products USBM research station in Bartlesville, OK. Prior to 1920,
Co. in Pittsburgh, and in 1925 the Imperial Gas Company in Oberfell had studied hydrocarbon behavior at the USBM in
Los Angeles. They tried to develop other markets for the light Pittsburgh, and after early association with Frank Petersen,
ends, such as LP-gas/air town gas distribution plants and for spent five years pioneering development of low pressure ab-
cutting steel. In 1932, the Kerrs authored the first chapter of sorber systems for a leading producer of natural gasoline
the Handbook of Butane Propane Gases on "A Chronology of [24]. The Phillips research group grew to include K. H.
Liquid Gas Development"[20]. Hachmuth, (dryness, CoBr test), T. W. Legatski (author of the
In 1912, F r a n k Peterson of the Bessemer Gas Engine original GPA LPG specification) and D. L. Katz (hydrocarbon
Company p u r c h a s e d rights to a 1909 patent to inject phase behavior, hydrates). The company was instrumental
naphtha gasoline into hot compressed natural gas to absorb in developing acceptable rail cars, freight rates equivalent
casinghead gasoline. He later patented a multistage com- to gasoline, a n d large consolidated facilities that made
pression/liquefaction process in 1912 [21]. These "hot blend- production more cost efficient.
ing" and "compression" processes were licensed to customers The NGAA (GPA) developed additional specifications for
using Bessemer compressors and gas engines. In 1914 he commercial propane and butane after the expiration and/or
patented "a liquefied fraction of n a t u r a l gas containing settlement of the composition and processing patents. These
ethane, propane and butane, substantially free of heavier hy- were first reported in the Proceedings of the 11th annual
drocarbons and from methane"[22]. He also developed one of Convention 1932 [25], and later published as the forerunner
the first tests to estimate the "wetness" of a gas sample based of GPA 2140-Liquefied Petroleum Gas Specifications. How-
on absorbing/desorbing the sample in a mineral seal oil. De- ever, there were no test methods attached to the first specifi-
tails of the test were held closely by the Bessemer Company, cations. These were added over the years as the technology
which ran the test for $5 per sample. The fee was returned to was developed.
any prospective producer who purchased Bessemer equip- At the same time, the California producers and marketers
ment [23]. The close association of the liquids producers and were active in related technical Eireas. The California Natural
equipment suppliers has endured and evolved into today's Gasoline Association formed in 1925 as a technical society of
GPA and GPSA (Gas Processor Suppliers Association). individuals, rather than a trade association of corporate mem-
The LPG industry grew very slowly prior to 1932. In the bers [26], and provided high caliber technical leadership to
early years, it was inhibited by a shortage of tanks and mate- the emerging industry. Western Gas published many techni-
rials due to WWI, by the wide variety of LPG mixtures and cal articles in Butane-Propane News [27], Eind the first edition
equipment, and by competition from the casinghead and nat- of the "Handbook Butane-Propane Gases" in 1932. While not
ural gasoline business. The entire infrastructure for LPG was a standard or specification, the handbook contained a large
new, and there were many technical problems (and costs) as- amount of technical information on LPG production, distri-
sociated with production, transportation, equipment, and bution and use. It was an important reference book for the en-
appliances. E q u i p m e n t a n d transportation costs were of tire industry, including the "downstream" distribution and
p a r a m o u n t importance, since the cost of the fuel itself was so marketing segments not covered by the GPA. These hand-
low. During this period there was litigation on several patents books were maintained into the 1980s. They are no longer in
associated with the production (and therefore the use) of print, but are still widely available in technical libraries. Ad-
LPGs of various compositions. Most notable were the Saybolt ditioneil information may be available from other gas indus-
patent for absorbtion, held by Standard Oil, and the "stabi- try associations that have been active over the years, such as
lization" patent, held by the Carbon and Carbide Company the National Bottled Gas Association (now NPGA [28]), Com-
(now Union Carbide). Both patents were eventually held to be pressed Gas Association (CGA [29]), or other regional gas
invalid. In addition, the first significant regulations on tanks, marketing associations such as the Pacific Gas Marketers As-
rail cars, equipment, tariffs, production limits, etc., were sociations, Pacific Gas Association, and others. These were in-
p u t in place, t h r o u g h Government agencies such as the volved in development of related areas, such as equipment,
B u r e a u of Explosives, Interstate Transport Commission, pressure vessel, appliance, installation and transportation
Texas Railroad Commission, National Fire Protection codes, standards and regulations. However, they do not ap-
Association, and others. pear to have been active in development of either product
standards or test methods for consumer LPG products that to-
Many now-familiar company and brand names appeared,
day is under the jurisdiction of ASTM.
including Blaugas, Phillips (Philgas), Rockgas, Carbide (Py-
rofax), Skelly (Skelgas), Shell (Shellane), and S t a n d a r d
(Flamo). Phillips and Carbide were two of the founding mem-
History—LPG Properties a n d Thermodynamics
bers of the ANGM (NGAA, GPA), and are generally credited
with developing the m o d e m LPG business. Frank Phillips, Many people consider the work conducted in this area during
founder of Phillips Petroleum, purchased the Snelling patent the 1920s and 30s to be synonymous with the development of
rights, and marketed "Philgas" in the mid 1920s. Phillips Chemical Engineering as a separate discipline.
established an active research department, and did much of High pressure crude, condensates, and LP gases have phys-
the early laboratory research on liquefied gas. George G. ical properties and a commercial importance that made them
the principle target of early research in thermodynamics and commercially important for manufacture and use of LPG.
chemical processing. LPG and NGL were probably the first This includes water [35], H2S, C02, COS, N2, mercaptan,
commercially important, large volume materials that were and others [36].
handled and processed near or above the critical temperature Development of Thermodynamic Equation of State (EOS)
of components or mixtures. methods now allows calculation of most properties of even
Critical phenomena had been observed in single compo- complex mixtures directly from composition [37]. In most
nents as early as 1823. In 1861, Thomas Andrews observed cases, properties such as vapor pressures, enthalpies, bubble
the similar phenomena when he found that carbon dioxide points, dew points, adiabatic flash compositions and the like,
could not be liquefied at any pressure at temperatures higher can be calculated about as accurately as they can be measured
than 31°C. He hypothesized that such a state existed for all directly. This includes LPG mixtures around their critical
fluids and called it the "critical point" [30]. Andrews's points, and "retrograde" condensation, and more recently
experiments were first made public in the 1863 edition of W. temiaiy solid/liquid/vapor and hydrate systems [38].
A. Miller's textbook entitled "Elements of Chemistry" [31].
The phenomena of isothermally condensing a gas mixture to
form liquid by reducing pressure and isobarically heating a LPG S P E C I F I C A T I O N S
gas-liquid mixture to form a single-phase liquid were first ob-
served by J. D. Kuenen in 1892 when he was studying the
History of ASTM LPG Standards
phase behavior of the binary system (carbon dioxide +
chloromethane). He called these phenomena "retrograde Virtually all of the technical developments relating to ASTM
condensation" of the first kind and the second kind, standards were done through GPA/GPSA member compa-
respectively [32]. nies, and Government/Industry sponsored Research at orga-
In the mid 1920s Dr. Walter Podbielniak developed the nizations such as the USBM, Institute of Gas Technology
first practical low temperature fractional distillation test (IGT) and Gas Research Institute (GRI). The GPA research
that allowed the composition of NGL mixtures to be accu- reports and standards and the GPSA Engineering Data Book
rately determined [33]. The "Pod" column was quickly have been a primeiry source of technical information for the
adopted by the industry and improved over the years both industry. These are available on a commercial basis, both to
in accuracy and automated operation. It was the industry GPA members and non-members [39].
standard until it was eventually replaced by gas chromato- The GPA maintained the LPG and NGL standards from
graphic analysis in the mid 1950s. "Downhole" samples first publications in 1921-32 until 1960. By this time, LPG
from high pressure formations taken at underground tem- had become an important consumer fuel, widely available
perature and pressure were found to contain substantial and with an ever increasing diversity of applications. Na-
amounts of dissolved "liquid" methane. This violated the tional Standards were needed to ensure universal acceptance
then accepted principle within the industry that no material throughout the downstream industry, and to address
could be a liquid above its critical temperature. The theories potential regulatory and liability issues inherent to producer
on retrograde condensation in gas processing by Dr. Lacy only-specifications. In 1961, ASTM published D1835 specifi-
in a 1932 API paper were greeted with a great deal of cations for commercial propane and butane that were tech-
skepticism by the gas processing industry [34], but it cer- nically identical to the GPA specifications, including GPA test
tainly put technology development into high gear. This methods. In 1964, ASTM published D2154 Special Duty
caused quite a stir at the time, as retrograde condensation Propane, which was similar to GPA HD-5, but later incorpo-
was, as the name implies, the exact opposite of what was ex- rated this grade into D1835 in 1975, adding butane-propane
pected. This created a great need to understand the phase mixtures. The GPA 2140 specifications are still maintained
behavior of high-pressure and supercritical mixtures, both by the GPA, and remain technically equivalent to ASTM
for crude oil reservoir pressure management and for pro- D1835. ASTM test methods adapted from the original GPA
duction of high-pressure condensate. Within a decade of in- methods are now used in both standards.
tensive research and development, cycling plants for Specifications and many test methods for LPG/NGL prod-
methane re-injection, liquefaction (refrigerated liquid natu- ucts not covered in D1835 are still maintained by the GPA.
ral gas), LPG dehydration, and sweetening processes were This includes GPA 3132, which is the current version of the
all commercialized. original 1932 Natural Gasoline specification, and a variety of
A large amount of technical data generated in this era is other NGL products, chemical feedstocks, sampling meth-
still used today. For example, the tables and graphs in the last ods, and test methods. The GPA 2140 LPG specification is
published edition of the "Handbook Butane-Propane Gases" widely used for contractual purposes within the upstream
were essentially unchanged from the first edition, published gas and fractionation segments of the industry. The products
in 1932. Similarly, the GPSA Engineering Data Book has covered under ASTM D1835 and GPA 2140 specifications are
been in continuous publication, and the 11th edition is now often referred to as "spec" products. All of the others tend to
available in U.S. engineering or metric versions, and on CD- be called NGL's, such as C2+ ("see-two plus," meaning
ROM. Tables of information for installers that are derived ethane and heavier), fC4 (field butane), etc. For example,
from this data is still in use today in publications such as "spec butane" means that it conforms to one of the consumer
NFPA 58 and CAN/CSA-B 149.2 (the respective United States products in D1835 or GPA 2140, or another industry specifi-
and CDN "propane installation codes"). There is a large cation or purchase/sale contract. The composition of "NGL
amount of related work on other vapor-liquid equilibria for Mix," or "C2-I-" or "condensate "can vary over wide ranges,
the LPG gases, their mixtures, and other materials that are and are not manufactured to strict composition limits.
NGL mixes and other "non-spec" products are not sold to The ASTM and GPA LPG specifications have withstood the
the pubUc. They are intermediate products, suitable for test of time remarkably well. They have undergone numerous
transport and storage, but intended for further processing. revisions in response to improved technology and/or industry
They are manufactured and sold between companies with the needs [42]. The vast majority of these have been associated
technical resources to define and control the quality within with sampling procedures and test methods, and only occa-
the available processing capabilities at the time. They usually sionally with minor changes to the limiting values [43]. The
have additional test methods and limits for both purity and actual composition and properties of LPG produced in 1932
trace components that may be deleterious in downstream is essentially unchanged from LPG produced today.
processing [40]. This can vary over wide limits under The ASTM D 1835 standard has formed the basis for many
contract terms. international standards, including ISO 9162, and at this time
The sampling and test methods are still important for is the framework for virtually all the world-wide commerce in
"non-spec" products, but not for the same reasons as for the LPG [44].
"spec" products in D1835. For example, the market value of
an NGL mixture is determined by the composition, since
Sampling
once fractionated, the ethane, propane, iso-butane, butane
and C5-I- condensate fractions each have their own market There are three sampling methods commonly referenced in
value. The market value of an NGL mix is therefore depen- North America: ASTM D 3700 (floating piston cyhnder), D
dent on the accuracy of the analysis, but the composition 1265 (80% fill "open" cyhnder), and GPA 2174 (floating
may vary over wide limits as agreed to by the purchaser and piston cylinder and on-line composite sampler).
seller. As a result, no ASTM product specifications are neces- None of the sampling procedures are guaranteed to ob-
sary for these materials, but many ASTM/GPA sampling and tain a representative sample for all specifications or test
test methods are used. The accuracy and precision of these methods, under all conditions. For example, a floating pis-
methods are still very important to the industry. ton cylinder is capable of taking a liquid sample with no
ASTM D1835 specifications for "commercial propane" and vapor generation that can deplete light ends and dissolved
"butane-propane mix" do allow the purchaser and seller to gases. However, machined interior metal surfaces can make
agree on composition limits for propane/propylene and this unreliable for trace levels of corrosive materials that
butane/propane. These grades could be used as specialty con- can react with the interior surfaces, especially for longer
sumer fuels, such as brazing gas (or higher BTU heating fu- term storage or transport. An 80% fill cylinder can have an
els, or aerosol propellants), and are therefore included in the interior coating to make it less prone to loss of trace corro-
ASTM standard. The ASTM standards are rarely used for sive molecules. However, the composition is slightly
commercial contracts such petrochemical feedstocks and the changed by venting liquid to establish the 20% vapor space
like, as even nominally similar processing units can have that is necessary to protect against over pressure from ther-
different feedstock requirements. Processing contractual mal expansion of the liquid.
agreements tend to be less restrictive on composition, and ASTM and CGSB are addressing this by allowing the use of
more restrictive on trace contaminants, depending upon the coated D 1265 cylinders for routine use for "specification"
capability and tolerance of the intended processing unit. products, where the small but predictable loss of light ends is
In North America, propane is the only widely available LPG not significant. Laboratory measurements and Equation of
fuel for consumer use. Ethane and butane are used in other State calculations confirm that the vapor pressure reduction
fuels and chemicals applications. Ethane is converted to ethy- between using D 3700 and D 1265 is less than 1.6 psi at the
lene and used predominately in the manufacture of plastics 208 psig specification limit. This is not significant with re-
and chemicals. Butane is used predominately as a blending spect to the reproducibility of the vapor pressure test
component in winter gasoline, an alkylation feedstock to method, and would only be of concern at or near the
make high octane unleaded gasoline, gas cracker feedstock specification limit, at high (7-8%) ethane contents [45,46].
for chemicals production, or as a refinery fuel gas when the The D 2163 hydrocarbon composition by gas chromato-
price for butane drops below the industrial price of natural graph (GC) method is being revised to allow D 1265 "for com-
gas. Propane is sometimes referred to as "butane" in the North position," with a recommendation that D 3700 floating piston
American retail market, and several companies still use "bu- cylinder method be used for highly accurate results or when
tane" in their corporate name. The reason has its roots in his- trace gas analysis is required. ASTM D 3700 is currently
tory [41 ], as butane was more prevalent in the early years, but being revised to limit the scope to ASTM D 1835 "spec" prod-
has since been replaced by propane. Similarly, "HD5" ucts. This avoids the complications from sampling high pres-
propane is inherently a reference to GPA 2140 grade HD5 sure NGL's that may contain separated phases, inert gases,
(Heavy Duty, 5% max propylene). HD5 grade was developed and corrosive materials (for example, from production prior
to limit minimum octane number for engine applications, and to processing). A new appendix documents the various prob-
similar grades are found in all international specifications lems that must be addressed for sampling "non-spec" prod-
(See AutoPropane). The ASTM D 1835 "special duty" propane, ucts. GPA 2174 (Obtaining liquid hydrocarbon samples for
and CGSB 3.14 "Type 1" propane are generally taken to be GC) will be recommended for sampling "non-spec" NGLs and
functionally equivalent to GPA 2140 "HD5" propane, differing related materials. This also facilitates revision of D 2163
only in some sampling and test method options. Even when (composition by GC) to include options for using Flame Ion-
contracts are written around specifications that make no ref- ization Detectors (FID) for specification products. FIDs are
erence to "HD5," the designation "HD5" tends to be used in very linear detectors for hydrocarbons, but do not detect "in-
conversation, because it is more recognized. erts" (N2, Ar, CO2, etc.) that do not combust in a hydrogen
flame. These are not normally present in "spec" products, ex- Propylene has a low pure component octane value, and re-
cept at very low p p m levels t h a t are not significant for quires individual control (5% max) because it can be varied
intended use (see Composition below). widely in commercial grade. Traces of the other olefins are
effectively controlled by the m a x i m u m vapor pressure
(ethylene) a n d m a x i m u m C4-t- content (butanes, butylenes
Composition and Calculated Properties (Octane, and heavier).
Density, Vapor Pressure) The defining specification for ASTM D1835 "Special Duty"
D 1835 products composition limits are set at levels that are propane (GPA 2140 HD5) is the m a x i m u m 5 vol% propylene
stringent enough to satisfy the vapor pressure, octane content, intended to control the m i n i m u m octane n u m b e r for
(olefin), a n d volatility/residue r e q u i r e m e n t s of the vast severe service engine applications (HD5 is "Heavy Duty, 5%
majority of existing applications and equipment. Small com- maximum propylene"). Propane meeting the special grade
position differences within the bounds of the specification (HD5) specification would have a n octane rating of 95 or
are generally not significant, a n d do not affect either the greater by the D 2623 LP-method (if it were run). Commercial
value or the end use. For example, propane containing 1-2 grade with higher propylene content can still be used for
ethane has the same value and uses as propane with 5-6% lower severity engine applications. The true HD5 (propane
ethane. Similarly, propane containing 1% propylene has the optimized engines) market has yet to materialize.
same commercial value a n d uses as 5% propylene. As a This has resulted in decades of debate for the need for ac-
result, "Specification" products in D 1835 are relatively non- tual octane n u m b e r determination versus a linear sum calcu-
critical for hydrocarbon composition. lation. Gasoline and LPG blending is known to be non-linear,
but the LPG calculation method has prevailed This is proba-
The D 1835 products are relatively simple mixtures of a
bly more because the composition limits of "HD5" propane
small n u m b e r of components. This makes it feasible to esti-
are restrictive enough that non-linear blending effects are too
mate several properties that tend to blend linearly by simple
small to be significant. The same cannot be expected for
linear sum calculations. Calculation based on weighted lin-
blends of significantly broader composition [47], or for opti-
ear s u m of component values per D 2598 can be used as an
mized engine applications that are more optimized for the
alternate to D 1267 Reid vapor pressure, density and octane.
fuel. In addition, there are some discrepancies in the pure
Similarly linear sum of C4+ (butane and heavier) can be used
component octane values used in ASTM D 2598, EN 589 and
as an alternate to D 1837 volatile residue.
the original ASTM Motor LP Knock Test Method Develop-
ment as documented in SAE 670055. These differences are
C o m p o s i t i o n b y GC relatively small, generally within 1 octane number. However,
it may be necessary in the future to optimize either the cal-
Very little history was found on ASTM D 2163, Method for culation or the engine determined octane number, or as more
Analysis of Liquefied Petroleum (LP) Gases a n d Propane recently suggested, by methane number.
Concentrates by Gas Chromatography
The D 2163 GC method was originally based on u p to four The methane n u m b e r of a gaseous fuel is a knock engine test
different packed columns and thermal conductivity detectors using conditions similar to D2699 MON, but using methane
using calibrant gas calibration procedures. Two of the col- and hydrogen as the primary reference fuels. The method has
u m n packings were discontinued due to toxicity. The method not been standardized to date. The advantage of the methane
was expanded to allow other capilliary/PLOT^ columns and n u m b e r is that the test can be extended to include all gaseous
alternate detectors, but retained the original calibration fuels, including hydrogen, natural gas, LPGs cuid their mix-
procedures and precision statement. The method is currently tures, inert diluent gases such as N2 and CO2, and potentially
being u p d a t e d to allow columns based on resolution other combustible gases such as CO and HH3. In principle, it
performance, as well as FID detectors using response factors is possible to relate methane n u m b e r to octane number, but
referenced to methane, or other detectors of equivalent per- there are several difficulties in practice. The octane scale, with
formance using calibrant gas procedures. D 3700 will be the iso-octane having a value of 100, is extended to 120 with the
recommended sampling procedure, but D 1265 will be al- addition of about 6 mL/usg tetraethyl lead. This tends to make
lowed for routine use, except where highly accurate results the test increasingly insensitive to non-linear fuel effects in
are required for trace gases (see sampling above). the high range, and the use of TEL even in the lab is problem-
atic. Similarly, the methane n u m b e r does not respond well to
fuel effects at the low end of its range. Even so, a reasonably
Octane good correlation has been found to exist [48,49].
ASTM D 2623, Test Method for Knock Characteristics of Liq- Methane n u m b e r also appears to lend itself reasonably well
uefied Petroleum (LP) Gases by the Motor (LP) Method was to calculation based on composition. If so, then the calcula-
tion method would be preferred for routine operations,
originally used to rate octane n u m b e r of LPG mixtures. This
similar to D 2598 for LPG today.
used a standard CRC knock engine fitted with an LP-gas car-
buretor. It was withdrawn because the octane n u m b e r of This is a potential area of future research and standard-
these simple mixtures could be accurately estimated by linear ization.
blending of component octanes based o n GC analysis per D
2598. Olefins
^ PLOT: Porous Layer Open Tubular (usually KCl deactivated Some recent publications indicate that the olefin content of
alumina for LPG analysis). propane relate to cleanliness, stability or tailpipe emissions
in a similzir m a n n e r to gasoline [50,51]. However, there are three times the working pressure, often in the 12-15 000 psig
some significant differences, and there is no consensus at this range. Finally, all consumer cylinders, storage vessels, trucks,
time. Propane tanks are not atmospherically vented, so there and rail cars require periodic inspection and recertification.
is no oxidative stability concerns for propane, as there is for These considerations have essentially eliminated LPG vapor
gasoline and other fuels. LPG carburetor vaporizer deposits pressure (VP), per se, as a significant problem.
are associated with non-volatile residues, and not oxidative The LPG VP specifications indirectly control the maximum
gums from fuel olefins, thiophenes and other trace reactive concentration of light ends, principally ethane in propane
c o m p o n e n t s of gasoline. However, developers of m o d e r n and propane in butane. The manual "Reid" VP test method
LPG electronic fuel injection (EFI) systems have experienced was developed in a competition in the 1920s to improve upon
significant difficulties with both inorganic and organic de- the original U.S. Bureau of Mines "vapor tension" method
posits that interfere with the proper operation of injectors. (essentially a pressure gage on a length of 2 in. pipe). The
Propane derived from crude oil and natural gas contains es- competition was won by Dr. Reid (D323 Reid method), and
sentially n o olefins. Propane from refinery cracking processes an adaptation of this is used in D 1267 for higher VP (>26
contain olefins, which may can either processed further (alky- psi) LPGs. The test has changed little over the years. Many
lation, polygas), separated for propylene sales, or blended into laboratories are no longer equipped to r u n the LPG Reid
propane u p to specification or contractual limits. Refinery Method. It is now much more common to calculate VP from
propane usucJly requires removal of propylene to meet the composition by D 2163 using calculations in D 2598 than it is
ASTM "Special Duty" or GPA HD5 specification. to run a manned D 1267 Reid VP. However, D 2598 method
A recent study and review sponsored by the California Air has no component VP data for m e t h a n e (if it is present),
Resources Board (CARB) r e c o m m e n d e d relaxation of the which may force the use of the manual method in some cir-
propylene a n d volatile residue specifications for a u t o cumstances. In addition, D 2598 VP calculation is known to
propane, citing that a 10% propylene/5% butane fuel gave the be biased high (e.g., conservative) at high ethane contents,
best equivalent emissions performance [52]. The Board also due to use of a component VP extrapolated from above the
recommended a new limit of 0.5% m a x i m u m butenes, pen- critical point of ethane.
tanes, and heavier. These changes were proposed to preserve By historical convention, the VP of LPG is reported in
and enhance the current supply of auto propane fuel in Cali- "gage" or "gauge" pressure in pounds per square inch relative
fornia, while maintaining adequate emissions performance. to atmospheric pressure (psig). The pressure gauge used in
About half the propane produced in California is a byproduct the D 1267 LPG Reid method reads zero at the start of the
of refining processes [53]. test, but unlike D 323 or D 4953 the apparatus starts out liq-
This is a possible area of future research and standard- uid filled, and no air is introduced into the test apparatus
ization during the test. The test result is essentially the partial pres-
sure of the LPG relative to atmosphere, a n d the absolute
pressure is higher by the barometric pressure at the time of
Vapor Pressure the test. This has caused significant confusion over the years
Historically, vapor pressure was the most critical LPG speci- when using pressure transducers calibrated in psia units, or
fication, being responsible for most of the serious problems when reporting in metric units (kPa), which by definition
in the early days of the industry (see History of LPG). Vapor would be interpreted as being an absolute pressure. As a re-
pressure is invEiriably tied to pressure vessel and safety valve sult, the specifications require reporting in kPa (gage), which
certification and transportation regulations, so it is generally is not a true SI unit. Also, this difference is sometimes con-
viewed to be critical for regulatory compliance. However, fused with the high bias at high ethane contents when using
m o d e m pressure vessel standards as well as LPG production D 2598 calculation.
e q u i p m e n t a n d analyzers have all b u t eliminated vapor ASTM is currently developing a s t a n d a r d test m e t h o d
pressure as a significant operational problem. based on newer instrumentation similar to D 5191 and D
Certification standards vary by jurisdiction, but typically, a 6378 for gasoline. This method uses an absolute pressure
large safety margin is built into the system. For example, a transducer, so this requires that atmospheric pressure be
typical consumer cylinder pressure rated for 250 psig "work- subtracted from the result to report a VP (gage) final result.
ing pressure" would be pressure tested after manufacture to There is no universally accepted criteria for setting the max-
twice this (500 psig) and equipped with a "pressure relief imum VP specification for propane, and this is an area for fu-
valve" (pressure safety valve or vent) 250-500 psig, 50-100% ture research and international standardization. The first
of the test pressure. Propane, at the maximum specification GPA VP specification was 225 psig at 105°F set to meet the in-
pressure, would have to be heated to over 140°F to even reach sulated rail tank car requirements of Interstate Commerce
the opening ("cracking") pressure of the safety relief valve. In Commission (ICC). In 1955, the specification was revised to
addition, the actual burst pressure is controlled to typically at 215 psig at 100°F, mainly to use a single water bath for both
least three times the working pressure (manufacturers are re- natural gasoline and propane. Still later in 1955, the VP was
quired to pressure test 1 cylinder out of each lot to destruc- lowered to 210 psig at 100°F to meet United States DOT safety
tion as a quality control procedure for the quality of steel and standards for rail tank cars [54]. A variety of other regulatory
welds). It is common practice for the manufacturer to "over- limits also exist. This includes DOT 173.301 (f) (2), which lim-
build" cylinders to eliminate any uncertainty in the costly its VP in cyhnders to 300 psig at 1 SOT, Section 170.314 (c) 225
certification process. For example, sample cylinders rated for psig at 105°F, and Section 173.315 (c) (1) cargo and portable
1800 psig working pressure are often tested at about 5000 tanks at 250 psig at 115°F [55]. Other regulatory requirements
psig, a n d have burst pressures far in excess of m i n i m u m would be expected in different jurisdictions. The origined HD5
VP specification was 200 psig to promote heavy-duty engine -40°C. One hundred milliliters of pre-cooled liquid propane
applications, but was reset to the current 208 psig limit when was allowed to boil off ("weather") in a glass tube with a large
this market failed to develop as expected. drop of liquid mercury. Initially, the liquid propane temper-
Higher vapor pressure specifications allow slightly more ature would be at or below the normal boiling point of
ethane to be included in the blend, which increases supply propane (—42°C), and the mercury would be a solid (melting
slightly, and is potentially beneficial for very low (<-35°C) point = —39°C), and then maJce a "tinkle" sound in the glass
temperature operations. However, higher ethane content in when shaken. The temperature of the remaining liquid would
the gas phase can cause overly lean air/mixtures for some ap- increase as the lighter components boiled off. If a sufficient
pliance applications with first vapor withdrawal from a full quantity of butane or heavier components were present, the
tank, and rich operation from essentially pure propane when mercury would melt as the temperature of the remaining liq-
the tank is near empty. This wide swing in air/fuel ratio and uid rose above -39C, and "go thud" (a colloquialism for
the attendant problems of calibrating the air/fuel ratio in "failure" in some circles). The pass/fail criterion was that no
vapor withdrawal service also prompted the industry to more than 2 ml of liquid (mainly butane and heavier)
reduce the VP from 215 to 210 psig in 1955. remained when the mercury melted.
Current ISO 9162 specifications have a maximum VP of One artifact of the test was that propane near the specifi-
1550 kPa at 40°C, compared to 208 psig (1435 kPa) at 100°F cation limit could pass at high altitude (low barometric
for ASTM, GPA, and CGSB. This difference is larger than the pressure), but could fail at low altitude (higher barometric
difference in VP due to the small difference in test tempera- pressure). The boiling point of the mixture changed with
ture. Equation of state calculations indicate that the ISO pressure, but the melting point of mercury did not. The test
standard would correspond to about 213 psig at 100°F, mak- was modified when suitable low temperature alcohol ther-
ing the ASTM standard more conservative by about 5 psig. mometers became available. The 1960 version of the method
This difference is generally not significant in day-to-day reported the temperature when 5 ml of liquid remained, cor-
operations rected for barometric pressure. The original pass/fail limit of
The practical maximum for a universal multi-use fuel + 36°F was retained for butane and b-p mixtures, and a new
probably lies somewhere between the current ASTM limits of limit of -37°F (-38.3°C) was set for propane. The advent and
208 and the estimated ISO hmit of 213 psig at 100°F. wide use of the chromatograph permitted addition of a quan-
This is a possible area of future research and standard- titative limit of 2.5 vol% C4+ in propane and 2.0 vol% C5-I-
ization for butanes, based on GPA tests showing equivalence with
the weathering test. The weathering test was at one time go-
ing to be withdrawn, but it is still widely used as a field check,
Volatility Residue ("Weathering") and it was retained.
Most consumer propane applications withdraw vapor from These limits are known to be conservative, even for cold
the storage tank (vapor withdrawal) utilizing ambient air weather operations, confirmed by GPA tests at the University
temperature to provide the latent heat of vaporization. This of North Dakota in the winter of 1977-78 using 5-15 vol% bu-
works well down to about — 35°C or lower, until the VP with tane. However, there has never been any compelling techni-
auto-refrigeration of propane is not sufficient to satisfy ap- cal or economic justification to change this specification
pliance demand. Even thermal radiation to a black night sky [57], and the current limits are essentially unchanged from
can take away several degrees of operating temperature, the original intent in 1932.
which can be important when arctic nights can be up to six
months long.
The Volatility of Liquefied Petroleum (LP) Gas test (ASTM Dryness of Propane
D 1837) is an indicator of the nonvolatile materials present in Consumers need reliable operations when it is cold, but this
LP gas [56], and is intended to ensure that most of the LPG is is when icing is most prone to occur. As a result, "dryness" of
available for use, and that low volatility components do not propane is probably the most critical of all specification for
accumulate with repetitive tank fills. The tank will lose all downstream marketers and users. However, "dryness" is a
pressure and "suck a vacuum" below the normal boiling difficult property to quantify in the LPG world.
point of the remaining components, requiring supplemental The "dryness" of propane is determined by specification
heating, pumps and/or external vaporizers. If, for example, performance tests that indicate the suitability of use of the
excessive butane were collected in a tank after repetitive fills, LPG, but do not quantitatively measure water content. The
the user could experience low pressure when the level indi- dryness criteria are so stringent that "on-spec" propane gen-
cator showed plenty of "propane" (actually butane) still left in erally avoids the free water, ice, and hydrate formation re-
the tank. This is aggravated by the strong temperature de- gions under the conditions of most end use applications.
pendence of the "k" factor, or enrichment of the propane in However, some applications, such as an inadequately heated
the vapor relative to butane. The selective vaporization of the liquid vaporizer, may require even lower water contents,
lighter components and retention of heavier components be- and/or use of cryostatic de-icers such as methanol to avoid ic-
comes more efficient as the temperature decreases, making ing with propane that meets the specification "dryness"
this an increasing concern in colder climates. criteria.
The original weathering test was called the Mercury Freeze Propane and propane-butane mixtures are the only con-
Test, but was commonly called the weathering test, or the sumer fuels with a "dryness" specification that requires the
"tinkle and thud" test. The mercury was used as a tempera- water content to be well below the equilibrium saturation
ture indicator, since no thermometers were then available for level. It is not adequate to use visual rating criteria, such as D
4176 "Clear and Bright," or "visually free of undissolved wa- in LPG service, mostly because they lack the volatility to
ter" that is used for butane (and other fuels). It takes about provide icing protection in the vapor space.
20-40 p p m of free water in a fuel to visually detect a haze The meaningfulness of the valve freeze test becomes ques-
with the unaided eye. In essence, visual ratings only require tionable when the LPG contains anti-icing agents. The ASTM
t h a t the fuel does not contain a n excessive a m o u n t of D 2713 method is stated to be "non-applicable" when anti-
undissolved ("free") water. icing agents are present. The current ISO and ASTM wording
The butane test relies on visual detection of water collected of the "not applicable" footnotes are currently different, and
in the bottom of the sample cylinder, and not a haze rating. subject to interpretation. This is Ein area of never ending con-
The less stringent criteria is because auto-refrigeration of bu- troversy, a n d is probably the highest priority area for
tane does not cause temperatures low enough to cause ice/hy- research and standardization.
d r a t e formation. As a result the same criteria applies to None of the current LPG dryness methods (valve freeze,
b u t a n e as for other fuels. CoBr, Dew Point) have valid precision statements. The
Simple tank draining, which leaves the remaining propane pass/fail criteria Eire set at levels that historically have been
saturated with water, is not nearly enough to meet the LPG shown and are known to be suitable for most end uses. The
"dryness" criteria. The presence of free water at any time in a most c o m m o n test for LPG dryness (D2713) is based on a
propane system is sufficient to put the product severely off "valve freeze" criteria, where flow is restricted by ice/hydrate
spec and unusable without dehydration or the addition of formation in a restrictive orifice in a standard valve. The
methanol (see cautions below). This is critical for proper op- pass/fail criterion is intended as an indicator, to prevent a
eration of LPG handling equipment and appliances. Ice ac- broader range of problems, and not just freezing of a small
cumulation can block vapor or liquid fuel lines, Eind disrupt orifice valve flashing liquid p r o p a n e at —42°C. The other
proper operation of mechanical equipment, such as pumps, common test methods are based on the color of the hydrate
meters, filters, VEJVCS (fuel lock-offs), and especially regula- of Cobalt Bromide exposed to equilibrium vapor, and the wa-
tors (vaporizor/regulators). Icing can occur very quickly, and ter dew p o i n t of the equilibrium vapor. Similarly, the
can be difficult to diagnose. pass/fail criteria are set at a stringent enough level to avoid a
"Wet" propane is anything that does not pass the "dryness" broad range of problems based on field experience.
criteria, including the approximately 30-100% saturation It is relatively easy to meet the dryness criteria for propane
range, even when there is no free water. For example, a stor- with m o d e m production processes. However, the occasional
age tank of LPG that is deemed to be "wet" may or may not process failure of individual producers can affect m a n y
have any free water at the bottom of the tank. Water satu- others in pipeline gathering systems. Seasonal brine cavern
rated LPG (but n o free water) fails all of the dryness criteria storage, field dehydration facilities, steam/air cleaning of
by a wide margin. The presence of any free water amounts to storage tanks, hydrostatic testing, a n d use of c o m m o n
"gross" contamination. marine, pipeline, rail and truck facilities at EJI stages of dis-
"Wet" propane that does not contain free water responds tribution provide many opportunities for sporadic water con-
extremely well to low levels of methanol. Unlike ethanol, IPA, tamination.
and higher moleculetr weight alcohols, methanol does not in- In the occurrence of an off-spec dryness event, the techni-
crease the solubility of water in propane (or any other fuel). cal difficulties of sampling and analysis can be enormous, and
It is a popular misconception that methanol is an effective never certain. It is easy to show that propane is "on-spec," be-
de-icer because it increases the solubility of water in the fuel. cause the requirement is so stringent. However, when you are
Methanol decreases the solubility of water in fuels, and causes trying to figure out why the fuel is "off-spec," the "dryness" of
phase separation when it is injected into water-saturated fuel. propane quickly becomes the most exasperating specifica-
The phase-separated liquid is non-freezing, so it will not cause tion, even if it is not the most critical [58].
ice/hydrate blockage. When the LPG is sub-saturated with There is a general correlation between water content and
water, the methanol remains dissolved in the propane along the "drjmess" criteria, but even this is not certain due to non-
with the soluble water. It phase separates along with the wa- linearity of water solubility in propane with temperature,
ter whenever the temperature gets cold enough, and prevents relative linearity of the K ratio with temperature, and the pos-
the separated water/methanol mixture from freezing. If the sible presence of alcohol (especiEilly methanol), ice, and hy-
m e t h a n o l concentration is high enough in the separated drates. There are additional factors that mEike the dryness of
phase, it wiU not freeze at temperatures down to the normal LPG nvuch m o r e complicated t h a n simple solubility and
boiling point of propane of —43°C (i.e., nominal 50/50 vol% freezing for the other fuels. These are discussed below.
methanol/water mixtures Eire commonly used as windshield
de-icing fluid good down to —40°C). Phase Behavior of Dissolved Water in Propane
Methanol is very effective in LPG systems at preventing It is initially counter-intuitive that the concentration of water
freezing of separated phases, but if mis-handled can aggra- in equilibrium propane vapor, withdrawn from the vapor
vate the a m o u n t of separated phase that can accumulate at space of a storage tank, increases as the t e m p e r a t u r e de-
tank b o t t o m s , and can propagate phase separated phases creases. This is the key point of understanding water phase
through the distribution system. behavior in propane, and the related problems of dryness of
Other alcohols or glycols form "glass" phases with water, propane.
becoming increasingly viscous on t e m p e r a t u r e drop, b u t Water has a low solubility in LPG, similar to other "pure"
without freezing in the traditional sense. They are often de- parafins such as pentane, isomerate or alkylate. Since so lit-
scribed as forming "slushy ice" that is very resistant to accu- tle water is present, it is often confusing why dr3rness is so im-
mulation or blockage. However, these are reirely if ever used portant for propane, much more so than for other fuels that
contain more water. This section assumes no hydrate forma- tent a n d freezing behavior of the vapor phase is just as
tion, similar to other fuels. Hydrates will be considered important as the liquid phase.
immediately following. A c o m m o n phrase in the literature is that propane vapor
The formation of "free" or undissolved water from a drop has a much higher capacity for water than propane liquid.
in temperature is similar to other fuels, except that it occurs This is true, but doesn't provide much clarity. Water, with a
at a lower concentration level due to lower solubility. The sol- molecular weight of 18, would have physical properties
ubility of water in fuels increases with the temperature and closer to niethane (mw 16) and Neon (mw 20) if it were not
aromatics content of the fuel, ranging from about 100 p p m w for hydrogen bonding. Hydrogen bonding results in a very
in low aromatics parafinic fuels to over 500 weight p p m in dense, high boiling liquid water phase instead of a light low
high aromatics content gasoline or diesel fuels at 70°F [59], A molecular weight gas. However, when water is dissolved in
drop in temperature of water-saturated fuel causes the phase propane at low p p m levels, there is little hydrogen bonding
separation of a bulk (undissolved or "free") water phase to between the water molecules, a n d it behaves like a low
form as a "haze" of small water droplets. These tend to coa- molecular weight dissolved gas. Dissolved water in propane
lesce into larger droplets and gravity settles them to the bot- is much more volatile t h a n propane, and becomes enriched in
tom of the storage tank. Pure water ice (not hydrate) will only the vapor phase.
freeze if the temperature is below freezing. Since the solubil- The "K" ratio, or ratio of water concentration in the equi-
ity of water in propane is already low, there is m u c h less librium propane vapor vs. the water concentration in the
water available to phase separate with a drop in temperature. liquid propane decreases with increase in temperature, rang-
As a result, classical "fuel line freezing" is not very prevalent ing from over 20 (mole/mole) at low temperatures down to
in liquid propane systems, and most problems are associated about 5 at high ambient temperatures. Essentially the VP of
with smaller, m o r e easily plugged orifices in valves a n d propane increases faster with increasing temperature than
regulators than in m u c h larger diameter fuel lines. water, in essence "diluting" the water vapor at higher tem-
If free w a t e r is present (e.g., grossly c o n t a m i n a t e d peratures. Unfortunately, this makes the propane vapor in
propane), dispersed droplets can "super-cool" below freezing the tank more h u m i d when it is cold t h a n when it is hot,
in cold gases or liquids, including propane. This can result in making propane vapor more prone to icing.
rapid ice accumulation that tends to be most severe in the - 4 Several operational artifacts come as result of this phase
to — 10°C range, very similar to automotive carburetor icing behavior that are not intuitively obvious. For example, this
and aircraft wing or propeller icing ("rime" icing). As each su- also tends to moderate the absolute a m o u n t of water per unit
per-cooled droplet impinges on a surface, a portion of the wa- volume in the vapor phase over a wide temperature range.
ter spontaneously freezes, adding to the surface ice deposit at Propane vapor tends to be more prone to water condensa-
the impingement point. The remaining liquid water droplet is tion/freezing than p r o p a n e liquid. "Wet" off-spec propane
heated to 0°C by the heat of fusion, but is rapidly cooled again can be brought on-spec by venting equilibrium vapor, essen-
by the surrounding cold fuel. This causes the remaining wa- tially distilling the water out [60], and this process will be
ter to either freeze, or to form another smaller super-cooled more efficient at cool or cold temperatures. Large sample
liquid droplet, which can repeat the process to extinction. sizes are needed to do a valve freeze or CoBr test, because the
Flow patterns can create a small impingement point, and fil- sample changes water content as you withdraw equilibrium
ter/screen surface area that is already plugged diverts flow to vapor during the test. The CoBr and Dew Point tests are more
unobstructed areas. This can result in a very fast and efficient stringent at cold storage tank temperatures than hot. The
plugging mechanism. Ice accumulation in pipe elbows, me- valve freeze test (on the liquid) is not affected when the tank
ters, filters and screens is often associated with "snap" cool- is full, but could be affected when the tank is nearly empty
ing to just below freezing, a condition that favors formation (large vapor space = large volume to enrich water in vapor,
of super-cooled water hazes and "rime icing." Ice accumu- depleting or drying out the remaining small volume of liq-
lated under these conditions often looks like a translucent uid). Under some circumstances, it is very difficult to obtain
"milky white" thick coating t h a t appears to have been a representative sample. Simply exasperating!
"painted" on. These conditions are more commonly found in
production facilities, prior to final drying, but can occur dur- LPG Gas Hydrates
ing downstream distribution if water has gotten into the sys-
It is not widely appreciated how prevalent hydrates can be in
tem. Methanol is very effective at eliminating rime icing,
LPG systems. Few people outside of research laboratories
since only a very small concentration of methanol in the sep-
have ever seen a gas hydrate, even though thermodynami-
arated phase is required to reduce the freezing point to less
cally they are the most stable form of solid ("ice") in propane
than about -10°C.
systems. In fact, pure water ice is unlikely to form in liquid
Propane fuel systems are sealed under pressure, and not propane systems at all, unless the water content is very high,
vented to the atmosphere. Tanks in the distribution system and free water is present in the propane liquid, either on the
are never allowed to be totally liquid filled for safety reasons. tank bottom or as a dispersed haze in the liquid.
An equilibrium vapor phase is therefore always present in Gas hydrates are a class of ice-like clathrate solids formed
downstream distribution (but not necessarily in production from water and low molecular weight C1-C5 hydrocarbons,
facilities). Most end use applications draw equilibrium vapor including propane [61]. They consist of water "cages" that sur-
from the top of the tank, and large tanks always have a Pres- round or "enclathrate" the hydrocarbon molecules. Hydrate
sure Relief Valve (Pressure Safety Valve or vent in other ju- formation can be a significant problem for cold weather op-
risdictions). These are safety devices that vent vapor in the erations for gas and gas liquids production and processing, es-
event of an overpressure situation. As a result, the water con- pecially prior to dehydration. They can form in LPG process-
ing equipment, pipelines, and even under deep-sea conditions in some situations. Firstly, hydrates tend to form at free-wa-
due to gas seepage into cold ocean water (with the potential of ter surfaces. This is because propane type II hydrate has a
becoming a significant "new" energy resource) [62,63]. Hy- composition of a b o u t 17.1:1 mole ratio of waterrpropane,
drate blockages in pipes can be very hazardous. Depressuriz- which greatly exceeds the propane solubility in water. As a re-
ing one side of the line can result in the hydrate blockage be- sult, when a tank containing free water is cooled towards
coming a ballistic projectile, with the capability of causing zero, it will tend to form a thin layer of hydrate on the water
considerable damage. The propane-water and methane-water surface, like the first thin skin of ice on a pond, puddle, or ice
systems have been studied in great detail due to their com- cube tray. The hydrate layer becomes a barrier for propane
mercial importance. Several GPA and other research reports diffusion, effectively limiting the rate of further hydrate for-
are available detailing the phase behavior of hydrates [64]. mation. As the t e m p e r a t u r e drops further below 0°C, the
The c o m m o n industry "rule of t h u m b " is that hydrate for- underlying "metastable" water can freeze to water ice.
mation requires free water to be present, and that it cannot Thermodynamically, the hydrate and water ice should not
occur with sub-saturated, on-spec propane. Technically, this exist together; they are only there due to a kinetic rate limi-
is not true, but it is good enough for most applications, with tation. Under thermodynamic equilibrium conditions, water
some caveats to cover high dissolved water contents and high ice would not form until all of the propane is consumed first
pressures. Technically, free water does not have to be present forming hydrate, leaving water or water ice in equilibrium
for propane hydrate to form, but in such cases, there is so lit- with hydrate, and no propane liquid. As a result, mixing and
tle soluble water available for hydrate formation that it is turbulence are invariably factors in hydrate formation from
rarely a problem, or at least is not a more severe problem propane liquid.
t h a n if only water ice were formed. The presence of free Secondly, hydrates can form very quickly on tank surfaces
w a t e r in the hydrate formation t e m p e r a t u r e range can exposed to the vapor space by deposition from the vapor (i.e.,
cause severe problems because m u c h larger quantities of the opposite of sublimation). The equilibrium concentration
hydrate can form. Below freezing, there is no practical reason of water is always higher in the vapor phase, which favors hy-
to differentiate between hydrates and water ice in most drate formation from the vapor. This can be a very fast and
applications. "efficient" process, as there is no kinetic barrier, and the water
Propane hydrates are stable above the freezing point of vapor and propane are already mixed. Only the rate of diffu-
water. The higher the pressure, the higher the temperatures sion and convection of the water vapor limit the rate of hy-
at which they are stable. They can form at any temperature drate formation. Hydrate formation from saturated equilib-
below about 5.5°C (42°F) in propane at its saturated VP. No rium vapor depletes water from the vapor phase, essentially
externally applied pressure (for example, a pump) is required dehydrating it. Additional water will vaporize from the liquid,
for propane hydrates to form. Externally, the symptoms of and contribute to additional hydrate formation. If liquid wa-
having ice or hydrates in LPG systems are virtually identical. ter were in the tank bottom, and one waited long enough, all
They both form only when it's cold, they both accumulate of the water would eventually form hydrate at the tank bot-
and plug lines and orifices, and they both are "melted" by tom, or dissolve into the liquid propane, vaporize, and form
methanol, leaving the same a m o u n t of liquid methanol/water hydrate on the vessel walls that are exposed to the vapor. This
mixture at the bottom of the tank. The problems are the process would continue until all the free water was consumed,
same, the fix is the same, and the result is the same. Most of leaving only hydrate on the tank bottom and vapor walls. The
t h e time, it doesn't matter, a n d there is n o need to liquid propane in equilibrium with the hydrate can still be "off
differentiate between water ice and propane hydrate. spec" near the high end of the hydrate formation range. The
Gas hydrates are the "phantoms" of the LPG world, and are real fun begins when the tank gets emptied out and re-filled
notoriously difficult to "diagnose" when they do occur. They with dry or warmer propane, which immediately goes "off-
decompose (sublime) to water and hydrocarbon gas at ambi- spec" for no apparent reason, or the temperature changes
ent pressures very quickly, since they are essentially solids rapidly, and slugs of water or chunks of "ice" show up.
with a VP of about 80 psi. The sublimation rate can be high This can result in some truly exasperating situations when
enough to support a burning flame [65]. Often they are gone investigating water related problems in cold LPG systems.
by the time the e q u i p m e n t is depressurized and opened You are never sure if free water is present, or if the liquid or
for inspection. vapor is in equilibrium, or if any sample is representative.
It is always uncertain whether hydrate, pure water ice, or The basic concept of obtaining representative samples is
both are involved when icing occurs in LPG systems. The s o m e w h a t uncertain. You generally don't have a b o t t o m
biggest difference is that "icing" can occur between 0 and drain, and you can't see inside of the tank liquid or vapor
about 4.5°C in LPG systems, due to hydrate formation. It is space. When you open it up, it's all gone. This, plus the in-
r a r e for the t e m p e r a t u r e to be stable in this range long herent difficulties of sampling/measuring low p p m levels of
enough during a n icing episode to make it obvious that hy- water and methanol in LPG makes reliable quantitative mea-
drate and not water ice is the cause. The day/night tempera- surement of water virtually impossible in cool/cold weather,
ture difference is generally m u c h larger than this. However, without extraordinary attention to sampling and analytical
even w h e n this occurs, people will generally first tend to detail. Throw in a couple of different test methods with no
think that the thermometer is off by a couple of degrees, or precision statements, no calibrants, no reference standards,
that there is some auto-refrigeration somewhere, rather than no QCs and uncertain correlation, and "exasperating" is an
a hydrate event occurring above 0°C. understatement.
Hydrates can form both in the liquid and vapor phases, but It is left to the reader's imagination the many hours of stim-
there are some differences in behaviors that can be important ulating conversation possible between the lab, the process
engineer, the plant manager, and the receipt terminal. This is for a variety of conditions. Flashing liquid propane into even
a potential area of future reseetrch and standcirdization. moderate vacuums can attain temperatures below — 80°C.
Fortunately, the high VP of methanol makes it a very effec- The vapor pressure and solubility of water in propane below
tive means to eliminate ice or hydrate formation in both the —42°C is extremely low, so essentially all the dissolved water
liquid a n d vapor phase. Methanol, the lowest molecular that was present is converted to hydrate/ice. Liquid propane
weight alcohol, partitions between liquid and vapor phases vaporization systems almost always require external heating,
closest to water, a n d tends to protect b o t h phases from b o t h to convert all of the liquid to vapor, and to prevent
freezing. eventual freeze u p from ice. Transient conditions, for
Unfortunately, the specifications are silent on the use of example startup of automobile vaporizer/regulators in very
methanol, the test methods are inconsistent in response to cold weather, t e n d to be p r o n e to icing, until the engine
methanol, and there is no consensus between the upstream coolant gets w a r m enough to keep the vaporizer above
and downstream industries on the intent and extent of use of hydrate/freezing temperatures.
methanol in LPG. This is a potential Eirea of future research The methanol addition rates t h a t are r e c o m m e n d e d in
and standardization. various codes and standcirds for new tanks or for when mois-
Recently, some non-cryoscopic kinetic "hydrate inhibitor" ture is present) are intended to remove the free water in the
additives have been commercialized for processing/pipelin- tank, and leave only a small a m o u n t of methanol/water mix-
ing applications, but these are not applicable to specification ture prior to putting into service. They are not intended to
products [66]. provide protection where gross water contamination has oc-
curred or to allow weak water/methanol mixtures with high
Auto-refrigeration freezing points to remain in the tank. For this reason, the
Like any gas (except hydrogen) near ambient temperature, standards generally require inspection and removal of free
p r o p a n e vapor will undergo Joule-Thomson (JT) cooling methanol/water prior to putting the tank into service.
when depressurized (flashed) across a veJve, orifice, pressure Methanol is effective at preventing freeze-ups to very low
regulator, or other device. The cooling effect is dependent on temperatures, but there is no universally accepted criteria for
the process, whether it is adiabatic (a valve) or isentropic how much methanol to add to propane during downstream
(turbo-expander) or polytropic (something in between). The distribution as a preventative m e a s u r e . Many companies
JT cooling effect is not very large, about 0.25°F per psi drop in have optimized methanol addition rates based on actual tem-
the 30--40°F range for propane, but this can be significant un- p e r a t u r e s and/or dryness test results. These are effective
der certain conditions. In small regulators, the JT cooling is strategies with a relatively sound technical basis (see phase
offset by heat gained from the environment, tending to be behavior of m e t h a n o l ) . This is a potential area of future
isothermcd at low flow rates (high heating from ambient air, research and standardization.
low JT cooling from low flow). However, as the appliance de- Butane, with a normal boiling point of neetr 0°C is not ca-
m a n d and gas flow increases, there may not be enough con- pable of creating ice freezing conditions by auto-refrigeration
vective heating to overcome the JT cooling, and the system u n d e r normeJ conditions of use, and is treated as in other fu-
tends toweird adiabatic conditions. If the inlet propane vapor els with only a "visually cleeir" requirement. However, if bu-
is near water saturation (off-spec) and only slightly above the tane is used below ambient pressure, the same precautions
freezing point, the cooling effect can be sufficient to cause may have to be used, as the boiling point at reduced pressure
phase separation and ice formation at the expansion point. is below the freezing point of water, a n d ice/hydrate cam form.
Similarly, if the valve or regulator body is cooled below freez- Butane, propane and their mixtures are widely used as the
ing, then the high-pressure propane vapor at the regulator working fluid in large industrial and chemical process refrig-
inlet could be cooled below freezing by the cold valve body. eration applications, such as industrial chillers, gas process-
This results in inlet freezing, upstream of the point of ing, refinery gas processing, or reactor cooling in alkylation
vaporization, where the actual cooling occurs. A commercial processes. These are usucJly integrated into the production
technical bulletin (LP-24) is available from a regulator manu- processes themselves, so they are n o t very "visible," even
facturer dealing with vapor regulator inlet line freezing from though they are very large and very commonplace. All gener-
these effects [67]. Ice will tend to accumulate over time in a ally require some provision for w a t e r removal and icing
flowing system, until a blockage is eventually formed. If the protection.
propane liquid is substantially sub-saturated (i.e., on-spec),
the cooling from expansion of equilibrium vapor is generally Phase Behavior of Methanol in Propane
not enough to cool the vapor to the water saturation temper-
Methanol is a unique material in the LPG world. It is the only
ature (dew point), and no ice/water is formed (one reason why
alcohol with a lower molecular weight (31) than propane, and
HD5 and functionally equivalent specs are where they are).
the only one to be concentrated into the vapor (like water). As
When liquid propane is depressurized or "flashed," a frac- a result, it tends to partition and "travel" with the water, mak-
tion of the liquid will vaporize, cooling the entire mixture ing it very effective in preventing freeze-up in both the liquid,
down to the boiling point and dew point of the liquid/vapor vapor, and condensed vapor phases. The freezing point de-
mixture (they are the same if the mixture is in equilibrium). pression properties of methanol in water are very good, pro-
This cooling effect is large, for example resulting in liquid viding protection down to -40°C [68] and below. Methanol,
and gaseous propane at about —42°C at atmospheric pres- being a small molecule, has a high diffusion coefficient and is
sure. MoUier diagrams (pressure-entropy), pressure enthalpy very effective at dissolving water and hydrates. No other alco-
diagrams, or tables of thermodynamic properties can be used hol has this broad range of beneficial properties, so methanol
to quantify temperatures, pressures, enthalpies and entropies is the only alcohol that is commonly used in LPG systems.
The use of methanol is mandated under certain codes and solute values of water/methanol solubility in LPG below the
standards to minimize free water from tanks prior to putting saturation levels and at varying olefin levels are not accu-
t h e m into service or if water is reasonably expected to be rately known. This is a suggested area of research a n d
present [69]. standardization.
Methanol works by creating either a second non-freezing Ethanol and iso-propanol have a higher solubility and lower
separated phase in the liquid, in the vapor (hydrate), or the va- vapor pressure than methanol in liquid propane. They require
por if re-condensed. Methanol/water mixtures will not freeze, a significantly higher treat rate per p p m w of water present to
but will gravity settle, and tend to collect at tank bottoms, prevent formation of solids at — 40°C in both the liquid and
where it can be difficult to remove. This can promote other equilibrium vapor. To date, methanol is technically and eco-
problems such as corrosion and resulting sediment and filter nomically the best de-icer for propane.
plugging, which is undesirable in the downstream applica- In general, over-addition of methanol should be avoided, as
tions. As a result, there is a general consensus that propane drops in temperature or contact with water can result in most
should be manufactured as dry as necessary for "normal" op- of the methanol phase separating in distribution and storage
erations, and that methanol should be used as needed for new and causing problems. For example, if w a r m propane con-
tank commissioning, and cold weather operations in down- taining 1% methanol either cooled down to — 20°C or were
stream (post refining) distribution and use. contacted with water, then more than half of it will phase
Methanol is equally difficult to detect as water at low p p m separate and settle to the bottom of the storage tank as a
levels, especially in the field. As a result, the actual amounts non-freezing water/methanol mixture. This would amount to
of water or methanol present are rarely measured directly. It 500-1OOOL for a large rail car. This large volume of
is also recognized that methanol interferes with some of the methanol/water mixture has the potentieJ to accumulate in
c o m m o n "dryness" test methods once it has been added to downstream storage, to the point where individual small
propeme. D2713 "valve freeze" test is quite explicit in stating deliveries could contain gross quantities of water/methanol.
that the test does not apply to LPG containing antifreezing It is generally accepted that methanol should not be used
agents (although it is commonly used for this purpose in as an alternative to proper dehydration during production,
spite of this caveat). The CoBr test is believed to be relatively and that periodic use should be minimized. For the producer,
i m m u n e to methanol, but this test is not widely used. The the answer is to consistently make LPG very dry, and avoid
chilled mirror dew point test is affected by methanol, since it periodic "slugs" of water. For the marketer, who is subject to
phase separates with water. Electronic hygrometers (dew the downstream sources of water, the answer is to monitor,
point meters) m a y or may not be affected by m e t h a n o l and only use methanol when required during cold weather.
depending upon the principle of operation. This is also an area of r e c o m m e n d e d research a n d
In colder climates, it is common for methanol to be added standardization.
to bulk storage during distribution as a preventative mea-
sure. Long-term field experience indicates that this is a n ef- Sources of Water
fective strategy to minimize regulator freeze-up problems, so Water can be introduced into propane distribution systems
long as addition is controlled to the m i n i m u m required. Dif- from a vairiety of sources. Faulty production can leave excess
ferent companies have applied mzmy different criteria, in the dissolved water or free water in the LPG due to inadequate
absence of reliable field tests that can be used to monitor and dehydration. Water is used for hydrostatic pressure testing of
control water/methanol. This is an area of r e c o m m e n d e d large pressure vessels including tanks, trucks, and rail cars.
focus for future research and standcirdization Steam is used to clean and "inert" tanks for maintenance and
A 50 wt% methzmol/water mixture (common windshield change of service. Water can become trapped in tanks from
wiper Emti-freeze in cold climates) will not freeze down to previous wet loads due to internal "dead volume" at the
below — 40°C. Therefore, as long as any separated bottom of tanks due to valves or piping that is recessed for
methanol/water phase is at least this concentrated, no freeze- physical protection, a c o m m o n requirement of safety codes.
u p is possible under typical conditions of LPG use. Methanol Exposure of tanks to the atmosphere can result in moist air
is more soluble in propane than water, so more remains in condensing water on inside surfaces, where it becomes
the propane phase in equilibrium with the methanol/water trapped, and accumulates with each diurnal heat/cool cycle.
separated phase. Limited low temperature solubility data in- Free water in trucks or rail czirs tends to be persistent because
dicates that the methanol solubility in propane in contact of the low water solubility of water in p r o p a n e . A small
with a 50 wt% methanol/water solution at -40°C is about a m o u n t of water in a truck or rail car can render m a n y
400-800 p p m w [70]. This indicates that it would take about subsequent loads "off-spec."
400-800 p p m w methanol to prevent freezing down to about Recent changes to rail car pressure vessel certification re-
—40°C at ambient pressures for w a t e r saturated p r o p a n e quirements provide another opportunity to further reduce
(about 100 p p m w at 70°F). This is smaller than the solubility the use and occurrence of steam cleeming and hydrotesting of
of methanol in propane at ambient temperature, so methanol large pressure vessels (truck/rail). Work is ongoing in this
use tends to be "robust" so long as gross overdoses are cirea and several programs are planned. This is a suggested
avoided (and a dry grade of methanol is used). Slightly lower area of research and standardization.
treat rates would be expected for lower water contents, or if
freezing protection was only required to a higher tempera- Measurement of Water in LPG
ture. The lower limit to eliminate all solid formation at -40°C There has cJways been a desire in the LPG industry to have bet-
would be expected to correspond to the 400-800 p p m w solu- ter test methods for "dryness," especially for production and
bility of methanol in propane u n d e r these conditions. The ab- terminal bulk receipts, which are the two main control points
(See "dryness" sections above). This has been an elusive goal Similarly, the CoBr sind Dew Point tests would be expected
for many years, due the technical difficulties involved. to be somewhat influenced by gas composition, and espe-
The criteria for pass/fail on the CoBr test are as follows [71]: cially by olefin content. Olefins have a higher affinity for wa-
ter, and a correspondingly lower "K" ratio. Directionally,
Color Per Cent Humidity^ higher propylene content would make the test less severe, re-
quiring higher liquid water contents to obtain a test failure.
Green Very Dry Pass (rcirely seen)
Blue From nearly 0% to 30% Pass This difference has not been quantified, and is generally not
Lavender From 30% to 52% Fail considered to be significant for commercial propane.
Pink From 52% to 100% Fail There are a n u m b e r of other anal3îcal techniques that can
be used for the anedytical determination of water in LPG.
Some methods, such as the Karl Fisher, can be used but are
It is generally accepted that a 60 s valve freeze pass is about
difficult to apply to LPG, because of the physical properties.
equivalent to a CoBr pass, or a —26°C dew point and less than
Others, such as vapor phase determinations, can be influ-
about 35 p p m w water in the LPG liquid phase. However,
enced by sample size due to the very high "K" ratio of dissolved
these are not exact relationships, and there are several com-
water in propane. The cobalt bromide test, for example, rec-
plicating factors due to differences in phase behavior with
ommends at least 15 gallons of LPG sample if the test cannot
temperature and composition. Different people have made
be done at the storage tank with the equilibrium vapor. In
different assumptions in estimating equivalence between wa-
other cases, such as terminals supplied from underground
ter content, the liquid propane phase, and the CoBr test re-
cavern storage, there is n o source of equilibrium vapor avail-
sults. During the CoBr test, the equilibrium vapor sample is
able on-site, because all the vessels are liquid filled.
preconditioned with an ice bath to 32°F and 50 psig, slightly
below the saturation vapor pressure at 32°F. Most people Electronic hygrometers and "dew point" meters [72,73]
assume the humidity values in the table to apply at 32°F in have been successfully used, and while they have the neces-
doing the equivalence calculations. The a u t h o r noted that sary sensitivity, and are widely used in the natural gas indus-
"the values in this table were determined by series of tests on try [74], they are not currently recognized in the LPG
propane vapor containing various amounts of water over a standard. Care must be taken with their use, especially for
temperature range of from 35-70°F. The percents at which calibration a n d QC procedures to ensure that results are
the changes of color take place seem to be somewhat affected valid. Several new ASTM procedures are now available that
by t e m p e r a t u r e . However, the determinations were not allow adoption of on-line analytical techniques to product
accurate enough to assign closer values in the table." certifications, and LPG "dryness" is a prime candidate for
these new methods. Many companies have installed solid
In the test, the actual humidity of the sample is determined state electrometric probes at production facilities to monitor
by the bulk tank or bulk sample temperature, not the 32°F drying operations, and there is emerging interest in having
test t e m p e r a t u r e . The humidity of the equilibrium vapor these included as an alternate test method in the standard.
varies inversely with temperature at constant liquid water This is a recommended area of research and standardization.
content, due to the change in the "K" ratio. Therefore, there
Sampling and sample introduction also needs special care
is no single p p m water level of water in liquid propane that
and attention. Formation of hydrates can metke the storage
corresponds to a CoBr (or Dew Point) pass/fail level. The
time prior to analysis a factor. At high temperatures and hu-
equivalence level is inherently temperature dependent.
midity levels, the air in the lab can contain 20 000-40 000
Both the CoBr and Dew Point test methods are most severe
ppmv water vapor, and there can be more water adsorbed on
(conservative) at the lower temperature ranges. One can esti-
sample lines a n d cylinders t h a n is in an on-spec sample.
mate the amount of water in liquid propane that is required
More than one analyst has falsely reported the humidity level
to pass the test on the known dependence of "K" ratio and
of a plastic sample transfer line as an off spec LPG result.
water dew point (vapor pressure) in gases. This depends on
Recently, a new stain tube was developed for use as a field
what assumptions are made about the humidity level for fail-
test in natural gas pipelines that has a lower sensitivity to trace
ure condition (32% or 40%) and to what temperature the hu-
glycol used in natural gas dehydrating systems [75]. These
midity shown in the table applies (32°F versus 60°F). A
stain tubes still have an interference from methanol, but may
propane sample taken at 32°F has variously been estimated to
still have some application as a field test, for example on ter-
require less than 10-20 p p m w water in the liquid to obtain a
minal receipts prior to the addition of methanol. These cali-
passing result. A sample taken at 100°F has been estimated to
brated in the range 2-10 Ib/MMscft (traditional units for nat-
require less than 20-35 p p m w in the liquid to obtain a pass-
ural gas), which is equivalent to about 40-220 ppmv (multiply
ing result. This temperature dependence is not recognized in
by mole weight ratio 18/44 = 0.41 to convert to mass p p m as-
the test methods. However, the pass/fail criteria are severe
suming ideal gas at low pressure). This is in the correct range
enough that propane obtaining a passing result is considered
for use on LPG equilibrium vapor, so it can likely be adapted
suitable for use regardless of the temperature of the sample.
to use for LPG. This would be very similar to the GPA and
CGSB field methods for mercaptan odorant (see odorization),
^ The humidity of the equilibrium vapor is dependent on tempera- that use similar stain tubes calibrated in traditionetl natural
ture, since the wt. "K ratio varies from about 10 at 60°F to about 15 gas industry units, with appropriate conversion factors.
at 32°F. As a result, both the CoBr and Dew Point test methods are At present there is no standard test method for the use of
more severe (conservative) at 32°F than at 60°F (or higher). This tem-
perature dependence is not considered in the test methods, and the stain tubes, or electronic hygrometers or dew point meters
same pass/fail criteria is applied regardless of the temperature of the for LPG specifications. The ASTM natural gas standards
storage tank and equilibrium vapor. that use these m e t h o d s currently do not include LPG in
the scope. This is another area of recommended research and door use. The original "lamp" method is still listed in most
stEmdardization. specifications, but rarely, if ever used. A variety of newer in-
strument methods are in common use, and are under con-
sideration for inclusion in LPG specifications. Recently, the
R e s i d u a l Matter (Oil Stain & R e s i d u e )
requirement was changed to include the sulfur contribution
Non-volatile materials that are soluble in liquid propane tend from added mercaptan odorant, which is effectively a tight-
to a c c u m u l a t e at the point of p r o p a n e vaporization as a ening of the standard. The California ARB "HDIO" standard
residue or gum that can interfer with the proper operation of has an 80 p p m maximum sulfur limit.
some equipment. The oil stain test attempts to concentrate All LPG specifications have some provision for the control
non volatile residues that can be visually detected by putting of corrosive sulfur compounds to protect copper and copper
it dropwise on a clean filter paper. This test is quite subjec- based alloys commonly used in fittings and connections in
tive a n d can be influenced by the grade of filter paper, or storage, transportation, a n d appliances. ASTM D1838 is es-
color of the residue. Historically, the main purpose of the test sentially a modified ASTM D130 copper coupon corrosion
was to detect traces of compressor oils, a c o m m o n occurence test using pressure rated equipment for LPG. The same grade
in the early days of the industry, but less c o m m o n today. of copper strip and preparation procedures are used, and the
Other sources of heavy naaterials can be heat transfer fluids strip is suspended on a hook fixed to the outage (ullage) tube
from distillation processes, caustic, amine and glycols used in a purpose built stainless steel test cylinder with an O-ring
in some processes, greases and "pipe dope," sample cylin- removable top closure.
ders, hose plasticizers, or cross contamination with other hy- Sulfur based corrosion in LPG is a surprisingly complex
drocarbon fuels and lubricants if any c o m m o n equipment is subject, due to the chemistry of the reactive sulfur species that
used in distribution. can be present, smd the nature of the test [76]. Mixtures of cer-
Contaminants that form "oily residues" or "waxy solids" tain sulfur compounds are more corrosive than each alone,
with auto-refrigeration of vaporizing propane, especially in even if the individual compounds were present at higher con-
association with fine particulates, can interfere with proper centrations. This can lead to occasionally bizarre situations
operation of safety lock-offs, overpressure vents and regula- where two on-spec propane batches go "off-spec" upon mix-
tors. Non volatile additives are generally not recommended ing. The classic case is w h e r e one batch contains a small
for use in propane intended for vaporizing service, and spe- amount of dissolved elemental sulfur (S8), and the other a
cific warnings are included in D130 copper corrosion test trace of H2S (hydrogen sulfide) or COS (carbonyl sulfide).
pertaining to corrosion inhibitors ("masking agents"). Some Each batch can be on spec by a wide margin, but the mixture
higher boiling or polymeric materials may interfere with cat- can show a persistent fail, or even worse, an occasional fail.
alytic heaters or automotive catalysts if present in the liquid There is nothing like a persistent occasional fail to go into "dis-
propane. ASTM specifications currently do not include lim- pute mode," with no hope of short-term technical resolution.
ites for higher t e m p e r a t u r e evaporation limits. This is a Many hours of stimulating conversation are made possible
potential area of future research a n d standardization. between shippers on a c o m m o n pipeline system or storage fa-
Propane is a very poor solvent for parafin wax (n-parafins cility with such events. Each may sanctimoniously claim the
or near parafins) or for asphaltenes, and has been used in others to b e at fault, presenting credible data to prove their
commercial de-waxing and de-ashpalting processes. Contam- innocence with consistent Cu corrosion passes. Try devising
ination of LPG with "black" oils that contain asphaltenes a "round robin" to resolve that dispute.
(IFO, HFO, Bunker, Pitch, Crude) or distillate fuels that con- In the vast majority of cases, corrosion problems in LPG
tain wax (diesel, furnace oil, marine gas oils, kerosene, Jet) are associated with H2S, Sg (elemental sulfur, eight member
can result in the precipitation and collection of waxy or as- ring), COS (carbonyl sulfide), RSSxR (alkyl polysulfides),
phaltene solids. This can cause m u c h more severe operational HSSxH (polysulfanes), H2O (water) and O2 (in air). The most
problems than an oily liquid because of more severe impacts important are usually H2S (improper treating), Sg (usually
on equipment. Care must be taken to prevent cross contami- from oxidation of H2S) and COS hydrolysis (reaction with
nation of these materials. Sources for such contamination can H2O to form CO2 and H2S). Mixtures of H2S and elemental
include leaking heat exchangers, pipeline "dead legs" or idle sulfur (Sg) form very reactive polysulfur intermediates that
p u m p loops, meter provers or other distribution equipment are very corrosive, and react very quickly with most common
that may be inadequately cleaned from a previous service. metals. Trace H2S and Sg £U'e legendary for their difficulty to
Nonvolatile additives may be beneficial for certain applica- sample and analyze. Fortunately, lead acetate paper is very
tions, such as detergent/dispersant additives for autopropane, sensitive as a field test for H2S. Sampling and analysis for
similar to gasoline. However, this can introduce the need for trace Sg is always problematic.
a segregated fuel, since they can still be detrimental to vapor- Almost all copper corrosion problems are a direct result of
izing services. Maintaining a single universal grade would inadequate treating at the time of manufacture, and/or the
require additive injection at the point of dispensing. This is a highly non-linear blending characteristics of different sulfur
potential area of future research and standardization. types in propane from different sources.
Corrosion, H2S, a n d Sulfur Contziminants
Historically, the total sulfur content of LPG (sometimes Magnetic Residues ("Black Deposits") and Particulates
called the volatile sulfur content) was always much lower The occurance of iron oxide/sulphide magnetic residues was
than for other fuels, and this was important, especially for in- studied by the Propane Gas Association of Canada (PGAC
[77]) as a result of widespread problems especially in auto- Naturally Occurring Radioactive Materials
motive LPG fuel systems [78]. Iron particulates either from (NORM)
heat treating "mill scale" or corrosion processes can ad-
versely affect the operation of components that magnetically Sludges and tank scale from propane storage tanks, trucks
attract and trap these materials in the working mechanisms and rail cars, and filters/screens may contain Naturally
(e.g., magnetically coupled level gauges and electronic Occurring Radioactive Material (NORM) in the form of lead
solenoid valves). Collection of gross a m o u n t s of solid 210 (Pb'^'"). Similarly, equipment used for the transfer of
residues (magnetic or otherwise) can adversely affect opera- propane such as product pipelines, pumps and compressors
tion of filters, filter lock-offs, regulators, mixers, pressure re- may have detectable levels of radioactive lead 210 on inner
lease valves, etc., by mechancial blockage. Two to ten micron surfaces. Workers involved in cleaning, repair or other
(absolute. Beta 5000) filters have been found to be effective to maintenance of inner surfaces of such equipment should
remove these materials with good filter life (granular well avoid breathing dust generated from such activities. Suitable
behaved filter calie). codes of practice should be developed for these activities de-
tailing appropriate occupational hygiene and disposal prac-
tices [82].
Ammonia
A m m o n i a is not used in the production process, a n d is
generally removed by gas stripping and distillation if it is
present. Anhydrous a m m o n i a is widely used in agriculture as VOLUME CORRECTION FACTORS (VCF)
a fertilizer, and is transported in the same pressure rated FOR LPGS AND NGLS [83]
equipment as LPG. It is c o m m o n for rail and truck cargo ves-
sels to transport "anhydrous" during the spring and s u m m e r LPG has the lowest density, largest thermal expansion and
growing season. The s a m e rail or truck cargo tanks are compressibility and highest operating pressure of the com-
converted to LPG service for the fall and winter heating sea- m o n fuels. It is the only fuel where compressibility is signifi-
son. This is advantageous for optimal use of transportation cant e n o u g h that it can be taken into account both for
equipment, but offers increased chance of cross contamina- calibration of composition test methods and custody transfer
tion without adequate cleaning in the change of service metering. The original set of Volume Correction Factors
procedure. (VCF) were developed in an NGAA (GPA) sponsored research
Anhydrous e q u i p m e n t a n d LPG p r o d u c t i o n e q u i p m e n t p r o g r a m in 1942. It was first published as GPA standard
generally use only carbon or stainless steel fittings. Brass 2142. These factors were later adopted as national and
(copper alloy) veilves and fittings are commonly used in LPG international measurement standards as ASTM/IP 1250.
systems, particularly those at the dealer and consumer level. The Volume Correction Factors (VCFs) are used to correct
Ammonia can cause stress crack corrosion in brass and cop- observed volumes to the volume that would be observed at
per fittings at concentrations above about 5-10 ppmv [79]. standard conditions (60°F, 14.969 psia). These standard con-
There is no firm specification or guideline on the maximum ditions serve as a way to equitably use volumetric measures
allowable ammonia concentration of propane for either short in general commerce. They are derived from actual density
or long term exposures, Eind a level of < l p p m (detection by measurements on a wide range of LPG/NGLs, and are essen-
field litmus paper test) is usually recommended. tially the average values of the coefficients of thermal and
Field tests based on color change of wet red litmus p H pressure expansion. These factors are strongly correlated to
paper are adequate to detect ammonia down to about 1 ppm, the density of the material (e.g., the lower density the mix-
and provide an effective go/no-go test after change of service ture, the more compressible it is). As a result, the calculations
or at any time during distribution [80]. are iterative, and separate tables are published, each covering
The time required for the color change due to the field test a narrow range of densities. The differences are small, but
can also be used to judge the severity of the contamination. they do have large economic impacts because of the large
Very high (>20 ppm) concentrations cause a strong color volume of material involved.
change in only a few seconds. Moderately high (5 ppm) will D 1250 is the ASTM standard for calculating the VCF of a
cause a medium color change in about 10 s and low ( < l p p m ) petroleum mixture. This standard essentially directs the use
will cause slight change in about 30 s. of procedures published in the American Petroleum Institute
The litmus test is very sensitive to any material with even a (API) Manual of Petroleum Measurement Standards (MPMS).
slightly higher than 7.0 pH. This includes saliva (depending As of 1999, there are several procedures that may be used to
on what was last eaten), high p H potable ("tap") water in calculate the VCFs:
some regions, or soaps or detergents that may have been used • Chapter 11.1, Volume Correction Factors, gives procedures
to wash the hands or equipment. to determine the VCFs due to temperature for crude oils,
Controlled tests indicated that p r o p a n e with low con- refined products, and lubricating oils. However, since the
centrations of a m m o n i a would have n o effect on the upper limit on API gravity is 100° it applies only to the
concentration of ethyl mercaptan odorant [81]. heaviest of LPG.
• Chapter 11.2.1, Compressibility Factors for Hydrocarbons:
Halocarbons (Refrigerants) 0-90 "API Gravity Range, and 11.2. IM, Compressibility Fac-
There have been rare occasions of contamination of LPG tors for Hydrocarbons: 638-107 kg/m^ Range, give proce-
with halocarbon refrigerants or fire retardant (Freon ^M or dures to determine the VCFs due to pressure. Like Chapter
Halon '•'*'). These materials are miscible with propane, and 11.1, since the upper limit on API gravity is 90° it applies
will form noxious gases upon combustion. only to the heaviest of LPG.
• Chapter W.l.l, Compressibility Factors for Hydrocarbons: The VCFs are always based on averages on a range of ma-
0.350-0.637 Relative Density (60°F / 60"F) and -50°F to terials, or by interpolation between reference standards. In-
140 °F Metering Temperature, and 11.2.2M, Compressibility dividual mixtures that have similar density but different
Factors for Hydrocarbons: 350—637 kg/m^ Density (ISV) composition than either the average or reference may have
and —46°C to 60°C Metering Temperature, also give proce- significantly different expansion coefficients. Use of the
dures to determine the VCFs due to pressure. These standard VCFs will give a biased result on these mixtures.
procedures cover the lower densities indicative of most Provisions are made in the standards for contracting parties
LPG and NGL. to determine and use VCFs based on density measurements
on the individual material or mixture. Alternatively, to mini-
Until 1998, the VCFs due to temperature for the LPG and mize uncertainty, contracting parties may specify that the
NGL not covered by Chapter 11.1 were calculated from a va- density determination used for custody transfer be obtained
riety of sources. The major source was a set of Petroleum as close to the standard conditions as possible. This is easily
Measurement Tables published in 1953 by ASTM Inter- done for temperature, but is more complicated for pressure.
national and the Institute of Petroleum (IP). New implemen- In the past, pressure correction was often omitted or ignored,
tation procedures for liquids with relative densities (60760°) or based on measurements done at the time and temperature
of 0.3500 to 0.6880 (272.8 to 74.2°API) were p u b h s h e d a n d pressure of custody transfer. To accommodate existing
in 1998 as Technical Publication TP-25 Temperature Correc- industry practices, the new standard TP-25 contains two sets
tion For The Volume Of Light Hydrocarbons. This is a GPA of tables, one for temperature correction alone, and the other
publication, but GPA, API, and ASTM have jointly adopted it for combined temperature and pressure correction.
[84]. These procedures are based on an experimental pro-
gram sponsored by all three above organizations. Based on
this expanded database the TP-25 factors are different by as
much as 0.2-0.8% from the 1953 Table factors. AUTO PROPANE
The underlying procedure in TP-25 is quite different from
the fairly empirical equation forms used in the other stan- LPG has been used as a spark ignition motor fuel for over 40
dards. The TP-25 factors are determined from the interpola- years, especially in fleet and workplace applications. The pri-
tion of the properties of reference fluids via a corresponding mary advantages over gasoline in these markets are related to
states formulation. Corresponding states theory has a rich availability, cost, and tailpipe emission levels. Fleet opera-
history for the use of correlating various t h e r m o d y n a m i c tions can operate from centrally located refueling sites,
properties. This particular formulation is unique in that it avoiding the need for widespread availability at retail gaso-
uses the relative density at 60°F as the interpolating variable. line service stations. The lower operating cost for fuel may
The calculation of the density at a temperature is based on a offset the cost of conversion, with a net benefit for high
comparison of the properties of the reference fluids at the mileage applications such as taxi or delivery fleets. The
same reduced conditions. All the reference materials and crit- breakeven mileage generally varies between 5000 to 25 000
ical properties required to do the calculations are available in km/year, depending mostly upon the presence and level of
the standard. Government incentives for conversion cost, registration and
The organization of the VCF standards in the API Manual differential fuel taxation. The tailpipe and environmental
of Petroleum Measurement Standards is being changed. The benefits depend mostly upon the technology and calibration
revised Chapter 11.1, Temperature and Pressure Volume Cor- of the engine using the fuel and to a lesser extent on the prop-
rection Factors for Generalized Crude Oils, Refined Products, erties of the fuel itself. However, with equivalent levels of
and Lubricating Oils, will combine the previous Chapter 11.1 technology, LPG tends to have a significant advantage with
and 11.2.1 temperature and pressure correction procedures emissions and emissions toxicity.
into a single unified procedure. The nominal API gravity Historically, both gasoline and propane employed similar
range will be —10° to 100°, so it will still only cover the heav- carburetor and intake manifold configurations. This allowed
iest of LPG. Two important changes will be that the single set widespread "aftermarket" conversion of engines from gaso-
of procedures will be valid for the customary and metric stan- line to LPG, using engine coolant driven vaporizer/regulators
dard temperatures (60°F, 15°C, and 20°C) and for measure- and various gas injector devices. These could be plates that
m e n t temperatures and pressures in customary or metric could be "bolted on" above or below the existing liquid gaso-
units. Chapter 11. Iwas approved for D 1250-2002 and will be line carburetors for dual fuel operation, or gas carburetors
published in 2003. for dedicated LPG use.
The revised Chapter 11.2, Temperature and Pressure Vol- LPG carburetor engines generally have lower tailpipe hy-
ume Correction Factors for Light Hydrocarbons, will use the drocarbon and carbon monoxide (HC,CO) emissions than the
TP-25 procedure as the basis for the temperature portion of equivalent technology gasoline engine, when no computer
its VCF procedures. It will cover the range of relative densi- feedback engine control strategies are used. This is primarily
ties (60°/60°) of 0.3500-0.6880 (272.8-74.2°API), just like TP- due to reduction/elimination of fuel enrichment for idle, throt-
25. Like the revised Chapter 11.1, this will contain a single set tle transient and high power engine operation. This made
of procedures valid for the customary and metric standard propane a preferred fuel for such indoor engine applications
temperatures (60°F, 15°C, and 20°C) and for measurement as forklifts, where indoor CO emissions must be minimized.
temperatures and pressures in the customary or metric units. The widespread introduction of tailpipe catalysts and elec-
Technical work is being done to incorporate pressure correc- tronic fuel injection systems to meet increasingly more strin-
tion procedures. It is expected that this revised Chapter 11.2 gent emission standards has made aftermarket conversions
will also be published in 2003. increasingly challenging on recent model automobiles to
LPG. Second generation conversion systems attempted to LPG could be an ideal fuel for emerging micro-turbine appli-
use the onboard sensors to control a parallel LPG injection cations a n d high-temperature partial oxidation (POx) fuel
system, often with very good results. However, the increased cells. LPG can be produced in high purity and low sulfur that
cost and engineering sophistication tends to limit application may be necessary for these applications.
to a few high volume platforms. Each has to be re-engineered
with every change to the gasoline system, and then main-
tained in the field. Even so, several of these conversions have LPG—SAFETY AND HANDLING
been quite successful, but the overall rate of North American
conversions declined. LPG F l a m m a b i l i t y
Recently, the highly integrated fuel injector/intEike manifold Propane is flammable in the a t m o s p h e r e at ambient
designs and more complex onboard control and diagnostic conditions between about 2-9.5 vol%, the Lower and Upper
systems have become the norm [85], but these significantly in- Explosive Limit (LEL a n d HEL), respectively. This corre-
crease the cost and complexity of conversion. Current Tierl, sponds to about 0.3 psia peirtial pressure for the LEL, and
Tier2 and more recently hybrid gasoline electric vehicles offer about 1.4 psia partial pressure for the HEL. LPG is normally
exceptional emissions performance. On the horizon are man- handled at pressures m u c h higher than this. LPG must be re-
dated lower emission standards and gasoline reformulation frigerated to less than — 100°C before the equilibrium vapor
that will further reduce or possibly eliminate the tailpipe pressure enters the explosive range. This is virtually unattain-
emission advantage once enjoyed by LPG conversions. With able in normal operations and would only be a concern in
reduced environmental credits. Governments have tended to some research or specialty applications. Thusly, physical
reduce incentives for conversion, resulting in longer break mixtures of gases, especicdly in air, is always more important
even time for operators [86]. As a result, the size of the North for LPG t h a n "flash point" considerations.
American LPG conversion fleet is declining rapidly, OEM Flammability is not a fundamental or t h e r m o d y n a m i c
built LPG dedicated or dual fuel vehicles is increasing. Major property of any material. It depends upon the circumstances
North American OEMs offer current technology LPG powered at the time, including gas mixture, temperature, pressure, ig-
low emissions light duty cars, trucks, and vans. Recently, nition energy, turbulence, aerosol, catalyst and even the na-
there has been renewed interest in development of low emis- ture of the surface and shape of the containment vessel. The
sion LPG vehicles in the Pacific Rim and in Europe. lower explosive limit is less sensitive to these effects than the
OEM vehicles are predominately factory conversions of higher explosive limits. For example, the LEL is almost to-
truck and van platforms aimed at fleet use [87,88]. The North tally insensitive to the a m o u n t of "diluent" gas added [90,91].
American carmaker's message to the p r o p a n e industry is The HEL is the most impacted with dilution by inert gas, es-
clear: The carmakers expect the s u p p o r t of the major sentially decreasing almost linearly to near the LEL at about
p r o p a n e industry players if they are to produce, sell and 40-50% dilution (10-13% oxygen vs. 2 1 % undiluted). The
maintain OEM vehicles [89]. flammable envelope terminates at the point that the HEL
This experience is different in other parts of the world, de- meets the LEL.
pending mostly upon fuel cost and tax structure. There is a The explosive envelope tends to enlarge at higher tempera-
general agreement that the technical problems either can or tures, but again more on the HEL side vs. the LEL side. The
have been solved (depending upon who you tcJk to). This in- change in LEL is in fact quite small, with only an 8% relative
cludes gaseous or liquid fuel injection systems that address change in LEL with a 100°C increase in temperature from
many of the problems of earlier systems, including tolerance ambient [92].
to trace contaminants, same as gasoline or diesel fuel. In general, it appears that any increase in temperature,
Several manufacturers of advanced fuel LPG injector pressure, gas composition, ignition energy, or configuration
systems have experienced problems with particulate/residues has a m u c h more profound effect on the HEL than the LEL.
in various areas of the country. Magnetic residues (predomi- Use of the LEL determined at ambient conditions can rea-
nately magnetite "mill scale" and tank cortosion products) sonably be expected to apply over a very wide range of con-
have been especially disruptive to some electronic solenoid/ ditions in typical LPG handling situations. This is not true for
injector designs. Widespread introduction of these systems is the HEL, which varies widely with similar changes in gas
likely to put additional emphasis on "cleanliness" of propane, composition, temperature, and pressure.
similar to that required for gasoline for fuel-injected cars.
Several OEMs have expressed concern for the m a x i m u m
LPG H a n d l i n g
sulfur contents of "HD5" propane, although typical sulfur
contents are significantly less than current specification lev- Most jurisdictions require that persons involved with the
els. These are now higher than some reformulated gasoline handling or transport of LPG or installing LPG equipment
specifications (RFG) This is a potential area of future be trained and licensed. This generally does not include fi-
research and standardization. nal connection of portable cylinders to consumer appliances
The use of a sulfur containing odourant (ethyl mercaptan) using approved fittings, but usually does include filling
adds u p to 30 p p m w sulfur to propane, which is significant of the portable cylinders or automobiles at the point of re-
with respect to future RFG regulations. This is another area tail sale.
of recommended research and standardization. LPG, like any fuel, is safe if properly handled. It has a rela-
There is an opportunity for LPG fuels to compete favor- tively n a r t o w explosive range, so explosions are rare. How-
ably, and even preferentially in future "clean fuels" markets, ever, spills and fires are similar to other volatile fuels and
especially if factored into future engine/drivetrain design. solvents. Certain properties of propane should be understood
to p r o m o t e safety in handling the fuel, and a p p r o p r i a t e potential of the resulting explosion is at its most powerful
responses in the event of a spill or emergency response. point. A one foot (25 cm) diameter round balloon filled with
LPG vapor is about 50% heavier t h a n air (molecular weight a stoicheometric mixture will provide a bang loud enough to
44 versus 29). Vapors will tend to settle in low points and cav- startle m o s t people in a typical small training room. The
ities in the absence of a ventilating air flow. Propane/air mix- same bcJloon filled with p u r e propane vapor (no air) will pro-
tures have densities closer to air, and are more easily mixed duce a fireball that will rise 6-8 feet. A larger balloon will
and dispersed from thermal or a m b i e n t air currents. For leave a black scorch mark from the pool fire on the ceiling
example, a mixture of one volume of propane vapor (MW 44) (measure carefully, do your safety checks, and have a fire
diluted 9:1 with air will only be 5% heavier than air (about extinguisher at hand).
the same relative difference as sea water a n d fresh water). It The flammability of n e a r explosive mixtures has not been
will still be above the explosive range, but will be prone to extensively studied in the presence of a stable combustion
dispersion from ambient air currents. The heavier than air source. Witness descriptions and injuries indicate that very
vapor density allows a potential and usually temporary pool- large h e a t energy releases are possible in n e a r explosive
ing. Leaking gases tend to exit from high-pressure sources at atmospheres.
a sufficient velocity to stir the air mass and cause mixing. Very few people have ever seen liquid propane. It is a clear
They will only tend to accumulate in low spots only in very colorless liquid that can easily be mistaken for water under
quiescent conditions. certain circumstances, particularly in cold weather. When
When propane or propane/air mixtures (above the HEL) propane liquid is sprayed into a collection container, only a
collect in low spots, there will cilways be an interface at the portion of the liquid initially vaporizes—^just enough to pro-
top of the vapor pool that is in the flammable range. This will vide the heat of vaporization and cool the remaining liquid
b u m very similarly t o any other flammable liquid. A very down to the — 42°C boiling points at ambient pressure. For
good safety demonstration is to fill a tall (high 1/d) nominal example, if liquid propane at 70°F is sprayed into a collection
500 m L beaker with pure LPG vapor, and leave it open in full container, only about 40 wt% of the propane will vaporize,
view for the duration of the training session. When asked af- and the majority will be collected as a liquid in the container.
ter several hours, most attendees generally believe that the The lower the starting temperature, the higher the yield of
"volatile gas" has escaped and is rapidly dispersing itself liquid. Propane liquid must be over 200°F (near the critical
through the cosmos. However, lowering a match slowly be- point) before all of the propane will vaporize upon flashing to
low the rim convinces everyone that not very much gas has ambient pressure.
escaped, a n d for approximately the next 15 s, you can see the Once collected, the liquid propane in the open container
flame level drop in the beaker, as the pool fire consumes the will stay at its boiling point, and boil at a rate determined
propsme. This is a "worst case" demonstration, as ambient air by the heat transfer into the container. If the container is
currents cannot penetrate and mix a tall vessel very far. How- made of a material that is a good insulator, such as a plas-
ever, it does serve to show that propane rich pockets of gas tic cup or pail, it can take several hours for the liquid
can be stable for hours, days, and even weeks in the absence propane to evaporate even at high ambient temperatures.
of strong wind or air currents of a velocity sufficient to mix Under stagnant air conditions, the heavier than air cold va-
the ambient atmosphere. It is important to vacate and prop- por itself provides additioned insulation as it spills over the
erly ventilate an enclosed area that may have been subject of top of the container. If the container is metal, then the boil-
a propane leak in the absence of ventilating airflow. ing rate is generally very high initially, until a layer of accu-
Small liquid leaks can turn large volumes of area into ex- mulated ice or frost provides some insulation. If a spill oc-
plosive mixtures under "ideal" circumstances. At room tem- curs at low temperature onto frozen ground or snow, the
perature, one liquid liter of propane expands to about 240 resulting liquid pool can be persistent for hours. If the spill
Liters of gas, which at 2% LEL is sufficient to create 12 000 L occurs at r o o m temperature onto a concrete floor, the evap-
of explosive atmosphere. It takes only a small liquid leak to oration rate is extremely fast. Liquid propane at room tem-
create a n explosive atmosphere in a confined area, if the perature on a horizontal surface tends to exhibit the
propane becomes well mixed. Since the entire system is un- "Liedenfrost effect" where the liquid behaves like water
der pressure, leaks can occur even when equipment is idle, droplets bouncing on the top of a hot stove, essentially rid-
and collect over a long period of time. ing on its own rapidly forming vapor. A spill under such cir-
Gas-Air mixtures may be brought below the flammable cumstances, for example a severed hose or inadvertently
limit by dilution with large volumes of non-flammable gasses opened valve, can barely leave time for occupants to vacate
such as nitrogen, carbon dioxide, steam or air [93] (see the area. Some jurisdictions require "excess flow" valves on
flammability above). Some precautions should be taken to consumer cylinders to limit the flow rate of a free flowing
prevent ignition by static discharge with some CO2 fire extin- propane discharge in the absence of a backpressure.
guishers. A gas inerted area may still present an asphjrxiation Any propane or BP mix liquid at atmospheric pressure has
hazard. The rapid venting of gas and especially of gas/liquid a normeJ boiling point that is far below the freezing point of
aerosols can create static chcirging situations. As a result, ig- water (and flesh and skin) and can cause "frost bite" or freez-
nition of vented "vapors" can occur at any time, depending ing "bums." Many a finger has been superficially frozen with
u p o n circumstance. LPG liquid inadvertently sprayed inside of a difficult to
Gas mixtures inside of the flammable region do not "bum" remove glove.
like a pool fire. They forcefully explode, generating a shock The rapid removal of vapor from a tank will cause the
wave a n d a sharp "firecracker" type of sound. The largest en- remaining liquid in the tank to sub-cool. For example, in the
ergy release is when the mixture is at stoicheometric, and the "worst case," if the valve is opened wide venting to the atmo-
sphere at 70°F, the hquid will cool down to the boiling point LP Gases at very high (explosive) concentrations are be-
(-42°C) after about 40 wt% of the liquid has vaporized. High lieved to be non-toxic, fast acting anaesthetic agents, as well
appliance demand and rapid vapor withdrawal rates gener- as being simple asphjîants. The terminology "propane nar-
ally results in a large amount of condensation or frost accu- cosis" is sometimes used, but this is not accurate. Narcotics
m u l a t i o n on the exterior of the c o n t a i n e r due to this generally refer to drugs that act at opiate receptor sites,
refrigeration effect. which is not where general anaesthetic gases act. However,
LP-Gas vapor upstream of the regulator can condense to a the term "narcosis" is quite generic. The c o m m o n definition
liquid if the lines external to the tank are at a lower tempera- is "to put to sleep, partially or totally" due to a general de-
ture than the tank, and this requires special attention to depression of the Central Nervous System (CNS), even though
tail, especially in cold climates. For example, during snap sleep, anaesthesia and narcotics are distinctly different in
cool situations, outside vapor lines cool down faster than the medical terms. There are some early references to LP gas
bulk storage tank, due to the higher thermal mass of the tank. being tried or used as a medical anaesthetic, and one of the
The higher storage tank pressure causes condensation of liq- LPG patent claims by F.P Peterson in 1914 was for use "in
uid propane in the vapor lines. This can result in vapor lines surgery as an anesthetic" [95]. However, only cyclopropane,
becoming filled with condensed liquid propane under snap nitrous oxide, ethers, and various halocarbons were used
cool conditions. clinically as anaesthetic gases, usually in combination with
other drugs.
Propane has a m u c h higher coefficient of thermal (and
pressure) expansion than other hydrocarbon fuels. Heating Persons exposed to high levels of LPG gas and expe-
an overfilled propane vessel can result in thermal expansion riencing CNS depression effects are in a very dangerous
of the liquid until the cylinder is fully liquid filled (the va- situation, since they are breathing explosive gas mixtures.
por condenses as the liquid expands). Very high pressures, Any ignition source could produce a fire or explosion, re-
exceeding several thousand psi, can be generated with fur- sulting in injury or death. Individuals vary widely in their
ther heating and liquid expansion in a liquid filled ("hy- susceptibility and tolerance to these effects. At high concen-
draulically locked") cylinder. Pressure safety vents will gen- trations, the effects of narcosis and h3ôxia will be con-
erally prevent this, b u t the resulting leak of liquid can founded, as they are outwardly similar in many respects,
become a fire hazard. All transportation codes require cylin- and will occur simultaneously. There is a range of symp-
ders to be only partially filled for this reason, but it is not toms with increasing concentration from the onset of CNS
commonly appreciated that this is relative to a reference effects, hypoxia, and asphyxiation: disorientation, light-
temperature (traditionally 80vol% fill at 60°F). This protects headedness, dizziness, drowsiness, loss of physical coordi-
against hydraulic lock u p to over 140°F for liquid fill at nation, impaired judgment, drunkenness, unconsciousness,
60°F. If the cylinder is filled at a temperature lower than and death.
60°F, it may be necessary to further reduce the fill density The CNS effect is believed to be dependent upon the con-
for storage and transport. Consult the authority having ju- centration of the gas in the lipid bi-layer (cell wall m e m -
risdiction for the applicable requirements. brane) of nerve cells. Different gases would be expected to
have a different potency, and require higher or lower expo-
sures to obtain the same CNS effect. The relative solubility of
LPG S a m p l e C y l i n d e r A p p r o v a l s different gases in olive oil (surrogate for lipid), water (surro-
Consult the Authority having Jurisdiction for pressure vessel gate for blood), can be compared to a very wide range of
certification r e q u i r e m e n t s for LPG sample cylinders (US materials that have well known physiological responses. By
DOT in United States and Transport Canada in Canada). At this method, the onset of einaesthetic effects is estimated to
present there is no international approval process for pres- be n e a r the lower explosive limit (—2%) for butane, a n d
sure cylinders. Authorities in adjacent or other jurisdictions about twice the LEL (—4%) for propane. Iso-butane causes
m a y not approve cylinders approved in one jurisdiction. drowsiness in a short time in concentrations of 1%, with no
Cylinders must be approved in all the jurisdictions in which apparent injuries from i-C4 or n-C4 after 2-hour exposure at
they are used for sample transport. Cylinders approved by the concentrations u p to 5% [96].
Authority having Jurisdiction u n d e r "equivalent level of The rapidity of both the onset and recovery of CNS effects
safety" criteria are acceptable provided that they are used in from gas exposure depends upon the speed at which the gas
accordance with the applicable permits or exemptions. For is transported into and out of the body. This is dependent
example, users may not subsequently alter valves or pressure upon the concentration of the gas in air, the breathing and
venting devices that are part of a permit or exemption. Peri- blood circulation rate, and the relative solubility of the mate-
odic cylinder inspections may be required [94]. rial in lipid (oil) and blood (water). Gases with low water
(blood) solubility and high oil (lipid) solubility tend to be the
fastest acting. The large volume of blood/water in the body
LPG E x p o s u r e tends to act as a "buffer" for water-soluble compounds, slow-
The health effects caused by exposure to LP Gases are much less ing accumulation and depletion from the nerve cells. The sol-
serious than its fire and explosion risk. LP gases at low concen- ubility properties of LPG lie close to cyclopropane, between
trations are non-toxic, and liquids have limited ingestion routes those of nitrogen and nitrous oxide/diethyl ether, where the
due to the physical properties of the materials. The Occupa- rates are well known. Cyclopropane anaesthetic, which is 4-5
tional Exposure Limits (GEL) are based mostly on the need to times more soluble in water than propane, is not altered or
avoid the explosive hazards by a wide margin. This is t5îcally combined in the body; the major part is exhaled within 10
20% of the LEL or lower, which is a much lower level than min, while full desaturation takes several hours [97]. LPG
would be set for short or long term toxicity, or Eixphyxiants. exposure above the explosive limit would be expected to in-
duce CNS effects quickly, certainly in less than 15 min, and over tetrahydrothiophene (THT). N u m e r o u s other studies
probably in less than 5 min. continue to indicate the EtSH remains the odorant of choice,
Persons installing new equipment, flushing lines, repairing, particularly for cold climates, where the relatively high
or re-lighting appliances, or investigating gas leaks are also volatility of EtSH is the closest to that of propane at low tem-
the most likely to be exposed to high LP-gas concentrations. A perature [102]. The volatility of E t S H and other potential
Consumer Products Safety Commission (CPSC) study noted odorants has been extensively studied and reported in IGT
that new LPG installations are more prone to accidents than and GPA research reports.
new natural gas installations and sponsored a n u m b e r of stud- Odorants are not effective wEiming agents in all cases.
ies relating to LPG odorization [98]. While the lighter than air Propane vapor is heavier than air and initially tends to set-
density and higher LEL of methane are undoubtedly major tle Eind accumulate in low points and cavities. Persons in
factors, the CNS effects may help explain the occasionally the vicinity of low points and cavities may not be exposed to
bizarre circumstances of some LPG accidents. localized gas pockets, b u t m a y b e at risk from an ensuing
The knowledge of possible impairment can be critical in fire or explosion. S u b s e q u e n t diffusion or convection
making decisions effective in reducing the accident rate. For can distribute LPG vapors t h r o u g h o u t a n area. Certain
example, a person flushing a line might realize the need to odorants are polar and/or chemically reactive, and can be
take a fresh air break instead of a "smoke" break, or ventilate depleted by reaction or adsorption. People differ in their
the area if it is u n d e r s t o o d t h a t the light-headed or tired ability to smell, and the sensitivity to odors generally de-
feeling may be due to explosive gas concentrations. creases with age or with impaired physical conditions such
Anaesthetics also sensitize the myocardium to the effects as colds or respiratory allergies. Prolonged exposure to
of epinephrine. Cardiac a r r h y t h m i a can occur when very odorants can cause olfactory desensitization. Other odors or
high concentrations of LP gases (above the HEL for propane) distractions can reduce the effectiveness of odorants as
are inhaled when the epinephrine level is elevated (e.g., anx- warning agents [103].
iety, exertion) cind possibly during hypoxic conditions. Ccir- Mercaptan odorants are susceptible to oxidation u n d e r
diac arrhythmia can have a sudden onset even with brief certain conditions, especially at high temperature and in the
exposures a n d may result in sudden death. This is an extreme presence of water, oxygen, or high oxidation state (red) rust
condition that is usually associated with substance abuse [3]. This is commonly referred to as "odorant fade"[103]. It is
(commonly called "huffing"). Similar problems have been re- now genercdly accepted that propane tanks in continuous ser-
ported in the nitrous oxide bottle gas industry. Additional vice do not experience odorant fade since there is no source
information is available on the web site of the Compressed of oxidant [104,105,106]. Much industry activity continues to
Gas Association [99]. focus on identifying a n d eliminating situations that can
result in odorant fade. In general there is a m u c h higher
awareness in the industry for the detrimental effects of air,
LPG Odorization rust, and water in pressure vessels [107-109].
LPG odorization requirements reside in different jurisdic- Recent changes to rail car pressure vessel certification re-
tions in different countries. The U.S. requirements are not in quirements provide another opportunity to further reduce
the ASTM D1835 specifications, but in NFPA 58 and 19 CFR, the use and occurrence of steam cleaning and hydrotesting of
and State Regulations. Canadian requirements are in the large pressure vessels (truck/rail). Work is ongoing in this
CGSB LPG product specifications that are referenced in var- area and several programs are being planned.
ious Provincial and Federal Regulations. Odourants can be partially or fully removed by absorption,
Historically, manufactured gas was odorized as a warning for example in cases where the LPG has permeated through
aid due to the risk of carbon monoxide poisoning. Manufac- clay-like soils that have high surface absorption capacity.
tured gas often contained high levels of CO, which was a GPA, ASTM, and CGSB have developed field tests for
higher risk than flammability. Over time, a variety of materi- mercaptan odorants using stain tubes, and this allows reli-
cils, including mercaptans, acetylene, and mixed refinery sul- able semi-quantitative monitoring of odorant levels during
fides were used as odoureints. LPG production from sweet distribution. ASTM D 6273-98 Standard Test Method for Nat-
natural gas wells had no olefins and a low sulfur content, so u r a l Gas Odor Intensity (odor m e t e r "sniff test") can be
had a n intrinsically low odor. Initially, there was no require- applied to LPG as well natural gas. These are not necessary
ment to odorize gas distributed for fuel purposes, as it was for monitoring odourization equipment, as verification of
non-toxic relative to manufactured gases. However, a num- proper tj'pe and quantity of odourant can be done by a vari-
ber of fires and explosions with non-odorized natured gas and ety of means. These include measures of weight, volume,
LPG highlighted the need to odorize as a warning aid to de- injection pulses, on-line analysis, calibrated "day pots," etc.
tect leaks. LPG odorization is now a regulated requirement in and these features are generally included in commercially
all North American jurisdictions. available odorant injection systems. An NPGA/PGAC Joint
Natural Gas Euid LPG odorization has been the subject of Task Force on LP-Gas Odorization developed a set of recom-
substantial product liability litigation, stretching over several mendations in 1991 to assist in their desire to improve LPG
decades of work on the technical, political, and legcd issues safety. All producers and terminal operators w h o odorize LP-
involved. These are summarized in a series of IGT sponsored Gas should establish formal, rigid procedures and responsi-
technical symposia [100], CPSC, GPA, NPGA, PGAC, and bilities for proper odorization [110]. These sire advisory in
BERC sponsored rescEirch, as well as transcripts of various n a t u r e a n d compliance is voluntary. I n d e p e n d e n t cross-
product liability cases. Current North American Odorization checks have found to be effective to detect several "single
practices are based on 1977 BERC smalysis [101] indicating fault" injector system failure m o d e s that could otherwise
ethyl mercaptan (EtSH, or EM) to be a preferred odorant have gone unnoticed [111].
USES OF LPG • portable generator sets (fixed on larger RVs)

• golf carts, maintenance equipment, turf and lawn mowers
Industrial • pyrotechnic/flame special effects
fork lifts, indoor carburetor engines (floor sweepers, wash-
ers, etc.) Aviation
oxy/propane cutters, heating/annealing, high pressure • airport r a m p equipment (i.e., airstairs, luggage tugs, etc.)
welding • 12/24 Vdc piston engine pre-heat (indirect fire)
"plumber" torches, portable soldering irons, small torches • hot air balloon
hand torches (pallet shrink wrap, localized heating/burning)
worksite heating/ventilating (lineman's tents, below grade Marine
sites) • LPG powered "jet" boats
refrigeration (compressor cycle), evaporation, or specialty • "overslung" barbecue/cooking
(vap pipes)
pavement heating for grinding/recycling, roofing tar Emergency
heating
• standby generators, compressors, heat/cool
ground thawing, ice/snow melting, concrete heating, etc.
• stable long term emergency fuel supply
propellant for aerosol sprays, cosmetics, shaving cream,
perfumes, etc. Mining
propellant for paint sprayers, paint airbrush (including PB
mix) • mineshaft ventilation air heating
solvent for cleaning, reaction, diluent/chilling, precipita- • mine site cookhouse stoves, quarters heating
tion • water pumps to liberate coal seam methane
remote "smart" gen sets with remote start/stop, telemetry
Medical Power
integrated standalone packages (power generation, ventil-
late, heat/cool) • cyclopropane anesthetic
portable soil/trash reclamation, sterilization • microturbine and distributed power systems
jackhammers (construction road work) • stationary generators
• standby fuel for gas interruptible supply
Transportation
autopropane (conversions) and OEM Acknowledgments
cargo heaters, engine coolant pre-heaters, ice removal The author acknowledges review and significant technical in-
heavy duty truck alternate fuel (fumigation and OEM) put from Dr. H. ICing, ExxonMobil Research (hydrates), John
hydrocarbon fuel for reforming fuel cell applications Jachura (VCF/density), Dr. D.Y. Peng (Peng-Robinson EOS),
retrofit of small engines to tighter emission standards Dr. H.J. Ng, DBRA Research Associates (Ng-Robinson EOS,
utility right of way maintenance hydrates), Larry. R. Robertson, DaimlerChrysler (auto-
micro-turbine hybrid vehicles propane), Alex Spatura, Adept Group, (autopropane a n d
extensive review), Ian Drummond, lOL Industrial Hygiene
Agriculture (exposure/CNS), Dr. Byrick, Uof Toronto (CNS), Dr. Roth,
grain drying, bam/brooder heaters, orchard heaters, weed University of Calgary (CNS), Nancy Bourque, lOL Research
control Library (literature and patent searches), Tim Eaton, Superior
general shop heat/power/oxy welders, etc. Propane Inc.(uses). Thanks to Mark Sutton and Ron Brunner
Colorado Potato Bug eradication, potato guns (GPA) for access to draft publication TP16 on history of LPG
farm animal m a n u r e dehydration/sterilization (esp. swine/ specs (hopefully to continue to publication). Special thanks
chicken) to Ron Cannon (GPA, retired) for input, review, and liberal
weed control as alternative to herbicides to control runoff reference to his excellent book "The Gas Processing Indus-
"scare crow" devices try—Origins and Evolution." This is highly recommended
irrigation water pumps reading for anyone in the industry, and a good book for both
libraries and reception areas.
Utility Gas
The author acknowledges the support of Imperial Oil Ltd.
bulk or refrigerated storage for peak shaving in NG systems for the information/communications resources used in the
bulk vaporizer, distribution of LPG like NG preparation of this chapter.
Residential
cooking, heating, clothes drying, hot water
catalytic/radiant/pipe radiant heaters, mantel lights REFERENCES
h o m e barbeques, refillable lighters, hair curlers, b b q
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MNL37-EB/Jun. 2003
Motor Gasoline
B. Hamilton^ and Robert J. Falkiner-^
T H E SPARK IGNITION ENGINE HAS REMAINED THE POWER PLANT OF nology levels, and have produced the "World Wide Fuel Char-
CHOICE for personal transport for almost a century, and the ter" (WWFC) on this basis. The WWFC receives serious
fuel specifically formulated for SI engines is called gasoline consideration when nations and economic regions are revis-
(U.S.) or petrol (UK). Gasoline h a s evolved continuously ing fuel specifications, even though it is not an accredited
since it was first produced in quantity to meet the burgeon- consensus standard, and is the subject of ongoing technical
ing demand from mass production of the automobile in the debate. ASTM Standard Practices, Test Methods and Specifi-
early 1900s. It was first produced from light naphtha batch cations continue to be key to domestic and International
distilled from crude oil and liquid condensate from natural Specifications and Regulations, and are used globally
gas production, and in the early days, had no test methods or through affiliated ISO Standard Writing Organizations.
specifications at all (see Chapter 2, Liquefied Petroleum Gas). Specifications for n e w generations of engines (electric/
It became a carefully formulated mixture of hydrocarbons hydraulic hybrids, gasoline direct injection, fuel cells, micro-
and additives, seasonally blended to m a t c h local ambient turbines) and catalysts (lean b u r n , heated, selective re-
conditions, providing good performance and efficiency for duction, HC absorption, particulate trap) have yet to be
constantly changing vehicle fleet. More recently, gasoline has developed. The trend continues to be more restrictive in com-
been reformulated to reduce various emissions and minimize position and variation than in previous gasolines.
the impact of automobiles on urban air quality.
For the first 60 years of gasoline production, formulation
and manufacture were focused on optimizing desirable per- HISTORY OF GASOLINE
formance properties, cost, and yield. Increased octane al-
lowed increased engine power and fuel efficiency. Volatility L e a d e d Gasoline ("Pre-control")
was controlled to minimize vapor lock, carburetor icing,
In the late 19th century, fuels, for the automobile were coal
stalls, sag, hesitation, hard starting, and other measures of
tar distillates and the lighter fractions from the distillation of
"driveability" performance. Stability additives were devel-
crude oil. It's believed that a gasoline fraction was separated
oped to minimize auto-oxidation, and detergents to keep car-
by Joshua Merrill in Boston, and was used for lighting. It was
b u r e t o r s clean. Increased yield from crude oil and other
also used in Nicolaus Otto's first four-stroke cycle engine in
sources made gasoline more available and affordable. Gaso-
1876. By the late 1800s the early refiners were producing
line properties are increasingly influenced by regulatory re-
volatile gasoline by batch distillation from crude oil. Natural
quirements intended to reduce air and water pollution during
gas producers were making volatile naphtha from the hydro-
manufacture, distribution, and use. Gasoline is controlled at
carbon condensed from compressed natural gas (condensate,
many regulatory levels, including national, state/provincial,
casinghead, or "natural" gasoline). There were no standard
and in some cases, city or municipal.
test methods or national specifications, or definition of qual-
The current generation of North American "Tier 0" and ity. Some of the earliest standard test methods were not de-
"Tier 1" vehicles for current emissions standards have con- veloped until the 1920s, allowing development of the first
verged towards electronic fuel injected engines and "3-way widely accepted gasoline specifications. Some test methods
catalyst" emission control systems. Globally, automakers are developed in the 1920s are still in use today, such as the Reid
facing increasingly stringent "Tier 1" emissions limits for the Vapor Pressure (originally developed for casinghead gaso-
2004-2009 time period. While it has been recognized that line) and Distillation (the oldest currently used ASTM gaso-
meeting the Tier 2 emission standards will be a challenge for line test method, first published in 1930). The D86 was based
gasoline vehicles, the U.S. EPA does not expect t h a t any on tests developed for casinghead or "natural gasoline" by the
major technological innovation will be required to achieve predecessor organization of the Gas Processors Association
compliance. However, low sulfur gasoline must be available (GPA). The data triggered a n intensive discussion of the rela-
for these standsirds to be feasible. In turn, the automakers are tionship between gasoline distillation profile (volatility) and
promoting global fuel specifications based on vehicle tech- engine performance, such as vapor lock, oil dilution, knock,
and "sooting."
' Research Associate, Industrial Research Limited, P.O. Box 31310, Automotive engines were rapidly being improved and re-
Lower Hutt, New Zealand. quired a more consistent and suitable fuel. New test methods,
^ Fuels Technical Associate, Quality Assurance and Development
Group, Imperial Oil Ltd., I l l St. Clair Ave. W., Toronto Ontario, specifications, and refining processes were developed to bet-
Canada. ter separate and increase the octane of components. Com-
61
pression absorption and continuous fractional distillation in e m i n e n t public health officials campaigned against the
"pipestills" replaced batch distillation with a continuous pro- widespread introduction of alkyl leads [7], but after a review,
cess in the 1920s. The first "sweetening" processes were the U.S. Surgeon General decided in favor of use in 1926. The
developed to remove smelly and corrosive sulfur compounds. toxicity of TEL soon became apparent, as it was originally
Thermal cracking was introduced just prior to World Weir I, handled and added in concentrated form at the point of sale.
followed by steam cracking, coking, fluid catalytic cracking, This was changed to point of production to eliminate han-
reforming, catalytic hydrogenation (hydrotreating), a n d dling of alkyl lead concentrates outside of refineries, where it
many others. Gasoline specifications were developed to con- could be better controlled.
trol the composition, properties and performance of the fin- Alkyl lead is unique among organometallic additives in that
ished gasoline, with the three m a i n areas of octane, volatility, alkyl halides were effective "alkyl lead scavengers" to prevent
and cleanliness. buildup of alkyl lead oxides and related solids in the engine
Fixed bed cracking/reforming was introduced in the early and exhaust system. This allowed lead Eilkyls to be used at
1930s, which significantly increased the octane of "cat-naph- m u c h higher concentrations than any other organometallic.
tha" relative to "straight-run" or thermally cracked naphtha, The alkyl lead chloride and bromide had a lower melting
with a good alkyl lead response. Higher octane of the gasoline point and higher vapor pressure than the oxide, resulting in
components allowed production of some of the first "pre- the alkyl lead being "scavenged" and expelled with the ex-
mium" gasoline, called "high-test" at the time, a reference to haust. About 1-1.5 times the molar amount ("theories") to
their higher octane n u m b e r test result. During World War II, make the alkyl lead tetrahalide was used to provide good
continuous fluid cat cracking and semi-continuous reform- scavenging. Aviation gasoline uses only one theory of alkyl
ing processes were developed, along with cateJytic desulfur- bromide to protect against chloride induced corrosion of the
ization, which further increased the alkyl lead response. Pro- hotter exhaust valves. Tricresyl phosphate (TCP) has also
cesses were developed to convert C3 and C4 olefins from cat been used as a alkyl lead scavenger (mostly in avgas), to form
cracking into gasoline by polymerization (polygas) and alky- alkyl lead phosphate that has a lesser tendency to form glow-
lation (alkylate). Highly leaded cracked naphtha, reformate, ing deposits, foul spark plugs, or accumulate deposits in avi-
and alkylate blends were ideal for aviation gasoline for high ation exhaust side turbochargers.
compression and turbo/supercharged aviation engines devel-
oped during WWII, using "performance number" octane rat-
ings based on the increased percent power attained above the History of Octane Ratings
baseline of 100% iso-octane fuel. With rare exception, all post
WWII North American automotive gasoline contained TEL. In 1921, the Co-operative Fuel Research Committee (CFRC)
was formed to research fuels and engine performance [8].
In the early 1950s changes in engine designs and driving
The CFR engine was developed to evaluate knock perfor-
patterns required the re-introduction of the Research Octane
mance of fuels under controlled conditions, measuring knock
Rating. Automakers utilized military technology to continue
intensity with a bouncing pin knockmeter. In 1927 Graham
to increase the engine compression ratio, requiring higher
Edgar developed a n octane rating scale based on high and
octane n u m b e r fuels. The octane race occurred during the
low reference fuels, and showed that fuels had Octane Rat-
1960s, as high performance engines required fuels with in-
ings between 40-60. This became the C.F.R. Research Octane
creased octane. The octane increase was non-linear with
N u m b e r in 1930. The RON test method was first published in
alkyl lead concentration, with diminishing returns, so there
1932, became a tentative method in 1947, and was adopted as
was an economic limit to the maximum amount used. The
an ASTM standard in 1951.
m a x i m u m permitted concentration in gasoline was 1.14g
Pb/1, which was well above the optimum alkyl lead response Graham Edgar used two pure hydrocarbon isomers that
for most refinery streams. Highly leaded premium gasoline could be produced in sufficient purity and quantity as refer-
was produced for use in high-compression ratio big-block ence fuels for rating the anti-knock ability of fuel. These were
"muscle cars," with RON as high as about 105. For the inter- "normal heptane," which was commercially available in suf-
ested reader, a more detailed discussion of the history of ficient purity from the distillation of Jeffrey pine oil, and "an
gasoline is presented elsewhere [1-3]. octane, named 2,4,4-trimethylpentane" that he first synthe-
sized (commonly Ccdled isooctane today, although there are
17 different isomers possible, and about five prevalent C8 iso-
H i s t o r y o f Alkyl L e a d i n G a s o l i n e mers from C4 alkylation). The heptane and iso-octane were
given the arbitrary octane n u m b e r s of 0 and 100, respec-
During the 1910s, laws prohibited the storage of gasoline on tively. These have similar volatility properties (see Table 1),
residential properties, so Charles F. Kettering modified a specifically boiling point, thus the varying ratios 0:100 to
Spark Ignition (SI) engine to r u n on kerosene. However the 100:0 would have consistent vaporization behavior. The vol-
kerosene-fueled engine would "knock" and crack the cylinder u m e percentage of isooctane in the binary blend that gave the
head and pistons. He assigned Thomas Midgley, Jr. to con- same knock intensity as the fuel being tested was assigned as
firm that the cause was the kerosene droplets vaporizing on the Octane Number of the sample.
combustion, as he presumed. Midgley demonstrated that the The early work quickly identified that the "highest useful
knock was caused by a rapid rise in pressure after ignition, compression ratio" (efficiency, power) was related to the CFR
not during pre-ignition as believed. The combination of TML Research octane number. The sulfur-containing gasoline was
and TEL along with alkyl bromide and chloride alkyl lead initially restricted because sulfur in gasoline inhibited the oc-
scavengers were widely used stEirting shortly after discovery tane-enhancing effect of the alkyl lead. In addition, different
by teams led by Thomas Midgley Jr. in 1922 [4-6]. Several fuels had different "susceptibility" or octane response to the
CHAPTER 3: MOTOR GASOLINE 63
TABLE 1—Selected properties of normeil heptane and iso-octane.

Melting Point, °C Boiling Point, "C Density, g/ml Heat of Vaporization, MJ/kg
Normal heptane -90.7 98.4 0.684 0.365 at 25°C
Iso octane -107.45 99.3 0.6919 0.308 at 25X
alkyl leads. Parafins have the best alkyl lead response, fol- to form traces of organo-halogen c o m p o u n d s , including
lowed by napthenes, olefins, and aromatics, while the re- dioxins [11]. It is unlikely that high levels of TEL use would
sponse of alcohols is negative. The RON of the gasoline could have continued even if a lead-tolerant catalyst h a d been
be increased from 60 to 75, and the "highest useful compres- found.
sion ratio" increased from 5.3 to 6.8, increasing the constant- Separate regulations were put in place to minimize the
speed fuel economy by about 30%. amount of alkyl lead (primeirily TEL) used in the remaining
The Motor Octane N u m b e r (MON) was developed in 1932, leaded gasoline produced and sold, creating "low lead" in a
using conditions that better matched actual vehicle knock series of reductions in 1985/86. A smaller fill nozzle diameter
performance climbing the long constant grade hill at Union- was adopted for nonleaded gasoline to prevent misfueling
town, Pennsylvania. This method is similar to the operating catalyst cars with leaded gasoline. In the United States, alkyl
conditions of the current Motor Octane procedure [9,10]. The lead could not be knowingly added to nonleaded gasoline,
MON test was a tentative method from 1933 to 1939, when it and the maximum allowable concentration of 0.05 g/usgal
was adopted as a n ASTM standard. During the late 1940s (13 rng/L) was applied as a contamination limit for "inciden-
through the middle 1960s, the Research method became the tal contact" with leaded fuels during distribution. Other ju-
m o r e i m p o r t a n t rating because milder conditions m o r e risdictions have slightly different legal definitions and con-
closely represented the octane requirements of the vehicle t a m i n a t i o n limits for nonleaded gasoline, b u t the t e r m s
current engines and driving conditions. Most retail fuels were "nonleaded" and "unleaded" tend to be used interchangeably,
marketed according to their research octane rating. even if this is not technically or legally correct in all cases.
Octane ratings of leaded gasoline decreased from the "octane
race" levels, a b o u t 1.5-3 AKI lower for RUL a n d PUL,
1 9 6 3 C l e a n Air A c t , V e h i c l e E m i s s i o n S t a n d a r d s respectively.
a n d Alkyl l e a d P h a s e d o w n
Some predominately smEJl engines were designed for 87
During the late 1950s and 1960s, ambient air quality deterio- AKI nonleaded fuel, but were "alkyl lead tolerant," because
rated, especially in densely populated urban areas. ReseEirch they could meet the emission standards of the time without a
quickly identified the "primary pollutants" in raw exhaust catalytic converter, so could use either leaded or nonleaded
(HC, CO, and NOx) and sunlight driven photochemical reac- gasoline.
tion to be a major source of SMOG (SMoke + fOG). Ground The last p r e m i u m leaded gasoline was sold in 1981, and the
level ozone and other "secondary poUutcints" are formed by last regular leaded in 1996 in the United States, and in 1990
photochemical reactions driven by sunlight. The concentra- in Canada.
tions of pollutants followed a daily pattern determined by Alkyl alkyl lead has been credited variously with allowing
driving cycles ("rush hours"), daytime sunlight intensity, and rapid development of high power Eind efficiency SI engines,
local geography and wind patterns, with the most severe area and even being a deciding factor in aviation in World War II.
in the U.S. being southern California. The original Clean Air It is not widely appreciated that Thomas Midgley's other fa-
Act was passed in 1963 "to protect and enhance the quality of mous discovery, perfluorocarbon refrigerEint, had the same
the Nation's air resources." The first vehicle emissions stan- dichotomous history [12] as alkyl lead. It provided enormous
dards were imposed in California in 1966 a n d Federally in social benefits, b u t was eventually b a n n e d d u e to strato-
1968. The early attempts to reduce HC and CO with carbure- spheric ozone depletion. It was replaced with less long-lived
tor calibrations and thermal reactor ("thermactor," air + halocarbons that are decomposed at lower altitudes.
time delay) type exhaust systems were only about 60% effec-
tive for HC. However, this was still a larger drop (est. 10.6
g/mile to 4.1 g/mile HC) than all of the emission reductions Nonleaded Gasoline
since, due to the high emission rates at the time. A n u m b e r of Introduction of the first Conventional Oxidation Catalyst
attempts were made to develop "lead-tolerant catalysts" and (COC) systems required nonleaded a n d low phosphorous
"alkyl lead traps" that would allow continued use of leaded gasoline to protect the exhaust catalyst over the useful life-
gasoline. However, several new potential problems with con- time of the car. Alkyl lead Euid phosphorus are potent catalyst
tinued widespread use of leaded gasoline were found, and "poisons" that slowly decreased catalytic activity, eventually
R&D to develop viable exhaust oxidation catalysts went into resulting in near total deactivation of the converter. Phos-
high gear. phorous contents were reduced to sub-ppm levels by elimi-
Alkyl lead is a toxin by itself, and there was a drive to re- nating the use of phosphate ester based corrosion inhibitors.
duce exposure levels from m a n y sources, ranging from alkyl Alternate corrosion inhibitor additives were readily available,
lead solder in pipes, food cans, toothpaste tubes, alkyl lead so phosphorus reduction did not pose a problem to fuel man-
pigment in paints, and edkyl leads in gasoline. In addition, the ufacturers. It did require the automzikers to significEintly re-
alkyl lead scavengers ethyene dibromide and ethylene dichlo- duce oil consumption, as the only remaining significant
ride could react with u n b u m e d hydrocarbons in the exhaust source of phosphorous was from crankcase lubricant. Re-
placing the octane boost from alkyl lead was a big problem The United States EPA may grant waivers for nonleaded
for the fuel manufacturers, as there was n o readily available gasoline formulations that are shown by testing to not cause
replacement. This required significant changes to both fuel or contribute to emission device failures. A waiver request is
and engine design. granted if the EPA does not decline the application after 180
Gasoline manufacturers found that it was possible to pro- days. In 1978, the EPA granted the first waiver for 10% by vol-
duce, on average, a nonleaded regular gasoline with an 87 u m e of ethanol. The EPA subsequently issued waivers for
AKI and about 91 RON in the United States, and a premium gasoline containing a variety of alcohols, ethers, and mix-
95 RON in Europe and elsewhere. United States automakers tures, of which MTBE and ethanol (gasohol) are the most
built engines with EGR and reduced compression ratios ini- commercially important today. A complete technical assess-
tially around 8:1 for use on 87 AKI non-leaded gasoline to re- ment (including extensive references) for the application of
duce engine-out NOx to regulated levels. Air injection re- alcohols and ethers as fuels and fuel components is available
duced HC and CO by oxidation over a COC. Efficiency and from API [14].
fuel economy were reduced because of the compression ratio In 1981 the EPA ruled that fuels with u p to 2 wt% oxygen
reduction. However, this was more t h a n offset by Corporate from aliphatic alcohols or ethers were "substantially similar"
Average Fuel Economy (CAFE) regulations in 1975 that re- and thus did not need a waiver. In 1991 the maximum oxygen
quired average LDV fuel economy determined in standard content was increased to 2.7 wt% oxygen. To ensure suffi-
tests to increase over a period of years u p to 27.5 mpg. This cient base gasoline was available for ethanol blending, the
was accomplished with a variety of technologies. Vehicle EPA also ruled that gasoline containing u p to 2 vol% of
size, weight, and rolling/wind resistance were dramatically MTBE could subsequently be blended with 10 vol% of
reduced ("downsizing"). The majority of the fleet converted ethanol.
to front wheel drive, using more efficient transverse L4 and
V6 engines and transmissions, both using lower viscosity and
friction modified lubricants. Vapor Controls
Premium unleaded (PUL) gasoline was introduced in the As the tailpipe emissions were reduced by improved exhaust
United States later, in response to the higher Octane Re- emission control systems, other h y d r o c a r b o n emission
quirement Increase (ORI) relative to historical experience sources became more important. This includes hydrocarbons
with leaded fuels. This allowed production of "premium pre- from evaporation or fugitive emissions of gasoline during
ferred" or "premium required" cars, predominately tur- distribution and storage, vehicle refueling, vehicle at rest, or
bocharged and knock sensor equipped engines that could vehicle during use. The United States CAA required summer
take advantage of the increased octane. ASTM specifications reductions in VP in two phases in 1989 and 1992, to reduce a
do not m a n d a t e octane number, and historically U.S. fuel number of fugitive emission sources (running loss, diurnal,
producers set octane numbers in response to market forces. refueling.. .). Summer vapor pressure controls have virtually
In North America the most c o m m o n octane grades are now eliminated hot driveability problems. They tend to be design
RUL87, MUL89, PUL91/92, and SUL93/94. related, appearing as "select model" problems when they
occur.
Stage 1 vapor control systems reduce truck loading vapor
1 9 7 0 U S E P A C l e a n Air A c t a n d 1 9 7 7 A m e n d m e n t
emissions at terminals and at service stations during loading
The 1970 U.S. Clean Air Act (CAA) established the Environ- and unloading of trucks. At the service station, the vapor
mental Protection Agency and required a 90% reduction in space of the truck is connected to the vapor space of the un-
automotive emissions by 1975 (HC/CO) and 1976 (NO^). This derground tank, whose vapor is displaced ("vapor balanced")
resulted in the widespread introduction of conventional oxi- back into the truck during fuel delivery. The truck returns to
dation catcilysts and nonleaded gasoline in 1975 in response the terminal, where the hydrocarbon saturated air delivery
to the HC and CO standards. These regulations were "tech- truck are collected and sent to a Vapor Recovery Unit (VRU)
nology forcing" especially for NO^, and the U.S. Congress put or to a Vapor Destruction Unit (VDU, combustor, flare) as the
an interim NOx standard in place until 1978. The 1977 Clean truck is loaded.
Air Act Amendments required reduction in HC in 1980 and Stage 2 systems reduce point of sale vehicle refueling emis-
CO and NOx in 1981. This resulted in the widespread intro- sions. Vapors from the vehicle tank are vapor balanced with
duction of sophisticated "three-way catalysts" computer con- the underground storage tank, or sent to an absorber or com-
trolled closed loop air-fuel ratio control with exhaust oxygen bustor. Newer systems incorporate vapor p u m p s to remove
sensors in most 1981 model year cars. The 1977 CAA amend- the exact amount of air from the fill pipe as volume of gaso-
ments contained the first provisions that controlled the prop- line dispenses, and do not require the rubber nozzle "snout"
erties of "future" gasoline. It had a general requirement that to make a vapor tight seal. These systems are recognized by
gasoline be "substantially similar" to fuel or fuel additives air slots near the nozzle tip to remove air from the fill spout
used to certify 1975 or subsequent years vehicles [13]. The via an annular tube in the delivery hose. Vehicles are also
intent was that future gasoline would not render the new cat- equipped with enhanced activated carbon canisters (bigger
alysts or emission controls ineffective over time. The EPA capacity than required for diurnal control) to treat the vehi-
subsequently promulgated the "substantially similar" ruling, cle tank vapor while refueling. These are subsequently de-
which had a more detailed definition of the meaning. It eilso sorbed by a small airflow and burned in the engine during
provided that additives containing only C, H, O, N, S (which normal use, once specified vehicle speeds and coolant tem-
combust to the regulated emissions) did not require a waiver peratures are reached. Some activated carbons used in older
at concentrations below 0.25 vol%. vehicles do not function efficiently with oxygenates, but mod-
ern carbon canister systems can reduce evaporative emis- "complex" models used in EPA and most other North Ameri-
sions by more than 95% from uncontrolled levels. On-board can gasoline regulations. Measured emissions were corre-
canister systems tend to make Stage 2 balancing redundant lated to gasoline properties in a wide variety of vehicle emis-
as the on-road population equipped with enhanced canister sion system types. These spreadsheet type correlation models
systems increases. predict emissions from all sources associated with using
gasoline in vehicles. They tcike into account the time of year
(winter/summer), gasoline composition as measured by eight
1 9 9 0 CAA A m e n d m e n t s ( R e f o r m u l a t e d a n d parameters (called the model parameters), and an assumed
Conventional Gasoline) on-road vehicle fleet with a mixture of various generations of
A more complete technical discussion on Reformulated Gaso- emission control tjrpes. A copy of the complex model spread-
line (RFG) is contained in ASTM Research Report D02:1347 sheet ("Final.exe") can be downloaded from the EPA web
[15], and in numerous other Government and Industry Publi- site. California Phase 2 RFG allows a "Predictive Model,"
cations [16]. Officially published sources of information should similar to the EPA complex model, as an alternative to the
always be used for regulatory compliance purposes. A summary original Phase 2 composition based requirements.
of the United States EPA gasoline, additive, and related regu- For Phase I, for example, the CAA specifies no increase in
lations is available at http://www. epa.gov/otag/gasoline.htm. NOx emissions, reductions in VOC by 15% during the ozone
A chronology of EPA emissions control regulations is avail- season, and specified toxins by 15% all year. These criteria
able at http://www.epa.gov/ otag/12-miles.htm. indirectly established vapor pressure and composition limits
The 1990 Clean Air Act (CAA) amendments and California that refiners had to meet. The percent reductions are calcu-
Air Resources Board (CARB) Phase 2 (1996) specifications lated with the complex model, which predicts volatile organic
required further reductions in tailpipe emissions, more strin- compounds (VOC), specified toxic air pollutants (TOx), and
gent test procedures and vehicle on-board monitoring tech- nitrogen oxides (NOx) as a function of eight composition re-
nology, and new "clean fuels" programs. These established lated model inputs. Sulfur, benzene, vapor pressure, %oxy-
emission limits for reformulated gasoline, compared with gen and aromatics have the largest impact on predicted emis-
typical 1990 "baseline" gasoline. The first stage, the "Simple sions. D86 evaporation volumes E200 and E300, and olefin
Model" was an interim stage between 1 Jan. 1995 to 31 Dec. content have lesser, but still significant impact. Federal regu-
1997. The second stage, the "Complex Model" h a d two lations reduced vapor pressure and benzene directly, how-
phases: Phase I (1995-1998) and Phase II (2000+). ever, aromatics or other parameters could be limited to meet
Metropolitan regions with severe ozone air quality prob- emissions criteria [17]. For example, a fuel with the maxi-
lems were required to use reformulated gasoline containing m u m permitted 1.0% benzene requires total aromatics to be
at least 2.0 wt% oxygen to reduce 1990 volatile organic car- limited to about 27% to meet the emissions reduction
bon compounds by 15% (1994), and reduce specified toxic requirements.
emissions by 15% (1995) and 2 5 % (2000). Because of a lack Federal (EPA) RFG and California Phase 2 RFG composi-
of data, the EPA was unable to define the required parame- tion limits require the use of oxygenate. The California Phase
ters for the CAA, so an advisory committee containing repre- 2 RFG requires the hydrocarbon composition of the RFG to
sentatives of regulatory, petroleum industry, environmental, be significantly more modified than the existing oxygenated
and consumer interests recommended a two-stage system for gasoline to reduce unsaturated hydrocarbons, volatility, ben-
implementation ("reg-neg"). The EPA also gave the refining zene, sulfur, and the reactivity of emissions. California Phase
industry a choice of standard, based on either "per gallon," 2 does not require the use of oxygenates in the summertime
(Never To Exceed, NTE, or "cap" limit), or "averaged," based if using the "Predictive Model" except for federal ozone non-
on volumetric averages over an annual or seasonal produc- compliance areas of the state where the EPA RFG limits ap-
tion period (Yearly Pool Average, YPA, or summer/winter). In ply as well.
some jurisdictions, regulations include requirements around Oxygenates were first added to gasoline as a high percent-
sampling, test methods, and validation/demonstration of test age level blend component (as opposed to a p p m level de-
proficiency, as well as certified third party testing, auditing, icer) to extend gasoline supply supported by some State and
and field "attest" monitoring. Provincial Governments with a reduced gasoline tax rate. In
Areas in attainment with air quality objectives continued to 1992, 2 wt% oxygen gasoline was mandated in cold, high al-
use "conventional gasoline." The "anti-dumping" provisions titude areas starting in 1994, as a means to "lean" the mix-
of the regulation ensured that the quality of conventional ture, and reduce unburned HC and CO by over 10% in car-
gasoline was not degraded to facilitate production of RFG. b u r e t e d vehicles. However, some oxygenates such as
Conventional gasoline must be blended to provide equivalent methanol, ethanol, and light ethers increase the vapor pres-
emissions of the national baseline gasoline (default for do- sure of the gasoline, causing increased evaporative emissions
mestic or import), or individual refiner's baseline based on that reduced or reversed the benefit. Newer Tier 0 and later
prior production. The intent of these "anti-dumping" restric- technology cars have very fast adaptive feedback loops to
tions was to ensure emission improvements and non-attain- control the oxygen content in the exhaust to near stoichio-
ment did not result in emission increases in areas currently metric using the oxygen sensor [18]. These vehicles are much
in attainment with the National Ambient Air Quality Stan- less sensitive to fuel effects, so the net benefit of oxygenates
dards (NAAQS). Emission improvements had to be made by decreases with time, as the older predominately carbureted
increased refinery processing for the manufacture of RFG. engines are retired from service. Other researchers have ob-
The Auto-Oil Air Quality Improvement Research Program served similar reductions when oxygenates are added to re-
(AQUIRP, "Auto-Oil") provided the basis for the "simple" and formulated gasoline on older and newer vehicles, but have
also shown that NOx levels may increase, as also may some average at 30 ppm. In 2006, the average will be 30 p p m and
regulated toxics [19-21]. cap 80 p p m , with some areas and refineries having until
By 2000, MTBE was the preferred oxygenate in RFG, but 2006-2009 to comply. The EPA also n o t e d that gasoline
concerns about toxicity and water pollution were mounting. should not be advertised as "low sulfur gasoline" unless it
MTBE has a m u c h higher (4.3 wt%) solubility in water t h a n contains 95 p p m sulfur or lower.
hydrocarbons, a relatively low bio-degradability, and very California has legislated faster implementation of a 30
low o d o r threshold. This makes MTBE objectionable in YPA, 80 NTE sulfur standard, and others, such as North Car-
potable water at trace concentrations, and a concern for wa- ohna's SB 953. Part II of that law, NCOS 119-26.2, proposes
ter contamination from spills, leaks and marine engines us- the same for after January 1, 2004.
ing gasoline-containing MTBE. In 1999, California applied to The Tier 2 LDV stcindards are the same for cars and light
the Federal government for a waiver from the Federal RFG duty trucks, whether diesel or gasoline, so include both non-
requirement concerning oxygen content to eliminate MTBE. methEuie organic gases (NMOG) and Particulate Matter re-
However, that application was declined in J u n e 2001. In quirements (PM essentially for diesels and NMOG essentially
March 2000, the EPA provided advance notice of its intent to for gasoline). Different phase in periods apply for different
initiate rulemaking pursuant to section 6 of the Toxic Sub- size vehicles. Light duty car a n d truck phase-in starts in 2004
stances Control Act (TSCA) to eliminate or limit the use of with 100% compliance by 2007. M e d i u m duty passenger
MTBE as a fuel blend component. Several U.S. FederEil and vehicles and heavy light duty trucks will be phased in begin-
individual state bills have proposed elimination of MTBE ning in 2008, with full compliance in 2009. A new class of
since t h e n including two U.S. Federal Energy bills. At the medium-duty passenger vehicles (MDPV), < 10,000 GVW, in-
time of this writing, use of MTBE is likely to be either banned cludes large Sport Utility Vehicles (SUV) and vans intended
or significantly restricted. to carry less thzin 12 passengers. These will be treated the
Canadian refiners m u s t meet either a 1.0 wt% benzene same as HLDT and have interim emission standards that ex-
NTE, or optionally a 0.95 wt% YPA and 1.5 wt% NTE, effec- pire in 2008.
tive July 1, 2000. In addition, a 72/91 summer/winter Ben- The standard defines 11 "Bins" rEinging from Bin #1 "Zero
zene Emission N u m b e r (BEN) requirement is based on the Emission" to Bin #11, which is compEirable to current LDV
complex model, not including olefins. The BEN is the s u m of standards. The average Bin #5 NOx = 0.07 g/mile which rep-
exhaust a n d n o n e x h a u s t benzene, excluding calculation resents a reduction of about 70% from current levels. The
terms of the complex model using olefins. There eire several highest emissions Bin #9 to #11 expire after the phase in pe-
measurement and reporting differences between the U.S. and riod, contributing to a lower long-term average. More strin-
Canadian RFG regulations. One Canadian province (BC) has gent particulate matter emission standards are established in
VOx and NOx requirements based on the full complex model, 2004 for most light trucks. The NMOG standards vary de-
but using a BC baseline gasoline for the calculation. Severed pending on which of various individual sets of emission stan-
other Canadian Provinces have standalone s u m m e r Vapor dards manufacturers choose to use in complying with the av-
Pressure regulations. Canadian vehicle emission standards erage NOx standard.
have tended to follow closely u p o n U.S. 49 state require- The Tier 2 Vehicle emission program increases the useful
ments, with some differences in phase in schedules. life of the vehicle to 120 000 miles and introduces new, more
severe evaporative emission test procedure. This is expected
to result in widespread adoption of "deadhead" gasoline fuel
2 0 0 4 + Vehicle and Fuel Regulation (Future RFG) systems, that place the fuel p u m p , filter, and pressure regu-
lator inside of the gasoline tank, with n o liquid gasoline
In April 2000, new Federal Tier 2 criteria for vehicle emis-
return line from the engine compartment back to the teink.
sions and fuels were announced phased in beginning in 2004
This eliminates a n u m b e r of external mechanical connec-
and extending to 2007+. OfficieJly published sources of in-
tions that contribute to the fugitive emissions etnd life of ve-
formation should always be used for regulatory compliance
hicle compliance.
purposes. Full details of the regulations cire available on the
United States EPA website at http://www.epa.gov/otaq/cert/- The Canadian Environmental Protection Act (CEPA) re-
veh-cert/bOOOOl.pdf (Document EPA420-B-00-001). Copy of quires refiners and importers to meet either a 170 ppmw sul-
the final rulemaking is available at http://www.epa.gov/- fur NTE over a 30 month interim period ending Dec 31, 2004,
OMS/regs/ld-hwy/tier-2/frm/fr-t2pre.pdf. or a 150 p p m average with an 300 NTE in the last half of the
interim period. Gasoline is required to be 30 p p m YPA, 80
These stcindards apply to both diesel and gasoline powered
p p m NTE starting Jan 1, 2005. One Province (Sask.) has im-
light duty vehicles, and to fuels for these vehicles. The regu-
pending oxygenate (ethanol) requirements for 2005.
lations allow early-adopters to obtain credits that cEin be used
later and traded, encouraging rapid introduction of low sul-
fur gasoline, starting in 2000, well ahead of the 2006 dead-
GASOLINE PROPERTIES
line. Temporary, less stringent standards will apply to a few
small refiners t h r o u g h 2007. I n addition, temporary, less Gasoline Composition
stringent steindards will also apply to a limited geographic
cirea in the western U.S. for the 2004-2006 period. Hydrocarbons
Most U.S. refiners and importers must meet a corporate Gasoline can contain over 500 different hydrocarbons with
average gasoline sulfur standard of 120 p p m and a cap of 300 between 4 and 14 carbon atoms per molecule. Detailed de-
p p m beginning in 2004. In 2005 the cap remains at 300 ppm, scriptions of structures can be found in any chemical or
with the corporate average reducing to 90 p p m and refinery petroleum text discussing gasoline [22]. The C3 and lighter
hydrocarbons are too volatile to be used as a blending com- there is usually less than 2.5% "unknown" content in a typi-
ponent of gasoline. Both methane and propane are widely cal RUL and less than 1% in a typical PUL. There are small
used as an SI engine fuel using pressurized fuel systems and concentrations of additional isomers that are undoubtedly
various designs of gaseous carburetors or fuel injectors. Hy- present below the nominal 50 p p m w detection level of the
d r o c a r b o n s larger t h a n about C14 are too heavy (nonstandard methods using Flame Ionization Detectors. These
volatile), and tend to contribute inordinately to oil dilution tend to be highly branched CIO to C14 olefins, isoparafins,
and incomplete combustion a n d "soot" related problems. and napthenes because of the large n u m b e r of isomers that
These functional limitations result in gasoline having a typi- can be produced within each carbon n u m b e r in this range.
cal boiling range of about 25-225°C at atmospheric pressure. The magnitude of the "undetected" hydrocarbons can be in-
Vapor pressure, Driveability Index (DI) a n d model based ferred to be less than about 0.5% for a complex gasoline by
emission criteria all tend to narrow this boiling range by re- comparing results of high and low resolution methods.
moving the highest and lowest volatility ranges. The m u c h smaller number of isomers possible for aromat-
The type and concentration of the various hydrocarbons in ics makes the measurement of aromatics by FID detectors
any given gasoline blend can be determined by high resolu- more feasible since essentially all of the possible aromatics
tion gas chromatography, typically using 50-100 meter cap- up to about CI2 are identified. As a result, Canadian regula-
illary columns to obtain the high resolution required. The tions use a Cap-GC/FID method for both benzene and total
n u m b e r of different hydrocarbons in any given blend de- aromatic reporting.
pends upon the tjê and severity of processing at any given
refinery. Composition surveys [23] on nonleaded gasoline Saturated Hydrocarbons (Paraffins, Alkanes)
showed that gasoline blended with high percentages alkylate Saturates are the most chemically stable species, and com-
or low severity reformate could contain less than 175 differ- prise 20-80% of gasoline, with 30-60% being typical. The oc-
ent hydrocarbon types. Gasoline blended with catalytically tane ratings of these compounds depend on the branching
cracked naphtha tended to contain more than 350 different and n u m b e r of cEirbon atoms. The octane primary reference
molecules. fuels are both saturated hydrocarbons (0 = heptane, 100 =
U.S. regulations use a n ASTM external calibration GC- 224 trimethylpentane). Additional information is presented
Mass Spec method for regulatory benzene and aromatic rein Table 1. The interested reader is directed to a standard or-
porting. Current versions of the ASTM GC method peak ganic chemistry text for further detail on these and the other
tables identify over 400 different hydrocarbons by formula, classes of hydrocarbons.
and a n additional 50+ as "unknown." Most methods also
measure the c o m m o n oxygenates if present. Since the FID Unsaturated Hydrocarbons
detector is linear, the percentages of parafins, olefins, Unsaturated hydrocarbons are less stable as compared to
napthenes, indanes, aromatics, and unknowns can be esti- saturates. The upper limit of both olefins and aromatics can
mated by linear sum (commonly called a PONAU or PIANO be limited by emissions or other specifications. Table 2 con-
methods, which are acronyms of the first letter of the hydro- tains information about the various classes of unsaturated
carbon t5rpes detected). With over 400 compounds identified, hydrocarbons.
TABLE 2—Unsaturated hydrocarbons.

Alkenes • Olefins, contain single carbon-carbon double bonds
• Usually stable, depends upon molecular type
• Clean burning, reduces VOC but increases NMOG reactivity
• More reactive than alkanes, higher octane ratings.
• Present in gasoline 0-25% (10-15% typical)
Dienes • Olefins containing more than one carbon-carbon double bond
• Usually unstable especially if conjugated (n, n+2 double bonds)
• More be significantly higher reactivity, toxicity and air reactivity
• <<1 % generally required for stability
Alkynes • Acetylenes, contain carbon-carbon triple bonds
• Considered very reactive, only present in trace amounts, and usually in some poorly-refined gasolines
• <<0.1% generally required
Arenas • Very stable, high octane. 10-50 vol% (25-35 vol% typical).
(Aromatics) • Tend to be limited by emission models
• Benzene > > > toxicity than other aromatics, regulated separtately
• Alkyl benzenes not considered smoke precursors, as they have vaporized and are not present at the
end of combustion, (see PNA)
PNA (Polynuclear • Condensed ring aromatics (naphthalenes, alkyl napthalene, trace 3 ring)
Aromatics) • Generally controlled to < < 1 vol% by boiling point or other specifications (220-225°C vs. 260°C
dimethyl napthalene)
PAH (Polycyclic Aromatic • Di-alkyl PNA are potent smoke precursors, and are very detrimental to spark ignition engine
Hydrocarbon) operations.
• Naphthalene and methylnaphthalene boil at 218°C and 230°C and are not considered to be potent
smoke pre-cursors. Di-methylnaphthalenes boiling above allows it to ring close on de-hydrogenation
to form a larger PNA. It turns it from a "chain ender" molecule to a "smoke precursor". The extra
methyl group on the aromatic allows this process to continue to completion of a multi-ring smoke
molecule.
Many other control measures can be used to control the same property.
TABLE 3—Properties of selected oxygenates. in the environment (see History of Gasoline). Nonleaded
Energy Content, Heat of Vaporization Oxygen Content specifications and regulations limit alkyl lead contamination
Net MJ/kg MJ/kg Wt% to 5 mg/L (Canada) and 0.05 g/gal (13 mg/L) (U.S.).
Methanol 19.95 1.154 49.9 ASTM D 910 Aviation Gasoline lOOLL (low lead) has been
Ethanol 26.68 0.913 34.7 reformulated from the original 100/130 grade with the addi-
MTBE 35.18 0.322 18.2
tion of aromatics (toluene) to reduce TEL to the lowest level
ETBE 36.29 0.310 15.7
TAME 36.28 0.323 15.7 necessary to maintain the octane number and aircraft per-
Gasoline 42-44 0.297 0.0 formance. Avgas is generally handled in segregated distribu-
tion systems, so is generally not a significant source of alkyl
lead contamination in automotive gasoline. With no other
source of alkyl lead contamination, typical trace alkyl lead
Oxygenates (as Blend Components) levels in North American gasoline are usually undetectable
See History of Gasoline (nonleaded and RFG). Table 3 pro- by standard test methods.
vides properties of selected oygenates that are used as gaso-
line blend components. Methylcyclopentadienyl Manganese Tricarbonyl (MMT)
As the toxicity of the alkyl lead and the halogenated scav-
engers became of concern, alternatives were considered. The
Gasoline Additives
most notable of these is methylcyclopentadienyl manganese
Additives are compounds added in trace a m o u n t s (<2500 tricarbonyl (MMT), an organo-manganese compound with
p p m in the EPA "substantially similar" ruling), to enhance similar antiknock properties as TEL, but at m u c h lower con-
some property of the fuel, or performance of the engine, ve- centrations to obtain about 1-2 octane n u m b e r increase. It
hicle, or emissions. Specifications and regulations allow for was used in the United States in nonleaded gasoline in the
additive use, and in some cases, require additive use, for ex- mid 1970s, b u t a n application for an EPA waiver was de-
ample deposit control additives (DCA), which are beneficial clined in October 1978, effectively banning it in nonleaded
for in-use emissions. gasoline in the United States. In December 1995, the EPA was
forced to grant the waiver in U.S. conventional gasoline (not
Oxygenates (De-icers, Gas Line Anti-Freeze) RFG), and MMT can be used in conventional gasoline up to
Aliphatic alcohols and ethers added at 5-15 vol% are consid- 1/32 g Mn/usg (8.3 mg/L) in all states except California, where
ered to be blending components and not "additives." How- it is regulated separately [24]. In a separate case, the court
ever, at lower concentrations, low molecular weight alcohols, held that EPA's new rules that require pre-meirket testing of
especially methanol, ethanol, and iso-propanol, are effective new gasoline additives did not apply to MMT. The EPA has
de-icing additives, commonly available as "gas line anti- stated it intends to monitor MMT use, but MMT was used in
freeze." Alcohols are typically used in the 500-2500 ppmv only 0.02% of gasoline in 1998.
(0.05-0.25 vol%) range for this purpose, and function by pre- MMT has a high toxicity in concentrated form, but the
venting traces of water (typically from temperature drop and combination of relatively low volatility and its miscibility
condensation) from freezing in the vehicle fuel system. A with aromatic hydrocarbon solvents allows it to be stored
higher rate may be required for larger water contaminations, and handled with tjîcal equipment. MMT is light unstable
or to prevent carburetor icing, which is accumulation of ice with a half life of about 30 s in strong sunlight, forming a
in the carburetor throat and throttle plate. The cooling of characteristic red "rust" colored precipitate (Mn02). This ox-
high humidity combustion air is caused by throttling (Joule ide is softer t h a n iron oxides, and is not considered to be
Thompson cooling) and fuel evaporation heat of vaporization abrasive even at much higher concentrations than typically
(auto-refrigeration). Gasoline with higher VP, Eind lower TIO used in gasoline.
and T50 (high "front end" volatility) has a higher propensity MMT has been in continuous use in Canada since the first
for producing carburetor icing introduction of nonleaded gasoline in 1972 to a maximum of
IPA is approved as aviation fuel system icing inhibitor 18 mg/L Mn, without major incidents. Most problems at-
(FSII Type 2) at a treat rate of 1 vol% in aviation gasoline tributed to MMT are associated with excessive exhaust or cat-
(ASTM D 4171). Other alcohols and glycols have also been alyst temperatures. These cause the manganese oxide to "ce-
used for carburetors or fuel line icing, including hexylene gly- ram" and form a gas impermeable glass that can coat and
col, propylene glycol, dipropylene glycol, and various glycol effectively deactivate the catalyst [25] This is also associated
ethers. Methanol is the most commonly used for gasoline fuel with front face catalyst plugging, due to the "sticky" nature of
line freezing protection in fuel-injected vehicles in cold cli- the glass. Field experience indicates that this is not a serious
mates. De-icers are not commonly used in automotive fuels problem in tj^jical driving cycles, including Tier 0 and 1 ve-
in warm/cool climates, due to the low population of carbu- hicles equipped with OBDII emission control monitoring sys-
reted engines susceptible to carburetor icing. Some carbu- tems. Two provincial inspection a n d m a i n t e n a n c e (I&M)
reted utility engines may require alcohols for operation in se- programs using IM240 (d3mo driving cycle) and ASM2525
vere icing conditions ( > 8 5 % relative humidity, 0-10°C). (25 m p h steady state dyno) test cycles have not found or iden-
tified any emissions related problems due to MMT on model
Alkyl Lead Compounds years 1982 to present.
Alkyl lead compounds are n o longer used in North American Proponents claim benefits in NOx reduction, protecting the
automotive gasoline, because of the detrimental effects on catalyst from long term deactivation by sequestering catalyst
exhaust catalysts and concerns for health effects of alkyl lead poisons (Zn, P, Pb) or coke, fuel cost benefits, emissions re-
duction from reduced refining severity, and lack of adverse 3. Metal Deactivators, typically about 10 p p m of chelating
health effects. Opponents cite high exhaust temperature cat- agent such as N,N'-discJicylidene-l,2-propanediamine is
alyst plugging, exhaust gas sensor "rich shift" for the NOx ef- added to inhibit copper catalyzed air oxidation of gasoline
fect, spark plug tracking, and the potential for adverse health 4. Ferrous Corrosion Inhibitors, about 5-20 p p m of oil-
effects. soluble surfactants, are added to prevent aqueous-based
Dozens of controlled and noncontrolled tests and surveys corrosion caused either by water condensing from water-
over 35 years have failed to conclusively resolve the debate saturated gasoline, or from condensation from air onto the
[26,27,28], probably because the test result depends upon the walls of almost-empty gasoline tanks that drop below the
specific automobile year and model being tested and how the dew point. Many pipelines require addition of corrosion
test is done. inhibitor for protection of pipeline and storage tanks. The
Several countries are considering MMT as an alkyl lead re- NACE 0172 "rust" test is commonly used to establish
placement additive to facilitate alkyl lead phasedown. addition rate for corrosion protection. A variety of com-
p o u n d s are effective as corrosion inhibitors, including
Iron based Organo-metallics dimer carboxylic acid esters, amides, alkanolamides, and
Other compounds that enhance octane have been suggested, hydroxyesters. Phosphorus based corrosion inhibitors are
b u t usually have significant problems such as toxicity, cost, no longer used in nonleaded gasoline because phosphorus
a n d increased engine wear, especially if used at high is a potent catalyst poison, and is controlled by both ASTM
concentrations. specification and regulation. ASTM specifications allow,
Dicyclopentadienyl iron (ferrocene) a n d nickel carbonyl but do not require, corrosion inhibitor or corrosion
have been promoted as alternatives to alkyl lead and MMT. testing.
For example, the addition of 0.02-0.04 g/L ferrocene with 5. Lubricity additives are occasionally used in gasoline, and
0.05-0.10 g/L tertiary butyl acetate is reported to increase the are usually similar in chemistry to corrosion inhibitors,
AKI of susceptible gasoline hydrocarbon feedstocks by 4-6. but at higher treat rates.
More recently, ferrocene has been promoted as an octane 6. Copper corrosion inhibitors are occasionally used to miti-
enhancer at lower levels of 9 mg/L Fe to avoid any significant gate sulfur-based corrosion of copper or other easily cor-
deposition or wear problems. The benefit is reduced to about roded base metals if/when used in fuel systems.
1-1.5 octane n u m b e r at this level (similar to MMT). Unlike 7. Anti-wear additives are used to control wear in the upper
m a n g a n e s e oxides, iron oxides do not ceram at high cylinder and piston ring area that the gasoline contacts,
temperature. and for valve sticking. They are usually very light hydro-
Iron pentacarbonyl (Fe(CO)5) was used in Germany at lev- carbon oils ("top" oils, "solvent" oils), although synthetics
els of 0.5% or less in gasoline during the 1930s. While the cost are now preferred, due to potential problems with com-
was low, the carbonyl decomposed rapidly when the gasoline bustion chamber deposits. If permitted, phosphorus-based
was exposed to light to form iron oxides. It also has a rela- additives can also be used in engines without exhaust cat-
tively high vapor pressure, and is extremely toxic in concen- alyst systems.
trated form, so must be handled with care. Use of the additive 8. Cleanliness or Deposit-modifying Additives are used to
at high concentrations in gasoline caused excessive deposi- mitigate (keep clean) or reduce (clean up) deposits. Some
tion of iron oxide (Fe304) on the spark plug insulator, caus- specific types of deposits are discussed below.
ing short circuits. The precipitation of iron oxides in the lu- • Carburetor Deposits—Additives were required w h e n
bricating oil also led to excessive wear rates [29]. crankcase blow-by positive Crankcase Ventilation (PCV)
Iron picrate (trinitro phenate) and related oil soluble iron and exhaust gas recirculation (EGR) controls were in-
chelates are sometimes sold as aftermarket additives with troduced (in the 1950s on some engines). Some fuel
various performance claims, but are not used in commercial components reacted with these gas streams to form de-
production. posits on the throat, throttle plate and idle air bleeds of
carburetors and some throttle body injectors.
Performance Additives
• Fuel Injector Deposits—Deposits can form in the annulus
Most other additives are added to address specific safety or or sealing surfaces in some pintle needle or poppet valve
p e r f o r m a n c e properties of gasoline. Typical examples injector designs during hot soak (>100C), suspected to
include: be mainly from the oxidation and polymerization of the
1. Oil-soluble dye was originally added to leaded gasoline at least volatile or unsaturated hydrocarbons. The addi-
about 10 p p m to prevent misuse of leaded gasoline as an tives that prevent and unclog these tips are usually poly-
industrial solvent, and is now also used to identify grades butene succinimides, polyisobutylamines, or polyether
or brand of product. Red dyes are currently used in the amines, and are often used in combination with "flu-
U.S. and Canada to mark fuels that have different taxation idizer" or "solvent" oil.
rates for different uses. • Intake Valve Deposits—IVDs caused major problems in
2. Antioxidants (oxidation inhibitors) typically phenylene di- the mid-1980s with widespread introduction of elec-
amines (PDA) or hindered alkyl phenols, are added to slow tronic fuel injectors a n d three way catalyst systems.
down oxidation of hydrocarbons, especially unsaturated Some vehicles experienced severe driveability problems
hydrocarbons. These additives are "sacrificial," and once even when fully warmed, even though the amount of de-
consumed, the oxidation reactions rapidly become auto- posit was considered acceptable by historical carbureted
catalytic, increasing exponentially in rate to form soluble engine standards. It was proposed those new fuels and
and insoluble gum ("varnish"). engine designs were producing a more porous deposit
on the valve tulip (fuel side) face. The close proximity of sulfur containing additives in the future. (See Reformu-
the liquid fuel injector caused some liquid fuel to be ab- lated Gasoline for more detail.)
sorbed in the deposit, causing lean/rich transients re- 3. Gasoline may be contaminated by other partially soluble
sulting in hesitation, misfire, and excess emissions. De- or miscible liquids, such as kerosene, diesel, and oxy-
posit Control Additives (DCA) were mandated in 1992 in genates. Oxygenated fuel can have a higher solubility of
California and Federally in 1995 and by CGSB specifica- water-soluble contaminants, as well as allowing water-sol-
tion in 1994 due to the emissions increase. Intake valves uble c o m p o n e n t s to c o n t a m i n a t e any fresh water that
operate about 300°C, and if the valve is kept wet with comes into contact with it.
thermally stable oil in conjunction with a dispersant/de- 4. "Adulterants" or "extenders" have occasionally been delib-
tergent, deposits tend not to form. Solvent oil/disper- erately added to gasoline to increase the volume sold. Ma-
sant/detergent additives that are effective with IVD also terials used have included new or used solvents, used lube
tend to be effective for fuel injector deposits. Gasoline oil, formic/acetic acid, heJogenated solvents, refrigerants,
factors implicated in these deposits include unsaturates dry cleaning solvents, silicon oils/caulking/adhesives, and
and alcohols, as well as oil leakage through the valve even PCBs. Deliberate adulteration is usually involved
guides. with a criminal activity for illegal waste disposal or fuel tax
• Combustion Chamber Deposits—CCD were targeted in fraud. Some jurisdictions now have "contaminated fuels
the 1990s, as they are responsible for significant in- regulations" that prohibit these activities.
creases in emissions. Severe deposit accumulation re- 5. Particulate contaminants, such as dirt and corrosion prod-
sulted in CCD interference (CCDI) where the deposit ucts, can be readily removed by standard filtration proce-
contacted the cylinder head at TDC, resulting in noise, dures, and increasingly stringent cleanliness requirements
and eventual engine damage. Additives have a limited are resulting in a n increasing use of microfiltration at
ability to remove pre-existing CCD, so DCA additives are truck loading and/or point of sale.
tested for their propensity to avoid formation of CCD rel-
ative to the base gasoline. Gasoline factors that con-
tribute to heavier deposits are the presence of alcohols GASOLINE COMBUSTION
or olefins. Gasoline manufacturers now routinely use
additives that prevent IVD and also maintain the clean- Spark Ignition Engines
liness of injectors. These usually include surfactant and
Spark ignition engines are ideally suited for light duty trans-
light oil to maintain the wetting of important surfaces.
portation uses. Their relatively lightweight (compared to
Intake valve deposits can also have significant adverse
other internal combustion engines), wide REM range, broad
effects on emissions, and deposit control additives are
torque band, and high maximum RPM/power provide good
now standard to reduce emissions and provide clean en-
performance with a m i n i m u m number of transmission gears.
gine operation.
Vehicle spark ignition engines are air throttled to control
power, a n d have inherent limitations on peak cylinder tem-
Trace Constituents and Contaminants peratures and pressures due to engine "knock," so are ther-
1. Free Water—"haze" is considered to be a contaminant, as- mally less efficient than compression ignition engines. As a
sociated with corrosion, filter plugging, and freezing prob- result, diesel engines d o m i n a t e the high torque, low r p m
lems. The large difference in density usually allows water heavy-duty truck, marine, locomotive, and stationary power
to settle out from traditional gasoline, and most additive applications. Smaller high-speed diesel engines comprise
packages are checked for any propensity to stabilize a wa- only a small percentage of the light duty vehicle market in
ter haze and prevent water dropout. Gasoline components North America, but are more prevalent in Europe. This is
are often dried at the refineries supplying gasoline into driven mainly by their significantly higher fuel efficiency,
very cold winter distribution systems, to prevent water to which provides a significant market advantage, especially in
phase separate due to condensation on cooling down. regions with high fuel prices.
Most specifications have a dryness, "clear and bright," Electronic fuel injection has replaced carburetors on es-
(such as ASTM D 4176 for distillate fuels) or some similar sentially all Tier 0, Tier 1, and later model automobiles. This
"suitable for use" criteria. facilitates "closed loop" computer control of air/fuel ratio, to
2. Sulfur, nitrogen, and oxygen are naturally occurring trace maintain exhaust composition within a n a r r o w range re-
constituents of crude oil, and are present in fuels at the quired for optimal operation of a "3-way" catalyst. The name
p p m level. These CEin be present as ashless, combustible, "3-way" is a reference to effectiveness for all three regulated
additives. Nitrogen is typically not regulated in gasoline exhaust emissions: u n b u r n e d hydrocarbons (HC), carbon
formulation because the source of nitrogen in NOx emis- monoxide (CO) by air oxidation, and oxides of nitrogen (NOx)
sions is from atmospheric N2, and not the fuel. The maxi- by chemical reduction with HC/CO. These systems require
m u m sulfur specification prior to regulation was t3îcally the engine to operate in a narrow air-fuel ratio band on both
0.1-0.15 wt%. Current California a n d future U.S. a n d rich and lean side of stoichiometric, to maintain both the reg-
Canadian regulations will reduce sulfur to a yearly pool av- ulated emissions HC, CO, and NOx and O2 in the optimal
erage 30 p p m by 2005/6. Regulated changes to the baseline range where they react to extinction.
gasoline used in any predictive model based regulation Hybrid gasoline-electric vehicles couple internal combus-
equates to a change in the gasoline production required for tion engines with an electric motor for peak power and tran-
equivalence, including sulfur, which has a large impact on sient engine operations to obtain ultra-low "steady state"
the predicted emissions. This would restrict the use of any emissions with no significant loss in performance. A smaller,
generally m u c h higher voltage battery set stores enough fuel volume delivered at constant pressure. The adaptive
power for several minutes of high power electric motor oper- maps would start out at mid-range (128), and the total num-
ation for cold start or accelerations. This allows a n u m b e r of ber of milliseconds injector open time would be the sum of
very efficient and ultra low emission driving cycles, since the the corresponding cells of the three tables for the engine
majority of SI engine emissions are due to transient opera- speed and load at that instant of time. The ECM would mod-
tions and cold start, before the catalyst heats up. The SI en- ify them according to the response of the oxygen sensor. If it
gine can shut down (zero emissions) during cold start or if was consistently lean for several seconds (too much oxygen
required for urban ZEV emissions. It can run at steady state in the exhaust) then the ECM will add one n u m b e r to the fast
(for example on the highway) letting the electric motor han- learn block, making it 129, and adding one unit of time to the
dle variable power requirements (hills, wind load, comers, injector open time, slightly enriching the mixture. This con-
etc.) that would otherwise cause increased emissions from tinues until the fast learn block hits its upper limit, when the
transient SI operation. It can be r u n at a higher steady state ECM t3?pically adds one to the long term block cell, and resets
power, using the electric motor as a generator to recharge the the fast learn to its mid value. The long term and fast learn
batteries. Elimination of transients tends to provide highway blocks are similar to a "course and fine" control, where the
fuel efficiency in urban driving cycles, and ultra low emis- fast learn steps are smaller, but occur faster. The long term
sions (lower t h a n the Super Ultra Low Emission Vehicle map, as the n a m e implies, adjusts for long term trends, for
(SULEV) level. The 2004 Tier 2 LDV Bin #2 NMOG standard example a slow drop in fuel rail pressure due to a p u m p wear-
of 0.01 g/mile is about a 90-95% reduction from current lev- ing out over the lifetime of the car, a partially plugged fuel fil-
els (0.125-0.25 g/mile), over 99.8% reduction from the 1990 ter, or slowly fouling fuel injectors. The fast learn block takes
levels (4.1 g/mi), and 99.9% reduction from precontrol care of smaller but faster changes, such as changing altitude,
(est. 10.6 g/mile). humidity, or tank to tank gasoline composition differences,
such as switching between high and low aromatic or oxy-
Other hybrid vehicle types have been proposed, such as
genated gasoline. This is also the reason that composition
diesel-electric or gasoline-hydraulic, or gasoline-flywheel,
mandates are less effective for newer cars than older cars,
but only gasoline-electric are being commercialized at this
especially oxygenates for cold high altitude CO control, as the
time. It is anticipated that both current RFG and 30 p p m sul-
ECM quickly adjusts the air-fuel ratio according to the oxy-
fur future RFG will be compatible with hybrids, but that the
gen sensor readings at the time.
lower sulfur will provide slightly lower in-use emissions.
Gasoline Direct Injection (GDI) engines (Spark Ignition Di- One artifact of this system is that a dead or disconnected
rect Injection, SIDI, etc.) have thermodynamic efficiencies battery can cause memory loss of the adaptive maps, so that
between SI and diesel engines, and may be commercialized the vehicle drivability can be very poor while the ECM
in the near future. Fuel requirements for GDI have not been reloads the m a p with data appropriate for the car, engine,
established. Exhaust particulate matter may be more critical fuel, and ambient conditions at the time.
for GDI than for current engine/emissions systems. All U.S. a n d Cdn LDVs n o w have on-board diagnostics
version II (OBDII) that monitor the critical emission system
Engine Management Systems components for conditions that cause high tailpipe emissions
Engine management systems are now an important part of or are detrimental to continued operation. The ECM lights
the strategy to reduce automotive pollution. A typical m o d e m the Malfunction Indicator Light (MIL) light on the dash,
engine system would monitor and control: mass airflow (or commonly called the "check engine" light. OBDII warns of
MAP/RPM calculated air flow), exhaust oxygen sensor malfunctions such as engine misfires, exhaust catalyst failure
(lambda sensor), knock (vibration/noise) sensor, EGR, throt- (inferred from oxygen sensor time delays), and evaporative
tle plate angle, manifold air temperature and pressure, crank emissions failure such as a leaking gas cap (fuel tank pres-
angle, and transmission gear. These systems can compensate sure). Chronic misfire, for example causes combustion of un-
for altitude (MAP), ambient air temperature (MAT), fuel oc- b u m e d air/fuel on the catalyst, with the potential to generate
t a n e (knock sensor), humidity, a n d gasoline composition so much heat that the catalyst activity drops, or the catalyst
(oxygen sensor, adaptive map). The engine control module substrate melts.
(ECM, computer) then sets the ignition timing and fuel in- The air-fuel ratio is controlled at part throttle by a closed
jector open time (fuel flow), and fuel injection timing with loop system using the oxygen sensor in the exhaust and the
crank angle that are appropriate for the current engine oper- knock sensor (if equipped). Typical engine calibrations
ating conditions. enrich the air-fuel ratio for smoother, stall free idle when in
Almost all TierO/1 engine control systems incorporate closed loop control, and hold a faster idle after cold start
"adaptive memory maps" or adaptive learning strategies. The when in open loop, until the catalyst becomes heated and
fuel m a p (or schedule) conceptually consists of three blocks "lights off." The a m o u n t of idle enrichment used is often
of data organized like three sheets in a spreadsheet, with the adjusted according to the air t e m p e r a t u r e at the time of
rows and columns representing different RPM and manifold engine start (similar to the function of a choke on a carbure-
vacuum, which together define the engine load. The three tor acting against a bimetal temperature spring that held the
sheets contain fuel injector open time for the factory "base- choke on longer when cold until the engine heated up).
line" settings, the long-term block learn, and the short-term
block learn. Conceptually, the data is a c o m p u t e r binary Air - Fuel Ratio and Stoichiometry
n u m b e r such as 0 to 255 for an 8-bit computer. This might Ideally, hydrocarbons and oxygenates in gasoline combust
represent, for example, how many milliseconds the fuel in- smoothly to form water, carbon dioxide, and heat energy,
jector should be held open, since open time is proportional to with no other by-products. Non-ideal combustion affects
emissions, efficiency, engine durability, and vehicle opera- all the fuel inside a b o m b calorimeter and measuring the heat
tion. Severe engine knock is associated with loss of efficiency released as evidenced by a t e m p e r a t u r e increase u n d e r
a n d engine damage. If there is excess fuel ("rich" air/fuel controlled conditions. If the combustion is not complete,
ratio), the combustion is not complete, and carbon monoxide carbon monoxide (CO) and/or unburned or partially com-
(CO) will be formed, Eilong with u n b u m e d or partially burned busted fuel will be formed, resulting in a lower than true
hydrocarbons (HC). As CO can be burned to produce CO2, it energy content. The reported heat of combustion depends on
is " u n b u m e d " fuel, so t h e r e is a d r o p in efficiency a n d what happens to the water produced from the combustion. If
increase in emissions. Nitrogen oxides are formed as a result the water remains as a gas, then it cannot release the heat of
of conversion of nitrogen (N2) in air to various nitrogen vaporization, thus producing the net (or lower) heat of com-
oxides (NOx). High peak combustion temperatures promote bustion. If the water were condensed back to the original fuel
NOx ("lean" air/fuel ratio, high intake air temperature, low temperature, then the gross (or higher) heat of combustion is
humidity, high barometric pressure, high load). reported.
The required mass or volume of air to provide sufficient For internal combustion engines, the net heat of combus-
oxygen to achieve this complete combustion is the "stoichio- tion is more appropriate, as the water is emitted as vapor.
metric" mass or volume of air. Insufficient air creates "rich" The engine cannot utilize the additional energy available
mixtures, and excess air creates "lean" mixtures. The stoi- when the steam is condensed back to water. This is some-
chiometric mass of air for a gasoline is related to the carbon: times confused for lower emd higher thermal efficiency of
hydrogen ratio of the fuel. The procedures for calculating the diesel versus spark ignition engines or the lower/higher net
stoichiometric air-fuel ratios are fully documented in SAE J heating value of diesel fuel versus gasoline. However, the
1829 [30]. However, oxygen (20.9476 vol%). Nitrogen net/gross or lower/higher heating value oiany fuel is simply a
(78.084%), and Argon (0.934%) comprise 99.966 vol% of the reference to whether the water of combustion is condensed
atmosphere. The use of nominal masses (O2 = 16) versus nat- and captured by the process, or exhausted as a vapor and lost
ural abundance masses (O2 = 15.994) and ideal gas assump- to the process.
tion (vol% = mole) will result in errors of less than 0.5%, be- Standard heats of combustion for hydrocarbon molecules
cause the errors tend to cancel (nominal MW of nitrogen and for reactions involved in combustion are available from
lower than natural abundance offset by higher MW of Argon a number of engineering and chemistry texts and references.
vs. nitrogen). This includes ASTM Dataseries DS4B, Physical Constants of
As a result, it is c o m m o n to assume that the non-oxygen Hydrocarbon and Non-Hydrocarbon Compounds, and others.
component of the air is nitrogen, which can be added to the Because all the data are available, the calorific value of fu-
equations when the exhaust compositions are required. The els can be estimated quite accurately from calculation de-
error is generally m u c h smaller than the analytical uncer- tailed GC analysis or by correlation with hydrocarbon fuel
tainty of the actual carbon hydrogen ratio of a real gasoline, properties such as the density, sulfur content, and aniline
by elemental analysis or cap GC. If needed, exact molecular point (which indicates the aromatics content).
weights can be calculated from molecular formula and stan- Oxygenates contain oxygen that has already reacted in the
dard periodic tables weight, or from ASTM GC method peak production process, and cannot provide additional energy at
tables for individual hydroccirbons. the point of use in the engine, so they have significantly lower
For n o r m a l h e p t a n e C7H16 with a molecular weight = energy contents. For an engine that can be optimized for oxy-
100.204: genates, more volumetric fuel is required to obtain the same
power. However, the decrease in volumetric fuel efficiency
C7H16 + 1 1 0 2 ^ 7CO2 + 8H2O
(mpg) tends to be less than the energy content decrease. See
The chemical stoichiometric combustion of hydrocarbons Table 4 for properties of selected oxygenates.
with oxygen can be written as: For a water-cooled SI engine with 2 5 % useful work at the
CxHy + (x + (y/4))02 -^ XCO2 + (y/2)H20 crankshaft, the losses may consist of 35% coolant, 33% ex-
haust, and 12% surroundings. SI engines have inherently
t h u s 1.000 kg of CyHife requires (1/100.204) * 11 * 2 * lower thermal efficiencies than diesel engines, mainly due to
16 = 3.513 kg of O2 and using approximation, throttling of the engine at partial power, and higher diesel en-
(3.513 kg of O2 + (3.513/32) gine compression ratio. Even at wide open throttle, equiva-
* (28*79.0524/20.9476) = 15.113 kg of air. lent displacement CI engines have higher thermal efficiency
because of higher compression ratio, so this advantage ex-
(Air-fuel ratio = 15.113 vs 15.179) tends over the entire operating range.
Octane rating is fundamentally not related to the energy
Gasoline Energy Content content, although the actual hydrocarbon a n d oxygenate
The energy content (heat of combustion) is the total amount components used in the gasoline will determine both the en-
of energy obtained by combustion of gasoline under standard ergy release and the antiknock rating. However, it is possible
conditions, usually at STP, as if the fuel and air started at STP, to make correlation between energy content and octane that
and the combustion products are cooled down to STP. Energy are mostly meaningless and often confusing. For example,
captured at other conditions will be different. For example, addition of ethanol to a blend can increase the octane, while
emitting a hot exhaust from an engine will not capture the decreasing the energy content, while adding pure aromatic
heat energy from cooling the exhaust back to STP. increases both. Add to this the difference between energy per
The heat of combustion is useful to compare fuels under fuel liquid volume versus energy per fuel weight, and one can
the same standard conditions. It is measured by combusting generate octane versus energy graphs that go up, down, or
TABLE 4—ASTM research and motor octane number test conditions.

Test Method ASTM D 2700 MON ASTM D 2699 RON
Engine Cooperative Fuels Research Cooperative Fuels Research
(CFR) (CFR)
Engine Speed 900 RPM 600 RPM
Intake Air Temperature 38°C Variable with Barometric P.
88 kPa at 19.4X,
101.6 kPa at 52.2°C (Temperature
Tuned with Toluene Standardization
Fuel ± 22C from lAT)
Intake Air Humidity 3.56-7.12 g HzO/kg dry air 3.56-7.12 g HaO/kg dry air
Intake Mixture Temperature 149°C (Temperature Tuned with Not Specified
Toluene Standardization Fuel
141-163''C)
Coolant Temperature lOOX 100°C
Oil Temperature 57°C 57°C
Ignition Advance Variable with Comp. Ratio 13 degrees BTDC (fixed)
14-26 degrees BTDC
Carburetor Venturi 14.3 mm Variable with Altitude
14.3 mm at 0-500 m
sideways, dependent entirely on what materials and units are condition is sufficient to ruin one's day (in addition to the
chosen. engine).
The octane (and autoignition temperature) of various hy-
drocarbons is related to their ability to withstand preflame
Gasoline Octane Performance Properties
conditions without decomposing into species t h a t could
Combustion and Knock in Engines auto-ignite before the flame-front arrives. Unburned "end
The critical fuel property of gasoline for internal combustion gases" ahead of the flame front encounter 700°C tempera-
engines is resistance to engine "knock," expressed as the oc- tures due to compression and heat transfer, and commence a
tane n u m b e r of the gasoline. During a normal (no knock) series of complex preflame reactions. These reactions occur
combustion cycle, a flame front travels smoothly from the at different t h e r m a l stages, with the first stage (around
point of ignition at the spark plug outweird toward the cylin- 400°C) commencing with the addition of molecular oxygen to
der walls. While this is occurring, the "end gas," or u n b u m e d alkyl radicals. The internal transfer of hydrogen atoms within
fuel/air mixture ahead of the flame front is heated and com- the new radical forms an unsaturated, oxygen-containing
pressed. If the end gases ignite before the flame front arrives, species following this stage. These new species are suscepti-
the resulting sudden pressure wave reverberates across the ble to chain branching involving the HO2 radical during the
combustion chamber, causing an audible engine knock. This intermediate temperature stage (400-600°C), mainly through
adversely affects output power and dramatically increases the production of OH radicals. Above 600°C, the most impor-
heat transfer to the piston and other combustion chamber tant reaction that produces chain branching is the reaction of
surfaces. While this can cause damage on its own if severe one hydrogen atom radical with molecular oxygen to form O
enough, knock induced preignition can cause rapid catas- and OH radicals.
trophic engine failure. This tends to be a runaway condition. ' Common antiknock additives work by interfering at differ-
Once started, it gets progressively worse until eventual en- ent points in the preflame reactions. The alkyl lead antiknock
gine failure, unless the throttle/load is cut quickly, as failure compounds interfere with hydrocarbon chain branching in
can occur in less than a few minutes. High heat transfer dur- the intermediate temperature range, where HO2 is the most
ing heavy knock can cause deposits or sharp edges (for ex- important radical species. Alkyl lead oxide, either as solid
ample combustion chamber deposit or exposed thread of a particles, or in the gas phase, reacts with HO2 and removes
spark plug) to overheat. This can act as a "glow plug" type ig- it from the available radical pool. This reduces the major
nition source, causing ignition of the charge before the spark chain branching reaction sequence that results in undesir-
on the next combustion stroke "preignition." This leads to ex- able, easily auto-ignitable hydrocarbons [31,32]. Oxygenates
cessively high combustion chamber temperature and pres- retard the progress of the low t e m p e r a t u r e or cool-flame
sure from combustion closer to TDC, and rapidly increasing reactions, consuming radical species, particularly OH radi-
knock intensity. Initial stages of knock damage look like pit- cals and producing u n s a t u r a t e d hydrocarbons like iso-
ting on the piston top, as if it had been attacked with an ice butene. The iso-butene would, in turn, consume additional
pick or awl. The increased temperature and heat transfer to OH radicals and produce unreactive, resonantly-stabilized
the piston top eventually causes melting of the crown land radicals, such as allyl- and methyl allyl-, as well as stable
down to the rings. The final stage is either catastrophic en- species such as allene, which resist further oxidation [33,34].
gine failure from thrown connecting rods (metal softening
near the piston wrist pin, causing the piston to separate from Anti-knock Ratings of Fuels
the connecting rod), or engine seizure (expansion of the pis-
ton, excessive friction heat, and loss of lubrication). Either The Anti Knock Index (AKI) is the average of the Research
Octane Number (RON, D 2699) and Motor Octane Number
(MON, D 2700), sometimes expressed as (RON+MON)/2 or and cylinder casting can be adjusted relative to the
(R+M)/2. The on-line Comparitor Engine method D2885 de- crankshaft using a crank handle to obtain the desired com-
termines octane numbers that are equivalent to "lab" RON pression ratio. The engines have a special four-bowl carbure-
and MON values, and can be used for blend certification and tor that permits individual bowl air-fuel-ratio adjustment
release. The RON and MON methods use two primary refer- and provides rapid switching between reference fuels and
ence fuels, n-heptane and 224 trimethyl pentcine, assigned oc- samples. A magnetorestrictive detonation sensor in the com-
tane numbers of 0 and 100, respectively. The knocking inten- bustion chamber now measures the rapid changes in com-
sity of the test fuel is c o m p a r e d to that of reference fuel bustion chamber pressure caused by knock, and the ampli-
blends. The volume percent of iso-octane in the blend that fied signal is measured on a "knockmeter" with a 0-100 scale.
gives the same knock intensity as the test fuel is taken as be- Only one company currently manufactures these engines, the
ing the octane n u m b e r of the test fuel (See History of Octane Waukesha Engine Division of Dresser Industries, Waukesha,
Rating). Wisconsin, 53186.
The same standard engine is used for both tests, but r u n at Two related methods can be used to obtain the octane
different test conditions. The conditions of the MON engine n u m b e r of the test fuel, the bracketing procedure or the
tend to simulate hot, highway driving, whereas the RON test "compression ratio" procedure. For the bracketing method,
is more like heavy acceleration from a traffic light. The dif- the engine compression ratio is adjusted to produce a m i d
ference between the RON a n d MON for a given gasoline range knock intensity of about 50 on the knockmeter, with
("sensitivity") depends upon the composition of the blend. the air-fuel ratio adjusted on the carburetor bowl to obtain
The RON and MON of parafins and isoparafins is almost the m a x i m u m knock. At least two blends of primary reference fu-
same, so high isoparafins (low aromatic, low olefin) blends els are made, one that is one octane n u m b e r above the ex-
tend to have low sensitivities, sometimes below four num- pected rating, and another that is one octane number below
bers. Aromatics have intermediate sensitivities and olefins the expected rating. The PRF blends are placed in different
have the highest sensitivity, so gasolines that have high cat- bowls with their air-fuel ratios adjusted for maximum knock
alytically cracked content (high olefins) will have high sensi- during rating. The higher-octane reference fuel should pro-
tivity (RON-MON), as high as about 14. duce a reading of around 30-40, and the lower reference fuel
ASTM D 4814 recommends a m i n i m u m MON of 82 for Reg- should produce a reading of 60-70. The actual fuel rating is
ular grade gasoline heavy-duty engine applications, but uses interpolated from the knockmeter readings of the sample and
AKI for all other recommended uses. Two different 87 AKI the two PRFs.
gasolines with extreme compositions could have a RON/MON For the CR procedure, a calibration curve is prepared of
of 94/80 or 89/85. On average they would give similar perfor- knock intensity versus compression ratio for a PRF blend
m a n c e over a range of engine operating conditions, but for that has a n octane n u m b e r within prescribed limits from the
certain applications one may be preferred over the other. For sample. The octane n u m b e r of the sample is the octane num-
a n engine operating under more MON like conditions, the ber of the single PRF used to calibrate the engine, corrected
87/85 blend will provide knock free operation at more severe for barometric pressure and difference in knock intensity us-
conditions than the 97/80 blend. In the late 1960s select Eu- ing the calibration curve. The D2885 "comparator" method
ropean automakers experienced catastrophic engine failures uses the CR procedure, but using a Standard Reference Fuel
on high speed Autobahn runs, even though the Research Oc- (SRF) instead of a PRF (see D 2885).
tane of the fuel was within specification. They discovered that
either the MON or the Sensitivity (the numerical difference Motor Octane Rating ASTM D 2700
between the RON and MON) also had to be specified to ensure The conditions of the Motor method represent severe, sus-
adequate performance under severe high speed Autobahn tained high engine speed, high load (but not wide-open throt-
condition. Similarly, many marine and utility engines run at tle) driving. For most hydrocarbon-fuels, including those
high load and WOT, and are susceptible to knock damage with either alkyl lead or oxygenates, the Motor Octane Num-
from too low a MON. In the late 1970s and early 1980s several ber (MON) will be lower than the Research Octeine Number
automotive and marine OEMs promoted development of an (RON).
even more severe octane method, due to concerns that the
high octane contribution from alcohol in the MON test did not Research Octane Rating ASTM D 2699
appear under their most severe wide open throttle engine op- The research m e t h o d settings represent typical high load
erating conditions. However, this was not pursued, Eind some (throttle opening) and low to medium engine speeds result-
OEMs recommended higher octane 89-91 AKI grades or no ing in low inlet mixture temperatures and moderate loads on
oxygenates or methanol for severe marine, snowmobile, out- the engine. See Table 5 for test conditions
board, or utility engine applications.
On-Line Analyzer Octane Rating ASTM D 2885
Procedure For Anti-Knock Rating Fuels On-line octane rating analyzers used in refineries are de-
Automotive octane ratings are determined in a standardized scribed in ASTM D 2885, taking a continuously flowing slip
single-cylinder engine with a variable compression ratio (CR stream of gasoline from current production, and measuring
4:1 to 18:1), operated under standard conditions (Table 4) the RON and MON continuously. The same engines and con-
Cooperative Fuels Research (CFR) engine. The cylinder bore ditions are used, so consequently results Eire equivalent to the
is 82.5 m m ; the stroke is 114.3 m m , giving a displacement of laboratory MON or RON procedure.
612 cm^. The piston has four compression rings, and one oil- Instead of "bracketing" the test fuel with primary reference
control ring. The intake valve is shrouded. The single head fuels, D 2885 uses "Standard Reference Fuels," commonly
called "protos" or "gold protos" that are production gasoline using a series of progressively lower octane fuels. Three sets
that have been rated by about 20 different laboratories, and of fuels are used: the primary reference fuels (PRF), and two
assigned the average value determined by the group. The SRF full boiling range fuels with high and low sensitivity (RON-
is required to be close in octane to the test fuels, so that the MON). In Europe, delta RON (100°C) fuels are also used. The
difference in octane n u m b e r can be derived from the differ- lowest octane fuel that provides knock free acceleration is the
ence in knock intensity between the SRF and the test fuel. ONR of the vehicle under the conditions of the test. Results
Standard Reference Fuels are developed through coopera- are then used to predict the performance of typical commer-
tive exchange programs, usuedly administered in association cial gasolines.
with an accredited Standcirds Writing Organization. Exam- The original "Uniontown" road octane rating procedure
ples in North America are National Exchange Group under used in development of the original MON test (see History
the auspices of ASTM, the Canadian Cooperative Exchange of Octane Ratings) has been replaced by a procedure devel-
under the auspices of the CGSB, and the Rocky Mountain Ex- oped by the Coordinating Research Council (CRC). In the
change, representing refiners in high altitude areas (now as- CRC E-15 procedure, the vehicle is tested under a proscribed
sociated with the NEG). set of environmental conditions and loads. The procedure
"trained raters" to detect audible knock during a series of
Octane Distribution Throughout Fuel Boiling Range part throttle accelerations using decreasing octane fuels un-
Severe knock can be experienced in some engines if octane til trace knock is detected. Three different series of gasolines
level is not distributed throughout the boiling range of a fuel, were used to establish the RON versus MON response of each
for example a low octane front end with a high octEine back vehicle, a zero sensitivity primary reference fuel, and two full
end. This "octane distribution" is most critical during changes boiling range fuels with low and high Severity (difference
in mixture flow in manifolds, such as sudden full throttle ac- between RON a n d MON). These three fuels represent the
celeration at low speed and high load. Under these conditions, extremes of RON and MON blending. By testing a large
manifold pressure drops suddenly at low airflow. The fuel can n u m b e r of cars, it is possible to statistically predict what per-
segregate by boiling range in the manifold, with the very centage of the on-road car population would be "satisfied"
volatile fraction reaching the combustion chamber first and, (no knock) with different RON/MON fuel blends. It is com-
if that fraction is deficient in octane, then knock will occur un- m o n to apply a correction factor or offset between technical
til the less volatile, higher-octane liquid fractions eirrive. raters and typical drivers, who have a m u c h lower threshold
Historically, small displacement engines tend to be the for detecting knock and perceiving it to be a problem.
most affected, as they experience the largest changes in man- Historically, operating conditions that require maximum
ifold conditions during n o r m a l u r b a n driving. Large dis- octcine are not consistent, but most often occur during fuU-
placement engines equipped with "hot spot" manifolds, in- throtde acceleration from low starting speeds using the high-
take mEinifold runners, etc., tended to be the least affected. est gear available. These can be difficult to reproduce on a
Most urbcin driving was at relatively low throttle range and at chassis dynamometer, so a distinction was always made be-
high manifold vacuum that tended to moderate these effects. tween an on-road and a dyno result. M o d e m dynomometers
The delta RON ratings Eire not currently used in the U.S. with better simulation of inertial, road, and wind loads and
M o d e m engines with short inlet meinifolds and Port Fuel engine cooling, produce equivalent results. A benefit is that
Injection are usually less sensitive to fuel octane distribution. the conditions can be more tightly controlled, so results do
However, the addition of nonhydrocarbon components into not require corrections for temperature, pressure, and hu-
reformulated gasoline of different volatility may affect sensi- midity differences from the standard conditions at the time
tive engines. of the test.
Leaded fuel octane distribution was good, as the tetram- Historical engine management systems used a system of
ethyl alkyl lead and tetraethyl alkyl lead octane volatility pro- centrifugal "bob weights" in the distributor for speirk advance
files were well characterized, and TML-TEL ratio could be and a "vacuum break" to delay spark advance/retard at low
adjusted to provide distribution of octane throughout the speed, high load. With only two parameters to change in
boiling range. Nonleaded gasoline must be properly blended addition to the basic spark timing of the engine, one or two
without using TML to obtain acceptable results. areas of high knock anywhere o n the speed/load range
The "Delta RON" test was developed to measure the differ- resulted in conservative timing at other conditions. If the crit-
ence in octane between the front £ind back "half" of the gaso- ical area was under MON like conditions, then the car would
line. The fuel is distilled to a specified temperature, which is be found to respond most to MON. M o d e m engine manage-
usually 100°C. Both the parent fuel and the distillate fraction ment systems can adjust the octane requirement by modify-
are t h e n rated using the Research Octane m e t h o d . The ing engine conditions that will vary the octane n u m b e r
difference between these is the delta RON (100°C), usually requirment, so adaptive learning systems are preconditioned
just called the delta RON. prior to testing.
During the 1990s, there have been some concerns in Eu- The m a x i m u m ONR is of most interest, as that usually
rope about the high sensitivity of some commercially avail- defines the r e c o m m e n d e d fuel. However, it is recognized
able nonleaded fuels. that trained raters are more sensitive to engine knock than
typical drivers, and that the general populace will have a
Octane Number Requirement (ONR) of Vehicles higher threshold for both detecting knock and perceiving it
The actual octane requirement of a vehicle is called the Oc- as being severe. As a result, it is common to apply a correc-
tane N u m b e r Requirement (ONR). It is determined by moni- tion factor or offset from technical ratings to predict con-
toring for the onset of knock while accelerating the vehicle sumer satisfaction.
76 MANUAL 3 7 ; FUELS AND LUBRICANTS HANDBOOK
ONR—Engine Design Parameters and constant volume of the working fluid (for most pur-
poses air is the working fluid, and is treated as an ideal gas).
The design of the engine and vehicle significantly affect the
Thermal efficiency reaches a maximum at a compression
fuel octane r e q u i r e m e n t for b o t h RON a n d MON. In the
ratio of about 17:1 for gasoline fuels in a SI engine, and
1930s and 40s, most vehicles would have been sensitive to the
fuel-injected engines with carefully designed mixture charge
Research Octane of the fuel, almost regardless of the Motor
concentrations and intake/combustion chamber design has
Octane. In North America, this tended to change after WWI
reached 12:1 on retail fuels with 98-100 RON. Continued
with widespread adoption of automatic transmissions, which
advances in engine technology have allowed gradual in-
made engines operate under more MON like conditions more
crease in compression ratio without increasing ONR from
of the time. For many years, the CRC did octane surveys of
87 AKI. This has been used to either increase fuel efficiency
each new model year of cars, and the results were widely used
in economy cars or to have higher power engines at the
to estimate the on-road octane requirement, and the best
same fuel efficiency in larger cars. These engines have sub-
RON/MON combinations to satisfy the most cars (on aver-
stantially higher compression ratio t h a n the "historical"
age) with the lowest octane blends. Different weightings were
curve established with the CRC engine (see History of Oc-
p u t on RON a n d MON, for example (R+3M)/4 to better
tane Rating].
match the measured octane n u m b e r to the average octane re-
quirement of the on-road car population.
ONR—The Air-Fuel Ratio
The advent of electronic adaptive engine controls and use
of knock sensors tends to have a more consistent spark and Stoichiometric combustion (air-fuel ratio = 14.7:1 for a typ-
fuel m a p over the entire engine speed and load range, in- ical non-oxygenated gasoline) is neither maximum power,
cluding transients like transmission shift points. This tends which occurs around air-fuel 12-13:1 (Rich), nor maximum
to m a k e adaptive feedback control cars equally likely to thermal efficiency, w h i c h occurs a r o u n d air-fuel 16-18:1
knock under any condition and equally responsive to RON (Lean). Air-fuel ratio can also be used as a knock control
and MON. This tends to make the AKI a good predictor of strategy, although at a severe emissions debit for a three-way
field performance in recent model cars. catalyst emission system. Enrichment is also used during full
Retarding spark timing for the purpose of knock reduction throttle operation to reduce knocking while providing better
causes loss of power a n d efficiency that can be incorporated power and driveability. Recent changes in U.S. emissions
into knock rating procedures, for example by measuring in- testing cycles will promote more control of wide-open throt-
crease in acceleration times with progressively lower octane tle mixture settings. Enrichment has also been used as a n
rating fuels. "emergency" strategy in turbocharged cars, as an alternative
to suddenly dropping turbo boost (power) to prevent run-
away knock during an emergency or passing maneuver. On
ONR—Manifold Air Temperature and Pressure
average, there is an increase or decrease in ONR of about 2
Increasing the air-fuel charge temperature and pressure in- AKI for each unit's increase (leaning) or decrease (enriching)
creases the peak cylinder temperature and pressure, and thus of the air-fuel ratio, respectively. This response varies con-
the tendency to knock. M o d e m engines generally pre-heat in- siderably between engines and at different RPMs. In the CFR
take air to a controlled temperature above ambient. Throt- octane n u m b e r tests, the carburetor float bowl level is ad-
tling the air to a lower manifold pressure results in a much justed to change the air-fuel ratio. The air-fuel ratio that pro-
lower peak cylinder pressure/temperature, and a lesser ten- duces the maximum knock intensity for that fuel is then used
dency to knock. Fuel evaporation and PVT expansion across to determine the octane n u m b e r of that fuel.
the throttle plate cool the intake mixture, making it slightly
sensitive to the engine temperature, which adds heat in the ONR—Engine Spark Timing
manifold and during the compression stroke. Increasing the
coolant temperature in a CFR engine by about 10°C increases Advancing the spark timing dramatically increases the
the octane n u m b e r r e q u i r e m e n t by about 2 AKI, so the tendency to knock. The tendency to knock increases as spark
coolant temperature must be tightly controlled for octane advance is increased. For an engine with recommended 6°
rating. Increasing the intake air (RON) or intake mixture BTDC (Before Top Dead Center) timing and 93 RON fuel,
(MON) temperature increases the octane requirement (in- retarding the spark 4° lowers the octane requirement to 91,
creases the severity of the test). This is used to advantage in whereas advancing it 8° requires 96 octane fuel. This
the RON and MON tests to "temperature tune" engines in dif- response varies considerably between engines and is most
ferent laboratories using Toluene Standardization Fuels pronounced at high RPM for any given engine (mostly an
(TSF). This ensures that the test severity of different engines artifact of delay time being measured by crank angle rotation
is a relative constant over a broad range of fuel compositions, rate).
since PRF are low aromatic, and TSF are high aromatic. In older engines, the basic timing was set by rotating the
distributor until the #1 cylinder spark was set at a prescribed
crank angle. Spark was advanced for RPM with a centrifugal
ONR—Compression Ratio "bob weight" on the distributor shaft, and retarded for load
An increase in Compression Ratio will require an increase in with a manifold vacuum diaphragm actuator acting against
fuel octane for the same engine design. Increasing compres- the spring loaded distributor plate. The timing of the spark is
sion ratio increases the theoretical thermodynamic efficiency advanced sufficiently to ensure that the fuel-air mixture
of an engine according to the standard equation b u m s in such a way that maximum pressure of the burning
Efficiency = 1 — ((l/compression ratio)^(gamma—1)), charge is about 15-20° after TDC. Heavy knock will tend to
where G a m m a = ratio of specific heats at constant pressure occur if peak temperature/pressure occurs earlier than this
point early in the power stroke, involving a larger quantity of In the United States and Canada, a mixture of Federal,
end gases igniting at high pressures (gas densities). Light State, and Provincial Government legislation and attendant
knock usually occurs later in the power stroke, involving less regulations proscribes gasoline requirements. Some states
end gas and a lower cylinder temperature and pressure (gas and associations of states may also specify regional gasoline
densities). A good analogy is that larger waves in higher den- properties to achieve regional environmental objectives
sity mercury inherently carry more energy and destructive that are within their jurisdiction. These regulations may
power than smaller waves in lower density water. reference accredited ASTM consensus standards, with or
Knock sensors equipped engine management systems re- without modifications. In some cases, ASTM sampling
tard ignition timing if knock is detected. If very low octane fu- and test methods are reproduced in regulations. This can
els are used, several octane numbers below the vehicle's ONR cause update problems, such as use of the wrong proce-
at the time, the ECM will have to retard spark timing so much dures for regulatory purposes, when either party changes
to eliminate the knock that both performance and fuel econ- procedures.
omy will significantly decrease. Maximum efficiency occurs The U.S. gasoline specifications and test methods are listed
when the engine is at incipient knock for the fuel being used in several readily available publications, including the
at the time, so trace or incipient knock is sometimes referred Federal Register, and the current Annual Book of ASTM
to as "the sound of economy." Standards.
Unlike fuel maps, knock sensor data is generally not used
to advance timing, only to retard it as an engine protection
strategy. The ECM will retard timing ("knock back spark") ASTM D 4814, Specification for Automotive
quickly until knock sensor indicates that it has stopped. It Spark-Ignition Engine Fuel
will then slowly advance the timing toward baseline, until
The scope of the standard states that "This specification
trace knock re-appears, and store that value in the memory
guides in establishing requirements of automotive fuels
map. Strategies to actively advance timing are more risky,
for ground vehicles equipped with spark-ignition engines."
since a failed knock sensor could cause the ECM to advance
It was first published as ASTM D 439 in 1937, and signifi-
timing into sustained heavy knock and engine damage. Some
cantly revised to include oxygenates including "gasohol"
systems are capable of "testing" the knock sensor by advanc-
(10% ethanol) and other alcohol blends that had EPA waivers
ing timing on individual cylinder firings to create a single or
(see 1970 EPA Clean Air Act). Several test methods were
small number of knocking cycles, to see if the knock sensor is
developed or modified for use with oxygenated fuels, such
still functioning. A "dead" knock sensor can be particularly
as Dry Reid Vapor Pressure, Tv/1, and new methods added
damaging on a turbocharged car, or a "premium required"
such as water tolerance and phase separation temperature
car, if run on too low an octane fuel.
requirements.
ONR—Effect of Engine Deposits It is a complex specification with many details that are be-
yond the scope of this chapter. However, in all cases, the re-
Typical new engines using nonleaded gasoline have an ONR quirements and the test method for each requirement fall
of about 4-6 AKI lower than the same engine at 25 000 km, into one of two categories, those that measure the properties
although some may experience 6-9 ONI, and some engines or quality at the time of sampling, and those that predict
can experience ONI of over 12 octane, depending upon driv- some future condition or performance. For example, a "Clear
ing cycle, engine, and fuel/lube. This Octane Requirement In- and Bright" procedure evaluates whether the fuel is "suitable
crease (ORI) is attributed to the formation of a mixture of or- for use" at the time of custody transfer or sale to end con-
ganic and inorganic deposits resulting from both the fuel and sumer. An oxidation stability result, on the other hand, is a
the lubricant. They build up and tend to reach an equilibrium "predictive" test, intended to predict if the fuel will be ac-
quantity in about 10-15 000 miles. However, differences in ceptable in the future, after some time in storage prior to sale
driving cycles can result in different equilibrium levels, with or use. Many tests are "rig" tests that rate relative perfor-
sustained hot engine operation tending toward the low end, mance of the gasoline to provide a reasonable estimate of
and cooler "stop and go" driving cycles tending toward the how the gasoline will perform in actual use. For example, D
high end. 130 (Test Method for Detection of Copper Corrosion from
Combustion chamber deposits produce the ORI by several Petroleum Products by the Copper Strip Tarnish Test) mea-
mechanisms: sures the relative degree of corrosivity under a proscribed set
• Reducing the combustion chamber volume, effectively of conditions. It uses a static coupon of a specified copper al-
increasing the compression ratio loy, prepared in a specified way, exposed to the product for a
• Reducing wall thermal conductivity, increasing the specified period of time at a specified temperature. In the
combustion chamber temperatures vast majority of cases, a "pass" on the D 130 test means that
• Catalyzing undesirable pre-flame reactions that produce the fuel will not cause significant corrosion to any copper
end gases with low auto-ignition temperatures. alloy parts exposed in the fuel system, and will be widely
acceptable to a broad range of vehicle fuel systems. However,
if the in-use conditions for any fuel system component
are more severe than the D 130 test conditions, then damage
GASOLINE SPECIFICATIONS. could occur even with a fuel that passes D 130. This could
happen if the component is heated hotter than test con-
ASTM or CGSB gasoline specifications are not legal require- ditions, or the part is in a "rubbing or rolling" tjfpe of ser-
ments unless they are required (referenced) in a regulation by vice that continually removes the protective oxide/sulfide
a government authority having jurisdiction.
layer, or the part metallurgy is more easily corroded than the Volatility
D 130 copper strip. Volatility is measured by the ASTM D 86 distillation, the
ASTM has two publications that are highly recommended Vapor/Liquid ratio Temperature (Tv/1 = 20), and one of
to those not familiar with details or intent of the test methods several vapor pressure test methods, most commonly ASTM
or specification. ASTM Manual on Significance of Tests for D 5191, which is used for regulatory reporting. All of the
Petroleum Products [35] and Guide to ASTM Test Methods for volatility measurements are somewhat related thermody-
the Analysis of Petroleum Products and Lubricants [36] are namically, being various combinations of vapor pressure
both instructive on reasons for the test and explanation of and cumulative boiling volumes. However the relationships
what and how the test is intended to measure. IdecJly, per- are not exact, because the standard tests are not ideal
formance or "rig" tests Eire representative of actual in-use ve- thermodynamic processes. Some examples of various ASTM
hicle requirements. Hopefully these two goals always coin- D 86 distillation effects are given in Figs. 1-3. An illustra-
cide, but it is always possible to "pass the test and fail the tion of approximate vapor pressure and volatility relation-
field" as any experienced fuels chemist will agree. Passing all ships is given in Fig. 4, comparing typical fuels with pure
the tests does not guarantee that the fuel is "suitable for use" hydrocarbons.
in all cases, especially in cases such as unusual contamina-
tion, or new car technology for which the existing standard Distillation, Evaporation Temperatures, and Driveability In-
tests don't consider, or when in-use conditions are more se- dex—The distillation volatility of a finished gasoline can be
vere than in the standard test method. Specifications Emd test expressed in several ways. One set uses the temperature at
methods are in a continual state of being updated as technol- fixed distillation points, such as the TIO, T50, and T90, re-
ogy continually advances. lated indices such as Volume Average Boiling Point (VABP)
or ASTM Driveability Index (DI)
Some gasoline requirements pertain to all volatility classes
(see Table 5). Driveability Index = DI = 1.5 * TIO + 3 * T50 + 1.0 * T90
Anti-knock Index (AKI) Maximum DI limits are specified in ASTM D 4814 for each
Anti-knock Index (AKI), also k n o w n as (RON+MON)/2, Volatility Class, ranging from 569-597°C, or 1200-1250°F.
"Pump Octane," ((R+M)/2), or "Road Octane" is the average Note that the conversion of DI from Centigrade to Farenheit
of the Research Octane Number and Motor Octane Number. units is DI(F) = DI(C) * 9/5 + 176, where 176 is the sum of
Dispensing p u m p "posting" requirements are based on AKI. the coefficients (1.5 + 3.0 -f- 1.0) * 32. Many companies use
The only accurate m e t h o d of m e a s u r i n g knock is to use volume percent evaporated (%Evap, or D-l-L) at fixed tem-
standard knock rating engines in ASTM D 2699/D 2700 or D peratures, which have an advantage over Txx controls, be-
2885, although several "field test m e t h o d s " are used for cause they blend more linecirly, and are more easily adapted
screening purposes. The ASTM gasoline standard does not to linear programming (LP) optimization controls. Both are
mandate octane levels, but lists levels appropriate for differ- in c o m m o n use at the operational level, because ASTM re-
ent applications. While limits are not specified, changes in quires Txx type controls while the complex model requires
engine requirements according to season and location are E200 a n d E300. The complex model spreadsheet has a con-
discussed. Fuels with an AKI of 87, 89, 91 (nonleaded), and version from Txx to Exxx built into the model.
88 (leaded) are listed as typical for the U.S. at sea level. Vapor Pressure and Tvfl—ÂSTM vapor pressure specifications
However, higher altitudes may specify lower octane num- are based on VP measured under standard conditions of 4:1
bers. Altitude derating of octane is m u c h less for nonleaded vapor liquid ratio at 100°F and Tv/1 20 to control gasoline
versus leaded gasoline because Tier 0/1 cars use manifold
front-end volatility. The Tv/120 is the temperature at which 20
absolute pressure/temperature (MAP/MAT) sensors to calcu-
volumes of vapor cire formed from one volume of the original
late air density, or absolute mass air flow sensors to control
liquid, measured by ASTM D 2533 or D 5188. The intent is to
air fuel ratio.
produce an isobaric flash prediction, something that is well
within the capabilities of m o d e m thermodynamic equation
of state (EOS) calculations.
TABLE 5—Detailed requirements for all volatility classes.
A Tv/120 corresponds to about 10% of the gasoline vapor-
Lead Content, max, g/L ized under conditions of the test (a fully vaporized gasoline
(g/U.S. gal)
Non leaded 0.013 (0.05)
would have a V/L of about 220-280 depending upon the
Leaded 1.1 (4.2) blend). As a result, there is a good correlation between mea-
Copper Strip Corrosion, No. 1 sured Tv/1 and linear sums of the VP a n d TIO, T20 u p to
max T50, so it is much more common to calculate Tv/1 than to
Solvent-Washed Gum measure it. Some companies use an index based on VP emd
Content, mg/100 mL,
max
%Evap at lower temperatures, historically 70°C (158°F).
Sulfur, max, mass% These are often called Vapor Lock Indices or "Hot Fuel
Non leaded 0.10 Handling," a reference to the origined purpose of these spec-
Leaded 0.15 ifications. A v/1 of 20 was originally chosen because, on av-
Oxidation Stability, 240 erage, a carbureted engine diaphragm type fuel p u m p could
minimum, minutes
Water Tolerance Water tolerance limits in terms of
handle about 20 volumes of vapor along with the 0.9 volume
maximum temperature for of the remaining liquid (Tv/1 = 20). Any higher temperature
phase separation are given in (more vapor) would cause the p u m p to become "vapor-
Table 13 of the specification. locked," and not be able to satisfy engine fuel dememd, cans-
-Base Max Summer Dl Msx Dl High Mid-fill -High Volatility
250
JMax Final Boiling Point (FBP) = 225 C
200
Max Summer T90 = 190 J
150-
u
p
I
100
Typical Summer RUL

Volatility Dl = 1150 .
IMin / Max Summer

T50 Range = 77-121
50 I
Higliest Summer
Volatility T50 = 70
Max Summer T10 = 70

li
10 20 30 40 50 60 70 80 90 100
Volume % Evaporated
FIG. 1—ASTM D 86 distillation and driveability index.
ing stalls or rough engine operation. The temperature when but are usually due to other mechanical factors and not
this occurs is called the Vapor Lock Temperature. The high ambient temperature. For example, a worn out fuel
ASTM specification has vapor-lock protection temperatures pump may not put out enough pressure to prevent vapor
based on a regional database of ambient temperature and formation in the fuel rail during a hot shutdown. The vehi-
elevation (barometric pressure). cle could experience a hard hot starting or no-start condi-
Fuel injected vehicles generally have submerged in-tank tion, because much lower mass vapor flow through the in-
fuel pumps, and operate at much higher liquid fuel line jector would cause an over lean air-fuel ratio. Similarly, a
(fuel rail) pressures, so eire much less prone to vapor lock partially blocked primary filter ("pick-up sock") can cause
problems. However, certain forms of vapor lock can occur. vapor lock on the suction side of the submerged pump at
-Ethanol MTBE Base
250
200 -
/
/
150
100
50
Significant decrease in T50 caused by
azeotrope effect of ethanol
0 10 20 30 40 50 60 70 80 90 100
Volume % Evaporated
FIG. 2—ASTM D 86 distlllation-ethanol and MTBE.
high temperatures. Routing fuel lines in areas that have cation for the finished gasoline. The vapor pressure is con-
high shutdown heat soak temperatures can also cause a hot trolled below specification maximums by limiting the
restart problem. amount of butane in winter and northern summer grades,
and butane plus some pentanes in the lowest vapor pressure
Gasoline and Gasohol Blending summer grades (below about 8 psi VP.)
The distillation volatility is controlled within specification Ethanol at 10 vol% (gasohol) increases the measured VP at
limits by varying the relative ratios of blend components to 100°F by about 0.8 in a high aromatic gasoline to about 1.2
make a finished gasoline. These range from butane (normal psi in a low aromatic gasoline. Ethanol is more soluble in
boiling point 0°C) to the highest boiling components with Fi- aromatics than saturates so the vapor pressure increase is
nal Boiling Points slightly higher than the 225°C FBP specifi- slightly influenced by aromatic content of the base fuel.
- A S T M D 8 6 — P R EOS
250 ^
JThcmiodynaniic Bubble Point TypiCcil inoroase in ASTM DBG final

di&hllalioM tuiiippidluic due to higher
200 - I Sciniplcs of this gasoline will not flash oi boil .it tlian one theoretical plate and icflux
toinpcratuicR bolow the bubble point, even if it is due to he.it lush at higci toinpci.ituics
at .1 tcnipciaturp iiighcr than thn ASTM D86 Initial
' Boiling Point
O 150
^ rhcoieticnl Single pl.itc distilkition cuivc
ffl 100
'Typical liiiti.il volume loss .iiid "hool«" on start of ASTM D8b

distilljtiuii b.iuscd by cumbin.ition of.
50
- gipatiii than one theoictii..)! pl.itp distillation finin licitiiig of

AS1MD86lnili.ii glassw.irc .iiid reilux duiing starl of thn distilLition
Boiling Point iJBP) - nun condensing ,iir HC v.ipor mixturi> at st.iit of test
10 20 30 40 50 60 70 80 90 100
Volume % Evaporated
FIG. 3—ASTM D 86 versus Peng-Robinson Equation of State.
100000
ASTM V.ipur Pri<s-.iiii- ri-iii^ji'i.iliiip

10000
1000
..•-•
Ntiiiii.il riu'lini) Piiiiil rii-.<.-iir>-
100 £
10 £
0.
CJ
A|iuiuxiiii.1li R.m.ii-••! V.i|iiii l>ii-.-iiii'

'C5 •il -W" i" Fl.i .'1 ''•HI.; T.>ii,|.i 1...SII11
CM' C6 £•7 Cq CIO
- 0.1
-0.01
-100 -80 -50 100 200 300
Temperature ( C )
FIG. 4—Vapor pressure relationships for fuels. Log P versus 1/T.

Several jurisdictions allow a nominal 1 psi waiver to accom- The D 130 test is a "static" coupon test, and may overpre-
modate "splash bending" of ethanol with a base gasoline. dict durability for more easily corroded alloys such as silver,
EPA has issued a waiver that does not require conventional or for rubbing, rolling, or heated soft alloy fuel system com-
gasoline with 9-10% ethanol to meet the required specifi- ponents. Field problems have been experienced with some
cations between 1 May and 15 September (see Nonleaded copper fuel p u m p commutators, silver alloy fuel sender unit
Gasoline). resister arrays and silver plated crankcase bearing cages with
gasoline that passes D 130. In general, silver alloys should not
ASTM Volatility Class Specifications be used in gasoline fuel systems without provisions for pro-
ASTM D 4814 gasoline specification defines six volatility tection from sulfiding. Copper alloy components that are ex-
classes of increasing vapor pressure, Tv/1 and Driveability posed to heat or rolling/rubbing action that removes the pro-
Index (DI). The TIO, T50 min/max and T90, FBP max limits tective oxide layer should be tested for long-term durability
define the allowable range of individual parameters within with a gasoline containing traces of corrosive sulfur (H2S,
each volatility class. VP and DI are generally the key blend- elemental sulfur).
ing p a r a m e t e r s for b o t h regulatory and specification
compliance. Maximum Sulfur Content
Insufficient volatility may result in difficult starting in cold Current ASTM and CGSB standards allow 0.10% mass maxi-
weather, poor cold start and warm-up driveability, engine m u m sulfur content for nonleaded gasoline, but lower levels
deposits and crankcase oil dilution, and increased tailpipe are required by various sulfur regulations (California or
emissions. Excessive front-end volatility can produce poor Canadian Sulfur in Gasoline regulation). Sulfur is oxidized to
fuel economy, poor hot driveability in fuel injected engines, SO2 over the catalyst, so essentially competes for reactive
vapor lock a n d c a r b u r e t o r icing in older engines, and sites that could otherwise be effective for HC, CO or NOx con-
increased r u n n i n g loss and evaporative emissions. The version. This appears as a temporary decrease in catalyst ac-
higher boiling fractions of the gasoline have significant tivity at high fuel sulfur levels, and leads to the requirement
effects on the emission levels of undesirable hydrocarbons for ultra low sulfur fuels to attain ultra low emissions.
and aldehydes. A reduction of 40°C in the final boiling point Sulfur can be indirectly limited by RFC composition
will reduce the levels of benzene, butadiene, formaldehyde, controls based on emission models (U.S. EPA complex
and acetaldehyde by 25%, and will reduce HC emissions by model, BC TOx/NOx a n d Canadian CEPA Benzene in
20% [37]. Similar emission effects were found in the auto-oil Gasoline regulation Benzene Emission N u m b e r (BEN) re-
program, and as a result, there are three volatility model pa- quirements. Both Canada and the United States have regula-
rameters in the complex model,VP, E200, E300 (Vapor pres- tions in place that will reduce sulfur to 30 p p m YPA phased
sure, percent evaporated at 200°F and 300°F, respectively) in between 2002 and 2010, coincident with introduction of
that influence predicted evaporative, tailpipe, and toxics low emission Tier 2 vehicles (See "Reformulated Gasoline"
emissions. The E200 and E300 model parameters have the for more details).
least influence of all the model inputs on the predictive model
emissions, and are often set at "worst case" values for the Maximum Phosphorus Content
purpose of blend planning (although actual values must be
used for reporting). The EPA limits phosphorus in all gasoline to 1.3 mg/L P, be-
cause phosphorus is a potent catalyst poison, and this limit
is reflected in the ASTM specification (see alkyl lead
Maximum Alkyl lead Content phasedown section for additional details). Typical levels of
The alkyl lead limits remain to cover fuels for off-road vehi- phosphorus in nonleaded gasoline are undetectable by the
cles. Leaded fuels can contain u p to 0.1 g Pb/usg (equivalent standard test methods.
0.029 g Pb/L low alkyl lead in Canada), but none are made
commercially. Nonleaded gasoline can contain u p to 0.013 g Oxidation Stability
Pb per liter in the U.S. (contamination limit with no deliber- Like all organic material, hydrocarbons are susceptible to air
ate addition) and 0.005 g Pb/L in Canada to protect catalytic oxidation over long periods of time. The peroxides formed
converters. (See sections on alkyl lead phasedown and non- from hydrocarbon oxidation are auto-catalytic, leading
leaded gasoline for more detail). to "runaway" reaction if not controlled. Reaction rates are
generally higher with u n s a t u r a t e d hydrocarbons, and are
Copper Corrosion catalyzed by parts per billion levels of soluble metals such as
Copper, silver, brass, and other "soft metal" alloys are suscep- copper. Motor gasoline may be stored up to six months, or
tible to corrosion from reactive sulfur molecules. The ASTM m o r e . They must not form soluble g u m that collects
D 130 "copper corrosion" test is intended to ensure that fuels at the point of vaporization, or precipitated insoluble g u m
are not corrosive to these trace components under normal use ("varnish"), or form soluble peroxides that will attack
conditions. More severe conditions could require even lower rubber/elastomers in the fuel system.
levels of corrosive sulfur. The total sulfur content is not cor- Antioxidants are added to most gasolines to slow down the
related with D 130 test performance, and in fact, some addi- rate of oxidation and prevent the oxidation from becoming
tives that are effective at mitigating copper corrosion them- autocatalytic, by forming a stable radical oxidation product
selves contain sulfur (see additives). Only the most reactive that does not react further. The antioxidant is sacrificial, and
types of sulfur molecules cause or contribute to D 130 copper is gradually consumed during this process. Once depleted,
corrosion. The copper strip test responds to reactive sulfur, the reactions will become autocatalytic, and the gasoline will
whereas the sulfur content reports the total sulfur content. eventually "break" and form peroxide gums as fast as oxygen
can diffuse into the liquid (mass transfer controlled oxida- additional gum is formed under the relatively mild condi-
tion). Some gasolines also require metal deactivators to mit- tions of the test procedure. It is not predictive of future
igate catalysis from 10-100 p p b traces of copper (most com- quality. It can identify help identify stale "peroxidized" fuels
monly from trace level corrosion of copper and brass alloys in the marketplace; Washed Existent gum is often reported
in contact with the gasoline during manufacture, distribu- to verify that a high unwashed gum is due to the presence
tion, or use). of Deposit Control Additives that contribute to unwashed
Oxidation stability tests generally expose a heated sample gum. A fuel that has both high ( > 1 0 mg/lOOmls) washed
of gasoline to oxygen for a prescribed period of time to ac- and u n w a s h e d g u m are generally considered suspect or
celerate the rate of oxidation and predict on a relative basis unacceptable.
how long the fuel will be stable under more tjîcal condi-
tions. In the ASTM D 525 Oxidation Stability test, the fuel Water Tolerance
sample is heated with oxygen inside a pressure vessel, and the D 6422 Water Tolerance (phase separation) method mea-
time until significant oxygen uptake (pressure drop, "break sures the highest temperature at which phase separation of
point") occurs is a relative measure of stability. The criteria gasoline - alcohol blends occur. It is not applicable to hydro-
are where the pressure drop exceeds 2 psi per 15 min. The au- carbon or ether oxygenated fuels. Water tolerance is particu-
tocatalytic reaction rate increases exponentially, becoming larly critical for gasoline containing alcohol. The separated
mass transfer controlled, and consuming all of the remaining lower phase alcohol-water-hydrocarbon phase settles to the
oxygen in only 15-30 min. ASTM D 4814 requires a m i n i m u m bottom of the tank where the p u m p suctions are, and tends
of 240 min (4 h) breakpoint, which is sufficient for most stor- to get moved down the distribution system and into cars if
age and distribution systems. This may require a higher level not found and removed. The remaining gasoline layer is of-
at the point of manufacture, since the measured oxidation ten off-spec after phase separation due to loss of octane from
stability will decrease over time as the sacrificial anti-oxidant alcohol and aromatics extracted into the alcohol layer. If dis-
is consumed. Other procedures not used in D 4814 are to pensed into a vehicle tank, it will not burn in engines, and so
weigh the oxidative g u m formed after a breakpoint test, it causes immediate stalls, and requires a complete fuel sys-
(commonly termed a "4 hour gum"), or longer term storage tem draining and cleaning. Like water, aqueous alcohol sep-
time tests at milder conditions to better simulate field storage arated phases contribute to corrosion and pickup of rust/dirt,
conditions. etc., and are also associated with accelerated filter plugging.
It is common practice to add sufficient antioxidant to meet Methanol has a low solubility in gasoline and requires a
a 360-600 min oxidation stability at the point of production, cosolvent if used in gasoline blending for that reason. Adding
so that 240 min is obtained at the point of sale. Factory fill methanol to an oxygenated fuel will increase the measured
gasoline generally requires a much-fortified gasoline for this separation temperature while adding ethanol, IPA, or other
purpose, as storage times of automobiles prior to Scile can be low MW alcohols will decrease the measured separation tem-
several months. This is especially true for some specialty fleet perature.
applications, such as police fleets, that may be made in large Water tolerance of gasoline with alcohols is very tempera-
production runs, with the cars stored for six m o n t h s or ture dependent; consequently diverse limits are established
more before going into service. Hydrocarbons air oxidation for the U.S. The limits vary according to location and month.
has been extensively studied, and is well documented in the For Alaska, North of 62 latitude, it changes from — 41°C in
literature. Dec-Jan to 9°C in July, but remains 10°C all year in Hawaii,
since it never gets that cold. This is the same control strategy
Soluble Gum (Unwashed and Solvent Washed "Existent as for s u m m e r t i m e high temperature and Tv/1 or VP, but
Gum") using the daily low t e m p e r a t u r e s versus the daily high
temperatures.
ASTM D 4814 limits unwashed gum to 5 mg/100 mL, and has
no washed (Existent Gum) requirement (used for aviation
gasoline). D 381 measures the amount of fuel soluble oxida- Other Nonspecification Properties
tive gums and nonvolatile additives remaining after evapora-
tion in the air (i.e., total nonvolatile materials in solution). Autoignition Temperature
Solvent washed "Existent Gum" measures the a m o u n t of The autoignition temperature of a fuel or even a single
gums remaining in fuel evaporated u n d e r air and t h e n molecule is not a thermodynamic property. It is the temper-
washed with heptane to remove additives and heavier hydro- ature at which high temperature decomposition products
carbons. Heptane is a poor solvent for highly oxidized, high will spontaneously c o m b u s t without a n external ignition
molecular weight gums. The heptane soluble portion is rela- source. It is heavily dependent on the conditions at the time
tively low molecular weight material that can accumulate at of the test, including such factors as what type and shape of
any point of gasoline vaporization (intake system deposits) container is used, and how long to wait to see if autoignition
and react further to form insoluble gums. The heptane insol- occurs. The conditions can be varied to simulate a specific
uble portion is representative of the more fuel-insoluble gum situation, and it is not intended to reflect engine conditions.
that can contribute to gum/varnish residue problems, for ex- There is a general correlation between the octane n u m b e r
ample filter plugging, sticking carburetor float bowl pintle of a fuel and the auto ignition temperature, because both are
needles where there is no vaporization, as well as intake sys- determined by molecular structure. Long straight chain hy-
tem deposits where there is vaporization. drocarbons produce large amounts of easily auto-ignitable
Washed and unwashed gums measure the amount of gum pre-flame decomposition, and tend to have low auto ignition
formed in the fuel u p to the time of the test, as no significant temperatures and octane numbers. Branchy and aromatic
hydrocarbons are more resistant, and have higher auto igni- the HEL explosive range. This can be estimated from Peng-
tion temperatures and octane numbers. However, correlation Robinson Equation of State calculations, since the LEL will
is not precise enough to be useful, and several lab rig tests occur when the vapor phase concentration of butane/pentane
based on auto ignition temperatures or related "cool flame" hydrocarbons will be in the 1.5-2 vol% range, and the HEL in
or "pre-flame" properties to predict engine octane numbers the 7-8 vol% range. At 14.7 psia barometric pressure, this
have failed to date. Autoignition temperature of gasoline and corresponds to a range of 0.1-0.2 psia and 1.0-1.2 psia hy-
other fuels can be measured by ASTM E 659, Standard Test drocarbon vapor pressure for the LEL and HEL respectively.
Method for Autoignition Temperature of Liquid Chemicals. Using these values, a typical 14.5 VP winter gasoline would
be expected to have an LEL ranging from about —75 to - 6 0 ° F
Heat of Combustion and Adiabatic Flame Temperature and HEL from about —25 to — 15°F, depending upon compo-
See section on Gasoline Energy Content for a discussion of the sition. A t5îcal 7.8 VP s u m m e r gasoline would be expected
gross and net heat of combustion (He). The He of gasoline to have an LEL ranging from about —50F to —35F and an
can be measured by ASTM D 4809, Heat of Combustion of HEL from 5-15°F. Canadian CGSB gasoline standards have a
Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision m i n i m u m VP to provide a wide margin between the HEL and
Method), or estimated by a n u m b e r of ASTM and other cor- the VP at extreme cold temperatures for various times of
relations. year.
The adiabetic flame temperature is the highest tempera- Diluent gases are much more effective at reducing the HEL
ture that combustion gases can attain under standard start- than increasing the LEL for all flammable hydrocarbon gas
ing conditions u n d e r adiabatic (no heat loss) conditions, mixtures. The flammable region disappears with the addition
where all of the energy of combustion goes toward heating of about 30% CO2 or 45% N2, and almost all of this change is
the combustion gases. There are only slight differences in due to reduction in HEL and not increase in LEL hydrocar-
combustion temperatures of blended gasolines, and the ac- bon concentration [38,39]. From this it can be estimated that
tual temperature in the combustion chamber is determined N2 gas containing less than about 10 vol% oxygen is non-
by other factors, such as load, spark timing, and engine de- flammable with hydrocarbon vapors, a "rule of t h u m b " that
sign. The exhaust gas temperature is much below the adia- is often useful for developing procedures for safe handling of
batic flame temperature because m u c h of the energy com- gasoline in nonstandard conditions.
bustion has been extracted as PVT work.
The adiabatic flame temperature can be measured directly Heat Capacity, Thermal Conductivity,
as a peak flame t e m p e r a t u r e (no applicable ASTM test and Heat of Vaporization
m e t h o d ) , or estimated from the carbon/hydrogen ratio, The thermodynamic bulk properties of gasoline are rarely a
stoichiometric formula and heat of combustion, or calcu- concern for automotive gasoline, but are occasionally re-
lated from composition with a suitable thermodynamics cal- quired for the sizing of specialized handling equipment.
culation, or estimated from density correlations (similar to Gasoline has a heat capacity of about 0.5 BTU/lb.F (0.5
the He). cal/gm.C), which is about half that of water. Hydrocarbons
would be considered to be a good insulator in the absence of
Flammability (LEL and HEL) convective flow heat transfer with a thermal conductivity of
The Lower and Higher Explosive limits (LEL, HEL) are the about 0.08 BTU/hr.ft.F near room temperature, about 20%
m i n i m u m and maximum hydrocarbon vapor concentrations that of water (.35 BTU/hr.ft.F). Because they are essentially
that will support combustion. The LEL is related the flash nonpolar, the heat of vaporizations of gasoline hydrocarbons
point of distillate fuels. Below the LEL there is too little hy- are only about 10-20% that of water on an enthalpy per mass
drocarbon fuel to support combustion, while above the HEL basis. Light aliphatics, such as butane, are in the low range,
there is too little air (oxygen) to support combustion. The sto- while branched isoparafins, etc. are in the high range, with
ichiometric mixture lies between the LEL and HEL, and rep- single ring aromatics in mid range. As a result, a fully blended
resents the mixture of complete combustion, maximum adi- gasoline has a heat of vaporization near a midrange of about
abatic flame temperature, and maximum energy release from 15% of water, or about 140 BTU/lb (80 kcal/kg). More de-
combustion of explosion. Distillate fuels are handled below tailed information is available in standard chemistry and en-
their LEL (Flash Point). Gasoline and naptha fuels are nor- gineering handbooks and manuals. There are no standard
mally handled above their HEL. Mixtures of gasoline and dis- ASTM tests for these properties, but they are well docu-
tillate fuels, or fuels with equilibrium vapor pressures that mented in the thermodynamics literature.
place the vapor space in the explosive range are extremely
dangerous. Any ignition source can cause Ein explosion in the Viscosity and Lubricity
vapor space or in fuel lines and vents. Once ignited, a flame The viscosity of gasoline is rarely a concern for automotive
can propagate down any pipe or vent that contains a com- gasoline. It is considered to be a very low viscosity fluid at
bustable mixture. Fuels with vapor spaces in the explosive typical a m b i e n t t e m p e r a t u r e s with a typical viscosity of
range require specialized equipment and procedures for safe about 0.5 cSt at room temperature, which is only slightly
handling (flame arrestors, anti-static provisions, gas inerting, lower than water (0.9 cSt) at the same temperature. Viscosity
etc.). does not change very much with temperature, similar to den-
The higher and lower explosive limits for gasoline are only sity, thermal conductivity, etc. Unlike more viscous lubri-
rarely a concern. The vapor pressure of gasoline keeps it well cants and heavier fuels, inherently low viscosity liquids such
over the HEL most of the time. It is only in extremely cold as gasoline and LPG are not very sensitive to temperature.
weather that a properly formulated winter gasoline can enter For example, a 0.7 cSt liquid would only be expected to de-
crease viscosity to about 0.1 cSt, with an increase of 100° Density, Refractive Index, and Dielectric Constant
centigrade [40]. Lubricity is determined by trace polar Density, Dielectric Constant, and Refractive Index are all
molecule content, b u t is generally very p o o r for gasoline. "bulk properties" of hydroccirbons that depend upon the n u m -
Clean absorbent treated gasoline range hydrocarbons (low ber of atoms, charges, and electrons per unit volume. When
polar content) are often used as the "poor" standard in lu- the composition is limited to only hydrogen and carbon in hy-
bricity test calibrations. Pumps for gasoline service must be drocarbon fuels, there are strong scientifically based relation-
chosen carefully due to the low lubricity and propensity for ships between these properties, and a strong correlation be-
accelerated p u m p wear. Centrifical, gerotor, internal gear, tween them for all fuels. Dielectric constant is rarely a concern
and other low contact p u m p designs are preferred over ordi- for gasoline, but is occasionally needed for some capacitance
nary gear pumps, which are seldom suitable for gasoline ser- gauging systems. For reasons of composition, the dielectric
vice. Similar wear problems can occur in some positive dis- constant of hydrocarbon fuels (not oxygenates) can be esti-
placement meters. The high vapor pressure of gasoline can mated as the square of the refractive index at the required
result in localized cavitation in some p u m p designs, with the temperature. The dielectric constant is a "bulk property" of
damage easily misdiagnosed as corrosion and/or wear. En- the fluid, similar to refractive index and density. All can be es-
gine mounted fuel p u m p s are usually diaphragm pumps, and timated with reasonable accuracy for oxygenates blends by
low pressure in-tank fuel p u m p s are usually turbine (centrif- volumetrically averaging the oxygenate and the hydrocarbon
ical) p u m p s for these reasons. High pressure automotive in component dielectric constants, refractive index, or density.
tank fuel p u m p s are usually two stage turbine/positive dis- Both refractive index and dielectric constant can be used to
placement pumps, with the second stage tjrpically usually be- estimate the density of a blend, which in turn is strongly cor-
ing a roller vane or gerotor type for use in a very "dry" (low related to Eiromatics content for typiccil blends. Both dielectric
lubricity) fuel. constant and refractive index have been used as control pa-
There are a n u m b e r of standard ASTM viscosity test meth- rameters for racing fuels for these reasons. Some commer-
ods suitable for gasoline, such as D 445, S t a n d a r d Test cially available field instruments use these principles to esti-
Method for Kinematic Viscosity of Transparent and Opaque mate oxygenate contents from optical measurements.
Liquids (the Calculation of Djoiamic Viscosity). Adaptations Gasoline vapor (predominately butane/pentane) is heavier
of several lubricity test m e t h o d s originally developed for dis- than air and can accumulate in low spots and cavities in the
tillate fuels can be applied to lighter hydrocarbons, although absence of a ventilating flow of air (see Chapter 2, Liquified
not covered with the scope (naptha range solvents are used as Petroleum Gas).
calibrants). These include D 6078 and D 6079, Scuffing Load Several s t a n d a r d ASTM test m e t h o d s are applicable to
Ball on Cylinder and High Frequency Reciprocating Rig Tests. liquid a n d gas density, refractive index, a n d dielectric
constant.
Conductivity and Static Electricity
Conductivity is rarely a concern for automotive gasoline, but
is occasionally m e a s u r e d if there is a concern for static
buildup during p u m p i n g . Retail dispensing hoses/nozzles ASTM/IP METHODS
and vehicle fill spouts Eire internally grounded, so there is
generally enough static dissipation to avoid problems. Some ASTM No. IP No. Title
static incidents have occurred with very low conductivity D 4806 Specification for Denatured Fuel
gasoline in plastic fuel lines (replaced by more conductive Ethcinol for Blending with Gasolines
plastic). Recently, ignitions have occurred during cold for Use as Automotive Spark-Ignition
weather with containers filled while sitting in plastic bed lin- Engine Fuel
ers (insulators) of pick-up trucks. Ignitions from static dis- D 4814 Specification for Automotive Spark-
charge from gloves/clothing during refueling are believed to Ignition Engine Fuel
be due to static accumulation on clothing, and not to charge D86 123 Test Method for Distillation of
accumulation from gasoline. Petroleum Products
Conductivity dissipating additives are effective in gasoline, D 130 154 Test Method for Detection of Copper
but do not provide protection if the charging rate is exces- Corrosion from Petroleum Products
sively high, and hardware changes are required. The same by the Copper Strip Tarnish Test
principles of electrostatics apply to gasoline as to other hy- D 323 Test Method for Vapor Pressure of
drocarbon fuels, except that the vapor space of gasoline tanks Petroleum Products (Reid Method)
are normally well above the HEL at the time and temperature D 3 81 131 Test Method for Existent Gum in Fu-
of use [41]. This is rarely a factor for automotive, as there is els by Jet Evaporation
little opportunity for vapor accumulation a n d ignition. In D 525 40 Test Method for Oxidation Stabil-
generzJ, gasoline should only be transferred under conditions ity of Gasoline (Induction Period
where there is free flow of air and good ventilation. Method)
Several standard ASTM test methods are available to mea- D665 135 Test Method for Rust-Preventing
sure conductivity of gasoline and other fuels. Static cheirging Characteristics of Inhibited Mineral
tendency is highly dependent upon equipment configuration. Oil in the
Consult ASTM D 4865, Guide for Generation and Dissipation Presence of Water
of Static Electricity in Petroleum Fuel Systems for more in- D 1266 107 Test Method for Sulfur in Petroleum
formation. Products (Lamp Method)
D 1298 160 Test Method for Density, Relative D 4053 Test Method for Benzene in Motor
Density (Specific Gravity), or API and Aviation Gasoline by Infrared
Gravity of Crude Petroleum and Liq- Spectroscopy
uid Petroleum Products by Hydrom- D 4057 Practice for Manual Sampling of
eter Method Petroleum and Petroleum Products
D 1319 156 Test Method for Hydrocarbon Types D 4294 336 Test Method for Sulfur in Petroleum
in Liquid Petroleum Products by Products by Energy Dispersive X-ray
Fluorescent Indicator Adsorption Fluorescence Spectroscopy
D2276 216 Test Method for Particulate Contam- D 4420 Test Method for Aromatics in Fin-
inant in Aviation Fuel ished Gasoline By Gas Chromatog-
D2533 Test Method for Vapor-Liquid Ratio raphy
of Spark-Ignition Engine Fuels D 4815 Test Method for Determination of C,
D2622 Test Method for Sulfur in Petroleum to C, Alcohols and MTBE in Gasoline
Products by X-Ray Spectrometry by Gas Chromatography
D2699 237 Test Method for Knock Characteris- D 4953 Test Method for Vapor Pressure of
tics of Motor Fuels by the Research Gasoline and Gasoline-Oxygenate
Method Blends (Dry Method)
D2700 236 Test Method for Knock Characteris- D 5059 228 Test Methods for Lead in Gasoline
tics of Motor and Aviation Fuels by by X-Ray Spectroscopy
the Motor Method D 5188 Test Method for Vapor-Liquid Ratio
D2709 Test Method for Water and Sedi- Temperature Determination of Fuels
ment in Distillate Fuels by Cen- (Evacuated Chamber Method)
trifuge D 5190 Test Method for Vapor Pressure of
D2885 Test Method for Research and Motor Petroleum Products (Automatic
Method Octane Ratings Using On- Method)
Line Analyzers D 5191 Test Method for Vapor Pressure of
D3116 Test Method for Trace Amounts of Petroleum Products (Mini Method)
Lead in Gasoline D 5453 Test Method for Total Sulfur in Light
D3120 Test Method for Trace Quantities of Hydrocarbons, Motor Fuels, and
sulfur in Light Liquid Petroleum Oils by Ultraviolet Fluorescence
Hydrocarbons by Oxidative Micro- D 5482 Test Method for Vapor Pressure of
coulometry Petroleum Products (Mini Method -
D3227 342 Test Method for Mercaptan Sulfur in Atmospheric)
Gasoline, Kerosine, Aviation Tur- D 5580 Test Method for Benzene, Toluene,
bine, and Distillate Fuels (Potentio- p,/m xylene, o-xylene, C9 and Heav-
metric Method) ier Aromatics in Finished Gasoline
D3231 Test Method for Phosphorus in by Gas Chromatography
Gasoline D 5599 408 Test Method for Oxygenates in Gaso-
D3237 Test Method for Lead in Gasoline by line by Gas Chromatography and
Atomic Absorption Spectroscopy Oxygen Selective Flame Ionization
D3341 Test Method for Lead in Gasoline- Detection
Iodine Monochloride Method D5845 Test Method for MTBE, ETBE,
D3348 Test Method for Rapid Field Test for TAME, DIPE, Methanol, Ethanol,
Trace Lead in Unleaded Gasoline and tert - Butanol in Gasoline by In-
(Colorimetric Method) frared Spectroscopy
D3606 Test Method for Benzene and D 6422 Water Tolerance (Phase Separation)
Toluene in Finished Motor and of Gasoline - Alcohol Blends
Aviation Gasoline by Gas Chro-
matography
D3710 Test Method for Boiling Range Dis- BIBLIOGRAPHY
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[26] "Chemiccd and Physical Properties," LSU Libraries, Louisiana [21] "Exhaust Emissions of Toxic Air Pollutants Using RFGs," Tech-
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NIST, Boulder, CO. Industrial Engineering and Chemistry Research, Vol. 36, 1944,
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MNL37-EB/Jun. 2003
Aviation Fuels
Kurt H. Strauss^
HISTORY publication of a specification for a n 82 octane unleaded

grade, intended for the certification of new engines having
Aviation Gasoline low octane requirements. Table 1 lists the pertinent aviation
gasoline properties in D 910, while Table 2 contains the re-
EARLY AIRCRAFT ENGINES WERE OPERATED o n ordinary straight- quirements for D 6227, Grade 82 UL.
r u n motor gasoline well into the 1920s [ 1 ]. Research then iso-
lated uncontrolled combustion as a major source of engine
overheating and failures, prompting a search for ways to cure Jet Fuel
the problem. The big step came in 1921 with the invention of Because of different combustion requirements, jet fuel
tetraethyl lead (TEL), a n unequaled knock resistance en- started as a completely different portion of the petroleum
hancer. The same period saw the development of the hep- barrel [2]. Early British engines used domestic kerosine, a
tane-isooctane scale still in use today for rating antiknock fuel that has not changed drastically over the years. German
properties in terms of octane numbers. For aviation gasoline, engines, also military, were operated on a mixture of kero-
the concept of rating knock resistance in special single cylin- sine and naphtha, probably to extend fuel availability. The
der engines resulted in the Aviation Octane Test Method (D progression of U.S. military fuels is illustrated in Table 3.
614), which tested fuels under lean fuel mixture conditions Both JP-3 and JP-4, which are blends of kerosine and naph-
simulating cruise operation. (In 1970 this method was re- tha, reflected Air Force concern over fuel availability, while
placed in the specification by the Motor Octane Method, D JP-5 is tailored t o Navy r e q u i r e m e n t s for carrier combat
2700.) An aviation gasoline specification, issued by the U.S. safety. JP-7 is a supersonic fuel in very limited use. Today, the
Air Corps in 1938, listed a 68 octane grade containing n o lead Air Force operates almost entirely on JP-8; in fact, this grade
and a 92 octane grade with a m a x i m u m of 6 mL TEL/gallon. has become the primary battlefield fuel to be used in gas tur-
As engine power output was increased by supercharging the bine and diesel powered ground vehicles as well as combat
fuel/air mixture, a second rating method, D 909, came into aircraft.
use to evaluate performance u n d e r rich take-off conditions,
so that by World War II both rating methods were required. For civil use, ASTM issued specification D 1655 in 1959,
Engine designers soon discovered the performance benefits containing three grades. Jet A and A-1 were kerosine-type fu-
of high octane, which permitted a higher octane fuel t o de- els differing only in freezing point, while Jet B was the civil
velop more power in a given engine or allowed a reduction in version of JP-4. Currently consideration is being given to re-
engine size with the same power output. Research on high moving Jet B from D 1655 and placing it into a separate spec-
octane fuel thus received a high priority and resulted in a 100 ification. The key properties of Jet A and A-1 are illustrated in
octane fuel by the beginning of World War II. While t h e Table 4. Corresponding specifications are issued by the UK
heroic performance of the RAF is widely recognized, it would Ministry of Defence as defence standards (Def Stans), with
have been impossible without the 100 octane fuel. Def Stan 91 -91 [3] being the technical equivalent of ASTM Jet
A-1. Jet A meeting D 1655 is the civil aviation fuel in the U.S.;
The dramatic j u m p in aviation activity in the late '30s and Jet A-1 meeting the combined requirements of D 1655 and
'40s witnessed a n increasing n u m b e r of aviation gasoline Def StcUi 91-91 is the civil fuel elsewhere. There is no British
grades, ultimately standardizing on five grades ranging from grade corresponding to Jet A. The latest effort at a true inter-
80/87 to 115/145. ASTM recognized this situation by issuing national jet fuel standard is a series of guidelines [4] issued in
D 618 as a civil aviation gasoline specification in 1944 to be 1999 by the IntemationEd Air Transport Association (lATA),
replaced in 1947 by D 910. However, jet engine introduction which includes Jet, A, Jet A-1, the Russian TS-1, and a Jet B
forced a steady decrease in gasoline volume and reduced the grade.
n u m b e r of grades over time so that by the '70s only two
grades, a low lead content 80 and a high lead 100 grade, re-
mained in commercial production. The 100 Low Lead grade
AIRCRAFT A N D ENGINE DESCRIPTIONS
(lOOLL) was introduced late in that period, permitting a sin-
gle fuel t o satisfy the requirements of both low and high oc- Aviation Gasoline
tane engines. The latest change in this picture was the 1997
Although a n u m b e r of military and some commercial aircraft
engines were liquid cooled, all engines produced after World
' 69 Brookside Rd., Portland, ME 04103. War II have been air cooled. These engines are generally of
89
TABLE 1—Key specification requirements for aviation gasoline."

Grade 80 Grade lOOLL Grade 100 ASTM Test MeAod
Knock Value, lean mixture
Motor method D2700
Octane number, min 80.0 99.5 99.5
tCnock value, rich mixture
Superchange rating D909
Octane number, m i n 87.0
Performance number, min 130.0 130.0
Tetraethyl lead, mL TEL/L max 0.13 0.53 1.06 D 3341 or D 5159
gPb/L max 0.14 0.56 1,12
Dye content
Blue dye, mg/L max 0.2 2.7 2.7
Yellow dye, mg/L max none none 2.8
Red dye, mg/L max 2.3 none none
Requirements for All Grades
Density at 15°C, kg/m^ Report D 1298 or D 4052
Distillation D86
Initial boiling point, ' Report
Fuel evaporated
10%vat°C max 75
40%v at °C min 75
50%v at °C max 105
90%v at °C max 135
Final boiling point, °C max 170
Sum of 10% + 50% evap. temperatures. "C min 135
Recovery volume, % min 97
Residue volume, % max 1.5
Loss volume, % max 1.5
Vapor pressure, 38°C, kPa min 38.0 D 323 or D 5190
max 49.0 or D5191
Freezing point, °C max -58 D2396
Sulfur, %m max 0.05 D 1266 or D 2622
Net specific energy, MJ/kg min 43.5 D 4529 or D 3338
Corrosion, copper strip, 2 h @ 100°C max No. 1 D323
Oxidation stability (5 h aging) D873
Potential gum, mg/100 mL max 6
Lead precipitate, mg/lOOmL max 3
Water reaction, vol change, mL max ±2 D 1094
Electrical conductivity, pS/m max 450 D2624
''For complete specification requirements, refer to D 910.
TABLE 2 --Key requirements for grade 82 UL aviation gasoline."

Property Requirement ASTM Test Method
Knock value, lean mixture D2700
Motor method octane number min 82.0
Color purple
Dye content D2392
Blue dye, mg/L max 7.5
Red dye, mg/L max 1.9
Distillation temperature, °C at % (svaporated D86
10%v max 70
50%v 66-121
90%v max 190
End point max 225
Residue, %v max 2
Recovery, %v min 95
Loss, %v max 3.0
Net speciflc energy, MJ/kg min 40.8 D 3338, D4529 or D 4809
Freezing point, °C max -58 D2386
Vapor pressure, kPa max 62 D 4953, D 5190, D 5191,
min 38 or D 5482
Lead content, g/L max 0.013 D 3237 or D 5059
Cu strip corrosion, 3 h @ 50°C max No. 1 D130
Sulfur, %m max 0.07 D 1266, D 2622, D 3120
D 4294 or D 5453
Potential gum (5 h aging) D873
mg/L
Alcohols and ether content D4815, D 5999, or D 5845
Combined methanol and etheinol, %ni 0.3
Combined aliphatic ethers, methanol and 2.7
ethanol as %m oxygen
"Refer to D 6227 for complete specification requirements.
CHAPTER 4: AVIATION FUELS 91
TABLE 3—U.S. military jet fuel chronology. the intermittent combustion, four cycle variety with a wet
Date of NATO Volatility crankcase oil system. In radial engines the cylinders are ar-
Issue Grade Specification Symbol and Freeze Point ranged in a circle with 7 o r 9 cylinders in a row and a n engine
1944 JP-1° AN-F-32, changed l l O ^ F m i n flash having one or m o r e rows. Alternately, in flat engines the
to MIL-F-5616 —60°C max freeze cylinders lie horizontally and oppose each other. Most of to-
1946 JP-l" not issued 2 psi max RVP day's production engines are the flat or pancake type with 4
1947 JP-S" AN-F-58, changed 5-7 psi RVP
to 8 cylinders. Some engines contain a supercharger to com-
to MIL-F-5624
1951 JP-4 MIL-F-5624, now F-40 2-3 psi RVP press the air and thereby increase the mass flow through the
MIL-PRF-5624 engine. The engine drives a propeller directly from the
1952 JP-5 MIL-F-5624, now F-44 140°F min flash crankshaft or through a set of speed reduction gears. Fuel is
MIL-PRF-5624 - 4 6 ° C max freeze carried either in rubber bladders or removable metal tanks,
1956 JP-6'' MIL-F-25656 High thermal stab. often in the wings, and flows to cEirbureted engines by grav-
- 5 4 ° C max freeze
1980 JP-7 MIL-T-38219, now 140°F min flash ity or is pumped to a fuel-injected engine by a tank-mounted
MIL-PRF-38219 - 4 3 ° C max freeze submerged boost p u m p . A low pressure engine p u m p then
1979 JP-8 MIL-T-83133, now F-34 100°F min flash supplies the fuel into the carburetor to be mixed with air or
MIL-DTL-83133 - 4 7 ° C max freeze injects it into the intake manifold under low pressure. In ei-
"Canceled. ther case the fuel has to be evaporated by the time it reaches
the cylinder because only vapors will b u m . Each cylinder
contains two spark plugs for safe operation. Water or a wa-
ter-alcohol mixture may be injected both to help cool the en-
TABLE 4—Key specification requirements for jet fuel grades Jet A, A-1, and B.'
Property Jet A or Jet A-1 JetB ASTM Test Method
Composition
Acidity, total, mg KOH/g max 0.1 D3242
Aromatics, %v max 25 25 D1319
Sulfur, mercaptan, %m max 0.003 0.003 D3227
Sulfur, total, %m max 0.3 0.3 D 1266, D 1552, D 2622
D 4294 or D 5453
Volatilitv
Distillation temp., °C D86
10% recovered, temp. max 205
20% recovered, temp. max 145
50% recovered, temp. max report 190
90% recovered, temp max report 245
Final boil, point, temp max 300
Distill, residue, %v max 1.5 1.5
Distill, loss, %v max 1.5 1.5
Flash point, "C min 38 D 56 or D 3828
Density at 15°C, k g W 775-840 751-802 D 1298 or D 4052
Vapor pressure, 38°C, kPa meix 21 D 323 or D 5191
Fluiditv
Freezing point, °C max - 4 0 Jet A -50 D 2386, D 4305,
- 4 7 Jet A-1 D 5901 or D 5972
Viscosity, -20°C, mm^/s max 8.0 D445
Combustion
Net specific energy, MJ/kg min 42.8 42.8 D 4529, D 3338 or D 4809
One of following shall be met:
(1) Smoke point, m m min 25 25 D1322
(2) Smoke point, m m and min 18 18 D1322
Naphthalenes, %v max 3.0 3.0 D 1840
Corrosion
Copper strip, 2 h @ 100°C max No. 1 No. 1 D 130
Stability
Thermal, 2.5 h at 260°C
Filter press, drop, m m Hg max 25 25 D3241
Tube deposit less thsm Code 3 Code 3
Contaminants
Existent gum, mg/100 mL max 7 7 D381
Water reaction D 1094
Interface rating max lb lb
Additives
Electrical conductivity, pS/m D2624
If Additive is used max 450 450
If required by purchaser min 50 50
"For complete specification requirements refer to D 1655.
gine and to increase power output. In addition to these tradi- compressor or "turbofan" may be mounted in front of the en-
tional engines, other designs, particularly for ultralight air- gine. This fan is driven by its own turbine section by a shaft
craft, are being introduced but are not described in detail in running through the core engine. Military engines may add
this chapter. Exhaust gases are discharged through mufflers, extra thrust by injecting fuel into the exhaust stream and
turbochargers or directly into the atmosphere. Compared to burning it in an afterburner at the expense of greatly in-
today's automobile engines, all these aircraft engines are rel- creased fuel consumption. Unlike reciprocating internal
atively simple and unsophisticated. combustion engines, these engines operate with continuous
With rare exceptions, aircraft piston engines are operated combustion where an igniter serves only to start combustion
with separate throttle and manual fuel/air mixture controls, and is then turned off. Gas turbine engines operate with lean
whether carbureted or fuel injected. On high performance fuel/air ratios well below stoichimetric (with considerable ex-
aircraft the pilot also controls the engine speed by means of cess air) to provide turbine inlet gas temperatures below the
separate manual propeller controls. During takeoff and climb normal combustion temperatures.
the fuel/air mixture is maintained "rich;" the purpose of the The fuel system of a modem transport aircraft is illustrated
excess fuel is to help cool the engine at high power condi- in Fig. 1. The fuel is carried mostly in the wing structure
tions. The fuel/air mixture is "leaned out" during cruise for where metal junctions are sealed with an elastomer and the
optimum fuel consumption. "Rich" in this context refers to a entire inside surface is coated with epoxy paint to prevent
mixture in which the fuel/air ratio is well above the stoichi- corrosion. Elastomeric bags are generally not used for fuel
metric ratio, while lean operation is run as close as possible storage, mostly to save weight. From the tankage, fuel is
to stoichimetric without overheating the cylinders. pumped by boost pumps to the engine high pressure pump.
The engine pump normally builds fuel pressure in two stages
with the first stage a centrifugal pump and the second stage
Jet Fuel a gear pump capable of delivering fuel at pressures as high as
Jet engines operate on a completely different principle. Air 10 MBCa (1400 psi.). The fuel control, the heart and brains of
flows through a compressor, is guided into a combustion sec- the fuel system, then meters the proper amount of fuel to the
tion where fuel is injected and burned and the resulting ex- combustion system with the excess fuel being bypassed back
haust gases are expanded in the turbine section, and then ex- to the second stage pump inlet. Fuel enters the combustion
pelled into the atmosphere. The turbine section drives the system through a fuel manifold, which distributes fuel
compressor, while the remaining energy in the exhaust around the engine and into fuel nozzles in the combustion
stream either reacts on the engine parts to push the engine by chamber. Note that the fuel passes through a series of heat
"jet propulsion" or is used to drive a propeller in "turboprop" exchangers, which reject heat from the hydraulic system,
fashion. For more efficient operation, a large single stage from the engine oil system, and from the auxiliary power sys-
Fueltank
Fuel quantity
gage Nozzles
uiuaiiuu
umiij
lanifold / I
ssembly /
A/Cheat
exchanger Integrated
Engine oil heat gen. drive
exchanger oil heat exch.
Fuel bypass tkiti
iLPress Stage\HPress Stage| Fuel

Control
FilterX
Engine Pump
Assembly
FIG. 1—Turbofan fuel system.
Horizontal
Stabilizer
I Tank (optional)
Surge Tank
Reserve Tank No. 3

Main Tank No. 3
Main Tank No. 4
Reserve Tank No.2
\y< >y \ DryBay
Center Wing Tank
Surge Tank\
Main Tank N o . 2 / /
MainTankNo.l f
Fuel Tank Volumes
Tank Liters Gallons
Main Tanks No. 2 and 3 47 675 12 594
Main Tanks No. 1 and 4 17 030 4499
Center Wing Tank 65 220 17 229
Reserve Tanks No. 2 and 3 5020 1326
Horizontal Stabilizer Tank 12 540 3313
Total Usable Volume 217 211 57 381
FIG. 2—Boeing 747-400 fuel tankage.
tern. (In some systems the heat from the hydraulic system is flight creates the highest fuel temperatures. In this entire
rejected in the fuel tanks.) Additional heat is added to the fuel flight the pilot controls all engine power settings with a sin-
by energy losses in the pump and by fuel recirculation gle throttle lever, while the engine fuel control adjusts, for all
through the pump. More heat goes into the fuel from the the variables.
compressor discharge air, which the fuel passes through to
get into the combustion system. This heat path highlights an-
other important function of the fuel, to serve as the heat sink PERFORMANCE REQUIREMENTS AND
that carries away excess heat from other systems and allows THEIR IMPLEMENTATION
other systems to operate.
Figure 2 illustrates the tankage arrangement of a Boeing A review of aviation gasoline and jet fuel specifications will
747-400 aircraft. At takeoff, each engine is supplied fuel from show that all are based on Vcirious performance tests rather
its own tank. After takeoff, fuel is taken selectively from the than closely defined product compositions. In turn, most of
center wing tank first to control wing stresses. For a typical the performance tests are empirical and do not define a prop-
flight each engine is started by rotating the compressor spool erty on an absolute basis; indeed many were developed to
to start air flowing. When airflow is sufficient to start com- solve specific operating problems. The following sections
bustion, fuel is injected and the fuel/air mixture is ignited. outline vetrious challenges faced by aviation fuels and their
The engine then accelerates under its own power to idle op- solutions.
erating speed and above. Maximum power at take-off is lim-
ited by either throttle demand or turbine inlet temperature Low Temperature—Fuel Related
limits. Take-off power is reduced as the aircraft climbs and is
further reduced at cruise altitude to minimize fuel consump- Jet Fuel
tion. At the end of cruise, power is further decreased to near Aviation fuels have to operate in an extremely wide tempera-
idle for descent. Because heat rejection is almost constant ture environment. In particular, jet fuel is exposed to very low
but fuel flow is near minimum, the descent portion of the temperatures due to operating conditions and fuel system de-
sign. This leads to two differing problems, one being normal In-flight aircraft operation is not permitted below a fixed
operation at cJtitude, the other involving steirting at very low fuel temperature differential above the specification maxi-
temperatures. In the wing tanks the fuel is in direct contact m u m freezing point. This limit is called out in the flight man-
with the lower wing skin which in turn is exposed to ambient ual of each aircraft. For Boeing aircraft the differential is 3°C
t e m p e r a t u r e s as extreme as — 100°C (—148°F). Although or 5°F, and for Airbus aircraft it is 4°C or 7°F. Operation at
aerodynamic heating at cnaise will wEirm the bottom wing lower fuel t e m p e r a t u r e s is avoided by aircraft routing
surface some 20-25°C or 36-45°F, the resultant fuel temper- through w a r m e r air, by using a fuel of lower freezing point,
atures at the wing skin Ccin still be very low. At these low tem- or in flight by increasing aircraft speed or decreasing altitude
peratures certain types of hydrocarbons in jet fuel come out when this condition appears imminent [7]. Limited U.S. Air
of solution. The most critical molecules are straight chain Force research also shows possible promise for additives that
paraffins [5] because they have the highest crystallization lower fuel freezing points [8]. However, the practicality of
temperatures of the hydrocarbons normally in jet fuel. When such additives in unproven.
these compounds come out of solution, they form a wax crys- Viscosity is the limiting property for jet engine starting be-
tal matrix that can prevent the liquid fuel within the matrix cause of its influence on fuel droplet size during atomization.
from flowing into a boost p u m p inlet [6]. Only 8-10% of nor- Viscosity is measured by D 445 and typical fuel viscosities are
mal paraffins in the fuel are required to form such a matrix. plotted against temperature in Fig. 3 [9]. Engines are de-
For safe operation the fuel freezing point is defined as the signed to start with fuel viscosities u p to a m a x i m u m of 12 cs
temperature at which the fuel is 100% liquid. This tempera- [10], a viscosity reached around - 4 0 ° C ( - 4 0 ° F ) for either Jet
ture is determined by D 2386 in which a sample is cooled in A or A-1. However, specifications allow a m a x i m u m viscosity
an isopropyl-dry ice bath until a crystal haze appears. The of 8 cs at —20°C (—4°F), which is taken as equivalent to 15 cs
sample is then weirmed until the last crystal disappears. That at —40°C. Starting problems are therefore occurring at far
melting temperature is reported as the "freezing point". Us- N o r t h e r n latitudes, particularly in helicopters, and are
ing the melting point avoids possible super cooling of the avoided by the use of Jet B or JP-4 fuel, which has lower vis-
sample during the cooling cycle. At this writing, three other cosity and increased volatility.
tests are permitted as alternates. They include D 5901 (Freez-
ing Point of Aviation Fuels—Âutomated Optical Method), D Aviation Gasoline
5972 (Freezing Point of Aviation Fuels—Automatic Phase
Aviation gasoline low temperature performance tends to cen-
Transition Method) and D 4305 (Filter Flow of Aviation Fu-
ter on engine starting. While fuel volatility is the key to fuel
els at Low Temperatures). However the last method cannot
evaporation a n d engine starting, the tight volatility limits
be used when fuel viscosity exceeds 5.5 cs at —20°C (—4°F).
allow little flexibility and force solutions other than fuel se-
In case of dispute, D 2386 is the referee method.
lection. Starting difficulties at low temperatures are com-
-50 -30 -10 10 30 50 70 90 110

Ten^rature, °C
FIG. 3—Typical viscosities vs. temperature.

0.10 -
0.06 h
0.04
0.02 Jet A, Jet A-1. JP-8
Aviation Gasoline
:§ 0.007
•o
"2 0.006
II
20 40 60 80 100
Ten^rature, °C
FIG. 4—Water solubility vs. temperature.
pounded by increased lubricating oil viscosities and de- ing and neither affects wax precipitation. Water concentra-
creased battery performance. High altitude operation does tions significantly exceeding saturation levels Ccin overwhelm
not normally present a low temperature problem because these additives. Techniques for monitoring free water levels
gasoline has a very low freezing point and most piston engine etnd keeping excess water out of aircraft are discussed later
aircraft do not fly at extremely high eJtitudes. under Quality Control. The freezing of atmospheric moisture
on the throttle plate causes carburetor icing in piston en-
gines; it is due to evaporative cooling by gasoline and trace
Low Temperature—Water Related levels of water in fuel play no part.
All hydrocarbons can dissolve a very limited amount of wa-
ter. Saturation limits for jet fuel and for aviation gasoline are
High Temperature
shown in Fig. 4 [9]. When water-saturated fuel is cooled, wa-
ter comes out of solution as free water. These low levels of Exposure to high temperatures represents one major differ-
free water do not present cin operating problem. However, as ence between aviation gasoline and jet aircraft fuel systems,
the fuel temperature goes below 0°C or 32°F, this free water in fact, high temperature exposure has not occurred in avia-
freezes into ice crystals that can plug filters and other fine tion gasoline-powered aircraft. Jet fuel presents a completely
passages. The problem is avoided by placing filters into a different picture. The first incidents, in the early 1950s, took
warmer part of the fuel system, by applying heat to critical fil- place in military J57 engines that suffered plugging of nozzle
ters when water freezing temperatures are noted, or by in- filter screens by fuel-caused carbon deposits [11]. Such plug-
cluding an anti-icing additive in the fuel. Diethylene glycol ging radically altered the exhaust gas temperature pattern at
monomethyl ether (diEGME), as described by specification the turbine inlet and resulted in turbine blade failures. In this
D 4171, Type III, can be added to jet fuel or aviation gasoline engine the fuel manifold that distributed fuel to the individ-
as an anti-icer in concentrations of 0.10-0.15% by volume. ual nozzles was located in the hot compressor discharge air
Ethylene glycol monomethyl ether (EGME) is no longer and some fuels formed carbon deposits in the manifold un-
listed in D 4171, but is still in limited use. Isopropyl alcohol, der reduced fuel flow conditions. These deposits broke off
per D 4171 Type II, may only be added to aviation gasoline. and plugged fuel nozzles. The particulsir problem was solved
Here specification D 910 warns that the addition of isopropyl by manifold redesign, but it also alerted the industry to the
alcohol to the 100 grade may lower its knock ratings. Both need for tailoring high temperature performance into the
additives only keep limited amounts of free water from freez- fuel.
FIG. 5—Jet Fuel Thermal Oxidation Tester (JFTOT).
Extensive research has pinpointed trace levels of certain cause more efficient engines have reduced fuel flows and
molecules and metals to be the criticeJ peirticipants in high therefore cause higher heat inputs into the fuel [14].
temperature oxidation reactions. Heteroatoms containing Fuel constraints have also been instituted. Although spe-
sulfur and/or nitrogen have been investigated in a number of cific heteroatoms have been found to oxidize rapidly in
model studies [12], which have found them to be as much as model studies, the large variety of materials involved in high
20 times more reactive than the base fuel. Oxidation trans- temperature oxidation as well as their low concentration pre-
forms these molecules into higher moleculctr weight materi- cludes their analytical identification on a routine basis.
als, which become insoluble and can plug filters or screens or Therefore, the jet fuel specification requires a performance
deposit on hot surfaces. In turn, such deposits have broken test, the Jet Fuel Thermal Oxidation Tester (JFTOT) by D
loose or have caused sliding parts to stick. Thus, these reac- 3241, to screen out product with unsatisfactory characteris-
tions involve only a tiny fraction of the total fuel going tics. The unit is illustrated in Fig. 5. In the apparatus, fuel is
through the engine, but their effect becomes significant be- pumped over a heated tube under pressure and then through
cause of the very large fuel volumes handled over a long pe- a metal screen with 17 micron openings, with both tube and
riod of time. Ultimately, the basic reason for fuel degradation filter being maintained at a temperature of 260°C (500°F).
is the fuel's use as a heat sink as pointed out under Engine De- Filter pressure drop is monitored during the test, and at the
scriptions. To curb the problem, the engine design approach end of the test, tube deposit color is competred to a color
has been to limit liquid fuel temperature to a maximum of standard. Normally the test is run only at the specification
190°C (325°F) [13]. However, fuel oxidation is a function of minimum requirement conditions and the quality margin
both temperature and exposure time so that lengthy residence available above this limit is unknown. Like many other time-
times at temperatures below this maximum have resulted in dependent tests the thermal stability test has poor precision,
operating difficulties. Paradoxically, improving engine design but the visual rating of deposit color plays a major part in the
over the years has increased the severity of fuel exposure be- poor precision [15]. Over the years, differing methods for rat-
ing of tube deposits have been proposed and rejected. Most ratings by the old Aviation method, D 2700 contains conver-
recently, a method of measuring deposit volumes by an ellip- sion tables from the Motor method to the Aviation method. It
sometric technique [16] has been developed as an alternate to is noted in passing that the Motor Method is the only rating
the visual rating but has not been adopted. method used for both aviation and motor gasolines.
An interesting side issue has been the catalytic effect of cer- The rich rating method, D 909, is more complex. Engine
tain metals on these high temperature reactions. This topic is output is measured and controlled by a dynamometer. Air
further discussed in the section on Corrosivity. into the engine is compressed Eind cooled. Both fuel and air
flow to the engine are metered. Engine loading by the dy-
namometer is increased at constant fuel/air ratio until knock
Combustion occurs. The same process is repeated at increasing fuel/siir ra-
More than any other performztnce requirement, combustion tios to develop a curve of knock-limited engine output against
requirements influence the differences between aviation fuel/cdr ratio. This curve is bracketed by similar curves using
gasoline and jet fuel. isooctane with varying concentrations of TEL as reference
fuels. The test fuel rating is established by interpolation be-
Aviation Gasoline tween reference fuel curves cind is usually expressed in terms
The requirements of spark-ignited reciprocating engines of performzince numbers, which are directly proportional to
have shaped aviation gasoline since its earliest uses. As the the engine power output. Thus, with a fuel having a perfor-
mixture of air and fuel vapor enters the cylinder and is com- mance number of 130 the engine developed 30% more power
pressed, the mixture must be ignited at a critical time in the than on straight isooctane.
engine cycle to provide maximum power through the expan- There are currently several research programs [17] related
sion of exhaust gases. Mixture autoignition, either through to knock testing and combustion requirements of aviation
compression ("dieseling") or by glowing deposits, will cause piston engines. The first program is establishing the octane
a loss of power and can result in detonation with severe me- requirements of a great variety of current production engines
chaniccd damage. Aircraft engines Eire particularly vulnerable to get an up-to-date definition of the relationship of the sin-
because of the extensive use of aluminum alloys and other gle cylinder laboratory engines to fl5'ing hardware. As part of
low melting point meteJs. Compression ignition cjin be alle- this effort, an Engine Octane Rating method has been issued
viated by spark timing retardation as well as maximum as D 6424. Preliminary results indicate that, while the old,
power reduction. However, either approach causes a perfor- large radicd engines are sensitive to both lean and rich knock
mance loss. Thus the importance of fuel knock resistance characteristics, the flat or pancake engines seem to be criti-
through adequate octanes cannot be overemphasized. CcJ in the cruise or lean operating mode only. The second pro-
Gasoline knock resistance is measured by the lean and rich gram is pointed toward the development of a high octane, un-
engine tests mentioned earlier. In the lean mixture method, leaded aviation gasoline. That search is driven by the fact that
D 2700, the test variable is compression ratio, which is the ra- 100 octane aviation gasoline is the only lead-containing fuel
tio of the total volume displaced by the piston to the volume left in the U.S. petroleum inventory and there is environmen-
above the piston at the top of the compression stroke. When tal pressure to eliminate lead wherever it exists. Ultimately,
testing Ein unknown fuel in the single cylinder D 2700 engine, the two programs should indicate the practicality of develop-
this ratio is increased until knock is detected. The condition ing an unleaded gasoline, which will satisfy the current in-
is then rated by making blends of n-heptane and isooctane ventory of engines requiring high octane fuel.
and adjusting the ratio of the components until a match is
noted with the test fuel. The percent isooctane in the match-
ing blend is the test fiiel's octane number. If fuel octane ex- Jet Fuel
ceeds 100, the match is made with pure isooctane containing A typical jet fuel combustion system is illustrated in Fig. 6.
differing levels of TEL. Because the specification requires Air is discharged from the compressor at pressures up to 20
Outer combustor casing

Fuel nozzle Inner liner
Turbine
inlet
Jet igniter Secondary

Primary comlnistion zone
zone
FIG. 6—^Turbofan combustion system.
9 8 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK
atmospheres (300 pounds per square inch) and temperatures gine smoke or soot but are not permitted because of ash for-
as high as 450°C (840°F) into the combustion system between mation. [20].
the outer and inner liners. The air then enters the inner Hner The level of sulfur oxides in the exhaust is directly related
through holes and slots carefully placed and sized to control to the total sulfur content of the fuel and any required reduc-
the air and gas flow patterns. Fuel is injected and atomized tion of these oxides has to be achieved by reducing total sul-
through one or more nozzles into the primary combustion fur content below currently allowed levels. Nitrogen oxides,
zone, where, after ignition, it will bum at temperatures ap- on the other hand, are purely an engine design function de-
proaching 2000°C (3500°F). Such gas temperatures exceed pending primarily on the maximum combustion tempera-
the operating limit of the turbine section and therefore more tures, the amount of mixing in the primary combustion zone,
air is added in the secondary zone to reduce exhaust gas tem- and the time at maximum temperature. Fuel characteristics
peratures to maximum levels of 800-1200°C or 1500-2200°F. play no part [19]. The same can be said for carbon monoxide
Thus, air provides oxygen for combustion, creates local tur- emissions in which fuel does not play a significant role [19].
bulence to stabilize flame location, cools the inner liner sur- Because the ultimate purpose of fuel is to furnish heat en-
face, and finsJly reduces exhaust gas temperatures. Note that ergy, the minimum heat content or specific energy is con-
the fuel line to the nozzle must go through the hot compres- trolled. Water vapor formed during combustion is not con-
sor dischcirge air and the engine designer must guctrd against densed in any aviation engine, therefore the net specific
excess heat flow into this line. energy is specified. As mentioned in D 910, the minimum
In the early days much effort was spent to discover a jet specification level for aviation gasoline is high enough to ef-
fuel property that would improve engine efficiency the way fectively limit the total amount of aromatics to about 25%.
that octane improves piston engine performance [18]. No Specific energy (formerly called heat content) can be mea-
such performance parameter has been found for jet engines. sured in a calorimeter per D 4809, where a small amount of
Fuel specification tests therefore serve primarily to limit un- fuel is burned in a pressure vessel, which in turn is immersed
desirable components that could shorten engine life. In gen- in a water bath. The released energy is calculated from the
eral, paraffinic molecules provide the cleanest combustion temperature increase of the water bath. Extremely precise
while aromatics tend to create the opposite conditions. thermometry is required for the desired accuracy of the re-
Several tests are used to measure fuel combustion quality. sults. Specific energy can also be estimated by equations
The simplest test is the Smoke Point, D 1322. A lamp with a based on pertinent fuel characteristics. One estimation
fuel reservoir contains a wick that can be lowered and raised method, D 4809, uses fuel density and aniline point; another,
and furnishes fuel to a flame. When the wick is raised, the D 3338, includes density, boiling point and aromatic content
flame increases in height, but at some height the flame begins as variables. D 3338 is gaining in popularity because of ani-
to smoke. This height varies with fuel composition. The max- line toxicity and because the required variables are already
imum flame height at which no smoke occurs is defined as being determined to assure overall specification compliance.
the fuel smoke point. Although the smoke lamp represents a
very simple combustion process, a large amount of research
has validated the good relationship between this test and en- Volatility and Flammability
gine combustion, with fuels having higher smoke points Volatility, a fuel's tendency to evaporate, plays a significant
showing cleaner combustion with reduced engine smoke or part on the ground and in the air. Some performance re-
soot as well as decreased flame radiation in older engines. quirements overlap between the two fuel t5rpes, others do not.
Engine studies have highlighted the poor combustion quality
of double ring aromatics or naphthalenes and these are there- Aviation Gasoline
fore measured by ultraviolet absorption at 245 nanometers Aviation gasoline volatility is a major factor in engine opera-
with a spectrophotometer (D 1840). Another much more tion because proper ignition requires fuel in vapor form. The
complex test, the Luminometer (D 1740), was designed to fuel, therefore, has to evaporate in the intake manifold before
rate fuels by measuring the radiation from a smoke lamp reaching each cylinder. This is particuleirly important during
flame, but the close correlation between this test and the starting. Volatility also affects vapor formation in fuel lines,
smoke lamp has caused the test to fall into disuse. Lastly, the which occurs when line pressure drops below the vapor pres-
measurement of total aromatics by fluorescent indicator ab- sure of the fuel, usually due to local overheating at low line
sorption (D1319) or by high performance liquid chromatog- pressures. Vapor lock takes place when the combined vol-
raphy (D 6379) is also listed as a combustion test. However, umes of vapor and liquid in the line exceed the volumetric ca-
this measurement does not correlate as closely with engine pacity of the engine pump so that the engine no longer gets
performance as does the Smoke Point and its prime signifi- the required amount of fuel. As a result, the engine will not
cance is as an indication of elastomer compatibility. Hydro- run until liquid fuel flow is restored. Lastly, volatility deter-
gen content by D 3701 has been proposed as a combustion mines the flammability of the vapor space (ullage space)
quality indicator and a substitute for aromatic content but above the fuel. This property is discussed later in this section.
has not been accepted in civil specifications because its rela-
tionship to elastomer compatibility is not established. Speci- Jet Fuel
fication combustion requirements are listed in Table 3.
Fuel volatility tends to have different effects on jet fuel opera-
Minor fuel composition changes have little or no effect on tion. Too high a volatility CcUi cause excessive evaporation or
combustion quality [19]. Therefore, low concentrations of or- even boiling in aircraft tankage during rapid climb when fuel
ganic materials as additives have little, if any, effect on com- vapor pressures equal the rapidly decreasing atmospheric
bustion. Additives containing heavy metals have reduced en- pressures at altitude. That problem caused the 1950s shift
280 •
260
240 • Jet A
220 •
200 •
180
160
140 . \ JetA-l,JP-8 \ JetB,JP-4
120
100 •
80 \
60 \ Avgas
40
20 ' •
0 1 1_ •
20 40 60 80 100
Percent Evaporated
FIG. 7—Fuel boiling ranges.
from JP-3 to JP-4 fuel by the U.S. Air Force [2]. Ullage Vapor pressure and flash point, while related, do not mea-
flammability in aircraft tankage is of concern and depends on sure the same property. The former measures the pressure
fuel type as well as in-tcink temperatures and pressures. Aside exerted by a fuel at a specific temperature, while the latter in-
from some effect on engine stcirting at very low temperatures, dicates the lowest temperature at which a flammable fuel/air
fuel volatility is not a major factor in jet engine operation. mixture is created. Typical fuel flammability ranges at sea
Fuel volatility is normally defined by the product's boiling level are summarized in Table 5 [9]. Below the lean limit
range and its vapor pressure. The boiling range is measured there is not enough fuel vapor in the air for combustion,
in a simple distillation apparatus, D 86, in which fuel is while above the rich limit there is not enough air. Only within
boiled off and then condensed at atmospheric pressure under the flammability limits is the mixture ignitable with an en-
closely controlled conditions. The test result is a relationship ergy source like a spark or flame. The drastic differences be-
of boiling temperatures to fuel percent evaporated. Typical tween aviation fuels are apparent. These flammability limits
results for Jet A [21 ], Jet A-l/JP-8 [23], Jet B/JP-4 [21 ] and avi- are not absolute but are influenced by the test equipment and
ation gasoline [22] are plotted in Fig. 7. The boiling range dis- test conditions and serve only as general guides with regard
tribution can also be measured by gas chromatography, D to vapor space flammability. For example, the fuel/air ratio in
2887, where the molecular distribution of a sample is com- a large storage tank is maximum at the fuel surface and de-
pared to a standard mixture of known boiling points. creases with increasing distance above the fuel. Tank vapor
Fuel vapor pressure is routinely measured at 38°C (100°F) space or ullage flammability therefore can vary in a tank, par-
by D 323 or D 5191. The resuh of the test, called the Reid va- ticularly because temperature is also not usually uniform.
por pressure (RVP), is the sum of the partial pressures of the Flammability limits are also strongly influenced by the effect
fuel constituents plus the partial pressures of dissolved air of ambient pressure on evaporation rate. Thus the change in
and water measured at a vapor to liquid ratio of 4:1. A true, flammability limits with increasing altitude (decreasing pres-
absolute vapor pressure where the vapor space approaches 0 sure) is shown in Fig. 9. The subject of aircraft tank flamma-
can be obtained at any temperature with D 6378. A summary bility is being revisited as the result of the 1997 crash of TWA
of typical absolute vapor pressures against temperature is Flight 800, which is attributed to the explosion of the "empty"
shown in Fig. 8 [9], but absolute vapor pressure is not deter- center tank in the fuselage [25].
mined on a routine basis.
Reid vapor pressure is specified for aviation gasoline and
Fuel Metering
Jet B but not for Jet A or A-1 because for these fuels the RVP
results are too low to be reliable. Instead, volatility for the The measurement of fuel quantity and fuel flow is important
kerosine-type fuels is measured by the flash point test. Fuel both for ground and for flight operations. On the ground
in a closed cup is immersed in a water bath, which is warmed
at a specified rate. Starting 10°C (18°F) below the expected
flash point temperature, a small flame is repeatedly inserted TABLE 5—TyplcEil fuelflammabilitylimits at sea level.
into the cup, which is closed between flame immersions. The Flammability Concentration Limits, %v
fuel temperature at which a flash of flame appears and dis- Avgas JetB Jet A JP-5
appears is reported as the flash point. The standard test in D
1655 is the Tag Closed Cup method, D 56, but other flash Lower (lean) limit 1.2 1.3 0.6 0.6
Upper (rich) limit 7.0 8.0 4.7 4.6
point tests are also in use. Because of differing surface to vol-
ume ratios and different heating rates these tests often give Flammability Temperature Limits, °C
consistently different results and these differences have to be Lower (lean) limit -44 -23 53 64
considered when comparing test results [24]. Upper (rich) limit -12 18 77 102
I
>
I
20 40 60 80 100 120 HO
Temperature, "C
FIG. 8—Typical vapor pressures vs. temperature.
product is bought, sold, or transferred on a volume basis. an arbitreiry scale, at 60°F. All are measured by hydrometer, D
Fuel volume changes with temperature, so the volume is usu- 1298, or by digital density meter, D 4052. Fuel height in most
ally corrected to a standcird temperature using the equations jet aircraft tcuiks is measured by gages based on fuel dielectric
or tables in D 1250. Use of the corrections results in consis- constant. These fuel heights are converted into tank volumes
tent inventories and product transfers. In the U.S. the stan- eind transformed electronically into mass units during aircraft
dard temperature is 60°F, outside the U.S. it is 15 or 20°C. Al- loading. Other aircraft gaging system use ultrasonic signals to
though different only in the fourth significant place, the measure tank fuel height. To deliver the proper fuel flow to
volume difference between 60°F and 15°C becomes signifi- the combustion system the engine fuel control is programmed
cant for leirge fuel volumes. All aircraft fuel measurement is to meter volume and to correct for fuel density and fuel tem-
on a mass basis: whether desiling with total aircraft take-off perature as well as other parameters.
and landing weight, maintaining mass balances and trim in
flight or when metering fuel flow into the engine and its com-
bustion system. Aircraft Range
Volume is measured in U.S. gallons or in liters. Mass units Aircraft range is controlled by the total heat content of the
include density in kg/m^ at 15°C, relative density - the ratio of fuel in the aircraft. Maximum range is limited either by the
fuel density to water density, usually at 15°C, and API Gravity, maximum allowable aircreift take-off weight (weight-limited)
or by the total volume of tankage on the aircraft (volume lim- mercaptan conversion processes such as Bender or Doctor
ited). Either one is determined by fuel density and, in special treating. Both elemental sulfur and hydrogen sulfide are cor-
cases, an optimum fuel density has been selected for a par- rosive to copper at levels of around 1 ppm [26], but exact lev-
ticular long distance flight. In normal operations such an ap- els at which unacceptable corrosion occurs seem to depend
proach is not feasible. Aircraft operations have to EJIOW for on the presence of other trace materials such as mercaptans.
the density range permitted by specifications and routes, Rather them limit either elemental sulfur or hydrogen sul-
which require maximum range, are usually avoided, particu- fide, copper corrosion is therefore minimized by the copper
larly because atmospheric conditions such as winds Eind pay- corrosion test, D 130, where pure copper is exposed to fuel at
load variability play a major part in determining fuel quantity 100°C (212°F) for 2 h. Copper appearance is compared to a
requirements. standard color chart and only minimal discoloration is per-
mitted. In addition, contact with copper or copper-contain-
ing eilloys is avoided as much as possible in aviation fuel sys-
CoiTOsivity tems and good housekeeping will prevent the proliferation of
sulfate reducing bacteria.
Copper
For jet fuel systems there is zdso great concern over copper
One of the early compatibility problems has been fuel attack content in the fuel as the result of copper corrosion. Copper
of system metals, particulcirly copper or copper-containing concentrations as low as 15-20 ppb have adversely affected
materials. In aircraft fuel systems this frequently involved thermal stability and copper levels above 30-50 ppb have de-
fuel attack on bronze pump bearings. The primary fuel con- creased this property below the specification minimum [27].
stituents involved in copper corrosion are elemental sulfur Copper sources have included refinery heat exchangers,
and hydrogen sulfide, although acidic components may also bronze heating coils in marine tankers as well as bronze fuel
play a part. The most common source of hydrogen sulfide has systems in Navy aircraft carriers. The reactant in an old mer-
been incomplete stripping of the gas after refinery hy- captan conversion process, Linde sweetening, can also be a
drotreating. Elemental sulfur (S), which is sulfur uncom- copper source.
bined with other elements, has tended to result from the Unfortunately, the relationship between the corrosion of
chemicEd reduction of water-soluble sulfates in tank bottoms copper or bronze parts and the pickup of copper in jet fuel is
by sulfate reducing bacteria or by the oxidation of hydrogen not clesu-ly established. Compatibility with copper-contain-
sulfide. Elementcil sulfur has also been a byproduct of older ing parts in the fuel system is controlled by the copper corro-
80 100
Temperature, °C
FIG. 9—Flammability limits vs. altitude.

sion requirement in the specification, but fuel passing tfiis re- hibitors must be injected into the fuel as early as possible,
quirement can dissolve the very low levels of copper, which preferably into the run-down line from the processing unit.
in turn can wreck thermal stability. At present the most reli- Aviation gasoline susceptibility to oxygen attack is evaluated
able way to avoid pickup is to avoid contact with the metal or in the Oxidation Stability test, D 873, in which fuel is exposed
to add an approved metal deactivator to chelate and deacti- to pure oxygen under pressure at 100°C (212°F) for 5 or 16 h.
vate the trace levels of copper in fuel. The fuel is then evaporated and the residue ("gum"), together
with any lead precipitate, is weighed. Based on storage tests
Cadmium conducted during World War II, passing test results are con-
The corrosion of cadmium-plated parts has been attributed sidered equivalent to one year of desert storage.
to mercaptan sulfur compounds, particularly in the presence Tests on straight-run jet fuels in the 1960s showed oxida-
of water [28]. Mercaptan sulfurs are measured by D 3227 or tion at high temperatures to occur before oxidation at storage
are limited qualitatively by the Doctor test, D 4952. temperatures. In fact, storage stability has not been a prob-
lem for such fuels. The D 873 requirement was therefore re-
Steel moved from D 1655. However, heavily hydrotreated or hy-
A form of corrosion in which the fuel plays an indirect role is drocracked jet fuels should contain oxidation inhibitor to
the rusting of mild steel by free water in fuel. Such corrosion assure the absence of peroxide formation. A test to establish
shortens the life of steel components but also is the source of peroxide-forming tendencies has been published by CRC
solid contamination, which ultimately has to be removed [30], but is not yet approved by ASTM and has not been in-
from aviation fuels. U.S. military jet fuels require the pres- cluded in specifications.
ence of fuel-soluble corrosion inhibitors, generally dibasic
acids, which form a protective molecular layer on the steel
Lubricity
surface. MIL-PRF-25017 defines the requirements for this
t3ê of additive and approved additives are listed in the Qual- In jet engine fuel systems a number of sliding metal surfaces
ified Products List for the specification. The dual function of are lubricated by fuel. Under low contact pressures (hydro-
these additives as lubricity agents as well as corrosion in- dynamic lubrication conditions) fuel viscosity assures sepa-
hibitors is discussed later in this chapter. Because these ma- ration of these parts. Under increased contact pressures or
terials are surface-active and can interfere with water re- higher sliding velocities (boundary lubrication) fuel viscosity
moval in the filter-coalescing process, their use in civil fuels alone will not prevent metal to metal contact and a thin layer
is very limited. Multi-product pipelines are protected by plac- of adsorbed polar material is also required to prevent surface
ing the additive into the non-aviation products. Fuel systems damage. Such material is present in straight-run fuels in very
at airports are usually internally coated to prevent rusting. low but adequate concentrations, but it is destroyed by high
Galvanizing or zinc coating is not an acceptable method for pressure hydrotreating or hydrocracking. Such fuels have
rust prevention in aviation systems because of the sacrificial therefore allowed metal to metal contact resulting in de-
nature of zinc, which can react with the TEL in aviation gaso- structive wear of gears in high pressure pumps and sticking
line or dissolve into jet fuel to form an ash during combus- of close-fitting servo valves in flow controls [31].
tion.
"Harsh" or "hard" fuels can be identified in the Ball on
Cylinder Lubrication Evaluator (BOCLE test), D 5001. Un-
Storage Stability der a specified load, a stationary steel ball rubs against a ro-
tating cylinder for 30 min. The contact area is submerged in
Petroleum products in long term storage are subject to low the test fuel and the entire test atmosphere is maintained at
temperature oxidation, which may cause the formation of a temperature of 25°C (77°F) and a relative humidity of 10%.
high molecular weight products that become insoluble and Afterward the ball wear scar is measured under a micro-
precipitate out. Olefins formed during cracking are particu- scope. There are currently no specification limits for this
larly prone to such degradation and are avoided in aviation test, but a wear scar above 0.85 mm represents a very "hard"
fuels. Straight-run jet fuels have excellent storage stability fuel. Today the test is used primarily by engine accessory
due to the presence of natural oxidation inhibitors. However, manufacturers who have to qualify their components on
processes such as hydrocracking or high pressure hy- very hard fuels to assure satisfactory field performance.
drotreating destroy these inhibitors, leaving the product vul- However, under pressure from the New Zealand airworthi-
nerable to oxygen attack. In jet fuels such peroxide formation ness authorities, the latest issue of DefStan 91-91 is the first
[29] has led to repeated localized incidents of nitrile rubber international specification to include a lubricity require-
deterioration in military service [28]. Such elastomer attack ment for certain fuels.
has not been reported with civil fuel in the U.S., probably due In service, very hard fuels can be rendered acceptable by
to the greater amount of fuel commingling. Similar degrada- the addition of as little as 10% straight-run product [32]. This
tion tends to occur in aviation gasoline, which contains no effect illustrates why lubricity problems have not been more
natural oxidation inhibitors and is therefore routinely inhib- wide spread, having generally been averted by the extensive
ited with oxidation inhibitor additives. commingling in most jet fuel systems. Problems have oc-
Peroxide formation is prevented by oxidation inhibitors, curred in locations where hard fuels from a single supply
normally hindered phenols, which scavenge free radicals that point were not mixed with other fuels and were supplied di-
are the first step in the complex oxidation process [12]. Ac- rectly to aircraft. Even then different components responded
ceptable inhibitors are listed by composition in the jet fuel differently and failures occurred only on certain parts, mostly
and aviation gasoline specifications. To be effective, these in- on older units not qualified on hard fuel.
Aside from hardwEire improvements, problem solutions in- tion:

clude blending of hcird fuels with strciight-run product or the
Catalyst
addition of lubricity agents. Experience has shown fuel soluble
C4 olefins + isobutcuie ^ Alkylate
corrosion inhibitors to perform as lubricity agents, although
minimum dosages may differ for each use. Acceptable addi- The olefins are separated from catalytic cracker products
tives are covered by two military specifications and their qual- while the catalyst is hydrofluoric or sulfuric acid. Alkylate
ified products lists. U.S. specification, MIL-PRF-25017, and consists of branched chain paraffins, mostly iso-octctne. This
British Standard Def Stan 68-251 define additives suitable as composition makes it a very high octane material of high
both corrosion inhibitors and lubricity agents. Neither of these veilue to the refinery which can use the material to increase
additive types are currently listed in civil specifications. the octane of either aviation or motor gasoline. In view of this
competition, as well as the low demeind for high octane avia-
tion gasoline compared to motor gasoline, there is concern in
Static Electricity the aviation community regarding the long term availability
Hydrocarbons are extremely poor electriccJ conductors but of the high octane aviation gasoline. This concern is sharp-
usually contain trace levels of ionizable materials, which ened by the uncertain future of tetraethyl lead. Like other
carry charges of static electricity. With the fuel at rest the petroleum products, the ultimate availability of this fuel is ex-
charges neutralize each other. When fuel is moved, ions of pected to be determined by market forces.
opposite charge are separated and an electrical charge is gen- Some blending is usually cEirried out for the high octane
erated [33]. Local turbulence generated by pumps or filters gasoline. Isopentane increases vapor pressure, while toluene
increases the charge, which is carried along unless the flow increases the "rich" rating. Tetraethyl lead, along with the re-
velocity is reduced sufficiently for the charges to recombine. quired scavenger and dye, is normally needed to reach the
When the fuel comes to rest, the charge leaks to ground. The necessary minimum octane levels. Oxidation inhibitor is al-
time required for the charge to bleed off depends upon the ways added to obtain storage life. Overall, aviation gasoline
fuel's conductivity. If conductivity is low, the charge may not has become a specialty product and, in the U.S., it is the only
leak off gradually but be dissipated instead in the form of a remaining fuel containing lead.
spark, which can become an ignition source. This process
takes place independent of system bonding or grounding.
However, all components of the fuel system, including the Jet Fuel
aircraft, are electrically interconnected or "bonded" to elimi-
Jet fuel processing starts with its separation from crude oil by
nate the possibility of spEirks due to stray currents or light-
distillation, with the jet fuel fraction in the 150-290°C
ning.
(300-550°F) boiling range. Depending on the crude, a few
Static electricity problems can be minimized by slowing such streams are directly suitable as jet fuel, but most require
the flow in lines, particularly after a filter, by providing an in- further treating. Mercaptan sulfurs are converted to disul-
ert atmosphere over the fuel or by adding a conductivity im- fides primarily by Merox treating; alternatively, they Eire con-
prover additive to the fuel. Stadis™ 450 is the only conduc- verted by hydrotreating to hydrogen sulfide which is stripped
tivity improver approved for jet fuel and for aviation gasoline. from the product. Other sulfur compounds may be removed
Outside the U.S. the additive is required in all jet fuel. In the by more severe hydrotreating. An increasing number of re-
U.S., conductivity improver use in jet fuel is limited because fineries are hydrocracking heavier streams to make high
commonly used clay treaters in terminals remove the addi- qucdity jet fuel with good low temperature characteristics. To
tive so that the fuel would require additive reinhibition. In- control thermal stability, streams from catalytic or thermal
stead, the emphasis is on providing charge relaxation by sys- cracking Eire excluded or are saturated by severe hydrotreat-
tem design and operation. Guide D 4865 provides an ing. Contacting by activated clay removes polar materials
excellent review of the subject. that deteriorate fuel-water separation and which may also
adversely affect thermal stability. Salt driers may be used to
remove free water.
Other Properties
Unless a refinery makes jet fuel by hydrocracking, jet fuel
Data on other jet fuel properties not covered by specifications yield and quality are dependent on product boiling range and
such as thermal conductivity, specific heat, enthalpy, heat of on the crude slate. Table 6 shows the general effect of chang-
vaporization, thermal expansion, dielectric properties, and ing boiling range on jet fuel properties when the product is
bulk modulus will be found in the CRC Handbook on Avia- made by distillation, followed by mercaptan treating [34].
tion Fuel Properties [9]. This handbook includes data on both Availability is maximized by making product with the widest
commercial and military fuels. possible boiling range. In turn, the boiling range tends to be
limited on the low distillation end by flash point, while the
maximum distillation end point is controlled by the specifi-
FUEL MANUFACTURING cation freezing point. The wide rEinge of yield and resultant
qucdity for some typical crudes are illustrated in Table 7 [35].
Aviation Gasoline The table also reflects the difficulty of simultaneously im-
Low octane aviation gasoline can be straight-run gasoline proving critical properties when using a single crude oil.
(grade 80) or based on premium grade motor gasoline (grade As pointed out in the section on History, commercial kero-
82UL). The high octane grades (100 LL or 100) are based on sine was the original jet fuel. Today, mEiny refineries make a
alkylate made by the process described in the following equa- single product saleable as either jet fuel, commerciEil kero-
TABLE 6—Effect of boiling range changes on product quality.

Lowering Initial Boiling Point Increasing Final Boiling Point
Increases Decreases Increases Decreases
Smoke point Density Density Smoke point
Hydrogen content Flash point Aromatic content Hydrogen content
MJ per kg Aromatic content Naphthalenes MJ per kg
Vapor pressure Naphthalenes Freezing point
Freezing point Viscosity
Viscosity MJ per m^
MJ per m^
Leading to Leading to
Better combustion quality Lower combustion quality
Better low temperature properties Poorer low temperature properties
Higher gravimetric heat content Lower gravimetric heat content
Poorer handling safety Higher volumetric heat content
Lower volumetric heat content Unchanged handling safety
sine, or diesel blending stock by having this product meet the compatibility with system materials. However, the proce-
specifications for the other products. Such a product is re- dures do not disclose whether an additive will affect perfor-
ferred to as dual branded kerosine and is divided and sup- mance that has to be evaluated by other testing. A similar
pHed to the differing uses at the distribution terminal. How- protocol does not exist for aviation gasoline, which has seen
ever, this approach has become more complex by differing very few additive changes over the years.
maximum sulfur limits for the two products in many parts of It should be noted that ASTM does not confer additive ap-
the world. An additional complication in the U.S. is an EPA proval. Such approval must be initiated by the airframe and
requirement for red dye in high sulfur diesel fuel. engine manufacturers and approved by the airworthiness
A current source of controversy and ongoing discussion is agencies. Additive listing in ASTM aviation fuel specifica-
the effect of non-petroleum crude starting materials and new tions simply recognizes such approvals.
processing on jet fuel quality. Jet fuel specifications are per-
formance based and reflect past experience. Therefore, they
Specific Additives
cannot guarantee satisfactory performance when a major
change from past practice occurs. For example, using coal or Most additives are described in earlier sections of this chap-
biomateriaJs as starting materials raises questions that can ter under specific properties, but Table 8 lists all jet fuel ad-
only be answered by additional testing beyond current spec- ditives contained in D 1655 together with their permitted
ifications. dosages. Oxidation inhibitors, metal deactivator, and con-
ductivity improver may be added at the discretion of the re-
finer. Other additives, such as fuel system icing inhibitors,
ADDITIVES can only be added with the agreement of the purchaser. The
fuel manufacturer or fuel handler must declcire all additives
and their concentration. Several military specifications make
General
mandatory the addition of oxidation inhibitor, conductivity
Allowable additives in aviation fuels are tightly controlled for improver, icing inhibitor, and corrosion inhibitors. Two new
safety and operational reasons. The procedures for evaluat- additive categories are u n d e r active consideration by the
ing the compatibility of additives with aviation turbine fuels ASTM committee and could be in the specification by the
a n d with aircraft fuel system materials are spelled out in time this article is printed. These additives are leak detection
ASTM Practice D 4054. The primary purpose of this practice materials smd biocides.
is to standardize additive testing requirements so that an ad- A new jet fuel additive category in military use are thermal
ditive manufacturer does not have to repeat the process for stability improvers, termed JP-8 -1-100 because they are in-
each engine or airframe manufacturer. The testing proce- tended to add 100°F (55°C) to the u p p e r thermal stability
dures are very detailed and lengthy to assure satisfactory limit of the fuel [13]. The additive combination consists of ox-
TABLE 7—Effect of crude oils on straight-run product quality.

Crude Oil Source
Property Alaska California Indonesia Arabia Libya
Boiling Range, °C 200-260
Yield, %v 10.3 5.7 8.7 12.3 13.5
Density, kg/m^ 828 801 817
Sulfur, %m 0.093 0.43 0.009 0.214 0.04
Smoke point, m m 20 17 28 24 23
Freezing point, °C -44 -70 -32 -40 -40
TABLE 8—Jet fuel additives listed in D 1655-98b. weeks to get from Texas to New Jersey, a distance of about
Antioxidants, 24 mg/L maximum 1500 miles (2500 km). Along each pipeline there are breakout
2,6-ditertiary-butyI phenol terminals, which are collections of tanks serving as distribu-
2,6-ditertiary-butyl-4-methyl phenol tion centers. Such tanks are also used to temporarily hold
2,4-dimethyl-6-tertiary-butyl phenol product where pipeline diameters change. In a number of in-
75% min. 2,6-ditertiary-butyl phenol, plus 25% max. mixed tertiary
and tritertiary-butyl phenols stances jet fuel is moved from a terminal to an airport by
55% min. 2,4-dimethyl-6-tertiary-butyl phenol, plus 15% min, 2,6- pipeline as well. In most instances such pipelines are smaller
ditertiary-butyl-4-methyl phenol, remainder as monomethyl and and are usually restricted to jet fuel.
dimethyl tertiary-butyl phenols
72% min. 2,4-dimethyl-6-tertiary-butyl phenol, 28% max. mono-
methyl and dimethyl tertisiry-butyl phenols Marine Transport
Metal deactivator, 2mg/L max at mainufacture of fuel, for retreatment
to total of 5.7 mg/L max N,N-disalicylidene-] ,2-propane diamine Outside the U.S., jet fuel tends to move from the refinery in
Electrical conductivity additive, 3 mg/L max at manufacture of fuel, so-called "clean" tankers—as distinguished from black oil
for retreatment to total of 5 mg/L max ships, which carry crude oil or residual fuel oil. Tankers vary
Stadis™ 450
Fuel system icing inhibitor, 0.10-0.15%v tremendously in size, although the largest ones carry only
Diethylene glycol monomethyl ether (diEGME) crude oils. As in pipelines, product sequencing is carefully
Leak detection additive, 1 ppm max controlled to minimize mixing. To reduce contamination by
Tracer A other products, shippers try to maintain certain compart-
ments or the entire vessel in jet fuel. Tanker compartments
today are usually epoxy coated to extend their life and also to
make t h e m easier to clean. E a c h c o m p a r t m e n t contains
idation inhibitor, metal deactivator and proprietary deter- cleaning equipment, which directs a high pressure spray of
gents and dispersants. Because the combination contains hot or cold sea water against the inside of the compartment.
powerful surfactants, currently only water-absorbing type fil- However, cleaning procedures must be CEirefuUy controlled
ter media (commonly called filter-monitors) will operate in to avoid contaminating jet fuel with cleaning compounds. A
the presence of water and the additive. However, a major ef- complicating factor in the handling of jet fuel is the inerting
fort to develop filter-separators capable of handling the addi- of compartment ullage space with engine flue gases. Such
tive holds considerable promise. compartments are kept seeded under slight overpressure and
Table 9 shows the aviation gasoline additives and their per- are normally not open for inspection or thorough cleaning.
mitted dosages as listed in D 910. They include tetraethyl lead
Marine transport on inland waterways is usually by barges,
fluid, which must contain two atoms of ethylene dibromide
which may carry their own propulsion equipment or may be
per atom of lead as well as one or more of three different
moved by tugs. Their construction tends to be more basic
color dyes. Blending two or more of the approved dyes makes
than that of tankers and usually does not include internal
additional colors. While dyes were originally required to
cleaning equipment. As a result operators tiy to keep barges
identify any fuel containing lead, today they serve both to
in the same fuel grade as m u c h as possible.
identify lead-containing fuel and to distinguish between the
several grades of aviation gasoline. Oxidation inhibitors, con-
ductivity improver and fuel system icing inhibitors are also
permitted. Note that aviation gasoline can include isopropyl
alcohol as an icing inhibitor, but jet fuel Cctnnot. TABLE 9—Aviation gasoline additives listed in D 910-98.
Anti-knock agent, maximum dosage depends on grade
Tetraethyl lead plus sufficient ethylene dibromide to provide two
atoms of bromine per atom of lead
TRANSPORTATION Dyes, maximum dosage depends on grade
Blue: 1,4-dialkylamino-anthraquinone
Yellow: p-diethylamino-azobenzene or 1,3-benzenediol 2,4-
Pipelines bis[(alkylphenyl)azo-]
Red: alkyl derivatives of azobenzene-4-azo-naphthol
In the U.S. most jet fuel is moved from the refinery by large Antioxidants, 12 mg/L max
multi-product pipelines handling all fuels from gasoline to 2,6-ditertiary-butyl phenol
diesel fuel. Lines with diameters as large as 40 in (100 cm) are 2,6-ditertiary-butyl-4-methyl phenol
employed. These lines are normally operated on a fungible 2,4-dimethyl-6-tertiary-butyl phenol
75% min. 2,6-ditertiary-butyl phenol, plus 25% max. mixed tertiary
basis where each product meets a single specification. All
and tritertiary-butyl phenols
suppliers meet that specification, the products then commin- 75% min. di- and tri-isopropyl phenyls plus 25% mstx. di- and tri-
gled and supplier identity is lost. Differing products are not tertiary butyl phenols
physically separated from each other, but operating the line 72% min. 2,4-dimethyl-6-tertiary-butyl phenol, 28% max. mono-
under turbulent flow conditions minimizes product mixing methyl and dimethyl tertiary-butyl phenols
N,N'-di-isopropyl-para-phenylenediamine
at the interface between products. Each pipeline product cy- N,N'-di-secondary-butyl-para-phenylenediamine
cle has its own product sequence to minimize interface ma- Fuel system icing inhibitors
terial, which is an off-specification mixture of at least two Isopropyl alcohol (IPA, propein-2-ol), max dosage recommended
dissimilar fuels. Pipeline flow is maintained by controlling by aircraft manufacturer
pressure a n d flow volume while p r o d u c t s are constantly Diethylene glycol monomethyl ether (diEGME), 0.10-0.15%v
added and removed. Products move at a speed of approxi- ElectricjJ conductivity additive, 3 mg/L max, for retreatment 5 mg/L
max total dosage
mately 5 m p h (8 km/h) and, in one pipeline, take about two Stadis™ 450
Product is loaded into tankers by shore-based pumps or by gets into the aircraft through one or more hoses coupled di-
gravity if shore tanks have sufficient elevation above the rectly to the aircraft fuel system. The entire hydrant system,
tanker. Off-loading, on the other hand, is by pumps located from the storage onward, is pressurized by a series of pumps
in the lowest part of the tanker or barge. This mode of oper- that maintain operating pressure right up to the aircraft. Un-
ation tends to leave a small amount of product at the bottom derground pressures of 700-1000 kPa (100-150 psi) are com-
of a compartment when the pump loses suction. The effect of mon but must be reduced to 315 kPa (45 psi) maximum at the
mixing this residue with the next product is covered in more aircraft inlet [36]. Unlike a fueller there is no pump abocird
detail in the section on quality control. the hydrant vehicle. A hydrant system avoids ramp conges-
tion but permzinently fixes the location of fueling stations. All
major airports and many smaller ones incorporate hydrant
Road Transport systems. VirtUcdly all airport fuel systems are commingled
Smaller volumes of product, particularly when moved rela- systems where each fuel grade meets the same specification
tively short distances, are handled by road transport. Such and there is no segregation by individual suppliers.
tanker trucks have several compartments and do not have
pumps aboard. Product is unloaded by gravity into under- B o n d e d Fuel
ground tanks or into a pump that lifts the product into above-
ground tanks. Truck size and weight is limited by road re- A separate fuel designation, applicable only to international
strictions. When possible aviation products are isolated to transportation, is "bonded fuel." Legally such fuel enters a
specific trucks to minimize contamination. Most aviation country under bond and must leave the country in interna-
gasoline is moved by truck because the volumes are too small tional transportation use. Bonded fuel is not subject to do-
for pipeline movements. Compared to large pipelines or wa- mestic taxes such as excise or sales taxes. Depending on cus-
ter transport, truck transport is the most expensive mode of toms regulations, bonded fuel must be handled as a
product transportation. completely segregated product in its own handling systems
while the fuel is in the country or it can be handled in regu-
lar distribution systems as long as its entire volume is ac-
Rail Transport counted for. While originally developed for marine transport,
the concept is equcdly applicable to aviation and is used in
In some areas of the world aviation fuel is moved in rail Ccirs.
some airports for intemationsJ flights. Its use is limited by
Rail transport does not have the flexibility of road transport;
economics as well as local customs regulations.
in the U.S. it is limited to Alaska.
Airports QUALITY C O N T R O L
Airport fuel systems vary widely depending on the type of
General Philosophy
product and the volumes handled by the airport. Low octane
aviation gasoline at small airports is handled through cabinet Quality control is intended to protect the fuel properties
dispensers similar to those in service stations. These units needed for safe aircraft operation. Toweurd that purpose air-
contain a meter, a hose, and a simple filter. The aircraft is craft certification requires the fuel to fully meet the specifi-
parked at the dispenser and fuel is placed into the aircraft cation to which the aircraft was certified. This process starts
"over wing" through the hose and a hand-held nozzle. At at the refinery where aviation fuel must fully meet the perti-
larger airports, high octane gasoline or jet fuel is loaded into nent specification. In addition, fuel quality also has to meet
tank trucks called fuellers, which drive to the aircraft. These other requirements not in the specification. In their simplest
fuellers incorporate a fuel tank divided into several compart- form those requirements are expressed as "clean and dry."
ments, two or more hoses, a filter, a meter, a pump, and other However, on its way from the refinery to the airport fuel is ex-
ancillary equipment. The hose may make a solid connection posed repeatedly to water, solid contaminants and to other
with the aircraft through a pressure coupling or the fuel may fuels in multiproduct systems. Quality control therefore be-
be placed into smaller aircraft over wing with a hand-held comes an exercise in avoiding that type of contamination,
nozzle. To avoid misfuelling, gasoline and jet fuel should not which cannot be corrected in the field, and removing other
be carried on the same vehicle. Also, where possible, differ- contaminants at reasonable expense by placing appropriate
ent nozzle sizes with matching filler restrictors are used for removal equipment at critical points in the system.
aviation gasoline and jet fuel. The advantage of fueller vehi-
cles is their flexibility of positioning; the disadvantage is
ramp congestion, particularly when as many as four or five Contaminants
truckloads are required for a jumbo jet. Airport congestion is Any material not originally part of the fuel is considered a
minimized by the use of hydrant systems. Two or more stor- contaminant. That definition includes free water, solids such
age tanks are linked to the passenger terminal by a large di- as rust or sand, microbial material, other fuels, unapproved
ameter pipeline, which runs underground alongside the air- additives as well as more unusual materials such as solvents,
craft loading gates. Each gate has at least one hydrant pit fertilizers, plastics, or paints soluble in aviation fuels.
containing an underground pressure connection. Trucks,
Because aviation gasoline and jet fuel have different criti-
termed hydrant vehicles, have one large hose, which is cou-
cal properties, quality control procedures as well as contam-
pled to the underground connection. Fuel moves through
ination removal equipment differ for each fuel type and are
that hose, a meter, a filter and other plumbing and ultimately
described separately in the following sections.
Aviation Gasoline els or other materials soluble in jet fuel. Unlike aviation gaso-
line, a major concern is over contamination with more
While all properties must meet pertinent specifications at the volatile materials that will lower the flash point. Solid and
aircraft, the most sensitive properties of high octane aviation water removal are more difficult with jet fuel because both
gasoline are the octane ratings and the volatility. Octane rat- the density and viscosity of jet fuel are higher than those of
ings are readily degraded by contamination with other distil-
aviation gasoline. The equipment to remove contaminants as
late products. The lower the octane of the distillate, the
well the quality control procedures are therefore more elabo-
greater the adverse effect. Experience has shown the "rich"
rate. In addition, a number of specialized field contamina-
rating to be the more sensitive, particularly because the
tion detection procedures are in use.
"rich" rating of most aviation gasolines tends to have less
margin above the specification minimum. This problem can
only be avoided by eliminating possible contact with other Contamination Removal Equipment
fuels such as might occur in switching between different
products in transports. Volatility degradation occurs through Filter-Separators
evaporation in storage and results in vapor pressure de- The heart of contamination removal equipment is the filter-
creases and changes in distillation cheiracteristics. Depend- sepcirator, shown diagrammatically in Fig. 10. Two sets of
ing on which component is lost through evaporation, there cylindrical filter elements are mounted on a deck plate or a
may also be a decrease in octane rating. Unfortunately, none meinifold in the case. First stage elements are termed coa-
of these effects are readily predictable. Instead it is necessary lescers, the second stage are separators. Both types usually
to reestablish the specification compliance status at specified have a 6 in (15 cm) diameter; the total element length is pro-
locations or time intervals. portioned to the maximum rated flow. Fuel flow in the first
Solids and free water removal is carried out primarily by stage elements is from inside to outside and outside to inside
settling in tankage at a rate of 15 min per ft (45 min per m) of in the second stage. In the first stage, at least one filtration
depth [37] and by further removal of solids with micronic fil- layer consists of tightly packed, hydrophobic glass fibers,
ters. Because of the lower density and viscosity of gasoline which force smeJl free water droplets to coalesce into leirger
compcired to jet fuel, contaminant removed from aviation droplets as fuel pushes the water droplets through the layer
gasoline is simpler and less complex as will be seen in the jet [38]. Other layers remove and hold solid particulates. Most of
fuel section. the coeJesced droplets slide down the outside of the first stage
There are no industry-wide quality control procedures for elements. Those water droplets too small to settle between
aviation gasoline. Instead, each company foUows its own pro- stages Eire prevented from exiting with the fuel by the second
cedures, which tend to be similar throughout the industry. stage, which is also hydrophobic. This second stage is made
Gasoline is fully tested against specification requirements at of Teflon-coated wire mesh or a special synthetic fabric sup-
the refinery and is then subjected to limited retesting upon ported by a perforated meted cylinder. The coalesced free wa-
arrival at the distribution terminal. The tests normally run at ter collects in a sump at the bottom of the case and is re-
that location are listed in Table 10, but they can differ be- moved by manually opening a drain valve. A high water
tween suppliers. Sample handling must be done in accor- indicator, usually a float or an electronic water level probe in
dance with D 5842 to avoid the loss of volatile components, the sump, shuts off the entire fuel flow if the water level rises
which can result in a low vapor pressure. Gasoline is again in- too high and threatens to be carried out with the clean fuel.
spected on airport arrival for appeeirance, color, and density. A direct reading differential pressure gauge measures the to-
Only a single product grade should be carried in the transport tal pressure drop across both sets of elements.
to the airport and in the fueling vehicle on the airport. In ad- Filter-separators are designed to keep operating when sub-
dition, product that has been in storage with no product jected to contaminated fuel. Their minimum performance is
movement in or out should be checked for specification com- governed by an industry specification issued by the American
plicince at six-month intervals. Petroleum Institute as API Specification 1581. This specifi-
cation delineates the solid and free water concentrations
added during qualification testing and dictates the maximum
Jet Fuel levels of both contamineint types permitted in the effluent.
Jet fuel contamination can be divided into two broad cate- The latest version of the specification, Issue 4, was published
gories: that which can be removed in the field and that which in early 2000 and to take effect in January 2002. It contains
cannot. The first category includes various solid contami- three test fuel types. Category C is Jet A plus a conductivity
nants and water, while the second category includes other fu- improver, a corrosion inhibitor aind a sulfonate. Category M
is JP-8 or JP-5 containing military additives. Category MlOO
is Category M plus the JP-8 + 100 additive. Category C is in-
tended for civil use, while the other two categories are for the
TABLE 10—Terminal receipt tests for aviation gasoline. U.S. military. Two performance levels are called out. Type S
Knock rating by ASTM D 909 (If not available, knock rating by ASTM is to be used where significant solids and water are expected.
D 2700) Type S-LD, with a lower dirt holding capacity, is intended
Distillation by ASTM D 86 where significcint water but low solids are expected. The stan-
Reid vapor pressure by ASTM D 323, D 5191, or D 5190 dard solid contaminant is 90%m A-1 ultrafine dust and 10%
Tetraethyl lead content by ASTM D 3341 or D 5059 m Copper as red iron oxide. These are major changes from Is-
Color by ASTM D 2392
Existent gum by ASTM D 381 sue 3 which specified Fischer red iron oxide of about 0,1 mi-
Electrical conductivity (if required) by ASTM D 2624 cron particle size as the solid contamineint and did not in-
iST STAGE
COALSECER ELEMENTS
(INSIDE TO OUT fLOW) 2ND STAGE
SEPARATOR ELEMENTS
(OUTSIDE TO IN FLOW)
INLET MANIFOLD
UTLET MANIFOLD
INLET
OUTLET
FIG. 10—Cutaway of filter-separator.
elude military fuels. Nominal coalescer pore size is expected further upstream because the elements have to be replaced in
to be between 0.3 to 0.5 microns. Second stage pore size is case of a shutdown by free water.
much coarser and is not designed for dirt removal. Approvals Two specifications govern monitor performance. MIL-M-
cover only specific elements in specific housings and are not 81380 is issued by the U.S. Navy. A specification issued by the
transferable to other housings. Institute of Petroleum (IP) is similar but requires a higher
While the U.S. military has issued its own specifications in solids holding capacity. This specification is being replaced
the past, the current trend is toward the use of equipment by a joint API/IP specification, API 1583. Both specifications
meeting the industry specification, API 1581. severely limit the amount of free water that Ccin pass through
the monitor before it closes off. These units generally have a
Water-Absorbing Cartridges or Monitors nominal 1 micron pore size rating. Latest specification revi-
Sometimes called fuses, these units are designed as a last sions eJso guard against media migration under greatly re-
chance safeguard, which shuts down a system in the presence duced flow rates.
of water in the fuel. Their primary component is a cellulose
layer that normally expands when wetted. By tightly con- Clay Treatment Vessels
straining this layer, it compresses when wetted and shuts off While similar in external appearance to filter-separators, the
fuel flow. Monitor elements are 2, 4, or 6 in. in diameter, de- elements in clay treatment vessels are filled with activated
pending on the application. The total length of elements is di- clay to adsorb polar materials such as surfactants. This clay
rectly proportional to the rated flow of the filter. Because of is the same as mentioned earlier in the Manufacturing sec-
their operating mode, monitors are located only at the last fil- tion, the big difference being in the depth of clay as well as
tration point just ahead of the aircraft, where they may be the the rate at which fuel passes through the clay. This difference
only final filter or be placed after a filter-separator. Alterna- results in a 50 times reduction in contact time and a similar
tively, some operators use them as a second stage in place of reduction in the vessel's capacity to remove surfactants. Field
the separator elements. Monitors can also be the final filters clay treatment vessels are therefore considered "polishing"
in aviation gasoline system. They are not normally placed units with rather limited adsorption capacity. They are nor-
mally intended to remove traces of polar additives picked up fuel usually being a water white color. Color rating methods
by jet fuel in multiproduct transportation systems. However, include Saybolt color by D 156, or the more recent tri-stimu-
this adsorptive capacity has mitigated against the general use lus method, D 6045. Either method is seriously handicapped
of conductivity additive because the wide presence of clay by the fact that on-specification jet fuel can have a range of
field units in the U.S. would remove the additive and require colors and color, as such, is not a jet fuel performance pa-
constant additive reinhibition. Conversely, outside the U.S. rameter. Only a change from the original fuel color is there-
the additive is in general use and clay treaters are not. There fore useful as a possible indicator of contamination, which
are no government or industry performance specifications has to be ruled out by specification tests.
covering clay treatment vessels. A requirement peculiar to the U.S. involves the use of red
dye to identify high sulfur diesel fuels and heating oils as well
Micronic Filters (also Microfilters or Prefilters) as untaxed diesel fuel and heating oil. While the dye is not re-
Another weapon in the cleanup arsenal consists of filter ele- quired in jet fuel, a number of cases of jet fuel contaminated
ments, usually made of pleated paper and mounted in a pres- with red dye have occurred by the mixing of jet fuel with dyed
sure vessel. These units remove only solid particles, but they product. Because of possible adverse effects on thermal sta-
do so at a much lower cost than filter-coalescers and are bility, the use of dye-contaminated fuel in aircraft is not per-
therefore placed ahead of filter-separators when significcmt mitted. A Boeing service letter [40] specifies the use of white
solid contamination occurs. Nominal pore sizes rajiging gen- bucket appearance as the measure of fuel acceptability. A
erally from 0.3-2 microns are in widest use in jet fuel and portable spectrometer capable of measuring dye levels quan-
from 0.5-5 microns for aviation gasoline, with the optimum titatively is under development in ASTM but is not currently
pore size selected on the basis of operating experience. Here approved. An extensive program is also underway at the
again, there are no government specifications for these units. Southwest Research Institute to establish acceptable dye
A specification for microfilters dated April 2002 has been is- concentrations in high temperature engine components [41].
sued as API/IP 1590.
Solid Particles
Filter Locations Solid particles are collected on special membrane filters
Although there are no industry standards for terminal instal- made of mixed cellulose acetate esters with an absolute pore
lations, fuel receipts tend to go through a micronic filter into size of 0.8 microns. Filter membrane requirements are de-
tankage. When going out of terminaJ tankage to an airport tailed in ASTM Research Report RR-D02-1012. For particle
the fuel passes through em optional micronic filter, followed collection the membranes are mounted in plastic monitors
by a clay treatment vessel and last through a filter-separator. that are encased in a brass housing. A fixed volume of fuel is
At the airport the minimum filtration is through a filter-sep- bled through the membrane off a flowing line under pres-
arator into storage, a filter-separator out of storage into fuel- sure. The solids content of the sample can be established
ing trucks, or into a hydrant system and through a final filter- quantitatively by weighing the dried membrane or the dirt
separator on the fueling vehicle into the aircraft. Filtration level can be described by comparing the membrane color to
into storage may be supplemented by a micronic or a clay a standard chart. Both approaches are described in D 2276.
unit, while the final filtration unit may be a monitor in place Because of the normal variability in particle size, color, and
of or in addition to the final filter-separator. density, there is no direct relationship between the two types
of assessments. The mass measurement must be done under
laboratory conditions, while the color rating is carried out in
Contamination Detection Equipment the field.
Much of the following equipment, while in extensive world-
wide use, has not been standardized by ASTM, but is de- Free Water
scribed in detail in ASTM Manual 5 [39]. A number of water detection methods, ranging from coarse
to precise, are in general use. Water finding paste, which
Visual Appearance changes color on contact with a water layer, is smeared on
The appearance of jet fuel is routinely checked in either a gaging sticks or tapes to disclose the depth of the water layer
one-liter jar made of clear glass or a white porcelain or stain- in a storage tank or ship's compartment. This process is often
less steel bucket. The glass is more likely to disclose the pres- called a "water cut." Suspended, free water is detected by sev-
ence of fine, suspended material, while the bucket allows the eral methods. Three methods used at plane-side include the
examination of a larger sample easily taken from a large Shell Detector, the Velcon Hydrokit, and the Metrocator test
drain line. In addition, the white bucket has proven most sen- [39]. Each test is calibrated to show a visible color change at
sitive to product color, which can indicate contamination the presence of either 15 or 30 ppm of free water, these levels
with other darker or dyed fuels. However, such appearance being called out in quality control procedures. These tests not
checks are only a gross measure of possible contamination only eliminate the operator judgement involved in visual ex-
and do not disclose levels of solids or free water that are not aminations, but are also more sensitive than the eye of a
visible to the neiked eye. More sensitive tests for contamina- trained operator who normally can detect a water haze down
tion are described in the following sections. to the 50 ppm level. The most sensitive test for undissolved
water is the Aqua-Glo test, D 3240, which can detect undis-
Product Color solved water down to 2-3 ppm. This test is based on the re-
Quantitative color measurement can be used for the detec- action of free water with a fluoresceine dye, which impreg-
tion of other petroleum products having darker colors, jet nates a fiberglass disk. After passing 500 mL of fuel through
the disk, einy increased level of fluorescence due to water is such precautions. An alternative is the use of approved bio-
measured under ultraviolet light and is translated into ppm cides mentioned earlier, but the possible adaptation of spe-
of free water. cific microbes to a biocide has to be kept in mind. The sim-
Water content can also be established in the laboratory by plest form of detection is a visual and olfactory examination
the Karl Fischer titration procedure, D 6304. However, this of water samples from jet fuel systems. Dark or black water,
procedure measures total water content or the sum of dis- together with a foul or rotten odor, are usually indicative of
solved and free water. Because aviation fuel filters do not re- microbial activity. Laboratory testing can indicate the viabil-
move dissolved water, measuring only free water by the pre- ity and type of microorganisms, but system inspection is usu-
ceding tests is a more effective way of checking the operation ally the best indicator of whether cleaning is required. Much
of filter-separators or monitors. more detailed information on the subject of microorganisms
in hydrocarbon systems will be found in a new standard
Surfactants guide, D6469.
Surfactants, or more properly surface active agents, are
molecules in which one portion is polar and is water soluble Quality Control Procedures
(hydrophilic). The other portion is non-polar and is oil solu-
ble (hydrophobic). As a result surfactants affect the surface U.S. Procedures
characteristics of fuel-water systems. Their concentration is Similcir to aviation gasoline, jet fuel is fully certified against
highest at the interface between water and hydrocarbon and pertinent specifications at the time of manufacture. In the
results in a decrease of the interfacial tension. Mixing the U.S. this is normally D 1655, Grade Jet A. Quality is often
fuel-water-surfactant system will form emulsions, which can rechecked after arrivEil in the terminal with the tests listed in
prevent small water droplets from settling out. In addition, Table 11. However, this test lineup is experience-based and
surfactants can affect the surfaces of fibers in filter-coa- Ccin differ significantly from one company to einother; thus,
lescers and prevent them from coalescing small water some shippers require complete specification recertification
droplets. Such cocdescers Eire considered disarmed. On the of product introduced into their system. Product is settled in
other hand, surfactants do not appear to affect monitor per- storage for one hour per foot of fuel depth [37]. The pressure
formance. drop across each filter is checked daily. Sumps are drained at
Surfactants are widely used in the petroleum industry as least weekly and after receipt of product. Periodically, usually
corrosion inhibitors, lubricity agents, conductivity im- once a month, the proper operation of the filter-separator is
provers, gasoline detergents, and cutting oil emulsifiers. checked by rurming a membrane test emd a free water check.
While coalescers are designed to operate with certain specific Once approved and settled, the product is shipped to the
jet fuel additives, which are surfactants, other surfactants airport by transport or pipeline. However, none of these op-
will disarm the elements and have to be detected and re- erations are governed by industry standcirds and it is the re-
moved. Of two available tests the less sensitive test, D 1094, sponsibility of the operating company to furnish on-specifi-
measures the ability of water and fuel to separate cleanly af- cation, "clear and bright" fuel to the airport.
ter mild shaking. Because of its dependence on ultra-clean Airport quality control is more systematic. The Air Trans-
glassware this test should be performed in the laboratory. A port Association of America (ATA) has issued a specification,
much more sensitive test, D 3948, evaluates the ability of a ATA 103, which is recommended for its member airlines or
miniature coalescer to remove very fine fuel droplets from a virtually EJI U.S. eind Canadian airlines. Additionally, mem-
fuel-water emulsion. By being self-contained and utilizing ber airlines can require the specification to be followed by in-
disposable components this procedure can be conducted in dependent airport biel dealers who supply these airlines. All
the field and avoids possible contamination by sample con- jet fuel delivered to U.S. airports must meet ASTM D 1655 in
tainers. As already mentioned, surfactants are removed from order to meet the certification requirements of the various
jet fuel by clay treaters, which adsorb polcir materials. aircraft. As indicated in Table 12, when ATA 103 is to be fol-
lowed, certain tests must be furnished by the shipper on the
Microorganisms specific shipment. Other tests are conducted at the airport
Many microorgstnisms can metabolize hydrocarbons, others during and after product receipt. Additional periodic testing
can utilize sulfur. Some require oxygen, others need its ab- to be carried out at the airport is listed in Table 13. Failure to
sence. Mciny exist naturally in soil or ground water. All have meet any of these requirements is cause for immediate inves-
one common characteristic—they must have undissolved, tigation.
free water to grow and reproduce. As a result, most microbial
growth is at the fuel-water interface. Metabolic products,
usually acidic, tend to be corrosive to metals, particularly alu-
minum. These products may also act as surfactants. Mi- TABLE 11—Terminal receipt tests for jet fuel.
croorganisms commonly form slimes or mats that can plug Density by ASTM D 1298 or D 4052
screens or filters. Unfortunately for jet fuel, the problem mi- Distillation by ASTM D 86
crobes prefer to metabolize normEil paraffins in the C12 and Flash point by ASTM D 56 or D 3828
higher range [42], molecules that are a common constituent Freezing point by ASTM D 2386, D 4305," D 5901, or D 5972
in jet fuels. Existent gum by ASTM D 381
Water reaction by ASTM D 1094
The most reliable defense against microbicil growth is the Electrical conductivity (if required) by ASTM D 2426
elimination of free water in jet fuel systems. Frequent drain- "If D 4305 is used it must be accompanied by measuring viscosity
ing of all sumps and system low spots is sai important part of at -20"'C by ASTM D 445.
It should be noted that ATA 103 includes other aspects of tional Air Transport Association (lATA) to be used by indi-
airport quality control as well, but these do not directly in- vidual airline members as part of contractual requirements
volve fuel quality. with suppliers. Ultimately, it is hoped to merge ATA 103 with
the LATA Guidelines to create a single set of worldwide air-
International Procedures port quality control procedures, but the success of this en-
Somewhat similar procedures are followed outside the U.S, deavor cannot be predicted at this time.
the primary difference being the issuing authority. Here the
procedures are being issued as guidelines by the Interna- Aircraft Procedures
Small amounts of water can become a problem if the water is
not removed from tank sumps. Older aircraft require a rou-
TABLE 12—Airport quality control per ATA 103. tine sumping procedure to remove the settled free water
Airport Receipt Requirements while newer aircraft have a water scavenging system that per-
forms this function automatically. If small quantities of wa-
Specification: ASTM D 1655, Jet A or A-1
Pipeline or Marine Delivery Truck or Rail Delivery ter are allowed to accumulate, boost p u m p inlet screens can
Tests from Shipper
ice over, biological growths can develop and, if large quanti-
ties are allowed to accumulate, exposure to engine flame-out
Visual-white bucket Visual-white bucket is possible.
API Gravity @ 60°F (15°C) API gravity ©eO^FClS^C)
Distillation
Flash point
Freeze point OVERVIEW AND CONCLUSIONS
Water reaction
Copper corrosion
Existent gum For safety reasons, specifications and handling procedures
Testing During Receipt at Airport
for aviation fuels are more tightly controlled than for other
products. Minor changes in fuel properties, cleanliness, or
When: Beginning (after line From compartment
displacement) contamination levels can have unanticipated effects on jet
before unloading
Every 2 h engine performance because of the complexity of m o d e m jet
Near end engines and the massive amounts of fuels that flow through
What: Visual-white bucket Visual-white bucket the engines. The current aviation fuel supply and delivery sys-
API gravity (within 1°) API gravity (within 1°) tem is based on accumulated experience, which has evolved
Membrane color over a long period of time. There is a reluctance to make
2 dry max/1 gsillon
3 wet max/1 gallon changes because the impact of such changes cannot always
A msix particles be predicted without a thorough investigation. The challenge
Free water 15 ppm msix for the future will be for the aviation technical community to
Flash point (multiproduct anticipate, identify, and eliminate possible fuel-related prob-
line only)
lems. These problems could arise from the incorporation of
After Receipt on Tank Contents new non-traditional supplies, changes in refinery processing,
Visual-white bucket the reformulation of transportation fuels resulting from
API Gravity @ eCF (15°C), within 1° tough, new environmental regulations, changes in the trans-
Distillation, within 8°C portation of fuel to the aircraft, and new engine emd aircraft
Flash point, within SX"
Freezing point, within 3°C° requirements. An additional challenge could come from mea-
''Variability allowed from supplier's certificate.
sures required to improve aircraft safety. Resolution of prob-
TABLE 13—Airport fuel quality requirements per ATA 103, other required checks.
Daily Required Checks
Filter pressure drop Change elements at 15 psi
Monitor pressure drop Change elements at 25 psi
Drain filter sumps Inspect with white bucket—one gallon sEimple minimum
Drain storage tank sumps Inspect with white bucket—one gallon sample minimum
Drain fueling truck Inspect with white bucket—one gallon sample minimum
Monthly Required Checks
Downstream each airport filter Free water 15 ppm max
Membrane color 2 dry/gal or 3 wet/gal
Particulate assessment A max
Drain hydrant system low points
Other Requirements
Filter element specification API 1581, Group B (Group C for final vehicle)
Monitor element specification IP specification for monitors
Replace coalescer elements Yearly, with one year extension
Replace monitor elements Every two years
Inspect storage tanks Yearly
Suggested settling time 1 h per ft (3 h per m) of vertical depth
lems can have an impact on legal issues such as the assign- D 3701 Test Method for Hydrogen Content of Aviation Tur-
ment of liability and can have large financial consequences. bine Fuels by Low Resolution Nuclear Magnetic
The complexities of the interactions between the technical, Resonance
legal, and financial aspects associated with aviation fuels can D 3948 Test Method for Determining Water Separation
therefore make it difficult at times to resolve problems, but Characteristics of Aviation Turbine Fuels by
such problems must be addressed to maintain and, if possi- Portable Separometer
ble, improve the reliability of the entire system. D 4052 Test Method for Density and Relative Density of
Liquids by Digital Density Meter
D 4171 Specification for Fuel System Icing Inhibitor
ASTM STANDARDS D 4305 Test Method for Filter Flow of Aviation Fuels at
Low Temperatures
Unless otherwise indicated all of the following standards are D 4809 Test Method for Heat of Combustion of Liquid Hy-
current. drocarbon Fuels by Bomb Calorimeter (Precision
Method)
No. Title
D 4865 Guide for Generation and Dissipation of Static
D 56 Test Method for Flash Point by TAG Closed Tester Electricity in Petroleum Fuel Systems
D 86 Test Method for Distillation of Petroleum Products D 4952 Test Method for Qualitative Analysis of Active Sul-
D 130 Test Method for Detection of Copper Corrosion fur Species in Fuels and Solvents (Doctor Test)
From Petroleum Products by Cu Strip Tarnish Test D 5001 Test Method for Measurement of Lubricity of Avia-
D 156 Test Method for Saybolt Color of Petroleum Prod- tion Turbine Fuels by the Ball-On-Cylinder Lubric-
ucts ity Evaluator (BOCLE Test)
D 323 Test Method for Vapor Pressure of Petroleum Prod- D 5191 Test Method for Vapor Pressure of Petroleum Prod-
ucts (Reid Method) ucts (Mini Method)
D 445 Test Method for Kinematic Viscosity of Transpar- D 5842 Practice for Sampling and Handling of Fuels for
ent cind Opaque Liquids Volatility Measurement
D 614 Test Method for Knock Characteristics of Aviation D 5901 Test Method for Freezing of Aviation Fuels (Auto-
fuels by the Aviation Method (discontinued 1970) matic Optical Method)
D 618 Specification for Aviation gasoline (discontinued D 5972 Test Method for Freezing of Aviation Fuels (Auto-
1946) matic Phase Transition Method)
D 873 Test Method for Oxidation Stability of Aviation Fu- D 6045 Test Method for Color of Petroleum Products by the
els (Potential Residue Method) Automatic Tristimulus Method
D 909 Test Method for Knock Characteristics of Aviation D 6227 Specification for Grade 82 Unleaded Aviation Gaso-
gasoline by the Supercharge Method line
D 910 Specification for Aviation Gasoline D 6304 Test Method for Determination of Water in
D 1250 Guide for Petroleum Measurement Tables Petroleum Products, Lubricating Oils, and Addi-
D 1298 Practice for Density, Relative density (Specific tives by Coulometric Karl Fisher Method
Gravity) or API Gravity of Crude and Liquid D 6378 Test Method for Determination of Vapor Pressure
Petroleum Products by Hydrometer Method (VPx) of Petroleum Products, Hydrocarbons and
D 1319 Test Method for Hydrocarbon Types in Liquid Hydrocarbon-Oxygenate Mixtures (Triple Expan-
Petroleum Products by Fluorescent Indicator Ad- sion Method)
sorption D 6424 Test Method for Octane Rating Naturally Aspirated
D 1322 Test Method for Smoke point of Aviation Turbine Spark Ignition Aircraft Engines
Fuels D 6469 Standard Guide for Microbial Contamination of Fu-
D 1655 Specification for Aviation Turbine Fuels els and Fuel Systems
D 1740 Test Method for Luminometer Numbers of Aviation
Turbine Fuels
D 1840 Test Method for Naphthalene Hydrocarbons in Avi- OTHER STANDARDS
ation Turbine Fuels by Ultraviolet- Spectrophotom-
etry U.S. Military Aviation Turbine Fuel and Additive
D 2386 Test Method for Freezing Point of Aviation Fuels Specifications^
D 2392 Test Method for Color of Dyed Aviation Gasolines
D 2700 Test Method for Knock Characteristics of Motor No. Title
and Aviation Fuels by the Motor Method MIL-PRF-5624 Turbine Fuel, Aviation Grades JP-4, JP-5,
D 3227 Test Method for Mercaptan Sulfur in Gasoline, and JP-5/JP-8 DT
Kerosine, Aviation Turbine and Distillate Fuels (Po- MIL-PRF-25017 Inhibitor, Corrosion/Lubricity Improver,
tentiometric Method) Fuel Soluble
D 3240 Test Method for Undissolved Water in Aviation Tur- MIL-DTL-27686 Inhibitor, Icing, Fuel System
bine Fuels MIL-PRF-38219 Turbine Fuel, Low Volatility (Grade JP-7)
D 3241 Test Method for Thermal Oxidation Stability of Avi-
ation Turbine Fuels (JFTOT Method)
D 3338 Test Method for Estimation of Net Heat of Com- ^ These standards are available from Defense Printing Service De-
bustion of Aviation Fuels tachment Office, 700 Robbins Ave., Piiiladelphia, PA 19111-5094.
MIL-M-81380 Monitor, Contamination, Aviation Fuel [7] Honsberger, B. A., "Jet A Exposure to Freezing on Very Cold
Dispensing System Temperatures," Boeing Company CommercicJ Airplane Group,
MIL-DTL-83133 Turbine Fuel, Aviation, Kerosine Type presented to CRC Group on Low Temperature Performance of
Aviation Turbine Fuel, June 1991.
(Grade JP-8)
[8] Unpublished minutes of the CRC Low Temperature Perfor-
mance of Aviation Turbine Fuels, Coordinating Research Coun-
U. K. M i l i t a r y A v i a t i o n T u r b i n e F u e l a n d A d d i t i v e cil, Atlanta, GA, May 1999.
Specifications [9] Aviation Fuel Properties, CRC Report No. 530, Coordinating Re-
search Council, Atlanta, GA, 1983.
These standards are available from Ministry of Defence, Di- [10] Final Report, Fuel Tank Harmonization Working Group of Avi-
rectorate of Standardization, 65 Brown Street, Glasgow G2 ation Rulemaking Advisory Committee, Federal Aviation Ad-
SEX. ministration, Washington, DC, July 1998.
No. Title [11] Rogers, J. D., "Turbine Fuel Thermal Stability," SAE Preprint
103T, Society of Automotive Engineers, National Aeronautic
Defence Standard 91-86 ATF High Flash AVCAT/FSII Meeting, Los Angeles, CA, 5-9 Oct. 1959.
Defence Standard 91-87 ATF Wide Cut AVTAG/FSII [12] Thermal Oxidation Stability of Aviation Turbine Fuels, Mono-
Defence Standard 91-90 AVGAS Gasoline Aviation 80 and graph /, R. N. Hazlett, Ed., ASTM International, West Con-
lOOLL (low lead) shohocken, PA, 1991, pp. 72-91.
Defence Standard 91-91 Turbine Fuel, Aviation Kerosine [13] Heneghan, S. P., Zabamik, S., Ballal, D. R., and Harrison, W. E.,
Type, Jet A-1 Ill, "JP-8 + 100: TheDevelopmentof High-Thermal-Stability Jet
Defence Standard 91-251 Fuel System Icing Inhibitor Fuel," Transactions oftheASME, Vol. 118, September 1996.
(FSII) [14] Strauss, K. H., "Survey of Current Engine Conditions," CRC Re-
Defence Standsird 68-251 Fuel Soluble Pipeline Corrosion port 573, Coordinating Research Council, Atlanta, GA, 1983.
[15] Strauss, K. H., "Thermal Stability Testing of Jet Fuel - A Critical
Lubricity Improving Additive
Review," Technical Paper 881532, Society of Automotive Engi-
neers, Aerospace Technology Conference, Anaheim, CA, 3-6
Industry Specifications Oct. 1988.
[16] Baker, C, David, P., Taylor, S. E., and Woodward, A. J., "Thick-
API/IP 1581 Specifications and Qualification Procedures for ness Measurement of JFTOT Tube Deposits by EUipsometry,"
Aviation Jet Fuel Filter/Separators Proceedings of 5th International Conference on the Stability and
API/IP Specification for Similarity for API/IP 1581 Aviation Handling of Liquid Fuels, Rotterdam, 1994, pp. 433^47.
Jet Fuel Filter/Separators [17] Unpublished minutes of the Groups on Aviation Engine Octane
API/IP 1583 Specifications and Qualification Procedures for Rating and Unleaded Avgas Development, Coordinating Re-
Aviation Fuel Filter Monitors with Absorbent T5rpe Ele- search Council, Atlanta, GA, 1995.
[18] Sherwood, W. D., "SST Fuels—A Major Airline Concern,"
ments
Preprint 911C, Society of Automotive Engineers, National Aero-
API/IP Specifications and Qualification Procedures for Avia- nautic and Space Meeting, Los Angeles, CA, 5-9 Oct. 1964.
tion Fuel Microfilters [19] Gleason, C. C, Oiler, T. L., Shayeson, M. W., and Bahr, D. W.,
ATA 103, Standards for Jet Fuel Quality Control at Airports "Evaluation of Fuel Character Effects on FlOl Combustion Sys-
LATA Guidance Material for Aviation Turbine Fuels Quality tem," AFAPL-TR-79-2018, General Electric Company, Cincin-
Control and Operating Procedures, Incorporating Joint In- nati, OH, June 1979.
spection Group Guidelines for Joint Airport Depots and [20] Lefebre, A. H., "Influence of Fuel Properties on Gas Turbine
Joint into Plane Combustion Performance," AFWAL-TR-84-2104, Purdue Uni-
lATA Guidance Material for Aviation Turbine Fuels versity, Lafayette, IN, January 1985.
[21] Dickson, C. L., "Aviation Turbine Fuels, 1998," National Insti-
tute for Petroleum and Energy Research, NIPER-175 PPS,
March 1998.
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reau of Mines, Petroleum Products Survey No. 39, 1964.
[1] Ogsten, A. R, "A Short History of Aviation Gasoline Develop- [23] Rickard, G. K. and Fulker, R., "The Quality of Aviation Fuel
ment, 1903-1980," Preprint No. 810848, SAE, West Coast Inter- Available in the United Kingdom Annual Survey 1997," Techni-
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[2] Dukek, W. G., "Aviation Fuel: Its Energy has Knit the World," [24] Gibbons, T. R., "Flash Point Methods Applicable to Jet Fuel,"
Standardization News, ASTM International, West Consho- Factors in Using Kerosine Jet Fuel of Reduced Flash Point, STP
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[3] Defence Standard 91-91: Turbine Fuel, Aviation Kerosine, Type [25] Final Report, Fuel Taiik Harmonization Working Group of Avi-
Jet A-1, Issue 3, Ministry of Defence, Directory of Standardiza- ation Rulemaking Advisory Committee, Federal Aviation Ad-
tion, Glasgow, FG2 SEX, United Kingdom, November 1999. ministration, Washington, DC, July 1998.
[4] Guidance Material for Aviation Turbine Fuel, fourth edition. In- [26] Smith, M., Aviation Fuels, G. T. Foulis & Co. Ltd., Henley-on-
ternational Air Transport Association, Montreal, Canada, March Thames, Oxfordshire, United Kingdom, 1970, pp. 369-371.
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DeGuizeman, R., "The Distribution of Higher n-Alkanes in Par- PA, 1991, pp. 111-113.
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Research Laboratory, Washington, DC, 10 April 1985. Thames, Oxfordshire, United Kingdom, 1970, pp. 117-118.
[6] Smith, M., Aviation Fuels, G. T. Foulis & Co Ltd, Henley-on- [29] "Determination of the Hydroperoxide Potential of Jet Fuels," CRC
Thames, Oxfordshire, United Kingdom, 1970, pp. 272-278. Report 559, Coordinating Research Council, Atlanta, GA, 1988.
[30] Pande, S. G, Black, B. H., and Hardy, D. R., "Development of a [36] Smith, M., Aviation Fuels, G. T. Foulis & Co. Ltd., Henley-on-
Test Method for t h e Determination of the Hydroperoxide Po- Thames, Oxfordshire, United Kingdom, 1970, pp. 192-196.
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MNL37-EB/Jun. 2003
Automotive Diesel and

Non-Aviation Gas Turbine Fuels
Steven R. Westbrook^ and Richard LeCren^
The diesel engine is now fully established in a variety of ap- nia. From this time until about 1900, kerosine for oil lamps
plications on land and in marine use. On land, it serves to was the most valuable fraction of the petroleum barrel. The
power trains, buses, trucks, and automobiles; to run con- fraction now known as gasoline was considered surplus and
struction, petroleum drilling, and other off-road equipment; burned. The heavier residual fraction was typically dumped
and to be the prime mover in a wide range of power genera- into pits or other convenient dumping grounds. The middle
tion and pumping applications. At sea, it serves both to pro- distillate fraction, which would eventually be used in diesel en-
vide main propulsion power and run auxiliaries. gines, was used in the town gas industry. It was used "either as
Gas turbine engines also serve in a wide range of applica- a source of domestic gas, or for enriching or carburetting wa-
tions. Over half the larger industrial gas turbines are in elec- ter gas, or as an absorbing agent or 'wash oil' for removing con-
tric-generation use. Other uses include gas pipeline trans- densable constituents from coal gas" [2]. This is the reason
mission, co-generation systems, and transportation. In the that this fraction is still often referred to as gas oil. Through-
military, gas turbines power a number of combatant ships out this time, the middle distillate fraction of the petroleum
both as main propulsion units and as the power source for barrel was primarily a leftover product with no leirge market.
auxiliary uses. Gas turbines are also used to power some mil- The invention of the diesel engine changed that for the better.
itary ground vehicles such as main battle tanks.
The quality criteria and methods for testing fuels for land
and marine diesel engines and for non-aviation gas turbines Compression Ignition Engines
are sufficiently similar to address in a common chapter. Ob- Since it's beginning in the 1890s, the diesel engine quickly be-
viously, certain criteria and tests will apply to one or the came the engine of choice for many industrial and marine ap-
other rather than both. For example, the cetane number, plications, applications where the larger, heavier, slower
which is a critical property for diesel fuels, is of limited sig- speed engine excelled in cost and performance when com-
nificance for gas turbine fuels. Conversely, sodium and vana- pared to alternative power plants of the time. However, the
dium content are important in assessing gas turbine fuels, diesel engine saw only limited use in automotive and aviation
but not those used in diesel engines. This chapter presents in- applications. After World War I, shortages of gasoline in Ger-
formation regarding fuels for both automotive diesel engines many helped stimulate work on the diesel engine, especially
and gas turbines. as an automotive engine. Diesel engines were used for
The petroleum industry started in the 1850s. Two factors propulsion on the Hindenburg.
were especially important as impetus. Machines were being Suppljdng fuel to the engine was the major obstacle to a
developed and they needed oil for lubrication. Also, oil lamps higher-speed, lower-weight engine suitable for automotive
were being used to light homes and offices and the whale oil use. Compressed air injection was complicated and the re-
traditionally burned in these lamps was growing increasingly quired air pump could not be substantially reduced in either
expensive. James Young, a Scotsman, had recently patented size or weight. In 1922, Robert Bosch set out to develop a
a process for converting coal to coal oil. Coal oil was less ex- fuel-injection system for diesel engines [3]. By early 1923,
pensive than whale oil but smoked and produced a foul smell about a dozen different designs had been developed and ini-
when burned. Then, in 1857, lamp maker A.C. Ferris pro- tial trials were underway by mid-1923. A final design was ap-
duced clean-burning kerosine that did not have a bad smell proved in 1925 and the first series production fuel-injection
[1]. The oil used for making the kerosine was being skimmed pump was on the market.
from natural crude oil seeps until Colonel Edwin Drake
drilled into one of the seeps, near Titusville, Pennsylvania, us- The fuel-injection system opened the door for wide spread
ing a rig of the type used for drilling brine wells. An oil boom use of the diesel engine in previously untried applications. By
was bom. the mid-1930s there were large numbers of diesel-powered
trucks and buses in service; but only small numbers of diesel-
During the 1860s, oil exploration and drilling expanded to powered automobiles. By the beginning of World War II in
Ohio, Termessee, New York, Kentucky, Colorado, and Califor- 1939, the diesel engine was in widespread use as an automo-
bile engine. The German military also used diesel engines for
many of their vehicles, including some aircraft [4]. Gasoline
' Manager, Petroleum Products Technology, Southwest Research In- engines, because of the logistics problems faced with a two-
stitute, P.O. Drawer 28510, San Antonio, TX 78228. fuel supply system, powered the Allied Forces almost exclu-
^ Consultant Engineer, Gas Turbine Combustion & Fuels, Retired,
3760 Sioux Avenue, San Diego, CA 92117. sively. Following World War II; the greater fuel economy of
115
>.
(0
Q
a.
m
CD
m
0 J
1950 1960 1970 1980 1990 2000

Year
Source: U.S. Energy Information Administration
FIG. 1—Diesel fuel supplied to the transportation sector.
the diesel engine caused a rapid increase in the use of the en- Following World War II, it was recognized that D 396 did
gine for automotive applications throughout Europe. The not sufficiently specify the quality of the fuel needed for
abundance of inexpensive gasoHne in the United States low- newer diesel engines. D 396 contains no specification for the
ered incentives for adopting the diesel engine in trucks and ignition quality of the fuel, as an example. So, in 1948, Com-
automobiles. Even still, throughout this period, the diesel en- mittee D2 published D 975-48 T, Tentative Specifications for
gine climbed in popularity for use in railroad, marine, and Diesel Fuel Oils.
heavy-construction equipment applications. The use of the
diesel engine increased until virtually 100% of current ma-
rine, trucking, railroad, construction, and much of the sta- Fuel Grades
tionary power generation applications operate on diesel en-
gines. The fuels used in these engines have, over time, varied When first published, D 975 contained specifications for
from natural gas to crude oil but the middle distillate, num- "three grades of Diesel fuel oils suitable for various t5rpes of
ber 2 grade liquid fuel, is the fuel of choice for many of these Diesel engines." The grades were No. 1-D, No. 2-D, and No. 4-
applications. Figure 1 shows the increase in diesel fuel usage D. Table 1 provides a description, of each grade, from the
for transportation since 1949 [5]. 1948 standard and the 1996 standard. It is interesting to note
that the description of Grade 2-D in the 1948 version did not
include automotive applications, reflecting the fact that
diesel engines were for heavy-duty use and large trucks. Fuel
DIESEL FUEL SPECIFICATIONS grades Low Sulfur No. 1-D and Low Sulfur No. 2-D were
added in 1993. These latter grades were added to comply with
From the turn of the twentieth century until the mid-1930s 40 CFR Part 80—Regulation of Fuels and Fuel Additives: Fuel
there existed no widely used consensus specification for fuel Quality Regulations for Highway Diesel Fuel Sold in 1993
for diesel engines. Those needing diesel fuel likely bought and Later Calendar Years.
whatever was available on the market that seemed like a us-
able fuel. In 1934, ASTM Committee D2 published D 396, The limiting properties included in the 1948 specification
Standard Specification for Burner Fuels. This specification were flash point, pour point, water and sediment, carbon
covers fuels for fuel-oil burning equipment (such as home residue, ash, distillation, viscosity, sulfur, copper strip corro-
heating oils). However, fuels of grades 1 and 2 in this specifi- sion, and cetane number. Since then, pour point has been re-
cation would have probably been acceptable for most diesel moved from the specification table. Other changes to the
engines of the time. D 396 was used in many purchase con- specification table have also occurred over the years. Table 2
tracts as the controlling specification, thereby allowing both is a summary of many of the major changes.
buyer and seller to agree on the minimum quality of the fuel.
Starting in the eeirly to mid-1930s, the demand for diesel fuel
began to rise at a steady rate in most of the industriEilized na- DIESEL FUEL PROPERTIES
tions of the world. (During World War II, this demand slowed
some owing to the essentially 100% use of gasoline by the Al- Table 3 contains the specific requirements for the fuels
lied Forces.) Diesel engines were becoming increasingly sen- covered by D 975. The properties listed in that table, along
sitive to the quality of the fuel in order to maintain optimum with other selected properties of importance, are discussed
engine performance. below.
CHAPTER 5: GAS TURBINE FUELS 117
TABLE 1—Descriptions of the fuels covered by into the sample and zJlowed to settle. After temperature
Specification D 975. equilibrium h a s been reached, the hydrometer scale is
Grade D 975-48 T D 975-98b read, and the temperature of the sample is noted. If neces-
No. 1-D A volatile distillate A special-purpose, light sary, the cylinder and its contents may be placed in a con-
fuel oil for engines distillate fuel for stant t e m p e r a t u r e b a t h to avoid excessive t e m p e r a t u r e
in service requiring automotive diesel engines variation during the test.
frequent speed and in applications requiring
load changes. higher volatility than that • ASTM D 4052, Standard Test Method for Density and Rela-
provided by Grade No. tive Density of Liquids by Digital Density Meter—Â small vol-
2-D fuels. u m e (approximately 0.7 mL) of liquid sample is introduced
Low Sulfur Not Applicable A special-purpose, light into an oscillating sample tube and the change in oscillat-
No. 1-D distillate fuel for ing frequency caused by the change in the mass of the tube
automotive diesel engines is used in conjunction with calibration data to determine
requiring low sulfur fuels the density of the sample.
and requiring higher
volatility than that API gravity (D 1298) is another measure of the density of fuel
provided by Grade Low that has been used for years. A fuel with a high API gravity is
Sulfur No. 2-D. a low-density fuel and a low API gravity fuel is a high-density
No. 2-D A distillate fuel oil of A general-purpose, middle fuel. It is calculated with the following formula:
low volatility for distillate fuel for
engines in industrial automotive diesel engines, API gravity, deg = (141.5/S)-131.5
and heavy mobile which is also suitable for
use in non-automotive Where 5 = density, kg/nr' at 15°C
applications, especially in
conditions of frequently
varying speed and load.
Low Sulfur A general-purpose, middle TABLE 2—Summary of the major changes" to Specification
Not Applicable
No. 2-D distillate fuel for auto- D 975 since it was first published.
motive diesel engines Year Changes
requiring low sulfur fuel. 1948 First published as a tentative standard.
It is also suitable for use 1950 Changes to pour point and viscosity limits.
in non-automotive 1953 Further clzirification of pour point and copper strip
applications, especially in corrosion limits.
conditions of varying
speed and load. 1959 Table 1 was revised to add a 90% distilled minimum
temperature for Grade 2-D, and add a revised min-
No. 4-D A fuel oil for low and A heavy distillate fuel, or a imum viscosity at 100°F for Grade 2-D.
medium speed blend of distillate and 1960 The nomograph for the calculated cetane index
engines. residual oil, for low- and method (then an appendix to the specification)
medium-speed diesel was revised.
engines in non- 1964 Section 2 was added to specify that the properties of
automotive applications the fuel apply at the time and place of delivery.
involving predominantly Section 4 was amended to permit use of Method D
constant speed and load. 56 as Ein alternate for Method D 93 to determine
flash points of Grade 1-D fuels.
1965 The viscosity and 90% distillation requirements for
Grade 2-D were revised.
1966 The sulfur limit for Grade 2-D was lowered from 1.0
Density wt% to 0.7 wt%. The cetane index method was re-
moved from the appendix and became D 976.
Density is the mass per unit volume of the fuel. This property 1967 The standard was adopted without revision and was
is not specified in D 975. However density is a fundamental no longer a tentative method.
physical property that can be used in conjunction with other 1968 The sulfur limit for Grade 2-D was lowered from 0.7
wt% to 0.5 wt%.
properties to characterize both the light and heavy fractions 1973 The allowable amount of water and sediment in
of petroleum cind petroleum products. Accurate determina- Grade 1-D was raised from trace to 0.05 volume
tion of the density of petroleum products is also necessary for percent.
the conversion of measured volumes to volumes at the stan- 1974 The cloud point requirement and the U.S. 10th per-
dard temperature of 15°C (60°F). While density is a factor centile temperatures were added as an appendix.
These are used to help set cloud point limits.
governing the quality of crude petroleum, it is an uncertain 1978 The viscosity limits were lowered for all grades.
indication of petroleum product quality unless correlated 1988-1990 Several changes in format. Standard D 4737 re-
with other properties. placed D 976 for the calculation of cetane index.
The two methods most commonly used to measure density 1992 Grades 1-D low sulfur and 2-D low sulfur were
added to the table. A footnote on the use of blue
are: dye in high sulfur fuel was also added to Table 1.
• ASTM D 1298, Standard Test Method for Density, Relative 1994 An appendix on the lubricity of diesel fuel was
Density (Specific Gravity), or API Gravity of Crude added.
1996 The footnote regarding the use of blue dye was
Petroleum and Liquid Petroleum Products by Hydrometer changed to reflect changes in the federal regula-
Method—The sample is brought to the prescribed temper- tions, which now require red dye.
ature a n d transferred to a cylinder at approximately the "Not all changes are included. Editorial revisions and most of the changes
same temperature. The appropriate hydrometer is lowered to appendices were left oft this list.
TABLE 3—Detailed requirements for diesel fuel oils."

Grade Low Grade Low
ASTM Test Sulfur Sulfur Grade Grade Grade
Property Method^ No. 1-D^ No. l-D"'' No. 1-D' No. 2-0*' No. 4-D'
Flash Point, °C, min. D93 38 52 38 52 55
Water and Sediment, % vol, max D2709 0.05 0.05 0.05 0.05
D 1796 0.50
Distillation Temperature, °C 90 % % vol D86
Recovered
min 282'^ 282^*
max 288 338 288 338
Kinematic Viscosity, mm^/S at 40°C D445
min 1.3 1.9 1.3 1.9 5.5
max 2.4 4.1 2.4 4.1 24.0
Ash % mass, max D482 0.01 0.01 0.01 0.01 0.10
Sulfur, % mass, max^ D 2622« 0.05 0.05
D129 0.50 0.50 2.00
Copper strip corrosion rating mjix 3 h D130 No. 3 No. 3 No. 3 No. 3
at SOX
Cetane number, min'' D613 40" 40" 40' 40' 30'
One of the following properties must
be met:
(1) Cetane index, min. 916f 40 40
(2) Aromaticity, % vol, msix 1319'" 35 35
Cloud point, °C, max 2500 ; ;
Ramsbottom carbon residue on 10% 524 0.15 0. 0.15 0.35
distillation residue, % mass, max
"To meet special operating conditions, modifications of individual limiting requirements may be agreed upon between purchaser, seller, and manufacturer.
''The test methods Indicated are the approved referee methods. Other acceptable methods are Indicated in 3.1.
"Under United States regulations. If Grades Low Sulfur No. 1-D or Low Sulfur No. 2-D are sold for tax exempt purposes then, at or beyond terminal storage
tanks, they are required by 26 CFR Part 48 to contain the dye Solvent Red 164 at a concentration spectrally equivalent to 3.9 lbs per thousand barrels of the solid
dye standard Solvent Red 26, or the tax must be collected.
''when a cloud point less than — 12°C is specified, the minimum flash point shall be 38°C, the minimum viscosity at 40°C shall be 1.7 mm^/s, and the minimum
90% recovered temperature shall be waived.
'Under United States regulations. Grades No. 1-D, No. 2-D, and No. 4-D are required by 40 CFR Part 80 to contain a sufficient amount of the dye Solvent Red
164 so Its presence Is visually apparent. At or beyond terminal storage tanks, they are required by 28 CFR Part 48 to contain the dye Solvent Red 164 at a concen-
tration spectrally equivalent to 3.9 lbs per thousand barrels of the solid dye standard Solvent Red 26.
'Ôther sulfur limits can apply In selected areas in the United States and In other countries.
^These test methods are specified in 40 CFR Part 80.
''Where cetane number by Test Method D 613 Is not available, Test Method D 4737 can be used as an approximation.
'Low ambient temperatures as well as engine operation at high altitudes may require the use of fuels with higher cetane ratings.
'It is unrealistic to specify low temperature properties that will ensure satisfactory operation at all ambient conditions. In general, cloud point (or wax appear-
ance point) may be used as an estimate of operating temperature limits for Grades Low Sulfur No. 1; Low Sulfur No.2; and No.l and No. 2 diesel fuel oils.
However, satisfactory operation below the cloud point (or wax appearance point) may be achieved depending on equipment design, operating conditions, and the
use of flow-improver additives as described in X4.1.2. Tenth percentile minimum air temperatures for U.S. locations are provided in Appendix X4 as a means of
estimating expected regional temperatures. This guidance Is general. Some equipment designs or operation may allow higher or require lower cloud point fuels.
Appropriate low temperature operability properties should be agreed upon between the fuel supplier and purchaser for the Intended use and expected ambient
temperatures.
Even though, as use of the International System of Units (SI) combustion. The nature of the fuel is an important factor in
becomes more common, use of API gravity decreases, API reducing ignition delay. Physical characteristics such as vis-
Gravity is arguably the most widely used cheiracteristic for cosity, gravity, and mid-boiling point are influential. Hydro-
"mass" of petroleum. carbon composition is also important as it affects both the
physical and combustion characteristics of the fuel. Straight-
chain paraffins ignite readily under compression, but
Ignition and Combustion Characteristics branched-chain peiraffins and aromatics react more slowly.
(Cetane Number) The first widely used measure of ignition quality was the
The first diesel engines were large and slow-speed and were diesel index, calculated as:
not particularly sensitive to the quality of the fuel they
Diesel Index = [(API Gravity)(Aniline Point)] /100
burned. As steady improvements were made to the engine,
there was a need to improve fuel quality as well. Gradually, The aniline point is the lowest temperature at which equal
the heavier, more viscous, diesel fuels disappeared with amounts of fuel and aniline are completely miscible. Aro-
lighter and higher speed engines. The higher speed engines matic compounds tend to exhibit higher density than paraf-
are more sensitive to the ignition quality of the fuel; there- finic compounds and they are better solvents. Therefore, a
fore, cetane numbers became the property of greatest con- fuel that is high in aromatics will generally have a lower ani-
cern to both producers and users. Diesel engine performance line point than a fuel that is high in paraffins. So, a high
is a function of compression ratio, injection timing, the man- paraffin fuel will tend to have a higher API Gravity and a
ner in which fuel and air are mixed, and the resulting ignition higher aniline point. This combination results in a higher
delay or time from the start of injection to the beginning of diesel index, which indicates better starting characteristics.
The diesel index equation may be misleading, especially with minimum cetane number of 40 [8] and this is the require-
blended fuels and fuels treated with ignition-improver addi- ment in D 975. Many engine manufacturers are now pushing
tives. to raise the specification minimum limit to 50 cetane in or-
By the mid-1930s, it was determined that a better mea- der to meet new engine emission requirements (see the dis-
surement of ignition quality was needed. The result was an cussion of the Worldwide Fuels Charter below).
engine test:
• ASTM D 613 Standard Test Method for Ignition Quality of
Cetane Index
Diesel Fuels by the Cetane Method—The cetane number of a
diesel fuel is determined by comparing its ignition quality Two ASTM test methods for calculating approximate cetetne
with those for blends of reference fuels of known cetane numbers were also developed for situations when performing
numbers under standard operating conditions. Varying the the engine test was not feasible. Two ASTM methods, and the
compression ratio for the sample and each reference fuel to equations for each, are:
obtain a fixed "delay period," that is, the time interval be-
• ASTM D 976, Standard Test Method for Calculated Cetane
tween the start of injection and ignition does this. When
Index of Distillate Fuels
the compression ratio for the sample is bracketed between
those for two reference fuel blends differing by not more Calculated Cetane Index = 454.74 - 1641.416 D
than five ceteine numbers, the rating of the sample is cal- + 774.74 0^-0.554 5 + 97.803 (log 5)^
culated by interpolation.
Where:
This test involves operating a standard, single cylinder, D = density at 15°C, g/mL, determined by Test
variable compression ratio engine using a specified fuel flow Method D 1298, and
rate and time of injection (injection advance) for the fuel B = mid-boiling temperature, °C, determined by
sample and each of two bracketing reference fuels of known Test Method D 86 and corrected to standard
cetane number. The engine compression ratio is adjusted for barometric pressure.
each fuel to produce a specified ignition delay, and the cetane • ASTM D 4737, Standard Test Method for Calculated Cetane
number is calculated to the nearest tenth by interpolation of Index by Four Variable Equation
the compression ratio values.
The cetane number scale uses two primary reference fuels. CCI = 45.2 + (0.0892)(rioN) + [0.131 + (0.901)B][r50N]
One, n-hexadecane (normal cetane), has excellent ignition + [0.0523 - (0.420)B][r90N]
qualities and, consequently, a very short ignition delay. This + [0.00049][(rioN)^ - (T'OTN)^] + 1075 -H 605^
fuel was arbitrarily assigned a cetane number of 100. The sec- Where:
ond fuel, a-methylnaphthalene, has poor ignition qualities CCI - Calculated Cetane Index by Four Variable Equation,
and was assigned a cetane number of zero. The a-methyl- D = Density at 15°C, determined by Test Method D
naphthalene was later replaced with heptamethylnonane, 1298,
which was calibrated against the original fuels and assigned DN =D- 0.85,
a cetane number of 15. The cetane number scale is now de- B = [e(-3-5XDN)] _ 1^
fined by the following equation for volumetric blends of the Tio = 10% recovery temperature, °C, determined by Test
two primary reference materictls: Method D 86 and corrected to standard barometric
pressure,
Cetane Number = % n-cetane TioN — Tio — 215,
-F 0.15 (percent heptamethylnonane) Tso = 50% recovery temperature, °C, determined by Test
Method D 86 and corrected to standard barometric
In practice, the primary reference fuels are only utilized to pressure,
calibrate two secondary reference fuels. These are selected T50N = Tso ~ 260,
diesel fuels of mixed hydrocarbon composition, which are Tgo = 90% recovery temperature, °C, determined by Test
designated as "T" and "U". "T" fuel typically has a cetane
Method D 86 and corrected to standard barometric
number of approximately 75 while "U" fuel is usucilly in the pressure,
low 20 cetane number range. Each set of "T" and "U" fuels are
TgoN = T90 — 310
paired and test engine calibrations define the cetane num-
bers for volumetric blends of these two secondaries [6]. In Both methods utilize fuel density and distillation values in
general, the contribution of various fuel components to bulk their calculations. Standard D 4737 is the more widely used
fuel cetane number can be described as follows [7]: method since it is the most recent and it better represents
current diesel fuels. Some limitations of calculated cetane in-
dex include:
Normal Paraffins > Branched Paraffins > Normal Olefins
> Branched Olefins > Naphthenes > Aromatics 1. It is not applicable to fuels containing additives for raising
cetane number.
=> Decreasing Cetane Number => 2. It is not applicable to pure hydrocarbons, synthetic fuels,
alkylates, or coal tar products.
Higher cetane number fuels tend to reduce combustion 3. Correlation is fair for a given type of fuel but breaks down
noise, increase engine efficiency, increase power output, if fuels of widely different composition are compared.
start easier (especially at low temperatures), reduce exhaust 4. Appreciable inaccuracy in correlation may occur when
smoke, and reduce exhaust odor. To assure acceptable cold used for crude oils, residuals (or blends containing residu-
weather performance, most modern diesel engines require a als), or products having end points below 260°C.
Numerous other cetane index equations/models have been with more deviation at the beginning and end of the distilla-
developed, used, and compzired to the ASTM equations but tion Eind less deviation at the center. For this reason, D 2887
they have never been formaHzed as a n ASTM standard. Addi- is not Ein accepted eJtemative to D 86 for specification pur-
tional information concerning some of these non-ASTM poses. That will remain the case until a suitable correlation
methods can be found elsewhere [9-11]. (correction factor) between the two is determined.
Figure 3 is the D 2887 gas c h r o m a t o g r a m for the fuel
shown in Fig. 2. The chromatogram illustrates the usefulness
Volatility / Distillation of the D 2887 method. The time axis can be correlated to car-
bon n u m b e r by using a known standard. Therefore, it is pos-
The distillation characteristics of a diesel fuel exert a great in- sible to obtain a "picture" of the carbon n u m b e r distribution
fluence on performance. Two methods are commolily used to in a given fuel. This method is also useful for identifying con-
measure distillation characteristics: taminants such as gasoline a n d engine oil.
• ASTM D 86, Standard Test Method for Distillation of The average volatility requirements of diesel fuels vary
Petroleum Products—Â 100 mL sample is distilled u n d e r with engine speed, size, cind design. However, fuels having
prescribed conditions that are appropriate to its nature. too low volatility tend to reduce power output Eind fuel econ-
Systematic observations of thermometer readings and vol- omy through poor atomization, while those having too high
umes of condensate are made, and from these data, the re- volatility m a y reduce p o w e r o u t p u t a n d fuel economy
sults of the test are calculated and reported. through vapor lock in the fuel system or inadequate droplet
• ASTM D 2887, Standard Test Method for Boiling Range Dis- penetration from the nozzle. I n general, the distillation range
tribution of Petroleum Fractions by Gas Chromatography— should be as low as possible without adversely affecting the
The boiling range distribution determination by distilla- flash point, burning quality, heat content, or viscosity of the
tion is simulated by the use of gas c h r o m a t o g r a p h y . A fuel. If the 10% point is too high, poor starting may result. An
non-polar packed or open t u b u l a r (capillary) gas chro- excessive boiling range from 10-50% evaporated may in-
matographic column is used to elute the hydrocarbon com- crease warm-up time. A low 50% point is desirable to mini-
ponents of the sample in order of increasing boiling point. mize smoke and odor. Low 90% cind end points tend to en-
The column temperature is raised at a reproducible lineeir sure low carbon residuals and minimum crankcase dilution.
rate and the area u n d e r the c h r o m a t o g r a m is recorded The temperature for 50% evaporated, known as the mid-
throughout the analysis. Boiling points are assigned to the boiling point, usucdly is taken as a n overall indication of the
time axis from a calibration curve obtained under the same fuel distillation chziracteristics when a single numerical value
chromatographic conditions by analyzing a known mix- is used alone. For example, in high-speed engines a 50%
ture of hydrocarbons covering the boiling range expected point above 302°C might cause smoke formation, produce
in the sample. From these data, the boiling range distribu- objectionable odor, cause lubricating oil contamination, and
tion can be obtained. promote engine deposits. At the other extreme, a fuel with ex-
Method D 86 is the specified method in D 975 for measur- cessively low 50% point would exhibit too low a viscosity eind
ing distillation characteristics. Figure 2 is a plot of distillation heat content per unit volume. Therefore, a 50% point in the
data for a single, typical diesel fuel using both methods. It is range of 232-280°C is desirable for the majority of higher
obvious from this plot that the two methods can give quite speed diesel engines. This t e m p e r a t u r e range usually is
different results. For most fuels, results like these are typical; broadened for Icirger, slower speed engines [12].
100 D86
D2887
- 80
I 40
on 20 -
0-"
100 150 200 250 300 350 400 450

Distillation Temperature, °C
FIG. 2—Distillation curves for a typical no. 2 diesel fuel (methods D 86

vs. D 2887).
good mixing. Combustion is impaired and power output and

economy are decreased. Low viscosity can lead to excessive
leakage past the injection pump plunger. Fuel metering be-
comes inaccurate and engine efficiency is reduced. Wear of
the fuel system components may increase because lubricat-
ing properties of fuels tend to decrease with viscosity.
Fuel viscosities for high-speed engines range from 1.8-5.8
centistokes (cSt) at 38°C. Usually the lower viscosity limit is
established to prevent leakage in worn fuel injection equip-
ment as well as to supply lubrication for injection system
components in certain types of engines. During operation at
low-atmospheric temperatures, the viscosity limit sometimes
is reduced to 1.4 cSt at 38°C to obtain increased volatility etnd
sufficiently low pour point. Fuels having viscosities greater
than 5.8 cSt usually are limited in application to the slower-
speed engines. The very viscous fuels commonly used in large
Time stationary and mcirine engines normally require preheating
for proper pumping, injection, and atomization.
FIG. 3—D 2887 gas chromatogram of a typical diesel fuel.
For the above reasons, some points on the distillation curve Cloud Point
are considered more important and are included in fuel spec-
All diesel fuels contain dissolved paraffin wax. As the tem-
ifications more often. Specification D 975 contains only a perature of the fuel decreases, so does the solubility of the
limit on the 90% point. Other specifications include require- wax in the fuel. At some point wax crystals will begin to pre-
ments for initial boiling point (more so for gasoline), 10%, cipitate. If enough wax precipitates the crystals can block fuel
50%, and to a lesser degree, 95% and final boiling point. flow through screens, filters, and other restricted passages in
the fuel system. The temperature at which the wax precipita-
Viscosity tion occurs depends upon the origin, type, refining, and boil-
ing range of the fuel. This temperature is known as the cloud
The method for measuring viscosity of diesel fuel is: point of the fuel. As the cloud point goes up, the suitability of
• ASTM D 445, Standard Test Method for Kinematic Viscosity the fuel for low-temperature operation decreases. The cloud
of Transparent and Opaque Liquids (and the Calculation of point of the fuel can be measured by the following methods:
Dynamic Viscosity)—The time is measured for a fixed vol-
ume of liquid to flow under gravity through the capillary of • ASTM D 2500, Standard Test Method for Cloud Point of
a calibrated viscometer under a reproducible driving head Petroleum Products—The specimen is cooled at a specified
and at a closely controlled and known temperature. The rate and examined periodically. The temperature at which
kinematic viscosity is the product of the measured flow a cloud is first observed at the bottom of the test jar is
time and the calibration constant of the viscometer. recorded as the cloud point.
The unit of measurement for this method is square mil- The following methods are variations of D 2500, including,
limeters per second (mm^/s), also known as centistokes (cSt). both automatic and automated methods:
This is currently the most widely used unit of fuel viscosity • ASTM D 3117, Standard Test Method for Wax Appearance
measurement in the United States. Other units used in the Point of Distillate Fuels
past, and occasionally still used in the present, include Say- • ASTM D 5771, Standard Test Method for Cloud Point of
bolt Universal Seconds (SUS) and centipoise. Petroleum Products (Optical Detection Stepped Cooling
For some engines it is advantageous to specify a minimum Method)
viscosity because of power loss due to injection pump cuid in- • ASTM D 5772, Standard Test Method for Cloud Point of
jector leakage. Maximum viscosity, on the other hand, is lim- Petroleum Products (Linear Cooling Rate Method)
ited by considerations involved in engine design and size, and • ASTM D 5773, Standard Test Method for Cloud Point of
the characteristics of the injection system. Fuel viscosity ex- Petroleum Products (Constant Cooling Rate Method)
erts a strong influence on the shape of fuel spray. High vis- For all grades of fuel listed in D 975, any of these test meth-
cosities can cause poor atomization, large droplets, and high- ods may be used to measure cloud point. Method D 2500 is the
spray jet penetration. With high viscosities, the jet tends to be specified method and the others are considered alternates. In
a solid stream instead of a spray of small droplets. As a result, case of dispute. Test Method D 2500 is the referee method.
the fuel is not distributed in, or mixed with, the air required Cloud point is the only control for low temperature oper-
for burning. This results in poor combustion, accompanied ability listed in the diesel fuel specification, D 975. Footnote
by loss of power and economy. In small engines, the fuel J to Table 1 in D 975 reads as follows:
spray may impinge upon the cylinder walls, washing away It is unrealistic to specify low temperature properties that
the lubricating oil film and causing dilution of the crankcase will ensure satisfactory operation at all ambient condi-
oil. Such a condition contributes to excessive wear [13]. tions. In general, cloud point (or wax appearance point)
Low fuel viscosity results in a spray that is too soft and does may be used as an estimate of operating temperature lim-
not penetrate far enough in the combustion chamber for its for Grades Low Sulfur No. 1: Low Sulfur No. 2; and No.
October—10th Percentile Minimum Temperatures

FIG. 4—Example 10th percentile minimum ambient temperature map from D 975.
1 and No. 2 diesel fuel oils. However, satisfactory opera- Pour Point
tion below the cloud point (or wax appearance point) may
be achieved depending on equipment design, operating Before a fuel can be burned in an engine it must first be
condition, and the use of flow-improver additives... Tenth pumped from the fuel tank. The lowest temperature at which
percentile minimum air temperatures for U.S. locations a fuel can be pumped is known as the pour point of the fuel.
Test methods for measuring pour point include:
are provided.. .as a means of estimating expected regional
temperatures. This guidance is general. Some equipment • ASTM D 97, Standard Test Method for Pour Point of
designs or operation may allow higher or require lower Petroleum Products—After preliminEiry heating, the sample
cloud point fuels. Appropriate low temperature operability is cooled at a specified rate and examined at intervals of
properties should be agreed upon between the fuel supplier 3°C for flow characteristics. The lowest temperature at
and purchaser for the intended use and expected ambient which movement of the specimen is observed is recorded
temperatures. as the pour point.
The tenth percentile temperatures Eire presented for each The following methods are variations of D 97, including,
U.S. state, except Hawaii, for each month from October to both automatic and automated methods.
March. They are presented in both tabular format and in • ASTM D 5949, Standard Test Method for Pour Point of
maps. Figure 4 is an example of one of the maps. Petroleum Products (Automatic Pressure Pulsing Method)
Realistic options to reduce the cloud point include: • ASTM D 5950, Standard Test Method for Pour Point of
1. Dilute the fuel with a low wax fuel such as grade No. 1 or Petroleum Products (Automatic Tilt Method)
kerosine. • ASTM D 5985 Standard Test Method for Pour Point of
2. Treat the fuel with special additives. Petroleum Products (Rotational Method)
3. Refine the fuel from crude(s) with lower wax content or re- The pour point should be considered only a guide to the
fine the fuel to a lower end point. lowest temperature at which a fuel can be used. In general,
4. It is also possible to add insulation and heaters to the ve- pour points are from 3-6°C below the cloud point for a given
hicle fuel system. This will not change the cloud point of fuel; however, it is not uncommon for the difference to be as
the fuel but will improve the low temperature operation. much as 11 °C.
For any given fuel, there will be no wax precipitation prob- ture, expressed as a multiple of 1°C, at which a test speci-
lems at temperatures above the cloud point. At temperatures men can be filtered in 60 s or less. Alternatively, a single
below the pour point, it is highly unlikely that the fuel will specimen may be cooled and tested at a specified tempera-
give satisfactory performance. It is not unusueJ to obtain sat- ture to determine whether it passes or fails at that temper-
isfactory engine performance with a fuel at ambient temperature.
atures between the cloud point and pour point. The degree of Figure 5 is a diagram of the LTFT test apparatus. The LTFT
performance and the temperature depend on the engine, the was designed to yield results indicative of the low temperature
vehicle design, and the fuel system configuration. Vehicles flow performance of the test fuel in some diesel vehicles. The
and fuel systems with small diameter lines, constrictions, test method is especially useful for the eveiluation of fuels con-
small porosity strainers and filters, and fuel lines exposed to taining flow improver additives. Please refer to Report No.
ambient temperatures or wind will tend toward poorer per- 528 from the Coordinating Research Council for a more de-
formance. Systems with insulation, supplemental heaters, or tailed discussion [15]. The LTFT was developed in the United
large sections of the fuel system in close proximity to engine States to simulate the low temperature behavior of diesel fuel
heat can probably expect better performance at lower tem- in the fuel tank of a diesel truck left overnight, in a cold envi-
peratures [14]. ronment, with its engine off. J. E. Chandler, zmd others, have
demonstrated that this test has shown excellent correlation
with field studies [16-18]. In spite of the demonstrated corre-
Low-Temperature Flow Test
lation to field performance, the LTFT is not as widely used as
As discussed above, the mere presence of wax crystals in a some other tests. The primary reason for this is the slow cool-
fuel does not guarantee the fuel will plug filters or other fuel ing rate (1°C per hour), which means that the time required
system components. The tendency of a fuel to plug screens completing an analysis can range from 12-24 h. Such test
and filters at low temperatures is a dynamic property depen- times are generally impractical for routine fuel testing.
dent on the size and shape of the wax crystals. (Vehicle fuel
system design is also a factor as discussed earlier.) For this Cold FUter Plugging Point
reason, numerous dynamic tests for low temperature oper-
ability have been developed. ASTM standardized one such The Cold Filter Plugging Point, CFPP, was developed for use
test in 1985: in Europe. The Institute of Petroleum publishes the method
• ASTM D 4539, Standard Test Method for Filterability of under the designation IP 309. It is similar to the LTFT with
Diesel Fuels by Low-Temperature Flow Test (LTFT)—The the following exceptions:
temperature of a series of test specimens of fuel is lowered • The fuel is cooled by immersion in a constant temperature
at a prescribed cooling rate. Commencing at a desired test bath, making the cooling rate non-linear but comparatively
temperature and at each 1°C interval thereafter, a separate much more rapid (about 40°C per hour).
specimen from the series is filtered through a 1 l-fjun screen • The CFPP is the temperature of the sample when 20 mL of
until a minimum LTFT pass temperature is obtained. The the fuel first fails to pass through a wire mesh in less than
minimum LTFT pass temperature is the lowest tempera- 60s.
Glass Tubing
6 10 Min Throughout
Vacuum Gage
Heavy Rulit>er Ttibing
Point A ^ 4 10 15 OD
2 Vacuum System
Rubber Stopper
Storage Lid
200 ML Sample
Glass Stem
Quality Flex lObing
Sample Container Sample Receiver

300 ML Tall-Form 400 ML Tall-Form
Beaker Beaker All Diminensions in Millimeters
t-TFT Sample Filtration Assembly
FIG. 5—LTFT sample filtration assembly (D 4539).
While the CFPP is the preferred method in Europe and is considered a combination of the best features of the two pre-
used in several European specifications, it appears to overes- vious methods. It is sensitive to small amounts of particles
timate the benefit of using some additives, most especially for and is even capable of detecting microscopic particulates. It
vehicles manufactured in North America [19,20]. is also a quantitative measure of the cleanliness of the fuel.
The quantitative measure is milligrams of particulate (con-
Cleanliness tamination) per liter of fuel. Currently there is no consensus
standard with a specification limit for D 6217. Many user
Diesel fuel cleanliness can mean many things to many peo- specifications, including some federal and military diesel fuel
ple. It is safe to say that most users would consider any fuel specifications, include a limit of 10 mg per liter for the results
that is visually free of undissolved water, sediment, and sus- of this analysis. Most users have found fuel that meets this
pended matter a clean fuel. Indeed, this is the cleanliness limit to give satisfactory performance in the vehicle.
(workmanship) requirement stated in D 975. However, it is
• ASTM D 6217, Standard Test Method for Particulate Con-
known that microscopic particulates in the fuel can lead to
tamination in Middle Distillate Fuels by Laboratory Filtra-
problems just as serious as the visible contaminants. The
tion—Â measured volume of about 1 L of fuel is vacuum fil-
three most common methods of measuring cleanliness of
tered through one or more sets of 0.8 /u,m membranes.
diesel fuel are:
Each membrane set consists of a tared nylon test mem-
• ASTM D 2709, Standard Test Method for Water and Sedi- brane and a tared nylon control membrane. When the level
ment in Middle Distillate Fuels by Centrifuge—A 100-mL of particulate contamination is low, a single set will usually
sample of the undiluted fuel is centrifuged at a relative cen- suffice; when the contamination is high or of a nature that
trifugal force of 800 for 10 min. at 21-32°C (70-90°F) in a induces slow filtration rates, two or more sets may be re-
centrifuge tube readable to 0.005 mL and measurable to quired to complete filtration in a reasonable time. After the
0.01 mL. After centrifugation, the volume of water and sed- filtration has been completed, the membranes are washed
iment that has settled into the tip of the centrifuge tube is with solvent, dried, and weighed. The particulate contami-
read to the nearest 0.005 mL and reported as the volumet- nation level is determined from the increase in the mass of
ric % water and sediment by centrifuge. the test membranes relative to the control membranes, and
D 2709 is the method currently specified in D 975. It is used is reported in units of glw? or its equivalent mg/L.
to measure the amount of visible water, sediment, and sus- • ASTM D 2068, Standard Test Method for Filter Plugging Ten-
pended matter. This method gives no effective measurement dency of Distillate Fuel Oils—A sample of the fuel to be
of the presence or amount of microscopic particulates. Many tested is passed at a constant rate of flow (20 mL/min)
would consider the level of contamination sufficient to pro- through a glass fiber filter medium. The pressure drop
duce readable results in this test to be gross contamination. across the filter is monitored during the passage of a fixed
However, this is an extremely sensitive test for contamina- volume of test fuel. If a prescribed maximum pressure drop
tion. The human eye is capable of seeing very small macro- is reached before the total volume of fuel is filtered, the ac-
scopic particles and the presence of 1 or 2 such particles tual volume of fuel filtered at the time of maximum pres-
could be considered a failure. In practice, the person con- sure drop is recorded.
ducting the test must exercise judgment based on experience
and the requirements of the end use for the fuel. The primary weakness of visual and gravimetric method is
that there is no generally accepted correlation between the
• ASTM D 4860, Standard Test Method for Free Water and Par- results of the test and the performance of the fuel in a vehicle
ticulate Contamination in Mid-Distillate Fuels (Clear and fuel system. That is, how long could the vehicle operate on
Bright Numerical Rating)—Visual inspection of the fuel that fuel before the fuel filter plugs or the water separator
sample for free water and particulate matter is performed fails? The British Navy first developed D 2068 as a dynamic
immediately when the sample is taken. A glass container is test of the cleanliness of fuel for shipboard gas turbine en-
used to view for water haze, and the fuel sample is swirled gines [21]. The test was designed around the specific require-
to create a vortex to detect the presence of particulate mat- ments of gas turbine powered ships in the British Navy. The
ter. A numerical rating for free water is obtained by filter- most important requirement was that the shipboard fuel fil-
ing a portion of the fuel sample at a programmed rate (50 ters had a nominal porosity of 1 /am. As such, a 1 /u,m pore
mL/45 s) through a standard fiberglass coalescer/filter. A size glass fiber laboratory filter is used in the test. Over the
portion of the effluent is used to establish a reference (100) years the test apparatus was upgraded, making it more auto-
level by a light transmittance measurement. Another por- mated.
tion of the unprocessed (unfiltered) fuel sample is then • ASTM D 6426, Standard Test Method for Determining Filter-
compared to the 100 reference-level. The results are reability of Distillate Fuel Oils—Â sample is passed at a con-
ported on a 50-100 scale to the nearest whole number. A stant rate (20 mL/min) through a standard porosity filter
test can be performed in 5-10 min. medium. The pressure drop across the filter and the vol-
D 4860 was developed to give a means to quantify the level ume of filtrate are monitored. The test is concluded either
of cleanliness of a fuel. As with D 2709, D 4860 only provides when the pressure drop across the filter exceeds 170 kPa
a valid measurement of visible contamination. The benefit of (25 psi) or when 300 mL have passed through the filter. Re-
this method is that the measurement is now an objective sults are reported as either the volume that has passed
measure of cleanliness. While this test does provide a quanti- through the filter when a pressure of 170 kPa (25 psi) has
tative result, it is far less sensitive than D 2709. been reached or the pressure drop when 300 mL have
Three other methods used to determine cleanliness of passed through the filter. In the latter case, the volume, if
diesel fuels are D 6217, D 2068, and D 6426. D 6217 could be and when 105 kPa (15 psi) was exceeded, is also recorded.
D 6426 is a modification of Method D 2068. The first dif- At this writing, neither D 2068 nor D 6426 enjoys
ference between the two methods is the pump used in each: widespread use in the U.S. However, of the two methods, D
D 2068 uses a piston pump whereas D 6426 uses a peristaltic 6426 is gaining the greatest acceptance in the U.S. This is due
pump. The second difference that D 2068 uses a 13-mm di- to two primary reasons: 1) the equipment to conduct D 6426
ameter, 1 fim pore size fiher and D 6426 uses a specially con- is more readily available than the equipment for D 2068; and,
structed test specimen, which is called an F-cell Filter Unit. It 2) the F-cell test specimen is regarded as more representative
is a disposable, precalibrated assembly consisting of a shell of automotive fuel filters than is the filter in D 2068. Despite
and plug containing a 2 5-mm diameter nylon membrane fil- the general recognition that the F-cell is more representative
ter of nominal 5.0/am pore size, nominal 60% porosity, with of automotive fuel filters, numerous attempts to correlate the
a 17.7-mm^ effective filtering area. Figure 6 is a schematic di- results from D 6426 with fuel filter plugging/filter life have
agram of the complete test apparatus. failed [22].
Despite the differences in equipment, both D 2068 and D
6426 have the same pass/fail criteria. A fuel fails the test if the
pressure drop across the filter reaches 105 kPa (15 psi) before
300 mL of test fuel passes through the filter. Stability
For the purposes of this discussion, fuel stability is defined as
the resistance of the fuel to physical and chemical changes
FLOW ADJUSTMENT KNOB
(D) brought about by the interaction of the fuel with its environ-
ment.
DISPLAYS
PRESSURE VOLUME VOLUME The chemistry of diesel fuel stability (instability) is com-
PRESSURE (psi) ((Si 0-25 psi) ((a! 0-15 psi) plex. In general, it involves the chemical reaction of precur-
TRANSDUCER
PERISTALTIC PUMP
sor species to form molecules of higher molecular weight.
\ PULSE The higher molecular weight species then become insoluble
\ DAMPENrNG
deposits in the form of either gums or particulates. The pre-
ay /lECIIANISM
TYGON®
PLA,STIC TIP
cursor species are usually sulfur and/or nitrogen containing
compounds, olefins, and organic acids. The reactions are of-
ten initiated by the oxidation of the precursors. Some dis-
TUBING
RUBBER STOPPER (VENTED) FILTER CELL
solved metals, especially copper but also zinc and even iron,
are known to catalyze the oxidation reactions. In the case of
METAL TUBE (STAINLESS STEEL) FUEL FLOW copper, as little as 10-30 parts per billion of dissolved copper
TUEL RESERVOIR COLLECTION is sufficient to catalyze deleterious reactions, depending on
CONTAINER
the fuel. The mechanism proposed by Pedley [23] (shown in
"FUEL SAMPLE PROCESSED FUEL Fig. 7) is perhaps the most cited example of these types of re-
actions. Although this mechanism explains many of the ear-
FIG. 6—Schematic diagram of filterability apparatus (D 6426). lier findings on diesel stability, it does not account for the for-
oxldatlon
1
Phenalenes Phenalenones Indoles
Acid
Indolylphenalenes
Acid/Oxidation
Fuel Insolubles
FIG. 7—Proposed mechanism of diesel fuel insolubles formation.

m a t i o n of all diesel fuel sediments. Other_useful reaction 20 """ /

schemes have been proposed [24-27]. The solvent strength of
/ /
f
the fuel is also a factor in that a high-solvency fuel can keep 18
some of the high molecular weight species in solution. / -^ '
Because the reactions and interactions Eire so numerous 16
,y
MULTILABORATORY / V^
and complex, it is quite possible to blend two very stable fu- M VISUAL RATINGS
/
els and obtain a very unstable fuel. In this case, each fuel pos-
\ / /
sesses one or more of the required precursor compounds.
« ^ s, //
When the fuels are mixed, the reactions proceed, and sedi- ujl2 Z /
ment is formed. Yet, had these two fuels never been blended, s' f
neither single fuel would have significantly degraded in stor- 10
\& /
age. There are three tjrpes of stability usually of concern for
/ ""^
diesel fuel. They are thermal, oxidation, and storage. Each of tX 8
these will be discussed separately. //
\
I
•
/ >
Thermal Stability w ^ / VISUAL RATINGS IN
T h e r m a l stability is the resistance of the fuel to change y ONE LABORATORY

'•
caused by thermal stress (elevated temperature). The recog-
/^ 2
nized ASTM test method is:
• D6468, Standard Test Method for High Temperature Stabil- 100 80 60 "JO 20
ity of Distillate Fuels—Two 50-mL volumes of filtered mid- PERCENT REFLECTION
dle distillate fuel are aged for 90 or 180 min at 150°C in (PHOTOVOLT MODEL 670 REFLECTION HETER WITH SEARCH UNIT W)
open tubes with air exposure. After aging and cooling, the
fuel samples are filtered. The amount of filterable insol- FIG. 8—Relationship of visual and reflection pad ratings.
ubles is estimated by measuring the light reflectance of the
filter pads. An unused filter pad and a commercial black
standard define the 100 and 0% extremes of the reflectance Arguably, this test is the most often used method to moni-
rating range, respectively. tor/predict fuel stability. The primary reason for its popular-
This method is based on a test that has been known by sev- ity is the short test time and simple equipment requirements.
eral names, such as: the Nalco 300°F Test, the EMD-Diesel This has made the 150°C test, in one form or another, espe-
Fuel Stability Test, the Union Pacific Diesel Blotter Test, the cially popular with many pipeline companies and others with
du Pont F 21 Test, and the Octel F 21 test [28]. This test dif- the need to monitor the quality of fuel but do it rapidly. Stavi-
fers from most other accelerated stability tests in that the test noha and Westbrook demonstrated that this test has poor
temperature is much higher and the amount of insolubles correlation to the generally accepted test for storage stability
formed is estimated rather than measured gravimetrically. In of diesel fuel (see D 4625 below) [31]. Bacha [32] and Henry
the earlier versions of the test, the a m o u n t of insoluble [33] reported that the 150°C test provides an indication of
residue formed during aging was estimated by comparing the thermal stability of distillate fuels exposed to high tempera-
test filter to a set of visual stEuidards called reference blotters. tures. The test method can be useful for investigation of op-
Filter pads from the test were rated on a scale from 1 to 20 erational problems related to fuel thermal stability. When D
with a rating of 1 assigned to a filter pad that is essentially 6468 is used to m o n i t o r fuel in production or storage, a
free of sediment. A rating of 7 or less was typically considered change in filter rating can indicate a relative change in in-
a pass. The reference pads were produced in both gray and herent stability of the fuel. No quantitative relationship exists
brown-tone prints. The reference pads were also produced to between pad ratings and the gravimetric mass of filterable in-
represent samples that were filtered through a Biichner fun- solubles formed during the test. Additional information on
nel or through a standard m e m b r a n e filter holder. The refer- the interpretation of results is found in Appendix XI of the
ence blotters were generally considered satisfactory to rate test method.
test filters that had sediment similar in appearance (color
and shape) to that depicted on the reference blotter. How-
ever, the visual ratings were subjective and different raters Oxidation Stability
had been found to rate the same pad as everything from a 4 Oxidation stability is the resistance of the fuel to change un-
to an 11. Also, raters within the same laboratory tended to der severely oxidizing conditions. In addition to exposing the
train each other, thus compounding the possibility for error. fuel to excess amounts of oxygen, oxidation stability tests
Henry [29] described a rating technique (originally proposed usueJly incorporate elevated test temperatures to accelerate
by Chevron Oil Company) t h a t used a reflectance m e t e r reaction rates. The method commonly used to measure oxi-
rather than a visual comparison. Figure 8 shows the relation- dation stability of diesel fuel is:
ship of visual and reflectance pad ratings. As expected, the re-
• ASTM D 2274, Standard Test Method for Oxidation Stability
flectance meter method yielded greatly improved precision
of Distillate Fuel Oil (Accelerated Method)—Â 350-mL vol-
compared to the reference blotters. The reflectance meter
u m e of filtered middle distillate fuels is aged at 95°C
was the technique selected when the method was standard-
(203°F) for 16 h while oxygen is bubbled through the sam-
ized [30].
ple at a rate of 3 L/h. After aging, the sample is cooled to ap-
proximately room temperature before filtering to obtain TABLE 4—Factors that influence the quality of
the filterable insolubles quantity. Adherent insolubles are diesel fuel in storage.
then removed from the oxidation cell and associated glass- Presence of Water Can lead to tank corrosion,
ware with trisolvent. The trisolvent is evaporated to obtain microbiological growth, and
the quantity of adherent insolubles. The sum of the filter- entrained water.
able and adherent insolubles, expressed as milligrams per Storage temperature Can accelerate or slow chemical
100 mL, is reported as total insolubles. (ambient temperature) reactions in the fuel.
Because for m a n y years this was the only standardized Vented, fixed roof tank Fixed roof tanks allow greater tank
method to measure stability of middle distillate fuels, it be- vs. floating roof tank breathing, which promotes water
condensation, oxygen replenishment
came a part of n u m e r o u s fuel specifications (mostly govern- in the ullage, and increases airborne
ment/military) and was widely used as a predictor of fuel contaminants in the fuel.
storage stability. Despite the wide acceptance as a storage Lined vs. unlined Lined tanks (those with an interior
stability test, most researchers agreed that, in fact, the results storage tanks coating) reduce or prevent exposure
of D 2274 had very poor correlation to actual, ambient stor- of the fuel to metal surfaces. This
age of the fuel. In addition, the precision of the test was ex- reduces corrosion of the tank. Metal
surfaces can also catsdyze some fuel
tremely poor. Many researchers have worked to improve the degradation reactions.
test. Chief a m o n g these is E. W. White of the U.S. Navy
[34,35]. Some of the factors he identified as having an effect Microbiological Leads to degradation of the fuel by
contamination metabolic by-products, corrosion of
on the results of the test are: the purity of the oxygen, stray metallic storage tanks, and
light impinging the sample during aging (especially ultra-vi- emulsification of water and fuel.
olet light), contact with metal surfaces (especially copper), Agitation of the fuel Promotes increased concentrations of
filter drying time, and heating bath configuration. Based on through tank filling air/oxygen and water in the fuel.
the work of White and others, many needed improvements and/or circulation of These factors influence the chemical
were made to the method. The precision of the test is better the fuel composition of the fuel.
Crude oil source and
now than when it was first published by ASTM. However, de- refining techniques
spite the improvements, the results continue to have poor
Commingling of fuels The mixing of two stable fuels can, on
correlation to ambient storage. Because this poor correlation rare occasions, result in antagonistic
is now more widely known, the use of the method to assess chemical reactions.
the stability of diesel fuels is very low.
Storage Stability
tion reactions, the presence of catalytic species such as met-
Storage stability is generally defined as the fuel's resistance to als, the a m o u n t of light, and the storage temperature. As
change during storage at ambient temperature and condi- mentioned above, the resistance of the fuel to these reactions
tions. Ambient storage is storage of the fuel in drums, storage is defined as its storage stability. Most researchers cJso go a
tanks, vehicle fuel tanks, or similar containers in the out-of- step further and define inherent storage stability as the resis-
doors. There are many factors that can influence the storage tance to change in the absence of environmental factors such
stability of a given fuel. The most c o m m o n factors are listed as metals and contaminants (i.e., in the absence of catalytic
in Table 4. The two tests for storage stability are: effects).
• ASTM D 4625, Standard Test Method for Distillate Fuel Stor- The inherent stability is important because it is a measure
age Stability at 43°C (nO°F)—Four-hundred mL volumes of the useful storage life of the fuel. For most diesel fuels un-
of filtered fuel are aged by storage in borosilicate glass con- der normal storage conditions,it may take several months or
tainers at 43°C (110°F) for periods of 0, 4, 8, 12, 18, and 24 even years for the deleterious reactions to generate enough
weeks. After aging for a selected time period, a sample is re- by-products to cause fuel-related p r o b l e m s . A user w h o
moved from storage, cooled to room temperature, and an- would like to store fuel would like to know what that length
alyzed for filterable insolubles and for adherent insolubles. of time is prior to putting the fuel in storage. To predict the
• ASTM D 5304, Standard Test Method for Assessing Distillate storage stability, therefore, we must simulate the storage and
Fuel Storage Stability by Oxygen Overpressure—A 100-mL measure the quantities of insolubles formed. To accelerate
aliquot of filtered fuel is placed in a borosilicate glass con- the process, the test must be performed at an elevated tem-
tainer. The container is placed in a pressure vessel that has perature. The question is how high above ambient to conduct
been preheated to 90°C. The pressure vessel is pressurized the test so as to accelerate the reactions and still keep the re-
with oxygen to 800 kPa (absolute) (100 psig) for the dura- sults representative of storage at ambient temperature. The
tion of the test. The pressure vessel is placed in a forced air Arrhenius [36] equation described in Fig. 9 can be used to es-
oven at 90°C for 16 h. After aging and cooling, the total timate the reaction rates for fuels stored at ambient to
amount of fuel insoluble products is determined gravimet- slightly above ambient temperatures. Under this relation-
rically and corrected according to blank determinations. ship, the reaction rate is accelerated approximately 1.7-3
All petroleum fuels u n d e r g o chemical reactions during times for every 10°C rise in temperature. The problem is that,
storage. The results of these reactions are usually g u m s , as the temperature rises, reactions that would not normeJly
acids, and/or particulates. The n u m b e r and rate of these dele- occur during ambient storage (or would occur with very low
probability) now begin to occur. The high-temperature reac-
terious reactions depends on the concentrations of reaction
tions result in other types of compounds, which can skew the
precursors, the concentration of oxygen available for oxida-
• ASTM D 93, Standard Test Methods for Flash Point by Pen-

k = Ae'^'' or k=A,J^ sky-Martens Closed Cup Tester—Â brass test cup of speci-
where:
fied dimensions, filled to the inside msirk with test speci-
Ea = activation energy
men and fitted with a cover of specified dimensions, is
R = gas constant
T = absolute temperature heated and the specimen stirred at specified rates by ei-
A = frequency factor (collision frequency) ther of two defined procedures (A or B). An ignition
source is directed into the test cup at regular intervals
Taking the natural logarithm of both sides and rearranging gives: with simultaneous interruption of the stirring until a flash
is detected.
lnfe=(-Ea/RXl/T) + lnA • ASrM D 3828, Standard Test Methods for Flash Point by
Small Scale Closed Tester Method A—Flash/No Flash Test—
Therefore, a plot of In A: versus 1/T gives a straight line whose slope is A specimen of a sample is introduced by a syringe into the
equal to -Ea/R and whose intercept is In A cup of the selected apparatus that is set and maintained at
the specified temperature. After a specific time a test flame
FIG. 9—Arrhenius equation.
is applied and an observation made as to whether or not a
flash occurred.
• Method B—Finite (or Actual) Flash Point—Â specimen of a
results of the aging test. Two early studies [37,38] demon- sample is introduced into the cup of the selected apparatus
strated the correlation between storage at 43°C and ambient that is maintained at the expected flash point. After a spec-
storage. They determined that 13 weeks at 43°C is equivalent ified time a test flame is applied and the observation made
to one year at ambient. Over the years, this relationship has whether or not a flash occurred. The specimen is removed
been redefined as 1 week at 43 °C is equal to 1 month at am- from the cup, the cup cleaned, and the cup temperature ad-
bient. These studies also established storage at 43°C as the justed 5°C (9°F) lower or higher depending on whether or
standard accelerated storage test, against which all other ac- not a flash occurred previously. A fresh specimen is intro-
celerated storage stability tests are compared. This test works duced and tested. This procedure is repeated until the flash
so well because the test temperature is such a small increase point is established within 5°C (9°F). The procedure is then
over ambient that the relative importance of the various re- repeated at 1°C (2°F) intervals until the flash point is de-
actions that create insolubles are not appreciably changed. termined to the nearest 1°C (2°F). If improved accuracy is
This makes the 43°C storage test an ideal research tool for desired the procedure is repeated at 0.5°C (1°F) intervals
studying storage stability of diesel fuels. until the flash point is determined to the nearest 0.5°C
(1°F).
Ironically, that which makes the 43 °C test such a useful re-
search tool also makes it useless for quality assurance and • ASTM D 6450, Standard Test Method for Flash Point by Con-
quzility control applications because of the long test times. tinuously Closed Cup (CCCFP) Tester—The lid of the test
For this reason, m u c h effort has been expended over the past chamber is regulated to a temperature at least 18°C below
25-30 years to develop a rapid test for fuel storage stability. the expected flash point. A 1 mL test specimen of a sample
In this context, rapid is generally defined as test times of 16 is introduced into the sample cup, ensuring that both spec-
hours or less. Very little success came of these efforts, with imen and cup are at a temperature at least 18°C below the
one exception. The U.S. Navy developed a test method that expected flash point, cooling if necessary. The cup is then
was eventucdly standardized as ASTM D 5304 \39'\. The ap- raised and pressed onto the lid of specified dimensions to
plicability of the test method was demonstrated in a project form the continuously closed but unsealed test chamber
conducted during 1992-1993 [40]. with an overall volume of 4.0 ± 0.2 mL. After closing the
test chamber, the temperatures of the test specimen and
the regulated lid are edlowed to equilibrate to within 1°C.
Flash Point Then the lid is heated at a prescribed, constant rate. For the
flash tests, an arc of defined energy is discharged inside the
Flash point is specified in D 975 primEuily for safety during
test chamber at regular intervals. After each ignition, 1.5 ±
transport, storage, and handling. A low flash point fuel can be
0.5 m L of air is introduced into the test chamber to provide
a fire hazard, subject to flashing, with possible continued ig-
the necessary oxygen for the next flash test. The pressure
nition and explosion. Low flash point can also indicate con-
inside the continuously closed but unsealed test chamber
tamination with low-flash fuels such as gasoline. The flash
remains at ambient barometric pressure. The exceptions
point of a fuel has no significant relation to the performance
are for the short time during the air introduction and at a
of the fuel in the engine. Auto-ignition temperature is not in-
flash point. After each arc, the instantaneous pressure in-
fluenced by variations in flash point.
crease above the ambient barometric pressure inside the
There are five ASTM test m e t h o d s for measuring flash test chamber is monitored. When the pressure increase ex-
point of diesel fuels: ceeds a defined threshold, the temperature at that point is
• ASTM D 56, Standard Test Method for Flash Point by Tag recorded as the uncorrected flash point.
Closed Tester—The specimen is placed in the cup of the
tester and, with the lid closed, heated at a slow constant Each of these three test methods contains an introduction
rate. An ignition source is directed into the cup at regular that is similar to the following:
interveJs. The flash point is taken as the lowest tempera- This flash point test method is a dynamic test method and
ture at which application of the ignition source causes the depends on definite rates of temperature increase to control
vapor above the specimen to ignite. the precision of the test method. The rate of heating may
not in all cases give the precision quoted in the test method bricity improver additive is required, to ensure satisfactory
because of the low thermal conductivity of certain materi- operation in the sensitive areas of the vehicle fuel system
als. To improve the prediction of flammability, Test [42].
Method D 3941, an equilibrium method was developed in Work in the area of diesel fuel lubricity is ongoing by sev-
which the heating rate is slower. This allows the vapor eral organizations, such as the International Organization for
above the test specimen and the test specimen to be at Standardization (ISO) and the ASTM Diesel Fuel Lubricity
about the same temperature. Task Force u n d e r Subcommittee E of Committee D2 [43].
• ASTM D 3941, Standard Test Method for Flash Point by the These groups include representatives from the fuel injection
Equilibrium Method with a Closed-Cup Apparatus—This equipment manufacturers, fuel producers, and additive sup-
method covers the determination of the flash point of hq- pliers. The charge of the ASTM task force has been the rec-
uids in which the specimen a n d the air/vapor mixture ommendation of test methods and a fuel specification for
above it are approximately in temperature equilibrium. Specification D 975. At this writing, two test methods are ap-
The test method is limited to a temperature range from proved:
32-230°F(0-110°C). • ASTM D 6078, Standard Test Method for Evaluating Lubric-
Method D 3941 should b e used to measure Eind describe the ity of Diesel Fuels by the Scuffing Load Ball-on-Cylinder Lu-
properties of material, products, or assemblies in response to bricity Evaluator (SLBOCLE)—Â 50-mL test specimen of
heat and flame u n d e r controlled laboratory conditions. It fuel is placed in the test reservoir of an SLBOCLE and ad-
should not be used to describe or appraise the fire hazard or justed to the test temperature of 25°C. When the fuel tem-
fire risk of materials, products or assemblies under actUcJ fire perature has stabilized, 50% relative humidity air is used to
conditions. However, results of this test may be used as ele- aerate the fuel at 0.5 L/min while 3.3 L/min flows over the
ments of a fire risk assessment that takes into account all of fuel for 15 min. During the remainder of the test sequence,
the factors that are pertinent to a n assessment of the fire haz- the 50% relative humidity air flows over the fuel at a rate of
ard of a particular end use. 3.8 L/min. A load a r m holding a non-rotating steel ball and
It is important to note that while D 3941 may be an ac- loaded with a 500 g mass is lowered until it contacts a par-
ceptable alternative m e t h o d for some applications, the tially fuel immersed polished steel test ring rotating at 525
method(s) listed in a given specification, such as D 975, rpm. The ball is caused to rub against the test ring for a 30-
should not be replaced without prior knowledge and consent s break in period before beginning an incremental-load or
of all interested parties. This is because the measured flash a single-load test. Wear tests are conducted by maintaining
point of a fuel is dependent not only on the composition of the beJl in contact with the particJly immersed 525- rpm
the fuel but also on the apparatus used to make the measure- test ring for 60 s. For incremental load tests, the test ring is
ment. ASTM Manual 9 describes many flash point test meth- moved at least 0.75 m m for each new load prior to bring-
ods, both U.S. and international [41]. It also lists pertinent ing a new ball into contact with the test ring. The tangen-
specifications/standards worldwide. tial friction force is recorded while the ball is in contact
with the test ring. The friction coefficient is calculated
from the tangential friction force. In the incremental-load
Lubricity test, the m i n i m u m applied load required to produce a fric-
Diesel fuel functions as a lubricant in certain items of fuel in- tion coefficient greater than 0.175 is an evaluation of the
jection equipment such as rotary/distributor fuel p u m p s and lubricating properties of the diesel fuel. In the single-load
injectors. In limited cases, fuel with very specific properties test, a friction coefficient less than or equal to 0.175 indi-
can have insufficient lubricating properties that can lead to a cated the diesel fuel passes the lubricity evaluation, while a
reduction in the normal service life of fuel p u m p s or injec- friction coefficient greater than 0.175 indicated the diesel
tors. Two fuel chciracteristics that affect equipment wear are fuel fails the lubricity evaluation.
low viscosity and lack of sufficient quantities of trace com- • ASTM D 6079 Standard Test Method for Evaluating Lubric-
ponents, which have a n affinity for metal surfaces. If fuel vis- ity of Diesel Fuels by the High-Frequency Reciprocating Rig
cosity meets the requirements of a particular engine, a fuel (HFFR)—Â 2-mL test specimen of fuel is placed in the test
film is maintained between the moving surfaces of the fuel reservoir of an HFRR and adjusted to either of the staxidard
system components. This prevents excessive metal-to-metal temperatures (25 or 60°C). The preferred test temperature
contact and avoids premature failure due to wear. Simileirly, is 60°C, except where there may be concerns about loss of
certain surface-active molecules in the fuel (such as acids and fuel because of its volatility or degradation of the fuel be-
heteroatomics) adhere to, or combine with, metallic surfaces cause of the temperature. When the fuel temperature has
to produce a protective film that also can protect surfaces stabilized, a vibrator arm holding a non-rotating steel ball
against excessive wear. The concern about fuel lubricity is and loaded with a 200-g mass is lowered until it contacts a
limited to the use of fuels with viscosities lower than those test disk completely submerged in the fuel. The ball is
specified for a particulcir engine. Also of concern is the use of caused to r u b against the disk with a 1-mm stroke at a fre-
fuels that have been processed in a manner that results in the quency of 50 Hz for 75 min. The ball is removed from the
elimination of the trace levels of the surface-active species vibrator a r m and cleaned. The dimensions of the major
that act as lubricating agents. Presently, the only fuels of the and minor axes of the wear scar are measured under lOOX
latter type shown to have lubricity problems resulted from magnification and recorded.
sufficiently severe processing to reduce aromatics substan-
A diagram of the test apparatus a n d a list of the test condi-
tieJly below current levels. Research is in progress to identify
tions for D 6078 and D 6079 are given in Figs. 10 and 11, re-
the chciracteristics of such fuels and where the use of a lu-
spectively.
OUTFUTTO
rmcTioM necxMUMNO
DEVICE LOAD
. " ^ Q P'O.
3 ^ ^ COtfTACT U>Ap
MEAW-OUTT
FNCUMATIC
PWTOM
S c h e m a t i c D i a g r a m of t h e Scuffing L o a d Ball-on-Cylinder
Lubricity Evaiuator (not including Instrumentation)
MANDREL ASSEMBLY •
SCREWS W REQ'a
BUTTON HEAD
••8-32
DRIVESHAFT ASSEMBLY
Ring and Mandrel Assembly (Cylinder)
Parameter
Test Conditions Value
Fluid volume 50 ± 1.0 mL
Fluid temperature 25 ± 1°C
Conditioned air^ 50 ± 1 % relative tiumidity at 25 ± 1°C
Fluid pretreatment: 0.50 U min air flowing through and 3.3 L/min air flowing
over the fluid for 15 min
Fluid test conditions: 3.8 L/min air flowing over the fluid
Cylinder rotational speed 525 ± 1 rpm
Applied Load
Break-in period 500 g
Incremental-load test 500 to 5 000 g
Single-load test user defined'
Test Duration
Break-in period 30 s
Wear tests 60s
*Fifty percent humidity should be achieved using equal volumes of dry and
saturated air. The SLBOCLE has a water column through which air passes and it
is assumed to be saturated when it exits this column.
"The applied load for the single test Is set at the pass/fail requirement for the fuel
being evaluated.
FIG. 1 0 — T e s t e q u i p m e n t a n d t e s t c o n d i t i o n s f o r s c u f f i n g l o a d b a l l - o n -
cylinder lubricity e v a i u a t o r ( D 6 0 7 8 ) .
Test Plata Lubricity Task Force is also working on possible revisions to

Loading the standard HFRR test to make it more sensitive to low lev-
els of lubricity additive.
Aromatics
Diesel fuel contains many types or classes of compounds in-
cluding paraffins, naphthenes, olefins, and Eiromatics. Com-
pounds that contain heteroatoms such as sulfur, nitrogen,
and oxygen are also present. Aromatics warrant discussion
because 1) they have an effect on the combustion quality of
Schematic Diagram of HFRR (not including
instrumentation)
the fuel, 2) typically, they are the only hydrocarbon type
listed in diesel fuel specifications (including D 975), and 3)
increased amounts of aromatics can have a negative impact
Test Conditions
on vehicle emissions.
Fluid volume 2 ± 0.20 mL
Stroke length 1 ± 0.02 mm
It is well known that an increase in the total aromatics con-
Frequency 50 ± 1 Hz tent of a diesel fuel can (and usually does) have an adverse ef-
Fluid temperature 25 ± 2°C fect on the ignition quality, i.e., cetane number of the fuel.
or Several methods are available for the measurement of aro-
60 ± 2°C
Relative humidity >30% matic content. They eire described below:
Applied load 200 ± 1 g • ASTM D1319, Standard Test Method for Hydrocarbon Types
Test duration 75 ± 0.1 min
Bath surface area 6 ± 1 cm^
in Liquid Petroleum Products by Fluorescent Indicator Ad-
sorption—Approximately 0.75 mL of sample is introduced
FIG. 11—Test equipment and test conditions for high fre-
into a special glass adsorption column packed with acti-
quency reciprocating rig (D 6079).
vated silica gel. A small layer of the silica gel contains a
mixture of fluorescent dyes. When the entire sample has
been adsorbed on the gel, alcohol is added to desorb the
sample down the column. The hydrocarbons are separated
The inclusion of a single fuel specification in the main in accordance with their adsorption affinities into aromat-
table of specification D 975 for Grade No. 2 requires further ics, olefins, and saturates. The fluorescent dyes are also
research because: separated selectively, with the hydrocarbon types, and
1. the correlation of the data among the two test methods and make the boundaries of the aromatic, olefin, and saturate
the fuel injection equipment needs further clarification, zones visible under ultraviolet light. The volume percent-
2. both methods in their current form do not apply to all fuel- age of each hydrocarbon type is calculated from the length
additive combinations, of each zone in the column.
3. the reproducibility values for both test methods are large. This test method was originally developed for the analysis
In the meantime, the following information may be of use of gasoline (spark ignition engine fuel). It is for determining
and serve as a general guideline to fuel suppliers and users. hydrocarbon types over the concentration ranges from 5-99
Westbrook and coworkers recommended that users moni- volume % aromatics, 0.3-55 volume % olefins, and 1-95 vol-
tor their fuel injection pumps for possible trends of abnormal ume % saturates in petroleum fractions that distill below
wear rates if the fuel has a scuffing load value between 2000 315°C. The test method may apply to concentrations outside
and 2800 g in Test Method D 6078 [44]. According to this pa- these ranges, but the precision has not been determined.
per, fuels with values below 2000 g will, in all probability, Samples containing dark-colored components that interfere
cause accelerated wear in fuel lubricated rotary-t5Tpe fuel in- in reading the chromatographic bands cannot be analyzed.
jection pumps. It should be noted that a properly-additized D 1319 was applied to and specified for diesel fuel usually
fuel might provide protection for fuel-wetted components because no other suitable method was available. As suitable
and yet not produce significant D 6078 test results as com- methods became standardized they grew in use but have not
pared to the non-additized fuel. replaced D 1319 in D 975. This is because the requirement for
Work at ISO indicates that a fuel with a 450-micron wear aromaticity currently included in D 975 comes from the re-
scar diameter or lower value at 60°C in Test Method D 6079 quirement in 40 CFR Fart 80. Since federal law requires D
(380 micron at 25°C) should protect all fuel injection equip- 1319, it is the method listed in D 975. Method D 5186, de-
ment [45]. Other SAE publications present data to show that scribed below, is more appropriate for diesel fuel and is often
some fuels and fuel/additive combinations can have values used in place of D 1319. However, in case of dispute, D 1319,
above this level and still provide sufficient lubricity protec- by virtue of it's status as the legislated method, is considered
tion to the equipment. the referee method.
Pump stand testing of fuels, although more expensive and • ASTM D 5186, Standard Test Method for Determination of
time consuming, is a more accurate means of evaluating the Aromatic Content and Polynuclear Aromatic Content of
lubricity of diesel fuel. At the time of this writing, the ASTM Diesel Fuels and Aviation Turbine Fuels by Supercritical
Diesel Fuel Lubricity Task Force is working on the develop- Fluid Chromatography—A small aliquot of the fuel sample
ment and standardization of a pump stand test method. The is injected onto a packed silica adsorption column and
eluted using supercritical carbon dioxide mobile phase. ers the determination of the aromatic hydrogen content
Mono-aromatics and polynucleEir aromatics in the sample (Procedures A and B) 8ind aromatic carbon content (Proce-
are separated from non-aromatics and detected using a dure C) of hydrocarbon oils using high-resolution nuclear
flame ionization detector. The detector response to hydro- magnetic r e s o n a n c e (NMR) spectrometers. Applicable
carbons is recorded t h r o u g h o u t the analysis time. The samples include kerosines, gas oils, mineral oils, lubricat-
chromatographic areas corresponding to the mono-aro- ing oils, coal liquids, and other distillates that are com-
matic, polynuclear aromatic, and non-aromatic compo- pletely soluble in chloroform and Ccirbon tetrachloride at
nents are determined and the mass % content of each of ambient temperature. For pulse Fourier-transform (FT)
these groups in the fuel is calculated by area normaliza- spectrometers, the detection limit is t5îcally 0.1 mol %
tion. aromatic hydrogen atoms a n d 0.5 mol % aromatic carbon
This test method covers the determination of the total atoms. For continuous wave (CW) spectrometers, which
amounts of mono-ciromatic and polynuclear aromatic hy- are suitable for measuring aromatic hydrogen contents
drocarbon compounds in motor diesel fuels, aviation tur- only, the detection limit is considerably higher and typi-
bine fuels, and blend stocks by supercritical fluid chro- cally 0.5 m o l % aromatic-hydrogen atoms. The reported
matography (SFC). The range of aromatics concentration to units are mole percent, aromatic- hydrogen atoms and
which this test method is applicable is from 1-75 mass %. mole% aromatic-Ccirbon atoms. This test method is not ap-
The range of polynuclear aromatic hydrocarbon concentra- plicable to samples containing more than 1 mass % olefinic
tions to which this test method is applicable is from 0.5-50 or phenolic compounds. This test method does not cover
mass %. the determination of the percentage mass of aromatic com-
pounds in oils since NMR signals from both saturated hy-
• ASTM D 6591, Standard Test Method for Determination of drocarbons a n d aliphatic substituents o n aromatic ring
Aromatic Hydrocarbon Types in Middle Distillates, High Per- compounds appear in the same chemical shift region. For
formance Liquid Chromatography Method with Refractive the determination of mass or volume% aromatics in hy-
Index Detection—A known mass of sample is diluted in the drocarbon oils, chromatographic or m a s s spectrometry
mobile phase, a n d a fixed volume of this solution is in- methods can be used.
jected into a high performance liquid chromatograph, fit-
ted with a polar column. This column has little affinity for It should be noted that there are several standard methods
the non-aromatic hydrocarbons while exhibiting a pro- for the analysis of aromatics. Each method yields a slightly
nounced selectivity for aromatic hydroccirbons. As a result different result and each is considered appropriate in differ-
of this selectivity, the aromatic hydrocarbons are separated ent situations. One reason for this apparent inconsistency is
from the non-aromatic hydrocarbons into distinct bands in that since a single molecule can contain several chemical
accordcince with their ring structure. At a predetermined moieties, it is possible to include it in several hydrocarbon
time, after the elution of the di-aromatic hydrocarbons, the classes. For example, a molecule could contain an aromatic
column is back flushed to elute the polycyclic aromatic hy- ring, a pciraffinic side chain, and a naphthenic ring. How
droccirbons as a single sharp band. should this molecule be classified? A hierarchy was estab-
lished to address this situation. Under this hierarchy, aro-
Method D 2425 offers a more detailed analysis but requires
matics are on top, then olefins, followed by naphthenes, and
considerable investment in i n s t r u m e n t a t i o n a n d sample
finally paraffin. Using this hierarchy, the example compound
preparation time. For these reasons, it is not typically used
would be considered an aromatic compound.
for routine ctnalysis of diesel fuel.
The level of aromatics in the fuel is also important as it
• ASTM D 2425, Standard Test Method for Hydrocarbon Types
relates to the potential for elastomer and seed swell prob-
in Middle Distillates by Mass Spectrometry—This test
lems. This is especially true for older vehicles/fuel systems.
method covers an analytical scheme using the mass spec-
Depending on the type of elastomer, prolonged exposure to
trometer to determine the hydrocarbon types present in
relatively high levels of aromatics, followed by a sudden de-
virgin middle distillates 204-343°C (400-650°F) boiling
crease in the amount of aromatics, can cause elastomeric
range, 5-95 volume % as determined by Method D86.
seals to shrink and thus leak. If the elastomers are too old
Samples with average carbon n u m b e r value of paraffins
and have taken a set, they Cctn also crack or break. This phe-
between C 12 and C 16 and containing petraffins from C I O
nomenon was widely seen in late 1993 and early 1994 when
and C 18 can be analyzed. Eleven hydrocarbon types are
mcindated reductions in fuel sulfur and aromatics content
determined. These include: paraffins, non-condensed cy-
went into effect. In most instances, the problems were
cloparaffins, condensed di-cycloparaffins, condensed tri-
solved by installing new seals made of less sensitive elas-
cycloparaffins, alkylbenzenes, indans or tetraJins, or both,
tomer.
C„H n.io (indenes, etc.), naphthalenes, CnH n.14 (acenaph-
thenes, etc.), CnH „.i6 (acenaphthylenes, etc.), and tri-cyclic
aromatics. Heat Content
Method D 5292 also offers more information than D 1319 The heat content or heat of combustion of a fuel is the
or D 5186. However, the results are reported in mole% rather amount of heat produced when the fuel is burned completely.
than mass or volume percent, which are normally required in Gross and net heats of combustion are the two values mea-
specifications. sured for the heat of combustion.
• ASTM D 5292, Standard Test Method for Aromatic Carbon The gross heat of combustion is the quantity of energy re-
Contents of Hydrocarbon Oik by High Resolution Nuclear leased when a unit mass of fuel is burned in a constJint vol-
Magnetic Resonance Spectroscopy—This test method cov- u m e enclosure, with the products being gaseous, other than
water that is condensed to the hquid state. The fuel can be ei- TABLE 6—Conversion factors for heat
ther hquid or soUd, and contain only the elements carbon, hy- of combustion values.
drogen, nitrogen, and sulfur. The products of combustion, in 1 cal (International Table calorie) = 4.1868 J
oxygen, are gaseous carbon dioxide, nitrogen oxides, sulfur 1 Btu (British thermal unit) = 1055.06 J
dioxide, and liquid water. 1 cal (I.T.)/g = 0.0041868 MJ/kg
1 Btu/lb = 0.002326 MJ/kg
• The net heat of combustion is the quantity of energy re-
leased when a unit mass of fuel is burned at constant pres-
sure, with all of the products, including water, being gaseous.
The fuel can be either liquid or solid, and contain only the el-
ements carbon, hydrogen, oxygen, nitrogen, and sulfur. The Calculate the net heat of combustion of the fuel corrected
products of combustion, in oxygen, are carbon dioxide, ni- for the sulfur, water and ash content in accordance with the
trogen oxides, sulfur dioxide, and water, all in the gaseous following equation:
state. For c o m p o u n d s with the same n u m b e r of c a r b o n
atoms, heat content increases as you go from aromatics to Qp (net) = (46.423 - 8.792^^ x 10"* + 3.70d X 10"^)
naphthenes to paraffins, on a weight basis. The reverse order X[l - (x+y + s)] + 9.4205 + 2.449;c
is correct if you measure on a volume basis. The same is true
for fuels. Denser fuels, such as diesel, have higher heat con- where:
tent on a volume basis. Less dense fuels, such as gasoline,
Qp = net heat of combustion at constant pressure,
have higher heat content on a weight basis. Chevron has re-
MJ/kg,
ported typical heat content values that demonstrate this rela-
d = density at 15°C, kg/m^,
tionship (see Table 5).
X = mass fraction of water,
Heat of combustion is usually reported in units of mega- y = mass fraction of ash, and
joules per kilogram (MJ/kg). Conversion factors to other s = mass fraction of sulfur.
units are given in Table 6. Heat of combustion can be esti-
mated by calculation from selected properties or measured This test method is useful for estimating, using a minimum
using b o m b calorimetry. The m e t h o d s typically used for n u m b e r of tests, the heat of combustion of burner and diesel
diesel fuel are discussed below. fuels for which it is not usually critical to obtain very precise
heat determinations. This test method is purely empirical. It
• ASTM D 4868, Standard Test Method for Estimation of Net
is applicable only to liquid hydrocarbon fuels derived by nor-
and Gross Heat of Combustion of Burner and Diesel Fuels—
mal refining processes from conventional crude oil. This test
This test method covers the estimation of the gross and net
method is valid for those fuels in the density range from 750
heat of combustion of petroleum fuel. The calculations use
to 1000 kg/m^ and those that do not contain an unusually
the fuel density, sulfur, water, and ash content. The equa-
high aromatic content. High aromatic content fuels will not
tions for estimating net a n d gross heat of combustion used
normally meet fuel specification criteria for this method.
in this method were originally published in the National
This test method is not applicable to pure hydrocarbons. It is
Institute of Standards and Technology (NIST) Publication
not intended as a substitute for experimental measurements
No. 97. The equations are:
of heat of combustion.
Calculate the gross heat of combustion of the fuel corrected
According to the m e t h o d the estimation of the heat of
for the sulfur, water, and ash content in accordance" with the
combustion of a hydrocarbon fuel from its density, sulfur,
following equation:
water, and ash content is justifiable only when the fuel be-
Q^ (gross) = (51.916 8.792^2 X 10- ') longs to well-defined classes for which a relationship be-
[1 (x+y +s)] + 9.420s tween these quantities have been derived from accurate ex-
perimental measurements on representative samples of these
where: classes. Even in these classes, the possibility that the estimate
= gross heat of combustion at constant volume, may be in error by large amounts for individual fuels should
Q
MJ/kg, be recognized. This test method has been tested for a limited
d = density at 15°C, kg/m^, number of fuels from oil sand bitumen and shale oil origin
and has been found to be valid. The classes of fuels used to
X = mass fraction of water (% divided by 100),
establish the correlation presented in this test method are
y = mass fraction of ash (% divided by 100), eind
represented by the following specifications:
5 = mass fraction of sulfur (% divided by 100).
1. D 396 Fuel Oils Grades 1, 2, 4 (light), 4, 5 (hght), 5 (heavy),
and 6
2. D 975 Diesel Grades 1-D, 2-D, and 4-D
TABLE 5—Typical density and heat content value of 3. D 1655 Aviation Turbine Jet A, Jet A-1, and Jet B
different fuels. 4. D 2880 Gas Turbine Grades 0-GT, 1-GT, 2-GT, 3-GT and 4-
Net Heat of Net Heat of GT
Density, Combustion, Combustion, 5. D 3699 Kerosine Grades 1-K and 2-K
Fuel g/cm^ Btu/lb Btu/gal
• ASTM D 4809, Standard Test Method for Heat of Combus-
Regular gasoline 0.735 18 630 114 200
Premium gasoline 0.755 18 440 116 200 tion of Liquid Hydrocarbon Fuels by Bomb Calorimeter (Pre-
Jet fuel 0.795 18 420 122 200 cision Method)—This test method covers the determina-
Diesel fuel 0.850 18 330 130 000 tion of the heat of combustion of hydroccirbon fuels. It was
designed specifically for use with aviation turbine fuels method covers the determination of sulfur in petroleum
when the permissible difference between duplicate deter- products, including lubricating oils containing additives, ad-
minations is of the order of 0.2%. It can be used for a wide ditive concentrates, and lubricating greases that cannot be
range of volatile and nonvolatile materials where slightly burned completely in a wick lamp. The test method is appli-
greater differences in precision can be tolerated. Under cable to any petroleum product sufficiently low in volatility
normal conditions, the method is directly applicable to that it can be weighed accurately in an open sample boat and
such fuels as gasoline, kerosine, Nos. 1 and 2 fuel oil, Nos. containing at least 0.1% sulfur.
1-D and 2-D diesel fuel and Nos. 0-GT, 1-GT, and 2-GT gas • ASTM D 4294, Standard Test Method for Sulfur in Petroleum
turbine fuels. Products by Energy-Dispersive X-Ray Fluorescence Spec-
The increased precision is obtained through the improve- troscopy—This test method covers the measurement of sul-
ment of the CcJorimeter controls and temperature measure- fur in hydroccirbons such as naphthas, distillates, fuel oils,
ments. residues, lubricating base oils, and nonleaded gasoline.
• ASTM D 240, Standard Test Method for Heat of Combustion The concentration range is from 0.05-5mass%.
of Liquid Hydrocarbon Fuels by Bomb Calorimeter—This • ASTM D 5453, Standard Test Method for Determination of
test method covers the determination of the heat of com- Total Sulfur in Light Hydrocarbons, Motor Fuels and Oils by
bustion of liquid hydrocarbon fuels ranging in volatility Ultraviolet Fluorescence—This test method covers the de-
from that of light distillates to that of residual fuels. Under termination of total sulfur in liquid hydrocarbons, boiling
normal conditions, this test method is directly applicable in the range from approximately 25—400°C, with viscosities
to such fuels as gasoline, kerosine, Nos. 1 and 2 fuel oil, between approximately 0.2 and 10 cSt (mm/s^) at room
Nos. 1-D and 2-D diesel fuel, and Nos. 0-GT, 1-GT, and 2- temperature. This test method is applicable to naphthas,
GT gas turbine fuels. This test method is not as repeatable distillates, motor fuels and oils containing 1.0 to 8000
and not as reproducible as Test Method D 4809. mg/kg total sulfur.
In this method the net heat of combustion is represented • ASTM D 1266, Standard Test Method for Sulfur in Petroleum
by the symbol Q n and is related to the gross heat of com- Products (Lamp Method)—This test method covers the de-
bustion by the following equation: termination of total sulfur in liquid petroleum products in
concentrations from 0.01-0.4 mass %. A special sulfate
Q„ {net, 25°C) = Qg {gross, 25°C) - 0.2122 X H analysis procedure is described in the method that permits
the determination of sulfur in concentrations as low as 5
where:
mg/kg.
Q„ (net, 25°C) = net heat of combustion at constant • ASTM D1552, Standard Test Method for Sulfur in Petroleum
pressure, MJ/kg Products (High-Temperature Method)—This test method
Q„ (gross, 25°C) = gross heat of combustion at constant covers three procedures for the determination of total sul-
volume, MJ/kg fur in petroleum products including lubricating oils con-
taining additives, and in additive concentrates. This test
H = mass % hydrogen in the sample method is applicable to samples boiling above 177°C
(350°F) and containing not less than 0.06 mass% sulfur.
Two of the three procedures use iodate detection. One em-
Total Sulfur ploys an induction furnace for pyrolysis, the other a resis-
tance furnace. The third procedure uses IR detection fol-
The test methods for measuring total sulfur in diesel fuel, as lowing p5Tolysis in a resistance furnace.
prescribed in D 975 are: The sulfur content of diesel fuel is known to affect particu-
• ASTM D 2622, Standard Test Method for Sulfur in Petroleum late matter (PM) exhaust emissions because some of the sul-
Products by Wavelength Dispersive X-ray Fluorescence Spec- fur is converted to sulfate particles in the exhaust. The
trometry—D 2622 is prescribed for the measurement of to- amount that is converted varies by engine; but reducing total
tal sulfur in Grades Low Sulfur No. 1-D and No. 2-D. This sulfur produces a linear decrease in PM in nearly all engines.
test method covers the determination of total sulfur in liq- Fuel sulfur can also adversely affect cylinder wear (through
uid petroleum products and in solid petroleum products the formation of acids) and deposit formation (many sulfur
that can be liquefied with moderate heating or dissolved in compounds are known deposit precursors).
a suitable organic solvent. The applicable concentration
range will vary to some extent with the instrumentation
used and the nature of the sample. Optimum conditions Copper Strip Corrosion
will allow the direct determination of sulfur in essentially The test method for copper strip corrosion is D 130.
paraffinic samples at concentrations exceeding 0.0010 • ASTM D 130, Standard Test Method for Detection of Copper
mass%. Corrosion from Petroleum Products by the Copper Strip Tar-
• ASTM D 129, Standard Test Method for Sulfur in Petroleum nish Test—Â polished copper strip is immersed in a given
Products (General Bomb Method)—The sample is oxidized quantity of sample and heated at a temperature and for a
by combustion in a bomb containing oxygen under pres- time characteristic of the material being tested. At the end
sure. The sulfur, as sulfate in the bomb washings, is deter- of this period the copper strip is removed, washed, and
mined gravimetrically as barium sulfate. compared with the ASTM Copper Strip Corrosion Stan-
D 129 is the prescribed method for the determination of to- dards (this is an adjunct available from ASTM Headquar-
tal sulfur in Grades No. 1-D, No. 2-D, and No. 4-D. This test ters).
The copper strip corrosion test covers the detection of the such as amyl nitrate, hexyl nitrate, or octyl nitrate, causes a
corrosiveness to copper of aviation gasohne, aviation turbine higher carbon residue value than observed in untreated fuel,
fuel, automotive gasohne, natural gasoline, or other hydro- which can lead to erroneous conclusions as to the coke-form-
carbons having a Reid vapor pressure no greater than 124 ing propensity of the fuel. Test Method D 4046 can detect the
kPa(18psi). presence of alkyl nitrate in the fuel.
Crude petroleum contains sulfur compounds, most of The carbon residue value of burner fuel serves as a rough
which are removed during refining. However, of the sulfur approximation of the tendency of the fuel to form deposits in
compounds remaining in the petroleum product, some can vaporizing pot-type and sleeve-type burners. Similarly, pro-
have a corroding action on various metals and this corrosiv- vided alkyl nitrates are absent (or if present, provided the test
ity is not necessarily related directly to the total sulfur con- is performed on the base fuel without additive) the carbon
tent. The effect can vary according to the chemical types of residue of diesel fuel correlates approximately with combus-
sulfur compounds present. The copper strip corrosion test is tion chamber deposits. The carbon residue value of gas oil is
designed to assess the relative degree of corrosivity of a useful as a guide in the manufacture of gas from gas oil. In a
petroleum product. It is very rare to find a commercially gas turbine it can be an indication of the tendency to form
available diesel fuel that fails the D 130 test. carbon deposits in the combustor.
Carbon Residue Ash

Carbon residue is the residue formed by evaporation and Ash is the non-combustible material in a fuel oil. It can be
thermal degradation of a carbon containing material. The present as either solid material or oil or water-soluble metal-
residue is not composed entirely of carbon but is a coke that lic compounds. These solid particles are the same as those of-
can be further changed by carbon pyrolysis. The term carbon ten designated as sediments. The concern for fuel systems is
residue is retained in deference to its wide common that these solid particles can result in wear and erosion ulti-
usage.The test method for carbon residue, as listed in the mately resulting in substandard or failing performance. The
diesel fuel specification is D 524. test method for ash is D 482.
• D 524, Standard Test Method for Ramsbottom Carbon • ASTM D 482, Standard Test Method for Ash from Petroleum
Residue of Petroleum Products—The sample, after being Products—The sample, contained in a suitable vessel, is ig-
weighed into a special glass bulb having a capillary open- nited and allowed to bum until only ash and carbon re-
ing, is placed in a metal furnace maintained at approxi- main. The carbonaceous residue is reduced to an ash by
mately 550°C. The sample is thus quickly heated to the heating in a muffle furnace at 775°C, cooled and weighed.
point at which all volatile matter is evaporated out of the This test method covers the determination of ash in the
bulb with or without decomposition while the heavier range 0.001-0.180 mass %, from distillate and residual fuels,
residue remaining in the bulb undergoes cracking and cok- gas turbine fuels, crude oils, lubricating oils, waxes, and
ing reactions. In the latter portion of the heating period, other petroleum products, in which any ash-forming materi-
the coke or carbon residue is subject to further slow deals present eire normally considered to be undesirable impu-
composition or slight oxidation due to the possibility of rities or contaminants. The test method is limited to
breathing air into the bulb. After a specified heating pe- petroleum products that are free from added ash-forming ad-
riod, the bulb is removed from the bath, cooled in a desic- ditives.
cator, and again weighed. The residue remaining is calcu- Knowledge of the amount of ash-forming material present
lated as a percentage of the original sample, and reported in a product can provide information as to whether or not the
as Ramsbottom carbon residue. Provision is made for de- product is suitable for use in a given application. Ash can re-
termining the proper operating characteristics of the fur- sult from oil or water-soluble metallic compounds or from
nace with a control bulb containing a thermocouple, which extraneous solids such as dirt and rust.
must give a specified time-temperature relationship.
This test method covers the determination of the amount
Low-Sulfur Diesel Fuel and Dyed Diesel Fuel
of carbon residue left after evaporation and pyrolysis of an
oil, and is intended to provide some indication of relative The Clean Air Act Amendments of 1990 established standards
coke-forming propensity. This test method is generally appli- for highway diesel fuel. The standards, in part, made it illegal
cable to relatively nonvolatile petroleum products that par- as of October 1, 1993, to manufacture, sell, supply, or offer
tially decompose on distillation at atmospheric pressure. for sale diesel fuel for highway use that has a sulfur content
Petroleum products containing ash-forming constituents as greater than 0.05% by weight (this amount is also commonly
determined by Test Method D 482 will have an erroneously expressed as 500 ppm). Similarly, it is illegal for any person
high carbon residue, depending upon the amount of ash to use fuel that has sulfur content greater than 0.05% by
formed. Values obtained by this test method are not numeri- weight in any highway vehicle. EPA also requires diesel fuel
cally the same as those obtained by Test Method D 189, or not intended for use in highway vehicles be dyed in order to
Test Method D 4530. Approximate correlations have been de- segregate it from highway fuel. Internal Revenue Service
rived (Fig. 12) but need not apply to all materials that can be (IRS) regulations require that tax-exempt diesel fuel be dyed
tested because the carbon residue test is applicable to a wide regardless of the sulfur level of the fuel.
variety of petroleum products. The Ramsbottom Carbon The original EPA regulation mandated the addition of a
Residue test method is limited to those samples that are mo- blue dye to fuel with greater than 500-ppm total sulfur.
bile below 90°C. In diesel fuel, the presence of alkyl nitrates However, the Federal Aviation Administration soon ex-
100
80
60
40
30
20
6
i
s
t—
4
3
s
CJ
£Q_ ^—^.
2
• « •
i.r *^
is
l±i *o
^5
1.0
0.8
0.6
eo
Q=
2 0.4
§ 0.3
^ 0.2
; 1 u
S I
g
0.10
0.08
0.06
0.04
0.03
0.02
0.01
0.01 0.02 0.03 0.06 0.10 0.2 0.3 0.4 0.60.81.0 2 3 4 6 8 10 20 30 40 60 80 100
CONRAOSON CARBON RESIDUE, PER CENT BY WEIGHT
(ASTM D 189)
NOTE 1—Âll dimensions are in millimetres.
FIG. 12—Correlation of conradson carbon residue (D 189) with ramsbottom carbon

residue (D 524).
pressed their concern that blue-dyed fuel might be confused high sulfur, have a m i n i m u m level of Solvent Red 164 that is
with the most c o m m o n grade of aviation gasoline, which is "spectrally equivalent to 3.9 pounds per 1000 barrels" of Sol-
also dyed blue. Based on this, the EPA changed the require- vent Red 26. This is over five times the a m o u n t required un-
ments to the use of red dye. The EPA now requires "visible der the EPA regulations. The IRS holds that the excessive dye
evidence of the presence of red dye" to identify high sulfur amount is required to allow detection of attempted tax eva-
fuels intended for off-road use. This typically requires that sion even after a five-fold dilution of the dyed fuel with
oil companies add a level of red dye equivalent to 0.75 undyed fuel. In practice, diesel fuel is taxed as soon as it
pounds per 1000 barrels of a solid Solvent Red 26 dye stan- leaves a terminal unless it has been dyed.
dcird. Solvent Red 26 was selected as the dye standard be- The change, in 1993, to low sulfur diesel fuel for on-road
cause it is a unique chemical and available in pure form. use brought numerous problems. Some of these include:
Diesel fuels are actually dyed with liquid concentrates of • A marked increase in the number of fuel lubricity related
Solvent Red 164 because this dye is more fuel soluble and failures of fuel-wetted engine components. This is primar-
less costly than the standard. Solvent Red 164 is a mixture ily attributed to the fact that the hydrotreating required to
of isomers that are very similar to Solvent Red 26, except remove the sulfur also removes naturally occurring fuel
the former incorporates alkyl chains to increase the solubil- components that would have improved the lubricity of the
ity in petroleum [46]. fuel.
Under the EPA regulations, any red dye seen in the fuel of • The requirements to dye the fuel at the early stages of the
a vehicle operating on-road triggers a n analysis of the fuel's distribution process m e a n that dyed fuel is often trans-
total sulfur content. Penalties are assessed based on the mea- ported through pipelines. While not a c o m m o n occurrence,
sured sulfur content of the fuel, rather than the mere pres- red dyed diesel fuel has been known to contaminate other
ence of red dye. fuels in the system. This occurs either through actual mix-
The IRS tcikes a slightly different path with its regulations. ing of the diesel with the other product or contamination
They require that tax-exempt diesel fuels, both low sulfur and of the other product with red dye residue on the wzJls of the
pipeline following a shipnient of dyed fuel. In the cases bers and supporting organizations [48]. In a letter dated April
where the contaminated fuel has been aviation fuel, the re- 2000, the members stated that the "Charter was first estab-
sult is usually the requirement to dispose of the contami- lished in 1998 to promote greater understanding of the fuel
nated fuel since most jet engines are not certified to oper- quality needs of motor vehicle technologies and to harmonize
ate on fuel with red dye. fuel quality world-wide in accordance with vehicle needs."
• Under the EPA regulations, kerosine used for home heat- The Charter contains four categories of gasoline and diesel
ing and other off-road applications must contain the red fuel as follows (see Table 7 for a listing of selected diesel fuel
dye. Since this fuel is not tcixed, the IRS does not require properties):
the presence of the dye. Unfortunately, the evidence re- • Category 1: Markets with n o or minimal requirements for
garding the possible health effects of using red-dyed fuel in emission control, based primarily on fundamental vehi-
un-vented kerosine heaters is minimal. Therefore, m a n y cle/engine performance concerns.
users of these heaters are reluctcuit to use red-dyed kero- • Category 2: Markets with stringent requirements for emis-
sine. However, if the user wants un-dyed kerosine, they sion control or other market demands. For example, meir-
must pay the tax so that it will not have to be dyed u n d e r kets requiring US Tier 0 or Tier 1, EURO 1 and 2, or equiv-
the IRS regulations. Understandably, m a n y kerosine alent emission standards.
heater users are upset about having to pay the tcix. The laws • Category 3: Markets with advanced requirements for emis-
do allow a refund of the tax, however, and many users (and sion control or other market demands. For example, mar-
in some cases, suppliers) are taking the necessary steps to kets requiring US California LEV, ULEV, and EURO 3 and
reclaim those monies. There is also work underway to de- 4, or equivalent emission standards.
velop information on the potential health effects of burn-
• Category 4: Markets with further advanced requirements
ing the dyed fuel in un-vented heaters. Users are encour-
for emission control, to enable sophisticated NOx and par-
aged to check with their fuel suppliers for additional
ticulate matter after-treatment technologies. For example,
information.
markets requiring US California LEV-II, US EPA Tier 2,
• Seal swell and elastomer compatibility problems brought and EURO 4.
about by the reductions in ciromatic content in low sulfur
fuels. This is discussed in the section on aromatics.
• It should be noted that the reductions in allowable sulfur Premium Diesel Fuel
have also had some positive effects. Aside from the obvious As discussed above, environmental regulations promulgated
improvements in engine emissions, the hydrotreating re- under the Clean Air Act Amendments have resulted in signif-
quired to remove the sulfur often means that the fuel has icant changes to the automotive diesel fuel manufactured
significantly better stability characteristics (through the re- and sold in the United States. These changes, coupled with
moval of precursors). The concomitant removal of aromat- rapidly changing engine technology, created the need to ad-
ics can also bring some improvement to the ignition qual- dress several fuel properties to ensure proper performance,
ity of the fuel. while cJso minimizing engine maintenance problems. There
The requirement to reduce sulfur levels in diesel fuel is now is also a segment of the automotive diesel fuel market that be-
a "fact-of-life" throughout the world. At the time of this writ- lieves that they can benefit from a fuel supply with properties
ing, the EPA is proposing legislation to reduce the maximum different from or in addition to, the m i n i m u m ASTM D 975
allowable sulfur level to I S p p m b y J u n e 1, 2006 [47]. The pri- specifications. Many fuel suppliers sell such fuels at a higher
mary impetus for this continued reduction in sulfur is the price. As a marketing tool, this fuel is often called "premium
need to protect exhaust-treatment devices installed on diesel diesel fuel." Other terms or descriptions have also been used.
engines, many of which are poisoned by sulfur. At the time of this writing, two major groups have proposed
definitions for premium diesel. Those two groups are the Na-
tioneil Conference on Weights and Measures (NCWM) and
World Wide Fuel Charter the Engine Manufacturers Association (EMA). In both cases,
The World-Wide Fuel Charter was jointly developed by the the proposed premium diesel is based on varying one or more
E u r o p e a n Automobile Manufacturers Association (ACEA), fuel properties.
the Allieuice of Automobile Manufacturers, the Engine Mcin- To ensure that the fuel consumer gets a "premium" prod-
ufacturers Association (EMA), the Japan Automobile Manu- uct for the higher price, the National Conference on Weights
facturers Association (JAMA), and numerous associate mem- and Measures (NCWM) took steps to develop a standardized
TABLE 7—Selected property specifications from world-wide fuel charter.

Property Category 1 Category 2 Category 3 Category 4
Cetane Number, min 48 53 55 55
Cetane Index, min 45 50 52 52
Sulfur, max, mass % 0.50 0.030 0.003 Sulfur-free
Lubricity, HFRR scar dia @60°C, (xm 400 400 400 400
Particulates, mg/L No Requirement 24 24 24
Total Aromatics, mass % No Requirement 25 15 15
TABLE 8—Diesel fuel properties referenced in NCWM definition been evaluated as a diesel fuel and as a blend component
of premium diesel fuel. with conventional petroleum diesel fuel.
Heating Value, Gross, Schaberg, et al. [53] tested two variations of the Sasol dis-
Btu/gallon, min D240 138 700 tillate fuels, a 2-D diesel fuel, a CARB (California Air Re-
Cetane number, min D613 47.0 sources Board) diesel, and three blends of the Sasol fuel with
Low temperature D 2500 or 2°C maximum the 2-D fuel. The Sasol fuels produced significantly lower en-
operability D4539 above the D 975
tenth percentile gine emissions than the 2-D and CARB fuels. The fuel blends
minimum reduced emissions in proportion to the amount of the Sasol
ambient air fuel in the blend. Other resesirchers have shown similar im-
temperature provements in regulated emissions, with the use of Fischer-
Thermal stability, 180 min. D6468 80% Tropsch fuels, as well [54-56]. The most significant potential
150°C, reflectance, min problem associated with the use of these fuels is lubricity.
Fuel injector cleanliness L-10 Injector
Flow loss, % max 6.0 Fischer-Tropsch fuels have very poor lubricity properties.
CRC rating, % max 10.0 There may also be some elastomer/seal swell problems, espe-
cially in older fuel systems, since these fuels have no aro-
matic compounds.
Biodiesel is also a potential alternative to conventional,
definition of premium diesel. An NCWM task force com- petroleum-derived diesel. Biodiesel is a renewable source of
posed of representatives from the oil industry, additive man- energy. In the United States, Biodiesel is a fuel comprised of
ufacturers, independent labs, and government agencies, with mono-alkyl esters of long chain fatty acids derived from veg-
the assistance of ASTM, prepared a set of requirements to de- etable oils or animal fats, designated BIOO. Biodiesel is regis-
fine premium diesel. In late 1997, the NCWM task force rec- tered with the U.S. EPA as a fuel and a fuel additive under
ommended that a fuel must meet any two of the five criteria Section 211(b) of the Clean Air Act. There is, however, other
listed in Table 8 before it can be labeled "premium diesel." usage of the term biodiesel in the market place. Biodiesel is
The NCWM adopted the plan at its 84th conference in 1999 typically produced by a reaction of a vegetable oil or animal
[49]. The definition became a model law and was automati- fat with an alcohol such as methanol or ethanol in the pres-
cally adopted by some states; elsewhere, it will only become ence of a catalyst to yield mono-alkyl esters and glycerin. The
effective if a state specifically adopts it. finished biodiesel derives approximately 10% of its mass
The EMA issued a Recommended Guideline (FQP-IA) for from the reacted alcohol. The alcohol used in the reaction
a premium diesel fuel. The proposed values are listed in may or may not come from renewable resources. Biodiesel
Table 9. From the EMA consensus position: blend is a mixture of biodiesel fuel with petroleum-based
diesel fuel designated BXX, where XX is the volume % of
This diesel fuel is considered to be "premium" insofar as it biodiesel.
may assist in improving the performance and durability of
engines currently in use and those to be produced prior to
2004. It is not intended to enable diesel engines to meet any
emissions standard or, in general, to improve engine ex-
haust emissions... It is intended as a "living document" in TABLE 9—EMA recommended guideline (FQP-IA).
that, as other needs or test procedures are identified, the Property Test Method Requirements
recommendation will be upgraded [50]. Flash point, °C, min D93 52
The most significant aspects of this Consensus Position are Water Eind sediment, % vol, meix D2709 0.05
its requirements for a minimum fuel lubricity, increased Water, ppm max D 1744 200
Sediment, ppm max D 2276 or 10
cetane number, improved cold weather performance, deter- D5452
gency, thermal stability, minimum energy content, and spec- Distillation, °C, % vol recovery D86
ifications regarding overall fuel "cleanliness." 90% max 332
95% max 355
Viscosity, 40°C, cSt D445 1.9^.1
Alternative Fuels Ash, % mass, max D482 0.01
Sulfur, % mass, max D2622 0.05
As in the early 1980s, research with alternative fuels is again Copper corrosion, max D 130 3b
on the increase. Whereas the earlier work centered on the Cetane number, min D613 50
suitability of alternative fuels to power diesel engines; most Cetane index, min D4737 45
Ramsbottom carbon on D524 0.15
of the current work is evaluating the potential these fuels of- 10% residue, % mass, max
fer to reduce engine emissions [51]. Fischer-Tropsch Liquids API gravity, max D287 39
and Biodiesel are the fuels that seem to show up the most in Lubricity, g, min D 6078(1) 3100
the current literature and reports. Accelerated stability, mg/L, max D2274 15
Detergency L-10 Injector
Fischer-Tropsch Synthesis is the process whereby natural CRC rating, max slO.O
gas or coal is converted into hydrocarbons. The product hy- Depositing test, % flow loss, max s6.0
drocarbons are usually upgraded to middle distillate prod- Low temperature flow, °C D 2500 or (2)
ucts such as kerosine and diesel fuel. Typically Fischer-Trop- D4539
sch diesel fuels have high cetane numbers, often greater than NOTE: Alternatively, lubricity can be measured by D 6079 with a maximum
70 cetane, no aromatic compounds, no sulfur, and a density wear scar diameter of 0.45 Jim at 60°C.
Diesel fuels must pass the Cloud Point (D 2500) or Low Temperature
of around 0.78 kg/L [52]. The Fischer-Tropsch liquids have Flow Test (D 4539) at the use temperature.
OH
O JL J. "^^lalyst HO
\ ^ ^ + 3(GH30H) ^ 3(RCOOCH3) +
O.^ ^ O OH
T
Triglyceride + 3 iVIetlianol "^^*^'^' 3 methyi-estiiers + Glycerol
R is usually 1 6 - 1 8 carbons with 1 - 3 0 = 0 bonds.
FIG. 13—Reactions of vegetable oil to form methyl-esthers.
TABLE 10—Detailed requirements for biodiesel (BlOO)." quirements for BlOO as found in PS 121. Diesel engines can
Test run on B1 GO; however, most of the testing in this country has
Property Method'' Limits Units been done on blends of biodiesel a n d low sulfur diesel. A
Flash point D93 100.0 min°C blend of 20% biodiesel with 80% low sulfur diesel (B20) has
(closed cup) been tested in numerous applications across the country. The
Water and D2709 0.050 max % volume limited testing thus far completed has shown that this fuel
sediment produces lower emissions of particulate matter, hydrocar-
Kinematic D445 1.9-6.0" mm 2/s
viscosity, 40°C bons, a n d carbon monoxide t h a n conventional diesel fuel.
Sulfated ash D874 0.020 max % mass NOx emissions can be slightly higher thcin with conventional
Sulfur^ D2622 0.05 max % mass diesel, unless the fuel system injection timing is optimized
Copper strip D 130 No. 3 max for B20.
corrosion
Cetane number D613 40 min BlOO has good lubricity properties and contains essentially
Cloud point D2500 Report to °C no sulfur or aromatics. However, it has a relatively high pour
customer point, which could limit its use in cold weather. Biodiesel is
Carbon residue" D4530 0.050 max % mass biodegradable, but this property may lead to increased bio-
Acid number D664 0.80 max mg KOH/g logical growth during storage. Biodiesel is also more suscep-
Free glycerin'^ 0.020« % mass
Total glycerin^ 0.240« %mass tible to oxidative degradation than petroleum diesel.
"To meet special operating conditions, modifications of individual limiting
Other eJtemative fuels that have been investigated for use
requirements may be agreed upon between purchaser, seller, and manufac- in diesel engines include ethers, alcohols, naphtha, and vari-
turer. ous gaseous fuels. Each of these has some advantage (such as
''The test methods indicated are the approved referee methods. Other ac-
ceptable methods are indicated in 5.3.
reduced engine emissions) associated with its use. However,
"SeeXl.3.1. much work remains to be done with these fuels, including
'Ôther sulfur limits can apply in selected areas in the United States and in building a distribution infrastructure, before they will be
other countries.
"Carbon residue shall be r u n on the 100% sample (see 5.2.10). widely used in diesel engines.
'See Annex 1 for test method. A gas chromatographic technique is being
converted to a standard test method.
*The test m e t h o d is u n d e r ASTM consideration by Subcommittee
D02.04.OL.
GAS TURBINE FUELS
This section discusses the fuels used in non-aviation (indus-
Soybean oil is the largest source of biodiesel in the United trial) gas turbine applications. The specification for indus-
States, however, oil from other plants is sometimes used. trial gas turbine fuels is D 2880, Standard Specification for
Biodiesel is a mixture of fatty acid methyl esters. The oils are Gas Turbine Fuel Oils. Table 11 contains the specific re-
combined with methanol in a process known as transesterifi- quirements for the fuels covered by D 2880. Comparison of
cation (Fig. 13). the specifications for diesel fuels and gas turbine fuels shows
The resulting mixture of fatty acid methyl esters has chem- that gas turbine fuels actually have fewer requirements.
ical and physiccJ properties similar to those of conventional Many of the individual property requirements of both speci-
diesel fuel. Provisional Specification 121 is the ASTM specifications are equivalent for corresponding grades. This is
fication for Biodiesel Fuel (BlOO) Blend Stock for Distillate demonstrated in Tablel2. The main differences are due to
Fuels. (At this writing, ASTM is working to approve PS 121 as operational difference of diesel versus gas turbine. As an ex-
a standard specification.) Table 10 contains the detailed re- ample, diesel fuel has a cetane number requirement whereas
TABLE 11—Detailed requirements for gas turbine fuel oils at time and place of custody transfer to user.'
Graded''
ASTM
Property Test Method" No. 0-GT No. l-GT'^ No. 2-Gr No. 3-GT No. 4-GT
Flash point °C (°F) min D93 f 38 (100) 38 (100) 55(130) 66 (150)
Water and sediment D2709 0.05 0.05 0.05
% vol max D1796 1.0 1.0
Distillation Temperature °C (°F) D86
90 % volume recovered
min 282
max 288 338
Kinematic viscosity 2 mm/s^ D445
At40°C(104°F)
min f 1.3 1.9 5.5 5.5
max 2.4 4.1
At 100°C (212°F) max 50.0 50.0
Ramsbottom
Carbon residue on 10% distillation D524 0.15 0.15 0.35
Residue % mass, max
Ash % mass, max D482 0.01 0.01 0.01 0.03
Density at 15°C k g W D 1298
max 850 876
Pour point«°C (°F) max D97 -18 -6
"To meet special operating conditions, modifications of individual limiting requirements may be agreed upon between purchaser, seller, and manufacturer.
''Gas turbines with waste heat recovery equipment may require fuel sulfur limits to prevent cold end corrosion. Environmental limits may also apply to fuel sul-
fur in selected areas in the United States and in other countries.
"The test methods indicated are the approved referee methods. Other acceptable methods are indicated in 6.1.
''No. 0-GT includes naphtha, Jet B fuel and other volatile hydrocarbon liquids. No. 1-GT corresponds in general to specification D 396 Grade No. 1 fuel and D
975 Grade 1-D diesel fuel in physical properties. No. 2-GT corresponds in general to Specification D 396 No. 2 fuel and D 975 Grade 2-D diesel fuel in physical
properties. No. 3-GT and No. 4-GT viscosity range brackets specification D 396 Grades No. 4, No. 5 (light). No. 5 (heavy), and No. 6, and D 975 Grade No. 4-D diesel
fuel in physical properties.
"Under United States regulations. Grades No. 1-GT and No. 2-GT are required by 40 CFR Part 80 to contain a sufficient amount of dye Solvent Red 164 so its
presence is visually apparent. At or beyond terminal storage taniks, they are required by 26 CFR Part 48 to contain the dye Solvent Red 164 at a concentration spec-
trally equivalent to 3.9 lbs per thousand barrels of the solid dye standard Solvent Red 26.
'when the flash point is below 38°C (100°F) or when kinematic viscosity is below 1.3 mm^/s at 40''C (104°F) or when both conditions exist, the turbine manu-
facturer should be consulted with respect to safe handling and fuel system design.
*For cold weather operation, the pour point should be specified 6°C below the ambient temperature at which the turbine is to be operated except where fuel
heating facilities are provided. When a pour point less than — 18°C is specified for Grade No. 2-GT, the minimum viscosity shall be 1.7 mm^/s and the minimum
90% recovered temperature shall be waived.
TABLE 12—Comparison of specification requirements components: compressor, combustor, and turbine. The pur-
for selected distillate fuels. pose of the compressor is to raise the pressure of the operat-
Parameter D396 D975 D 2069 D 2880 D 3699 ing fluid usually a ratio of 10 to 20 to 1. It is desirable to ac-
Flash point complish this pressure increase as efficiently as possible to
Water & sediment maximize the available thrust or horsepower, because the ef-
Distillation ficiency determines how much horsepower is required for
Viscosity
Carbon residue
the compression. The purpose of the combustor is to raise the
Ash temperature of the operating fluid. The combustor inlet tem-
Copper strip corrosion perature depends on the pressure ratio and efficiency of the
Density compressor. In more complicated cycles some of the heat in
Pour point the exhaust is recovered and used to increase the combustor
Sulfur
Cetane #
inlet temperature, which reduces the required temperature
Cloud pt. rise across the combustor and thus the amount of fuel re-
Freezing point quired. Current combustor outlet temperatures are in the
Burning quality 1093-1482°C (2000-2700°F) ranges. The combustor must ac-
Saybolt color complish this temperature rise efficiently. Current combus-
NOTE: An asterisk indicates the property is included in the specification. tion efficiencies are in the 99%-f range at most operating
conditions. Additionally the outlet temperature profiles have
gas turbine fuel does not. Because the specifications are so specific requirements.
similar, most fuels sold under one specification would also A gas turbine combustor operates at fuel-air ratios less
meet the requirements of the other. For this same reason, the than stoichiometric and below the lower flammability level.
properties and test methods for diesel fuel, as discussed Figure 14 is a simplified diagram of how the air is introduced
above, are equally applicable to gas turbine fuels. in a conventional combustor i.e., not a low emission com-
bustor. The figure shows the distribution of air for a com-
bustor with an overall air to fuel ratio of 70 to 1. About four
Gas Turbine Fuel Requirements parts of air per part of fuel are introduced in the swirler to
Industrial gas turbines are basically the same as aviation gas help stabilize the flame zone. Then, in the primary zone, 12
turbines in operation. A simple gas turbine has three major parts of air per part of fuel are introduced to provide enough
COMBUSTOR AIR DISTRIBUTION
FULL LOAD
46
Parts
Air OVERALL
AIR-FUEL
RATIO = 70
P = PRIMARY
S = SECONDARY
D = DILUTION OR TERTIARY
SW = SWIRLER
F = FUEL
FIG. 14—Simplified diagram of gas turbine.
air to provide approximately the stoichiometric amount of to those used in some heaters. Lower flow nozzles of this type
air required, making a total of 16 parts of air per part of fuel. are particularly sensitive to viscosity, which is why many en-
In the secondary zone an additional 6 parts of air per of part gine company specifications have a meiximum viscosity limit
of fuel are introduced making a total of 22 parts of air per regardless of temperature. More modern fuel injection sys-
part of fuel, which completes the reaction. The rest of the air tems, which utilize air to assist the atomization of the fuel,
(48 parts of air per part of fuel) is used to cool the combustor are less sensitive to viscosity but some limit is still required.
walls and to dilute the air-stream temperature down to the Another factor to be considered for light-off is the volatility
design turbine inlet temperature. of the fuel. The initial boiling point of the fuel must be con-
The major difference between an aviation gas turbine and sidered because, even if the fuel is well atomized, if it is too
an industrial gas turbine is that the aviation generates thrust heavy, light-off might not consistently occur.
to propel the airplane by exhausting hot gases at high tem- Smaller gas turbines (<10kW) tend to use distillates, while
peratures and velocities. The aviation turbine section only larger engines also use a mix of distillates and residuals or
has to generate enough horsepower to drive the compressor. pure residuals. Additional problems resulting from residual
In an industrial gas turbine the gases that would be ex- fuels include carbon deposits, increased combustor skin tem-
hausted in an aviation gas turbine are expanded across addi- peratures, and exhaust smoke.
tional turbine stages to generate shaft horsepower that can be
used to drive generators, pumps, gas compressor, etc.
Trace Metal Limits
Many industrial gas turbines use gaseous fuels but others
use a variety of liquid fuels ranging from naphtha to residual The effects of trace metals such as sodium, potassium, vana-
oils. Aviation gas turbine fuel requirements are quite narrow dium and lead on gas turbines are discussed in Appendix X2
because of the varying operating conditions (altitude, tem- of D2880. The sulfur content also is important because of its
perature, etc.), which impose limitations on volatility, viscos- interaction with sodium and potassium as well as the effects
ity, distillation range, etc. Industrial gas turbines are usually on exhaust emissions. These trace metals rarely occur in dis-
stationary. This means atmospheric conditions do not tillate fuels at the refinery. Since they can be introduced at
change as drastically as with aviation gas turbines. some point after the refinery, D2880 specifies that the limits
The operating conditions for the combustors for the two apply at the entrance of the combustor.
applications vary. Many industrial gas turbines operate at or Trace metals refer both to those metals present as metallic
necir design point for extended periods where an aviation gas compounds in solution and to metals present in particulates
turbine operates at take-off (full power) for a short time eind like rust. They are dissolved or suspended either in the fuel
then the power level is reduced to cruise for the duration of hydrocarbons or in free water present in the fuel. Although
the flight. In the following paragraphs, selected requirements lower levels of trace metals in a fuel will promote longer tur-
specific to gas turbine operation will be discussed. bine service from a corrosion standpoint, the specification of
The first consideration is light-off (initiating the combus- excessively low levels may limit the availability of the fuel or
tion process and accelerating the engine to idle). Factors such materially increase its cost. Table 13 suggests levels of trace
as the tjrpe of fuel injection system, fuel viscosity, and fuel metals that would probably yield satisfactory service.
volatility are important. In earlier gas turbines, the fuel in- Sodium and potassium can combine with vanadium to
jectors or nozzles were of the pressure atomizing type simileir form eutectics, which melt at temperatures as low as 566°C
TABLE 13—Trace metal limits of fuel entering turbine vary depending on the application, but it is always essential
combustor(s).'' that there is a fine and uniform dispersion of the additive in
Trace Metal Limits, mg/kg the fuel at the point of combustion.
Sodium plus For gas turbines operating at turbine inlet gas tempera-
Designation Vanadium Potassium Calcium Lead tures below 650°C, the corrosion of the high-temperature EJ-
No. 0-GT 0.5 0.5 0.5 0.5 loys is of minor importance, and the use of a silicon-base ad-
No. 1-GT 0.5 0.5 0.5 0.5 ditive will further reduce the corrosion rate by absorption
No. 2-GT 0.5 0.5 0.5 0.5 and dilution of the vEinadium compounds.
No. 3-GT 0.5 0.5 0.5 0.5
No. 4-GT (Consult turbine manufacturers) Lead Ccin cause corrosion and, in addition, it can spoil the
"Test Method D 3605 may be used for determination of vanadium, sodium,
beneficial inhibiting effect of magnesium additives on vana-
calcium, and lead. dium corrosion. Since lead is only rarely found in significant
quantities in crude oils, its appearance in the fuel oil is pri-
marily the result of c o n t a m i n a t i o n during processing or
transportation.
and can combine with sulfur in the fuel to yield sulfates with
melting points in the operating range of the gas turbine.
These compounds produce severe corrosion, and for turbines ASTM STANDARDS
operating at gas inlet temperatures above 650°C, additives
that control such corrosion are not yet in general use. Ac- No. Title
cordingly, the sodium-plus-potassium level must be limited, D 56 Test Method for Flash Point by Tag Closed Tester
but each element is measured separately. Some gas turbine D 86 Test Method for Distillation of Petroleum Products
installations incorporate systems for washing oil with water D 93 Test Methods for Flash Point by Pensky-Martens
to reduce the sodium-plus-potassium level. In installations Closed Cup Tester
where the fuel is moved by sea transport, the sodium-plus- D 97 Test Method for Pour Point of Petroleum Products
potassium level should be checked prior to use to ensure that D 129 Test Method for Sulfur in Petroleum Products
the oil has not become contaminated with sea salt. For gas (General Bomb Method)
turbines operating at turbine inlet gas temperatures below D 189 Test Method for Conradson Carbon Residue of
650°C (1200°F), the corrosion due to sodium compounds is Petroleum Products
of minor importance and can be further reduced by silicon- D 240 Test Method for Heat of Combustion of Liquid Hy-
base additives. A high sodium content is even beneficial in drocarbon Fuels by B o m b Calorimeter
these turbines because it increases the water-solubility of the D 445 Test Method for Kinematic Viscosity of Transpar-
deposits and thereby increases the ease with which gas tur- ent and Opaque Liquids (and the Calculation of Dy-
bines can be water-washed to obtain recovery of the operat- namic Viscosity)
ing performance. D 482 Test Method for Ash from Petroleum Products
Calcium is not harmful from a corrosion standpoint; in D 524 Test Method for Ramsbottom Ceirbon Residue of
fact, it serves to inhibit the corrosive action of vanadium. Petroleum Products
However, calcium can lead to hard-bonded deposits that are D 613 Test Method for Ignition Quality of Diesel Fuels by
not self-spalling when the gas turbine is shut down, and that the Cetane Method
are not readily removed by water washing of the turbine. The D 976 Test Method for Calculated Cetane Index of Distil-
fuel washing systems used at some gas turbine installations late Fuels
to reduce the sodium and potassium level will also signifi- D 1266 Test Method for Sulfur in Petroleum Products
cantly lower the calcium content of fuel oil. (Lamp Method)
Vanadium can form low melting compounds such as veina- D 1298 Test Method for Density, Relative Density (Specific
dium pentoxide that melts at 691°C, and causes severe corro- Gravity), or API Gravity of Crude Petroleum and
sive attack on all of the high temperature alloys used for gas Liquid Petroleum Products by Hydrometer Method
turbine blades. If there is sufficient magnesium in the fuel, it D 1319 Test Method for H y d r o c a r b o n Tjrpes in Liquid
will combine with the vanadium to form compounds with Petroleum Products by Fluorescent Indicator Ad-
higher melting points and thus reduce the corrosion rate to sorption
an acceptable level. The resulting ash will form deposits in D 1552 Test Method for Sulfur in Petroleum Products
the turbine and will require appropriate cleaning procedures. (High-Temperature Method)
When vanadium is present in more than trace amounts either D 2068 Test Method for Filter Plugging Tendency of Distil-
in excess of 0.5 mg/kg or a level recommended by the turbine late Fuel Oils
manufacturer, it is necessary to maintain a weight ratio of D 2274 Test Method for Oxidation Stability of Distillate
magnesium to vanadium in the fuel of not less than 3.0 in or- Fuel Oil (Accelerated Method)
der to control corrosion. An upper limit of 3.5 is suggested D 2425 Test Method for Hydrocarbon Types in Middle Dis-
since larger ratios will lead to unnecessarily high rates of ash tillates by Mass Spectrometry
deposition. In most cases, the required magnesium-to-vana- D 2500 Test Method for Cloud Point of Petroleum Products
dium ratio will be obtained by additions of magnesium-con- D 2622 Test Method for Sulfur in Petroleum Products by
taining compounds to the fuel oil. The special requirements Wavelength Dispersive X-ray Fluorescence Spec-
covering the addition of and type of magnesium-containing trometry
additive, or equivalent, shall be specified by mutual agree- D 2709 Test Method for Water and Sediment in Middle Dis-
ment between the various interested parties. The additive will tillate Fuels by Centrifuge
D2887 Test Method for Boiling Range Distribution of D 6426 Test Method for Determining Filterability of Distil-
Petroleum Fractions by Gas Chromatography late Fuel Oils
D 3117 Test Method for Wax Appearance Point of Distillate D 6450 Test Method for Flash Point by Continuously
Fuels Closed Cup (CCCFP) Tester
D 3828 Test Methods for Flash Point by Small Scale Closed D 6591 Test Method for Determination of Aromatic Hydro-
Tester carbon Types in Middle Distillates—High Perfor-
D 3941 Test Method for Flash Point by the Equilibrium m a n c e Liquid Chromatography Method with Re-
Method with a Closed-Cup Apparatus fractive Index Detection
D 4052 Test Method for Density a n d Relative Density of
Liquids by Digital Density Meter
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Liquid Fuels, San Antonio, TX, July 29-August 1, 1986. [40] Turner, L. M., et. al., "Use of ASTM D 5304 in Assessing Unsta-
[22] Beal, E. J., Hughes, J. M., and Hardy, D. R., "An Improved Fuel ble Diesel Fuel," Proceedings of the Fifth International Conference
Filterability Test," Proceedings of the Sixth International Confer- on Stability and Handling of Liquid Fuels, Rotterdam, the
ence on Stability and Handling of Liquid Fuels, Vancouver, B.C., Netherlands, October 3-7, 1994.
Canada, October 1997. [41] Wray, H. A., "Memual on Flash Point Standards and Their Use,"
[23] Pedley, J., et. al., "Storage Stability of Petroleum-Derived Diesel Manual #9, ASTM International, West Conshohocken, PA, 1992.
Fuel," Fuel, Vol. 68, 1989, pp. 27-31. [42] ASTM D 975-98b, Appendix X3, Annual Book of ASTM Stan-
[24] Taylor, W. F. and Frankenfeld, J. W., "Chemistry and Mecha- dards, Vol 05.01, ASTM International, West Conshohocken, PA,
nism of Distillate Fuel Stability," Proceedings of the Second In- 1998.
ternational Conference on Long Term Storage Stabilities of Liquid [43] Nikanjam, M., Crosby, T., Henderson, P., Gray, C , Meyer, K.,
Fuels, San Antonio, TX, July 1986. and Davenport, N., "ISO Diesel Fuel Lubricity Round Robin
[25] Beaver, B., "Long Term Storage Stability of Middle Distillate Program," SAE Paper No. 952372, SAE Fuels and Lubricants
Fuels from a Chemical Mechanistic Point of View. Part 1," Fuel Meeting, October 16-19, 1995, Toronto, Canada.
Science and Technology International, Vol. 9, No. 10, 1991, pp. [44] Westbrook, S. R, et. al., "Survey of Low Sulfur Diesel Fuels and
1287-1335. Aviation Kerosines from U.S. Military Installations," SAE Tech-
[26] Beaver, B., "Long Term Storage Stability of Middle Distillate Fu- nical Paper 952369, Society for Automotive Engineers, Warren-
els from a Chemical Mechanistic Point of View. Part 2," Fuel Sci- dale, PA 1995.
ence and Technology International, Vol. 10, No. 1, 1992, 1-37. [45] Nikanjam, M., Crosby, T., Henderson, P., Gray, C , Meyer, K.,
[27] Wechter, M. A. and Hardy, D. R., "The Use of Macromolecular and Davenport, N., "ISO Diesel Fuel Lubricity Round Robin
Oxidatively Reactive Species (SMORS) to Predict Storage Sta- Program," SAE Paper No. 952372, SAE Fuels and Lubricants
bility of Mid-Distillate Diesel Fuels," Proceedings of the 4th In- Meeting, October 16-19, 1995, Toronto, Canada.
ternational Conference on Stability and Handling of Liquid Fuels, [46] Bacha, J., Blondis, L., Freel, J., Hemighaus, G., Hoekman, K.,
Orlando, FL, November, 1991. Hogue, N., et al., Diesel Fuels Technical Review (FTR-2), Chevron
[28] Henry, C. P., "The du Pont F21 149°C (300°F) Accelerated Sta- Products Company, Sein Francisco, CA, 1998.
biUty Test," Distillate Fuel Stability and Cleanliness, ASTM STP [47] "Proposed Heavy-Duty Engine and Vehicle Standards and High-
751, L. L. Stavinoha and C. P. Henry, Eds., ASTM International, way Diesel Fuel Sulfur Control Requirements," United States
West Conshohocken, PA, 1981, pp. 22-33. Environmental Protection Agency, EPA420-F-00-022, May
[29] ibid. 2000.
[30] Research Report RR:D02-1463, ASTM International, West Con- [48] The interested reader can find additional information at the fol-
shohocken, PA. lowing internet sites: www.acea.be; www.autoalliance.org;
[31] Stavinoha, L. L. and Westbrook, S. R., "Accelerated Stability www.engine-manufacturers.org.
Test Techniques for Middle Distillate Fuels," Distillate Fuel Sta- [49] Handbook 130, "Uniform Laws and Regulations in the Areas of
bility and Cleanliness, ASTM STP 751, L. L. Stavinoha and C. P. Legal Metrology and Engine Fuel Quality" (2000 Edition), as
Henry, Eds., ASTM International, West Conshohocken, PA, adopted by the 84th National Conference on Weights and Mea-
1981, pp. 3-21. sures, 1999.
[32] Bacha, J. D. and Lesnini, D. G., "Diesel Fuel Thermal Stability at [50] EMA Consensus Position, Joint EMA/TMC P u m p Grade Speci-
300°F," Proceedings of the 6th International Conference on Sta- fication for Premium Diesel Fuel.
bility and Handling of Liquid Fuels, Vancouver, B.C. Canada, Oc- [51] Jett, B. T. and Kirkpatrick, A. T., "Alternative Fuels for DI En-
tober 13-17, 1997, pp. 671-684. gines," SAE No. SP-1412, Society of Automotive Engineers,
[33] Henry, C. P., "The du Pont F21 149°C (300°F) Accelerated Sta- Warrendale, PA, 1999.
biUty Test," Distillate Fuel Stability and Cleanliness, ASTM STP [52] Grimes, G., "Economics and Experience of Blending Fischer-
751, L. L. Stavinoha and C. P. Henry, Eds., ASTM International, Tropsch Diesel at Paramount Petroleum," presented at Gas-to-
West Conshohocken, PA, 1981, pp. 22-33. Liquids Processing 99, May 17-19, 1999, San Antonio, TX.
[34] White, E. W., " A Study of Test Variables Affecting Results Ob- [53] Schaberg, P. W., et al, "Diesel Exhaust Emissions Using Sasol
tained in the ASTM D 2274 Accelerated StabiUty Test," Proceed- Slurry Phase Distillate Process Fuels," SAE No. 972898, Society
ings of the Second International Conference on Long-Term Stor- of Automotive Engineers, Warrendale, PA, 1997.
age Stabilities of Liquid Fuels, San Antonio, TX, October 1986. [54] Clark, N. N., et. al., "Transient Emissions Comparisons of Alter-
[35] White, E. W. and Bowen, R. J., "A Study of Variables Affecting native Compression-Ignition Fuels," SAE No. 1999-01-1117, So-
Resuhs Obtained in the ASTM D 2274 Accelerated Stability ciety of Automotive Engineers, Warrendale, PA, 1999.
Test; Parts 2 & 3-Effects of Selected Chemical and Physical Fac- [55] Clark, N. N., et. al., "On-Road Use of Fischer-Tropsch Diesel Fu-
tors," Proceedings of the Third International Conference on Sta- els," SAE No. 1999-01-2251, Society of Automotive Engineers,
bility and Handling Liquid Fuels, London, U. K., September Warrendale, PA, 1999.
13-16, 1988. [56] Mintz, M. M., Wang, M. Q., and Vyas, A. D., "Fuel-Cycle Energy
[36] Chang, R., Chemistry-5th ed., McGraw-Hill, New York, 1994. and Emissions Impacts of Propulsion System/Fuel Alternatives
[37] Anon., "Storage Stability of Distillate Fuels and Blends," Bureau for Tripled Fuel-Economy Vehicle," SAE Report No. 1999-01-
of Mines Summary Report 1, Petroleum Experiment Station, 1118, Society of Automotive Engineers, Warrendale, PA, 1999.
MNL37-EB/Jun. 2003
Introduction to Marine
Petroieum Fuels
Matthew F. Winkler^
T H E MODERN PETROLEUM INDUSTRY began during the late 19th In the late 1940s and throughout the 1950s, motor ship fuel
century, although small quantities of petroleum were ob- systems a n d marine diesel engines struggled to operate on
tained as early as the 14th century. In Pennsylvania, Edwin residual fuels a n d to control reliability a n d m a i n t e n a n c e
Drzike drilled the first oil well in 1859, striking oil at a depth costs. The successful combination of modified diesel engines,
of 21 m. Drake's oil well was generally accepted as the start of improved fuel handling, a n d purification systems, together
the petroleum industry. Kerosine or lamp oil was the object with, new, reformulated cylinder lube oils led to the eco-
of the early refining industry. The simple distillation process nomic use of residual fuels in motor ships.
was conducted to obtain as m u c h lamp oil as possible from By the mid-1960s, about half of the world merchant fleet
the Pennsylvania crude oil. tonnage was powered by diesel engines. Then, the distillate
In 1870, the S.S. Constantine was the first of many sea ves- and residual fuel costs were jolted sharply upward in 1973
sels converted from coal to fuel oil. While trading in t h e and again in 1979 by t h e Middle Eastern oil suppliers re-
Caspian Sea, the vessel burned the residue from refined Rus- stricting oil supplies and raising crude oil prices. This caused
sian crude oil. Early oil burners were primitive a n d ineiB- the metrine fuel expenditure to become a significemt factor in
cient, b u t the crude oil was plentiful a n d n o attempt was the ship owner's operating costs, and caused overeJl propul-
m a d e to b u m the fuel oil economiccJly. sive efficiency to take on renewed significance. The result
In the early years of oil firing, t h e marine industry a n d was the rapidly declining popularity of steam-powered ves-
Lloyd's Register considered oil-fired instcJlations as experi- sels. The m u c h m o r e thermally efficient a n d economical
mental, with the vast majority of vessels still powered by coal diesel engine led to the dominant position in merchant ves-
at t h e end of the 19th century. sels that it still enjoys today.
Early 20th century fuel oils were used to a greater extent The goal of m o d e m m a r i n e diesel engines is to operate
in steam boilers and the marine industry experimented with with fuel efficiency a n d reability on cracked a n d heavier
oil-fired diesel engines in the M/T Vulcanus in 1910 and the residual fuels. Marine residual fuels provide the main source
MA'^ Seletndia in 1911. Then, during the period u p to the of energy that is used to transport the world's sea trade. More
outbreak of the first World War, fuel oil was used increas- ton-miles are moved by ship than by all other transportation
ingly in Marine Merchant vessels, predominantly in steam means combined. Therefore, marine fuels have become even
boilers. more importcint today to world trade.
In the early 1920s, zJmost all motor ships r a n on a distillate
fuel CcJled "diesel oil" while the oil-fired steam ships burned
a residual fuel called "boiler fuel." The quality difference be-
tween the diesel oil and the boiler fuel was considerable. PETROLEUM CRUDE OIL REFINING
In t h e mid-1920s, some m o t o r ships h a d experimented
with burning boiler fuel in the m a i n a n d auxiliary engines. Crude oil must be carefully refined to produce the main us-
However, there was no commercial benefit in burning boiler able products, such as gases, gasoline, kerosine, jet fuels,
fuel, since the smedl price differential between diesel fuel cind diesel fuels, lubricating oil base stocks, petrochemical feed
boiler fuel was offset by the increased mainteneince costs (re- stocks, waxes, bitumens, residucJ fuels, and even petroleum
sulting from burning boiler fuel). coke. The method and degree of the refining of crude oil a n d
By the beginning of World W a r II, about half of the world its inherent properties determine the quality and quantity of
marine fleet was oil fired. Of those ships, half were steam a n d any petroleum product produced.
half were diesel powered. Refining, design, a n d production of main petroleum prod-
As society increased the usage of distillate fuels for auto- ucts are dictated by the local, national, or international re-
motive, truck, railroad, and aircrzift, the increasing demand quirements for light and middle distillate products as well as
for distillate fuels increased the cost differential between dis- for petrochemiceJ feed stocks, which are the higher profit
tillate fuels and residuals. This economic incentive prompted products produced from crude oil. Recently, govemmentcJ
the Mcirine Industry to improve t h e technical feasibility of regulations to reduce air pollution have controlled sulfur,
burning residual fuels (boiler fuels) in marine diesel engines. carbon/aromatic a n d oxygen content, etc., of distillate and
residual fuels.
' Vice President, Seaworthy Systems, Inc., P.O. Box 965, Essex, CT The basic refining processes are distillation, cracking,
06426. blending, and storage.
145
Distillation another (secondary) process called "viscosity breaking" or

"visbreaking." In this process, the vacuum bottoms are
Fractional or atmospheric distillation is the oldest and most heated to a higher temperature and higher pressure for
basic refining process. The heated crude is charged to the cracking, although not as high as in the thermal cracking pro-
tower under pressure and a portion flashes to vapor while the cess. The high viscosity feed stock is converted to a residual
rest stays in the tower as a liquid residue. It consists of boiling fuel that is much lower in viscosity. While this visbroken fuel
the crude oil in a pipe-still at atmospheric pressure up to could be used as marine residual fuel with little or no blend-
371°F. Then the hydrocarbon vapors are directed to a frac- ing with a lower viscosity distillate, it has higher density,
tionating tower, as shown in Fig. 1. As the various lighter hy- higher carbon content, higher asphaltenes, and poorer igni-
drocarbons of the crude oil vaporize at different rates, the tion quality characteristics. Visbroken fuels are usually less
lighter, more volatile vapors rise high in the tower before con- stable and less compatible with other residuals than the orig-
densing and being drawn off. The heavier, less volatile vapors inal vacuum feed stock. These characteristics can present
condense and are collected lower in the tower. The residual problems for the fuel handling, fuel purification, and diesel
fraction is drawn off at the bottom. The fractions drawn from combustion process, which could lead to vessel delays and in-
the tower are called straight-run or virgin products. creased maintenance for the diesel engine.
In the 1950s, '60s, and early '70s, straight-run fuels pro-
duced from atmospheric distillation were the main residual
fuels used in marine diesel engines. Straight-run fuels pro- Cracking
vided good ignition quality, clean combustion, ease of fuel When heat is applied to hydrocarbons, their molecular en-
handling, ease of water separation, storage stability, and ergy increases and these molecules move faster. Additionally,
solid compatibility. Since the density was usually below 985 if pressure is applied to the liquid hydrocarbon and tempera-
Kg/m^, the shipboard settling tanks and old style centrifugal tures are increased further, the energy within the molecules
purifiers provided adequate treatment to remove water and can rupture the Ccirbon-carbon and carbon-hydrogen bonds,
sediment from the fuel. and the molecules "crack" into more, smaller molecules that
At complex refineries, the next refining process is vacuum have different chemical structures. Cracked products are hy-
distillation of the heavy bottoms from the atmospheric distil- drogen deficient compared to straight-run products of the
lation unit. This process is a modified atmospheric process same boiling range and some of the new, smaller molecules
where the pressure in the fractionating tower is reduced be- are unsaturated. Further, these unsaturated molecules tend
low atmospheric to a partial vacuum, as in Fig. 2. The atmo- to be more volatile and can be more unstable.
spheric tower residual is the feed stock for the vacuum distil- Two basic cracking processes can be used. The older of the
lation process to yield additional heavy distillates, and will two cracking processes is thermal cracking, which typically
further concentrate the metals and carbon content into the occurs at about 13 bar and 520-560°C. The long-chain resid-
vacuum bottoms. The vacuum bottom residuals are generally ual oil molecules are cracked or broken, producing some
used as feed stocks for other refinery processes. They are gen- short chain molecules and additional long-chain molecules.
erally not available as marine fuels due to the very high vis- These cracked hydrocarbons are then vaporized in a flash
cosity. The vacuum bottoms can be further refined by using chamber and flow to the fractionating tower where they are
GASEOUS
FRACTIONING
TOWER
GASOLINE
NAPHTHA
KEROSENE
NO. 2 CRUDE
DISTILLATE HEATER _.CRUDE OIL
f
REDUCED CRUDE
NO. 5 - 6 RESIDUE
FIG. 1—Atmospheric distillation of crude oil.

CHAPTER 6: INTRODUCTION TO MARINE PETROLEUM FUELS 147
VACUUM
DISTILLATION
CHARGE REDUCED
HEAVY ^ - CRUDE
DISTILLATE HEATER OIL
VACUUM BOTTOMS
GASOLINE "A,^
VISBREAKER
BLENDED WITH
CUTTING STOCKS-
NO. 6 EUEL OIL
DISTILLATE- "^y"
RESIDUUM
FIG. 2—Vacuum distillation.
condensed to produce additional light and heavy distillates. coated and fall to the bottom of the reactor. The carbon coat-
Therefore, thermal cracking increases the yield of distillate ing is removed in the regenerator, since the catalyst is expen-
fuels from crude oil and reduces the yield of residual fuels. sive. Once cleaned, the regenerated catalyst returns to the in-
Thermal cracking concentrates metallic content, carbon con- coming hydrocarbon feed stock to start the cycle over.
tent, and asphaltene content into the residual fuel, which re- During the FCC process, a small amount of slurry oil is pro-
duces combustion quality, increases carbon deposits, induced that contains small particles of catalyst known as cat
creases sulfur emissions, and decreases stability and fines. The slurry oil is normally decanted to reduce the con-
compatibility of the thermally cracked residual. centration of "cat fines" and then the slurry oil is blended into
The more modem cracking process uses a catalyst to re- the residual fuel stream. A number of cases have been docu-
duce the temperatures and pressures at which hydrocarbon mented where catalyst fines have been delivered to ship own-
cracking occurs and, therefore, has been named (fluidic) cat- ers in large quantities. These catalyst particles Eire very heird
alytic cracking, or FCC, as shown in Fig. 3. Catalytic cracking and abrasive and have caused rapid and severe wear to fuel
used a powdered (Quidized) catalyst, typically an alumina-sil- injection pumps, fuel injectors, cylinder liners, piston rings,
ica based material, which is in direct contact with the liquid piston grooves, and stuffing box seals. This is most evident
hydrocarbon feed stock. By definition, a catalyst is a sub- where conventional centrifugation and filtration have been
stance that aids and accelerates a chemical reaction, but ineffective. Effective five to seven micron filtration of the
which itself undergoes no permanent compositional change. residual fuels has proven to control damages from cat fines.
When kept in constant agitation and circulation by air, steam Hydrocracking is a process that uses high pressures and
or hydrocarbon vapor, the fine powdered catalyst flows like a the addition of hydrogen to crack refinery residues and to up-
fluid. In the beginning of the FCC process, hot, preheated hy- grade the resulting products through the addition of hydro-
drocarbon feed stock enters the reactor and is mixed with gen. Lighter hydrocarbon products exhibit lower viscosities
hot, regenerated, powdered catalyst. Within the FCC reactor, and lower sulfur levels because of hydrocracking. Since hy-
the hot feed stock vaporizes and fluidizes the catalyst at the drogen is added during the process, this process is more ex-
same time. Cracking then takes place within the reactor and pensive than thermal or catalytic cracking.
the hot, cracked hydrocarbon vapors pass into the fraction-
ating tower. These lighter, cracked vapors are then separated
into gases, gasoline components, light gas oil, heat oil, and a Refinery Blending and Storage
heavier product known as cycle oil. Marine fuel oils are blends of products from several different
The catalyst works in a continuous cycle. During the crack- processes. Combustion characteristics, handling properties,
ing reaction, the powdered catalyst particles become Ccirbon stability characteristics, and storage stability are all affected
FRACTIONING
TOWER
GASOLINE
REACTOR
NO 2
DISTILLATE
- -e-ATALYST-
HEAVY
GAS OIL
FIG. 3—Fluidic catalytic cracking.
by the composition of the blend. The blending processes be- tailed description of contamination can be found in the next
gin at the refinery. Heavy products produced at the refinery section.
cire expected to be in the residual fuel blend to varying de-
grees. The blending process allows lower quality residuEils to
be converted into more suitable fuel oils by the addition of PETROLEUM FUEL OIL CHARACTERISTICS
small qucintities of lighter cutter stock, such as light or heavy
distillates, or by adding cycle oils. When distillate/residual Fuel Properties—Physical
blends eire made, the solubility of the different components in
each other is important. When components Eire completely Viscosity (D-445)
soluble, the blend is considered compatible. Whenever a The viscosity of a fuel is a measure of the fuel's resistance to
blend is contemplated, the compatibility of the resulting flow. As a fuel is heated, the viscosity decreases, and as fuel
blend must be eveduated beforehand to prevent incompati- is cooled, the viscosity increases. Marine residual fuels Eire
bility problems that can cause excessive sludge accumulation still selected and purchased on the basis of a limiting viscos-
in storage, centrifugation, and filtration, and stratification in ity due to restrictions on fuel storage, handling, or engine fuel
the storage tanks. injection equipment. However, viscosity aJone is not the sole
As the refinery processes improve, and as crude oil distil- quality indicator, despite the fact that many purchasers of
late yields improve, a continuing decrease in the overall qual- m a r i n e fuels believe this to be t r u e . When purchasing
ity of cracked residuals used to produce blends for marine fu- straight-run (distilled, but not cracked) residuals, this prac-
els can be expected. tice of associating low viscosity with high quality became es-
In many refineries in the United States, all residual prod- tablished. This false sense of quality assurance was then cEir-
ucts are directed to the petroleum cokers, which convert the ried over into bu5ring m o d e m blended and cracked marine
residual products into light distillates and solid hydrocarbon residuals. As more intensive cracking and processing proce-
coke. At these refineries, n o residual fuels are sold or made dures are used to produce future marine fuels, the relation-
for the marine fuel industry. In the future, marine fuels could ship between fuel viscosity and fuel qucJity becomes more
compete with "cokers" for their feed stock requirements. An- and more misleading. For example, some heavily cracked 180
o t h e r use for residual fuel for U.S. a n d E u r o p e a n power cSt residuals have poorer overedl quality than the less-pro-
plants is decreasing due to environmental restrictions, cessed 380 cSt residuals.
thereby decreasing overall availability of residual fuel. Meirine residual fuels are preheated to lower the viscosity
A large percentage of fuel contamination can be traced to for more efficient fuel bunkering, trsinsfer, settling, centrifu-
the hydrocarbon storage and transportation process. Water gation, fuel injection, and atomization. With preheating, the
and debris (solids and fibers) are frequently introduced into viscosity of residual fuels drops and it is easier to separate
the marine fuel originating from barge and tanker transport, solids and water from the fuel. However, a limitation of 99°C
pipe line transport, and shore side tank storage. A more de- should not be exceeded because the water may flash to steeim
and, therefore, the centrifuge water seal would be lost. As a A marine fuel with a high density indicates that the fuel is
general rule, after centrifugation, fuel should not be heated heavily aromatic from being heavily cracked. Higher density
above 150°C, since some chemical changes may occur, gases fuels are likely to possess poor ignition and/or combustion
may be given off, or water may vaporize to form steam pock- qualities and could cause increased wear to the mechanical
ets in suction piping. An increase in primary fuel p u m p pres- components of the diesel engine.
sure could be necessary to prevent water/fuel vapor from
forming the more volatile fuel components in the fuel returns Ignition Quality (D 613 for Distillates)
piping from the injection pumps. Additionally, all m o d e m fuel (ISO 8217, Annex B for residuals)
systems should be closed (pressurized) systems with n o access The ignition quality of all marine residual and distillate fuels
to atmospheric pressure in mixing or vent tanks. Older ships is most important for diesel engines, since combustion starts
with open mixing tank systems should be upgraded to closed each cycle of operation. This is not critical for continuous
and pressurized fuel systems at the next yard period to better combustion cycles, such as those used for steam boilers and
cope with m o d e m , cracked, blended residual fuels [1,2]. gas turbine engines. In a diesel engine cycle there is always a
Another important parameter would be the viscosity index delay between the beginning of fuel injection and the start of
(VT) of the fuel, which is determined according to ASTM D ignition or the initial combustion of fuel. In a distillate fuel,
2270. The viscosity index is the linear relationship between the ignition queJity is indicated by the cetane number/cetane
viscosity and temperature. As a general rule, the lower the index. The ignition quality in a residual or blended fuel oil is
viscosity index the higher the fuel density for a given fuel vis- indicated by the Calculated Carbon Aromaticity Index (CCAI)
cosity because of the higher concentration of cracked residu- number. The lower the cetane number/index of a fuel or the
als present. A m o d e m cracked residual fuel could have a VI higher the CCAI number, the poorer the ignition quality of
of 10-15, whereas the older straight-run residuals can have a the fuel. This translates into a longer ignition delay, a lower
VI as high as 80. Many of the published temperature viscos- period of time between the start of fuel injection and the be-
ity/temperature curves and tables are based on residual fuels ginning of fuel ignition, and the rapid pressure rise associ-
with a VI of 65-70. Care should be exercised w h e n using ated with fuel ignition. The results of poorer ignition quality
these charts and tables since cracked residual blends can de- can be loss of power, poorer fuel economy, higher NOx emis-
viate widely from these data, since they are more viscous at sions, and even diesel engine damage [4,5].
lower temperatures. It is very important that a viscosity mon-
The characteristics of the crude oil and the degree of refin-
itoring and control system is used and calibrated periodi-
ery cracking are largely responsible for the ignition quality of
cally. By using these viscosity controllers, variations in vis-
a marine fuel. The combination of highly cracked fuels with
cosity indices from stem to stem will be automatically
high densities and blended or visbroken fuels with low vis-
compensated [3].
cosities results in the highest CCAI numbers and the poorest
ignition qualities for diesel engines. These high CCAI n u m b e r
Density (D 1298) fuels can cause serious operational limitations on medium
The density of a fuel is the mass-per-unit volume and is ex- speed and high speed diesel engines that have the greatest
pressed as grams-per-milliliter (g/mL) for liquid fuels. In re- sensitivity to ignition quality. Large, medium speed diesels
ality, density and specific gravity have very similar values and slow speed diesel engines operating at less than 400 RPM
and, for approximate purposes, could be considered the are m u c h less sensitive to the ignition quality of the marine
same. Originally, specific gravity at 60°F was predominantly fuel. Although m e a n piston speed has been considered a
used but, currently, meuine fuels will specify density at 15°C more precise method to categorize diesel engine speed, the
superceding specific gravity as the common usage. In 1977, Marine Industry generally accepts a slow speed diesel engine
the Worldwide Marine Industry officially adopted SI units, to operate below 249 RPM, a medium speed diesel engine be-
although it has tciken many years for the Marine Bunker In- tween 250 u p to 899 RPM, and a high speed diesel engine
dustry to adjust to the SI units. above 900 RPM.
Since all liquid hydrocarbon fuels expand their volume The ignition quality of a marine fuel can be calculated by a
when heated, their weight-per-unit volume decreases. There- CCAI nomograph or an equation. Most people use the nomo-
fore, the density (and specific gravity) must be reported at a graph to derive the CCAI, which is found in Fig. 4. The Inter-
standard temperature even though another temperature may national Mcirine Fuel Testing Laboratories calculate and list
have been used in the test method. ASTM D 1550 contains CCAI based on analyzed viscosity and density from the fuel
volume correction tables for reference. analysis reports.
The significance of fuel density revolves around the water-
fuel separating technology, such as centrifugal separators or Heating Value (D 4868)
settling tanks that operate on the difference of the densities Heating value is the quantity of heat produced by the com-
between the water and the fuel. Older centrifugal sepeirators bustion of a unit of marine fuel under specified conditions.
(purifiers) were limited to fuels at or below 991 density at The gross heating value is the sum of the heat produced by
50°C to control water removal efficiencies. The removal of the total combustion of the fuel and the heat released by the
free water and salt water are important to control damage, condensation of the water and SOx gases formed during com-
corrosion, and deposits in fuel injection systems; turbo bustion. This is primjuily applicable to a steam boiler power
chargers and boilers in diesel; and gas turbine engines. The plant. The net heating value is the gross heating value minus
more m o d e m centrifugal separators can efficiently remove the heat released by the condensation of the water (vapor)
water u p to a fluid density of 1.012 at 50°C. produced during combustion and the sulfur and metals con-
^1 800 ^800
(added) test flame but before it will bum continuously (fire
point). The flash point is an important indicator of the fire
820
810
and explosion hazards associated with a marine fuel. The test
equipment and test procedure are very important in obtain-
840
-820
ing accurate test results. A carefully conducted test will not
miss light fuel contamination that can depress the real flash
860
point. For most marine fuels that require heating, a mini-
830
mum flash point of 60°C is a prerequisite for storage safety.
880
-3 Even though marine fuels may test above 60°C for a flash
-840
900 point, after fuels are heated in storage tanks, vapors can col-
lect in the head space of the storage tanks that can flash be-
-850
920 low 60°C, which can cause safety concerns. Volatile vapors
can be produced at the surface of the hot heating coils so con-
860
940 trolling steam temperature (and pressure) of the heating coils
and maintaining flash arrester screens on aJl tank vents are
960 870 critical for shipboard safety [6].
980 880
Pour Point (D 97)
1000 890 Pour point is an indicator of the ability of a marine fuel to
flow at low temperatures. It is considered the lowest temper-
1020
-900
ature at which the fuel will flow when cooled under con-
trolled conditions. Pour point is not related to fuel quality but
1040
depends on the type of crude oil, refining process used, and
910
the use of fuel additives. As the fuel temperature drops, the
wax components begin to crystallize and impede the flow
-920
characteristics of the fuel. When stored, marine fuels should
5000 never be permitted to reach their pour points, because once
930 the fuel congeals, pumping may not be possible until the fuel
20000 is heated 10°C above its pour point. If a fuel has congealed,
50000
much more time must be allowed for heating since the con-
gealed fuel will not naturally flow to the heating coils.
-950
Ash (D 482)
FIG. 4—Nomograph for determining tlie CCAI. © International Ash from the marine fuels includes the inorganic metallic
Organization for Standardization (ISO). This material is repro- content, other non-combustibles, and miscellaneous contam-
duced from ISO 8217:1996 with permission of the American Na- ination. Metallics can contain a mixture of aluminum, cal-
tional Standards Institute on behalf of ISO. No part of this ma-
terial may be copied or reproduced in any form, electronic
cium, potassium, iron, vanadium, nickel, silicon, and
retrieval system or otherwise or made available on the Internet, sodium. Ash deposits can cause localized overheating and
a public network, by satellite or otherwise without the prior corrosion to the metal surfaces where they adhere, especially
written consent of the American National Standards Institute, to the exhaust valves. Excessive ash can cause abrasive wear
25 West 43rd Street, New York, NY 10036. of the cylinder liners, piston rings, injection pumps, fuel
valves, and injection tips. Catalyst fines can result in just such
tent. The net heating value is apphcable to a diesel engine. To abrasive damage.
obtain the full net heating value from a marine fuel, the diesel In marine fuels, some of the dispersed and insoluble metal-
engine must burn the fuel completely. As marine fuels in- lic compounds can be removed onboard by settling, centrifu-
crease in density and carbon content, it becomes increasingly gation, and filtration. However, fuel soluble metallics cannot
difficult to completely "bum-out" the fuel. To achieve com- be reduced by shipboard fuel handling equipment [7-9].
plete combustion ("bum-out"), all carbon must bum to car-
bon dioxide, all hydrogen must bum to water vapor, and all Cat Fines (ISO 10478)
sulfur must bum to sulfur dioxide. Catalyst (CAT) fines are small particles of aluminum silicate
The net heating value will be primairily influenced by den- used as a fluidic catalyst in the catalytic cracking units at
sity, water content, and sulfur content. As the fuel density in- modem refineries. Cat fines can be carried over from the cat-
creases, the carbon-to-hydrogen ratio increases, causing alytic cracker and can be found in marine fuels. Cat fines are
there to be relatively less hydrogen with its higher heating very hard and abrasive and can cause excessive wear of en-
value per unit weight. This results in a decrease in the net gine components, particularly fuel pumps, cylinder liners,
heat released during combustion. Water and sulfur also piston rings, and piston ring grooves.
cause the net heating value to be lower. To prevent severe abrasive damage, cat fines must be lim-
ited by fuel specification restrictions or by shipboard re-
Flash Point (D 93) moval settlement, centrifugation, or fine filtration of five to
The flash point is the lowest temperature at which a marine seven micron control. Cat fine control can be monitored by
fuel will support instantaneous combustion (a flash) from the testing the treated fuel for aluminum/silicon levels [10,11].
Water (D 95) (D 4176) 360

Water is a contaminant that enters mEuine fuels during trans-
port, usually when taken by tanker or barge over water. Salt
water can cause greater problems in marine fuels then fresh
water. Salt water has been considered the greatest single 340
cause of fouling, deposits, and corrosion, especially in the
higher temperature regions of the power plant. The presence
of water can initiate microbial growth in marine fuels. These
simple organisms must live in the water at the tank bottom 320
and feed on the marine fuel at the water/fuel interface. 1500 P S I ,
Water in the marine fuels can cause large volumes of cen-
trifuge sludge as a result of water-sludge emulsification dur- 900 P S I x
ing centrifugal separation. 300
Because of upcoming IMO and EPA exhaust gas emission
regulations, diesel engines may start using water in fuel
emulsions (made with potable water) to reduce oxidizes in
nitrogen (NOx), particulates and smoke. These water-in-fuel
emulsions can consist of u p to 50% additional potable water
I1 280
300 F*SI
and must be intentionally-made emulsions with a tightly con-

trolled water droplet size and a control on all larger size
droplets. Lastly, whenever the diesel engine is shut down, all
emulsion must be purged out of the fuel system such that the 260
shut down diesel fuel injection system contains no water-in-
fuel emulsion [12].
OPSI^
240
Fuel Properties—Chemical
Sulfur (D 4294)
Sulfur is a nonmetallic element that is chemically bound into
the marine fuel. Sulfur originates in crude oil and is concen- 220
0 1 2 3 4 5
trated into the higher density residual fractions. The mEirine
Sulfur [%]
residual fuel has capped sulfur content at 4.5 weight percent
to begin to control oxides of sulfur (SOx). When sulfur is FIG. 5—Acid dew point for diesel engine fuels. Reprinted with
burned in the diesel engine it causes several problems, pri- the permission of the Society of Naval Architects and Marine
marily in promoting corrosive wear of the piston rings and Engineers (SNAME). Material originally appearing in SNAME
cylinder liners and by causing deposits in the ring zone. Dur- publications cannot be reprinted without written permission
ing the combustion process, sulfur dioxide and sulfur triox- from the Society, 601 Pavonia Ave., Jersey City, NJ 07306.
ide form in the cylinder. These sulfur compounds then com-
bine with water vapor to form sulfurous and sulfuric acid,
which can cause aggressive corrosion. controlled conditions—the laboratory test for Micro Carbon
When sulfuric acid vapor leaves the cylinder and contacts Residue gives an overall guide to the carbon forming tenden-
low t e m p e r a t u r e surfaces of the heat recovery boiler, the cies of the marine fuel. As heavier crude oils are refined with
gaseous sulfuric acid condenses and forms highly corrosive the more intensive, secondary cracking process, the carbon
(liquid) sulfuric acid. So, in addition to ring and liner dam- concentration in the marine fuel can approach 18-20 weight
age, the sulfuric acid can attack valve guides, as well as the percent. Further, as the carbon content increases, the as-
cooler parts of the heat recovery boiler. phaltene content typically increases as well. Asphaltenes are
Diesel engines can be designed to prevent low temperature high molecular weight hydrocarbons that can adversely af-
corrosion by maintaining surface temperatures above the fect combustion, residue formation, a n d the compatibility of
sulfuric acid condensation temperature, as shown in Fig. 5. marine fuels. These high Ccirbon content marine fuels have
Sulfur in marine fuels is normally neutralized by using an al- poor combustion chciracteristics; increased carbon deposit
kaline (TBN) lube oil additive. The fuel sulfur level should be forming tendencies on injection nozzles; pistons and ports of
balanced against the lube oil TBN additives to just neutralize two stroke engines; increased ignition delays; and slow burn-
the sulfur. If too m u c h alkaline additive (TBN) is used, a ing constituents that can increase the thermal loading of
harmful (abrasive) level of alkaline material is produced that diesel engine components [13].
can increase the wear of the cylinder liner and the piston The asphaltene content in marine fuels influences the com-
rings. The average sulfur level in marine fuels today is 2.8-3.0 patibility of blends of light and heavy fuels and blends of ma-
weight percent. rine fuels from different liftings. An increase in purifier sludge
discharge or filter fouling is an early indication of incompati-
Carbon Residue (D 524) bility of fuels being mixed and/or high asphaltene levels.
Carbon residue is the coked material that remains after the Therefore, fuels taken on-board in different ports should be
marine fuel has been exposed to high temperatures under segregated in separate tanks (as on-board m u c h as possible)
and mixing fuels from different tanks on a single vessel should Fig. 7, which shows the critical ratios of metcdlic components
be avoided. and the large effect upon the ash melting temperature. It is
the molten form of sodium, vanadium, and nickel that causes
Compatibility (ISO 10307-2) the severe hot corrosion and deposits to form. No power
plant is beyond this problem since it affects steam boilers,
Compatibility is the ability of a fuel to form a homogeneous
diesel engines, and gas turbine engines.
mixture that is neither separated nor altered by chemical,
time, or temperature interaction. Marine residual fuel blends Oxidation (Storage) (ISO 3735)
can be considered a colloidal dispersion of high molecular
weight substances (asphaltenes) held in a chemical and/or Marine residual fuels are tjrpically stored in heated tankage
physical equilibrium in the fuel. If the equilibrium forces are on shore and in the ship. The higher storage temperatures
disturbed, the high molecular weight components (usually and the presence of air in the head space above the fuel in the
asphaltenes) are precipitated and dropped out of solution to storage tank both combine to age the fuel. As marine fuels
form a sludge or sediment. This can result in rapid tank age, they oxidize and begin to polymerize, forming sludge,
sludge buildup, clogged strainers, fouled filters and purifiers, gum, and resin that can foul heaters and filters as well as fuel
and damaged viscometers. Once into the diesel engine, in- injectors, combustion chambers, and the exhaust system. Ox-
compatibility can cause rapid fuel injection pump sticking, idation products can vary in form: some are soluble in ma-
fuel injector deposits, exhaust valve deposits, turbo-charger rine fuels while others are insoluble and result in the forma-
turbine nozzle and blade deposits, and carbon fouled waste tion of an organic sediment [11].
heat boilers [14].
Sediment (ISO 3735)
Vanadium and Nickel (ISO 14597) The insoluble organic products that result from oxidation of
marine fuels can combine with inorganic insolubles, such as
Vanadium and nickel are metallic elements that exist as fuel- rust, cat fines, and sand, to produce sediment. This sediment
soluble organometallic compounds. Vanadium and nickel,
originate in the crude oil and are concentrated in the marine
1600
residual fuels by the various refinery operations. Depending
on the origin of the crude oil, the vanadium and nickel levels
of the fuel can vary widely.
In the combustion process, vanadium and nickel can com-
bine (bond) with sodium (from salt water contamination) to
produce very aggressive, low melting point compounds that
are responsible for accelerated deposit formation and high
temperature corrosion of diesel engine components such as
piston crowns, exhaust valves, and turbo charger turbine
nozzles. Figure 6 shows for the relationship between vana-
dium and sodium. In steam boilers, these contaminants, to-
gether with sodium, can cause accelerated fouling of the
screen tubes and the superheater tubes as well as serious
high temperature corrosion of the superheater tubes. Gas
turbine engines are the most sensitive to both contaminants
due to the very high temperatures of the turbine section.
These contaminEints are fuel soluble, therefore they cannot
be removed from the fuel on the ship. If they are troublesome
to a particular engine, they must be limited at the time of fuel
purchase. The effects of vanadium and nickel can be neutral-
ized by using a metallic fuel additive such as magnesium or
calcium.
Sodium (ISO 10478)

Sodium is a metallic element that is extremely active chemi-
cally. Generally, marine fuels are essentially sodium free
when leaving the refinery. The vast bulk of the sodium in ma-
100
rine fuels originates through Scilt water contamination during VA
transport by tank ship or barge and can be removed by set- ITO 55 ' B5 ' 3D ~2!r
tling tanks or by centrifugal separator. Sodium or salt (NaCl),
if present in significant quantities, will become involved in Mixture Proportion [%]
severe high temperature corrosion and deposit problems. FIG. 6—Bonding relationship for vanadium and sodium.
When unfavorable ratios of vanadium combine with Reprinted with the permission of the Society of Naval Archi-
sodium in the fuel, they react during combustion (at high tects and Marine Engineers (SNAII/IE). IVIaterlal originaiiy ap-
temperatures) to produce eutectic compounds with ash melt- pearing in SNAIVIE publications cannot be reprinted without
ing points within the engine's operating temperatures. The written permission from the Society, 601 Pavonia Ave., Jersey
relationship between sodium and vanadium can be seen in City, NJ 07306.
1600
1500
/ 3Na20*V205
1400
o
§ 1300
Q. vp^
E
NA20*V 2O/5V2O
O)
1200
N a j O-VÔs
2Na20*V205
y
w
< 1100
5Na zO-VÔ/ 11V 2 0 \ /

1000
900
0 10 20 30 40 50 60 70 80 90
PRACTICAL FO ULING
ZONE NajO, MOL Percent
P
INCREASED FOULING RATE
FIG. 7—Phase diagram for sodium and vanadium. Reprinted with permission from ABS, Houston, TX.
can damage high-pressure fuel injection pumps and fuel in- chemical additives that have been the most effective are the
jectors. Sediment can be removed by gravity settling, filtra- stabilizers and dispersants, ash modifiers, biocides, demulsi-
tion, and by centrifugal separators. fiers, and emulsifiers [14].
Stabilizers and Dispersants
Fuel Additives
Stabilizers and dispersants tend to control the formation of
A fuel additive can be any material that, when added to a ma- new sludge and to aid in the dispersion of existing sludge. By
rine fuel, changes its properties, characteristics or perfor- limiting sludge, more of the hydrocarbon content of the
mance. As secondary refinery processing cracks fuels more sludge can be burned and there is less sludge to incinerate or
severely, the resultant meirine fuel quality becomes more dif- to offload in the next port. Asphaltenes can significantly con-
ficult to handle, store, and combust efficiently. The increased tribute to sludge production. By dispersing the asphaltenes
amounts of metallic components, ash levels, and carbon con- into very small particles with dispersant additives, sludge can
tents adversely affect the performance of the fuel treatment be reduced. Some additives work by using surfactants to fa-
system and the power plant itself. Fouling and corrosion of cilitate a surface film formation at the fuel/asphaltene inter-
engine components and increased tank, centrifuge, and filter face to stabilize the asphaltenes. The additional surface ten-
sludge levels can present costly challenges for the ship's engi- sion reduction tends to break the asphaltenes into minute
neers. As fuel cracking intensifies, the fuel density increases particles and stabilizes the fuel.
and it can make the centrifugal removal of free and emulsi- Additive additions are typically known as "tank treat-
fied water more difficult. ments." Usually, when this additive is first used, it dis-
In addition to the conventional methods of settlement, cen- solves/disperses existing sludge and organic sediment and it
trifugation, and filtration, a chemical (additive) approach places a heavy burden upon the centrifugal separators and
C£in sometimes offer a solution to a particular problem. The filters as it begins to clean up tanks, piping, etc.
Ash Modifiers Exhaust particulates and smoke b o t h relate to the ability of

These ash modifying materials can react with corrosive ele- the diesel engine to completely and efficiently b u m the ma-
ments of the fuel during combustion to raise the melting tem- rine fuel so little or no solid carbonaceous material remains.
peratures above the critical temperatures, thereby avoiding Therefore, the higher the micro carbon residue and asphzJ-
high temperature corrosion. Magnesium compounds repre- tene content, the higher the Ccirbonaceous pcuticulates and
sent one of the more popular ash modifiers since they are smoke that can be expected.
available in many forms and are relatively inexpensive. Prior Lastly, if stack opacity is regulated or if excessive smoking
to combustion, these chemicals are added so that the magne- is prohibited, the marine fuel should not contain used lube
sium combines with the vanadium (from the fuel) to form oil (either supplied with the fuel at bunkering or as the result
harmless, high-melting compounds that no longer adhere to of the disposal of used lube oil from the diesel engines on
and corrode the exhaust valves and seats, piston crowns and board). Used lube oil in marine fuels results in a blue colored
turbo charger nozzles in diesel engines and the superheater haze in the exhaust gases that cannot be reduced until all of
tubes in boilers. It is preferred to know the vanadium-plus- the marine fuel with used lube oil has been burned.
nickel content of the fuel to determine the proper additive us-
age. Overdosing of ash modifiers could produce h a r d de- P e t r o l e u m F u e l Oil T o x i c i t y
posits within the cylinder of a diesel engine, which can lead
to abrasive wear of the piston rings and cylinder liners. Marine fuel oils present a minimal health hazard when the
engineers practice high standards of personal and industrial
hygiene. A caution, however, is that extended exposure to
Demulsifiers marine fuels can cause skin dermatitis and even skin cEuicer.
These chemical additives cause small water droplets to coa- To minimize this possibility, these precautions should be
lesce and separate more readily from the marine fuel. They considered.
are typically added to the fuel storage tank before bunkering • Minimize skin and eye contact with marine fuels by modi-
fuel. They allow better water settling in storage, in the set- fying work procedures, if necessary.
tling tank, and in the centrifugal purifier. These demulsifiers • Always wear protective clothing, especially impermeable
are most effective when the water in the fuel exists as a fine gloves and eye protection.
dispersion or as an emulsion. • If clothing becomes fuel soaked, remove it and thoroughly
wash the affected skin with soap and water.
Biocides • Avoid carrying fuel soaked rags in pockets.
• Do not use light hydrocarbon solvents for removing fuel
These chemicals are toxic to microbiological growth in ma-
from the skin. Always avoid inhaling hydrocarbon solvent
rine fuels, tanks, and piping. This growth typically lives in the
vapors.
water at the bottom of a fuel tank and feeds on the fuel at the
interface between the fuel and the water. Since this growth • Avoid inhaling hot fuel mist or vapors since the fuel could
must live in water, the goal of good housekeeping practices is contain contaminants such as waste solvents, acids, and
to keep the tank bottoms drained of water. This is a challenge strong base mixtures that can sometimes get dumped into
since fuel transport is usually by barge or tanker over seawa- marine fuel tanks.
ter. A small quantity of biocide will keep the overall fuel sys- • Avoid accidental injection of marine fuel into the skin dur-
tem free of microbiological growth. Biocides should be se- ing the testing of fuel injection equipment by following test
lected carefully since some are fuel soluble a n d some are equipment directions and maintaining protective shields
water soluble. in place.
PETROLEUM FUEL SPECIFICATIONS

F u e l Oil I m p a c t o n E x h a u s t E m i s s i o n s
There are several marine fuel properties that can impact ex- When the combined requirements of the commercial and
haust gas emissions. Sulfur is the first fuel property to be reg- military marine fuels are considered, marine fuels represent
ulated by international and domestic rules. The International a small fraction of the refinery capacity. Marine fuels and, in
Maritime Organization (IMO) has limited sulfur to a maxi- particular residual fuels, are the end products of the major
m u m of 4.5%. Some localized regions, such as the Baltic Sea, shore side fuel producers' needs. Therefore, the refineries'
have imposed even lower sulfur levels. production is driven by shore side needs and the remainder
The next emission to be regulated will be Oxides of Nitro- is delivered into the marine industry. It is little wonder that
gen (NOx). The IMO will restrict new marine diesels installed the unique needs of the marine industry have little impact
after 2000 to NOx limits based upon the rotational speed of upon the quality of marine fuels [15].
the engines. Slow speed engines have the highest limits, Commercial m a r i n e fuels range from gas oil to m a r i n e
medium speed next, and high speeds have the lowest limits. diesel fuel, to blended marine diesel fuel, to blended residu-
The nitrogen content of marine fuels does contribute to NOx als, to heavy residuals.
emissions, b u t to date, no organization has attempted to limit Gas oils are clean, high quality, 100% distillate diesel fuels
fuel nitrogen. that are shipped and handled clean. If gas turbines are used
Ignition quality, cetane for distillate fuels and CCAI for in commercial service, the specifications will likely cedl for
residual fuels, has an impact on NOx produced in a diesel en- gas oil to maintain the very, very low trace metallic contami-
gine. Usually, the lower the ignition quality of the fuel, the n a n t levels required for long life. Gas oils are typically used
higher the NOx exhaust emissions. for emergency and lifeboat diesels.
Marine diesel oils (MDO) can be two very different fuels. duced a document called Annex VI of MARPOL 73/78, the reg-
MDO-light is similcir to gas oil but is handled in dirty barges ulations for the prevention of air pollution from ships, which
that carry residucd fuels. This produces a dark colored fuel, caps the sulfur level in marine fuels at 4.5 wt. percent and has
which is essentially all distillate, with a little additional sedi- a provision that will restrict the NOx production from marine
m e n t and a carbon residue below 0.2% (by mass). diesel engines after Jan 1, 2000. As time moves forward, the
MDO-heavy is roughly 85% MDO-light blended with 15% IMO will continue to regulate and restrict air pollution from
residual fuel and handled dirty in a residual fuel barge. Since marine diesel engines. In some cases, as in the SOx emissions,
MDO-heavy contains about 15% residual fuel content, this the air pollution control will be regulated by restricting fuel
should only be used in diesel engines that are designed to properties. Therefore, although the IMO MARPOL regula-
have a blended residual fuel capability. The carbon residue of tions are not strictly fuel specifications, they will achieve
MDO-heavy is typically above 1.5% (by mass). some of their regulation by restricting marine fuel properties,
Heavy Residual Fuels (HFO) have high viscosity and den- as has already been done with a fuel sulfur cap.
sity and, in many situations, they must be blended to a lower
viscosity and a lower density to be used in marine vessels.
ASTM Marine Fuel Specifications
Most marine residual fuels are blends of different residual
fuel stocks with lighter stocks, such as MDO and cycle oil. The ASTM D 2069-98 Fuel Specifications are similar to the
The blending process can r e d u c e sulfur, c a r b o n content, ISO 8217 standard in many ways. Figure 8 shows the ASTM
vanadium and ignition quality, as well as viscosity and den- detailed requirements for marine distillate fuels, and Fig. 9
sity. Residual fuels are still generally classed by viscosity, shows the ASTM requirements for marine residual fuels.
however, m a n y other properties are considered before a
residual fuel selection is made.
Military F u e l Specifications
Military marine fuels consist of all distillate fuels that meet
International Specifications
an individual country's fuel specifications but most also con-
The International Orgcinization for Standardization (ISO) has form to North Atlantic Treaty Organization (NATO) fuel
written a basic International Marine Fuel Specification 8217 specifications as well. Military fuels place additional restric-
and revised it several times since the original document was tions u p o n these distillate fuels to support the unique, multi-
published in 1987. The most recent revision was published in purpose military requirements, as well as to provide for ex-
1996. The ISO relies on the guidance Eind advice of the Inter- tended storage times. In the U.S. Mihtary, the MIL-F-16884
national Council on Combustion Engines (CIMAC), Heavy Fuel fuel specification requires a clean, stable distillate, somewhat
Committee, which consists of engine builders, major oil com- similar to marine gas oil, with additional properties and test-
panies, bunker suppliers, treatment equipment builders and ing required before acceptance. Therefore, MIL-F-16884,
consultants. CIMAC also publishes a distillate and residual fuel Diesel Fuel Marine (DFM), and NATO F-76 are the same fuel
specification but, since it is not voted upon by an international that requires dedicated clean handling to prevent transport
membership, it truly doesn't carry an international importance. contamination, which can cause the fuel to tail out of speci-
The International Maritime Organization (IMO) has pro- fication.
Property Limit DMX DMA DMB DMC

a
Density at 15°C, kg/m^ max. 890.0 900.0 920.0
Kinematic viscosity at 40°C, cSt * min. 1.40 1.50
max. 5.50 6.00 11.0 14.0
Flash point, °C min. 43 60 60 60
Pour point (upper), °C"
• Winter quality max. -6 0 0
• Summer quality max. 0 6 6
Cloud point, °C max. -16"
Carbon residue on 10% bttns, max. 0.20 0.20
Ramsbottom, % mass
Carbon residue, Ramsbottom, % mass max. 0.25 2.50
Ash, % mass max. 0.01 0.01 0.01 0.05
Sediment by extraction, % mass max. 0.07
Water, % vol max. 0.30 0.30
Cetane number min. 45 40 35
Visual inspection e e
Sulfiir, % mass max. 1.0 1.5 2.0 2.0

Vanadium, mg/kg max. 100
"There may be a maximum limit in some locations.
*lcSt=.lmm^/s
"Purchasers should ensure that this pour point is suitable for the equipment on board, especially if the vessel
operates in both the northern and southern hemispheres.
*rhis fuel is suitable for use without heating at ambient temperatures down to -15°C.
TTiis fuel shall be visually clear and bright.
FIG. 8—ASTM D-2069-98, Detailed Requirements for lUlarine Distillate Fuels.

The U.S. Navy uses a ciistillate fuel, JP-5, for aircraft gas
o o
turbine engines anci selected high speed diesel engines. This
w-1
1/^ CO (^ fuel is lighter than MIL-F-16884. It differs from other aircraft
fuel primarily by its higher flash point requirements (60°C vs.
q 38°C). JP-5 fuel must be handled and stored clean.
o o
Environmental Considerations
O O
It is possible that localized environmental regulations could
place more stringent limitations, beyond the International
anci/or Domestic Regulations, on fuel specifications. As pre-
o o fN
r<1 f l
fN viously reviewed, limits on sulfur, carbon content, and igni-
tion quality could be imposed to achieve a local regulation. If
X a catalytic converter was installed, the use of a very low sul-
O O fN
fN fur fuel would be prudent to preclude premature catalyst
fouling and poisoning.
O O
« FUEL TESTING
3
O O fN
fN _ A known fuel quality has been determined to be fundamental
I to reliable marine diesel engine operation. A comprehensive
O _:
0)
-O
fuel sampling and testing program is essential to ensure the
22 CO
CO
CD
&• 1/-1
O O fN CO
0) DC quality of the marine fuel lifted, and to ensure that the ship's
o ro rs > c fuel treatment system can properly clean, heat, and pump
 ^-^
•D s
k
fuel economy, and low exhaust stack emissions. Even if the
u.
«J CO 0 marine fuel is refined clean, shore side handling and storage,
> o <«C—
O as well as marine fuel movements, can and frequently do con-
(U ^
HH M c c taminate the fuel such that poor engine operation, acceler-
IT)
O O o a> o «
fN
"c E ated wear, or serious exhaust gas violation can occur. It is
x:
0} '5 critical that the ship's fuel treatment system can properly
g E cr
w O O c Q. 0) treat the bunkered marine fuel so that clean, high quality fuel
DC
o '3 can flow to the diesel engines.
cr
0)
' l -
nj CD
o>
•
p Q. .c CO
O O
E 0 Fuel Sampling
CO m o 1- CM
o fi cfi Fuel sampling is the critical first step in obtaining knowledge
o CD S
u o •a ^ 1- about the newly bunkered marine fuel. For a fuel test and
o o ro < analysis to be meaningful, it is critical that a representative
o 3
o sample be taken during the delivery of the fuel. A representa-
PQ o >%
(0
.«
J> tive sample requires continuous sampling throughout the en-
X3
o fS fN ^_, d tire bunkering operation, since marine fuels can stratify or
fO c iZ
.0} 0 can vary the blending ratios during the delivery period. Most
o
d
I ô
3
3 marine fuel testing services provide detailed directions and
equipment to take a continuous, representative sample. Also,
E Q.
ASTM D 4057 can provide detailed instructions on taking a
representative sample. The old practice of taking a "spot or
X
s ^ •S CD grab" sample is no longer acceptable.
i O
in
O 3
CO Shore Side Analysis
o c
Cl>
Sending the representative sample to a shore side laboratory
en in as soon as possible for accurate and complete analysis is
3
_l CO O
"5 strongly recommended. In addition to a comprehensive anal-
•g U
o u ysis, a shore side laboratory can confirm that a fuel meets the
> o o <= E S5 ISO purchase specifications and can alert the crew to con-
o -I|
•tîu o
I
o
i O g •1
> > T - CO
i. ^
taminants, incompatibility, abrasives, excessive water con-
tent, and other damaging aspects of the bunkered fuel.
Q.
I cd O
9i^l Lastly, since these independent shore side laboratories pro-
vide an unbiased analysis, they can facilitate the resolution of
disputes quickly and at low cost.
On Board Testing quently inspect and maintain the condition of the flame ar-
rester screens on the fuel tank vent lines, and careful and safe
Since the shore side testing can take 24-72 h, some operators use of the ullage equipment is imperative.
prefer to supplement the shore side testing with quick, sim- In a steam propulsion plant system, a duplex heater set
ple on board tests that are helpful in the short term. These heats the fuel to the atomizing viscosity prior to the fuel
quick on board tests provide the immediate results often reaching the boiler fire front.
needed to support decisions on fuel treatment system align-
In a diesel engine propulsion system, the settling tank de-
ments, adjustments, and operations. The alignments and ad-
livers heated residual fuel to the purifier heater set prior to
justments of the centrifugal separators can be effected by fuel
the centrifugal separator(s). It is important that the residual
density, water content, compatibility, abrasive content, etc.
fuel temperature to the separator stably remain at 98-99°C to
Typical on board tests include those for viscosity, density,
maintain high separator efficiency and to prevent boiling of
water, compatibility, and particle content.
the water (in the fuel) within the separator.
Service tanks or day tanks provide an additional opportu-
nity to further settle water and solids from the heated resid-
FUEL STORAGE SYSTEMS ual fuel. The service tank can be filled by the centrifugal sep-
arators and provides additional time for deaeration.
Steam, diesel, and gas turbine marine fuel storage, settling,
and transfer systems are very similar. Figure 10 illustrates a
steam propulsion plant with a 600 cSt residual fuel and diesel FUEL TRANSFER SYSTEMS
oil fill, transfer, and storage system. A diesel engine propul-
sion plant with its fill, storage, transfer, and centrifuged pu- The fuel transfer pump(s) is provided to move fuel from stor-
rification system is illustrated in Fig. 11. age to settling tank(s). The positive displacement transfer
The marine fuel transfer system provides the following pump(s) is protected by coarse suction strainers, pressure re-
functions: lief valves, and pump bypass lines. The flow rate of the trans-
• To transfer marine fuel from any storage tank to any other fer pump is established by the engine's fuel consumption rate
tank, such as to the settling tank. and the capacity of the settling tank. The operational flexibil-
• To strip solids and water from the bottom of the settling ity of the transfer system is provided by the arrangement of
tank(s) through the stripping and drain connections. the valves in the system. This valving can permit the fuel to
The marine residual fuel and marine diesel fuels are be pumped from any storage tank to any settling tank or to
bunkered through deck fill connections that should have sam- other storage tanks.
pling connections installed to allow continuous, representa-
tive fuel samples to be taken as the fuel is taken aboard.
Heated tanks are used for storing marine residual fuels, and STEAM PLANT FUEL SERVICE SYSTEM
unheated tanks for marine diesel fuels and gas oils. From the
residual fuel storage tanks, the transfer pumps forward the The simplest of the service systems is that of a steam plant. It
fuel to the settling tank(s). The residual fuel settling tanks be- consists of storage, settling, and service tanks; transfer and
gin the fuel treatment process by settling gross water and service pumps; and heater sets (see Fig. 10). The treatment
solids to the bottom. As soon as the settling tank is filled, it is system consists of a heated settling tank that allows solids
heated to 80°C, but not higher than 10°C below the fuel's flash and gross water to fall to the bottom of the tank [4].
point. By heating the fuel, the viscosity is reduced, the gravity The service system is also very simple, consisting of a
settling process is enhanced, and the fuel deaerates as well. pump, a heater, and a pressure (or flow) regulating con-
Once settled, the fuel is forwarded to the boiler fire front, troller. Most modern systems incorporate a quick-closing
after additional heating, as illustrated in Fig. 12. The settling fuel valve to shut down fuel flow if there is a flame out, loss
tank bottom drain connections permit the removal of settled of combustion air, or loss of fuel pressure.
water, sludge, and solids to the sludge tank. Two fuel service pumps, with one in standby, are provided
In the fuel transfer system, all piping should be traced, and each is capable of supplying the total fuel flow plus an
heated, and insulated to prevent the marine residual fuel additional msirgin, with the excess flow diverted back to the
from solidifying in the piping. The residual fuel storage tanks settling tank. Service pumps are typically of the positive dis-
all have heating coils to control tank temperature and to placement type that are fitted with a pressure relief bypass,
maintain the fuel at 10°C above the pour point until it is remote shut downs, and isolation valves (for servicing). The
transferred to a settling tank. pressurized fuel flows to the service heater sets where the
From the safety standpoint, experience has proven that ex- temperature is increased to provide for the proper fuel vis-
plosive atmosphere can collect in the tank headspace even cosity for atomization. The two heater sets (one in standby)
though the fuel oil temperature is well below the flash point. are steam heated shell and tube or plate type heat exchang-
This condition exists when cracked marine fuels contact hot ers, each with the capability of increasing the fuel to 145°C.
heating coils that are significantly hotter than the bulk fuel It is important to use properly sized heat exchangers and low-
temperature. Further, if shore side petroleum waste products pressure steam supply to prevent overheating the fuel as it
have been mixed with the marine fuel, the lower flash point passes through the heat exchanger. After the heater sets, the
of the waste products could greatly lower the flash point of fuel passes through duplex strainers, a viscometer, and a flow
the bulk marine fuel. Even worse, this lower flash point may meter and then to the burner management system at the
not be reported if the shore side sample was taken prior to the boiler Are front. All residual fuel piping must be trace heated
introduction of the waste. Therefore, the crew must fre- (usually by steam) and insulated.
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The marine diesel fuel storage (see Fig. 11) provides a sep- vice pumps, fuel heaters, sludge tank, and interconnecting
arate fuel supply for cold boiler start up and for the emer- piping must be designed to match and support the needs of
gency diesel generator. A small diesel fuel service tank is used the centrifuge.
to provide clean fuel for emergency operation when neither The piping system must be configured to allow centrifuge
steam nor electricity is available. This diesel service tank is operation in parallel or in series as either purifier/purifier,
located high in the machinery space so that gravity will sup- clarifier/clarifier, or purifier/clarifier. The centrifugal pro-
ply enough fuel pressure to start the boilers and diesel gener- cessed residual fuel then passes through very fine duplex fil-
ators in an emergency. tration units that remove abrasive catalytic particles (cat
fines) that pass through the centrifuges. After these fine fil-
ters, the residual fuel enters the service/day tank.
DIESEL PLANT FUEL SYSTEM From the service tank, the residual fuel is forwarded to the
diesel engine through the residual fuel service system as seen
Diesel engine power plants require more intensive and com- in Fig. 13. The service system raises the residual fuel temper-
plex fuel systems than those of steam plants. The contami- ature up to the fuel injection temperature as controlled by a
nants, water, solids, and debris that may have been allowable viscometer. An advanced service system will include a ho-
in a steam plant must be removed prior to diesel engine op- mogenizer to treat the residual fuel just prior to injection into
eration. When burning residual fuels in diesel engines, the the diesel engine. The service system flows two or three times
basic principles of settling, pumping, heating, and treating the maximum fuel consumption of the diesel engine. Older
are common to slow speed and medium speed diesels alike. A fuel service systems are atmospheric pressure mixing tanks,
typical residual fuel and diesel fill, transfer, storage, and while modem practice is to pressurize the entire system, re-
treatment system for diesel engine power plants can be seen move the mixing tank, and add a mechanical deaerator to
in Fig. 11. All residual fuel piping should be insulated and, if eliminate gases and water vapor from the injection pump dis-
the viscosity exceeds 380 cSt at 50°C, trace heating should be charge flow.
included under the insulation. The marine diesel fuel system moves fuel from storage to
Whenever emergency shutdowns occur to a diesel engine the service tank by a transfer pump or by a centrifugal puri-
operating on residual fuel, the viscous fuel will remain in the fier. The fuel can be transferred from the service tank to the
piping and heaters, and also in the injection pumps and high emergency diesel generator service tank by either transfer
pressure piping. If all piping and components have trace pump or centrifugal purifier.
heating and insulation, it is not a problem since the residual
fuel can be reheated and its temperature controlled by recir-
culation prior to restart. If the emergency will keep the en-
DIESEL FUEL SYSTEM COMPONENTS
gine shut down for a lengthy time, the residual fuel should be
purged from the piping with marine diesel fuel and this will Centrifuges
eJlow the trace heating system and the recirculating pump to
be secured. Additionally, if Einy maintenance is planned for The recommended centrifuge flow capacity is the quantity that
the fuel injection system, the work will be faster and easier can be treated at the highest separating efficiency. This flow
with marine diesel fuel in the piping system. capacity is based upon the d5Tiamic viscosity of the residual
When bunkering residual fuel and marine diesel fuel, both fuel at the temperature of separation. The maximum separa-
enter through sepjirate deck connections. Both deck connection temperature has an upper limit of 98°C. There is a risk of
tions must incorporate sampling equipment to permit con- the loss of the water seal in the centrifuge due to the formation
tinuous, representative sampling during the entire lifting. of steam bubbles. A thorough review of each centrifuge man-
This is considered the point of custody transfer and these ual will determine recommended maximum flow rates for any
samples will be key should a quality dispute arise. given residual fuel. The rule is to reduce the fuel flow through
As was the procedure in steam plants, marine residual fu- the centrifuge to slighfly above the fuel consumption of the
els for diesel plants are transferred to the settling tank(s) by diesel engine. Avoid the temptation to rush the fuel through
a transfer pump through a coarse strainer. The best practice the centrifuge and into the service tank so it overflows back to
is to duplex transfer pumps to prevent pumping problems. the settling tank and is recentrifuged. Peak centrifuge opera-
If a demulsifier chemical is to be used to aid in water or tion efficiency occurs when the flow is reduced to increase the
particulate removal, the demulsifier should be metered into residence time of the fuel within the centrifuge while main-
the suction strainer ahead of the transfer pump. Demulsifier taining a stable fuel temperature of 98°C.
chemicals work by facilitating the separation of water and Two properly sized, correctly adjusted and operated, self-
solids from the residual fuel, and this process begins in the cleaning centrifuges are considered absolutely necessary to
settling tank(s). After the settling tank(s), the centrifugal pu- provide a reliable diesel fuel treatment system. Most diesel
rifiers and clarifiers, from two to four centrifuges, are typi- engine warranties become invalid if adequate centrifuges are
cally installed to treat the residual fuel. These units include not used effectively. The following fundamental principles
supply pumps, heaters, and automated controllers. Centrifu- are necessary to establish and maintain effective centrifugal
gal separators, set up as purifiers and clarifiers, are widely separator procedures for marine residual fuels.
used. They are considered a reliable and efficient method for The centrifugal separators are the foundation of the diesel
treating and cleaning marine diesel fuel and marine residual fuel treatment system.
fuels if properly maintained and adjusted. Centrifugal puri- • To treat contaminated marine fuels, supplementary sys-
fiers have the clear advantage of being capable of removing tems are required in addition to the centrifuges. These sup-
large quantities of water and particulates. The centrifuge ser- plementary systems consist of fine filtration, demulsifier
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CHAPTER 6: INTROD UCTION TO MARINE PETROLEUM FUELS 163
chemicals, combustion catalyst chemicals, and homoge- before the separator efficiency has optimized. If residual fuel
nizer/emulsifiers. is recirculated to the settling tank during this time, no con-
• Each centrifuge must be supplied with a complete manual, tamination will be passed on to the service tank. Once stabi-
all necessary parts to operate as a purifier and as a clarifier, lized, the valving can be switched to allow properly cen-
a complete set of spare parts, seals, gaskets, etc., and a trifuged fuel to flow to the service tank.
complete set of specialized tools. Proper practice requires at least two centrifugal separators
• The combined centrifuge flow rate (for parallel operation) to be properly sized, adjusted, and operated. When operating
and the single centrifuge flow rate (for series operation) at the recommended flow rate for m a x i m u m separating effi-
must not exceed the diesel engine demand by more than ciency, each of the two separators must be capable of treat-
10%. ing the maximum fuel rate of the diesel engine(s) plus ap-
• All residual fuel centrifuges should be operated continu- proximately a 10% margin. For normal operation, the series
ously, even in port. This reduces fuel contaminants and in- method of a purifier followed by a clarifier is the preferred
creases the effective time for fuel treatment. flow path. The first separator operates as a purifier to remove
• To properly adjust and operate a centrifuge, these residual sludge, sediment, a n d water. The second separator is ar-
fuel properties must be known: ranged as a clarifier to remove any remaining sediment or
1. viscosity catalyst fines from the residual fuel. Additionally, the clarifier
2. density provides a backup to the purifier should it malfunction.
3. fuel oil compatibility Parallel centrifugal separator operation is recommended
4. water content when the residual fuel contains a high water content. The
5. ash content (or bottom sediment content) parallel operation allows each sepsirator to operate as a puri-
6. catctlyst fines content (as measured by aluminum plus fier at one-half the normal fuel flow rate. By doubling the res-
silicon content) idence time in each purifier, the water removal efficiency of
With this residual fuel information, fuel treatment deci- each purifier is enhanced. In the parallel configuration, both
sions can be made. purifiers provide the highest cleaning efficiency and, there-
fore, the cleanest fuel to the diesel engine. There is just one
• Whenever a residual fuel from a different bunkering is
problem: if either purifier should malfunction, there would
transferred to the settling tank, a density check of this new
be n o second stage of centrifugal separation to prevent con-
origin fuel should be made to determine if a gravity disk
tamination from directly entering the diesel engine.
change is needed in the purifier.
The decision to operate in series or parallel is a judgment
Since the centrifugal separator is the foundation of the
that the ship's engineers must make based upon reviewing
residual fuel treatment system, its reliable and efficient oper-
the analysis of the representative sample taken during the en-
ation is critical to the durability and reliability of the diesel tire bunkering operation. The fuel analysis must be examined
engines. The operation of the centrifuge must be thoroughly for viscosity, density, water content, sediment, ash, catalyst
understood by all shipboard engineers so they cein immedi- fines, and compatibility in addition to the expected voyage
ately troubleshoot any problems. The following conditions fuel flow rate.
can cause mal-operation of the centrifuges.
• Improper residual fuel handling such as improper or inad-
equate blending, incompatible residual fuels, and emulsi- Filters a n d Strainers
fied fuels. All marine residual fuel systems use coarse strainers to pro-
• Improper flow rate, such as varying flow rates, excessive vide gross protection from very large fuel contaminants. But
flow rates, or varying densities. in diesel power plants, fine filtration serves a major function
• Improper temperature control, such as varying tempera- in controlling highly abrasive solids from reaching the en-
tures or temperatures below 98 °C. gine. It is because of the high ash, sediment, and catalyst
• Improper water/fuel interface inhibiting a uniform flow of fines content of marine residual fuels that supplemental fine
fuel through all disks, usually caused by the installation of filtration is recommended. Even though the fine filtration is
an improper gravity disk. As the residual fuel properties considered as backup to the centrifugal separator system,
change, the gravity must be checked and changed (if nec- these filters are essential to ensure that the fuel delivered to
essary) to control the water/fuel separation zone for maxi- the diesel engine is free of damaging abrasive particles. All
m u m efficiency. fine filtration should be duplexed to allow cleaning and re-
• Improper operation with a water-in-fuel emulsion blocking placement of filter elements without a n interruption in fuel
efficient water and solids removal through the sludge zone. flow. An effective fine filtration system can provide positive
• Overloading the centrifuge with a n accumulation of protection from abrasive particles that would normally dam-
sludge, which is usually caused by extended desludging in- age high pressure injection pumps, injection VcJves, injection
tervals or by incompatible residual fuels. nozzles, cylinder liners, piston rings, and piston ring grooves
Another area of concern is the centrifuge valving to prevent in the piston. Typically, these fine filters require the filter el-
contamination from passing through the centrifugal separa- ements to be replaced at 2 0 0 0 ^ 0 0 0 h intervals under normal
tors during start up. Immediately after the separators, valv- operating conditions.
ing should allow the recirculating of residual fuel back to the Additionally, fine residual fuel filters can be used with ho-
settling tank during the centrifuge start up process. During mogenizers to reduce the asphaltene and sludge removal by
start up, a considerable time must be given to allow the flow filters. In fact, most of the matter collected in fine filters is
rate and the fuel temperature to be increased and stabilized non-particulate, organic hydrocarbon material. The basic
function of a homogenizer is to disperse the sludge and as- deaerator units to remove any gaseous or vapor bubbles from
phaltenes in the residual fuel to prevent the removal of these the r e t u r n fuel before the fuel gets back to the injection
hydrocarbons while passing through the fine filter. There- p u m p s . Closed, pressurized boost systems stre the best to pre-
fore, the homogenizer can greatly increase the life of the fil- vent operating problems when operating on high viscosity
ter elements as well as reduce the total quantity of sludge re- residual fuels, b u t they do require additional circulating
moved from the residual fuel. The reduction in sludge burden p u m p s to be effective.
reduces the problems and expense of sludge removal and de-
creases the wasted heating value of the lost sludge.
Fuel Service Heaters
Some fine filters have the ability to remove trace quantities
of free water missed by the purifiers. Even though trace wa- Two fuel heaters are needed in the service or booster system,
ter removal might seem insignificant, shipboard testing has with one clean heater on standby. Steam is the normal heat-
shown a 100% increase in injection p u m p life after the addi- ing m e d i u m for the t5rpical shell a n d tube or plate style
tion of fine filters to remove the trace water from the marine heaters. Frequently, duplex 20 to 40 mesh strainers protect
residual fuel. It is critical that the water sumps in fine filters the heater sets from piping debris. The heater sets should
are drained daily to prevent water from rising above the have the capability of heating the fuel to 150°F without ther-
sump level and wetting the filter elements. mally stressing the fuel in the heater (and coking the heaters).
Self-cleaning or auto-flushing filters contain metallic Heaters made from stainless steel, titanium, and aluminum
screens that automatically or periodiccdly back flush to clean are preferable over copper-based materiEds. The temperature
sections of the screen to allow for continuous operation. The control for the heater(s) should be the automatic viscometer.
sludge and debris back flushed must be treated and finally
discarded. A problem can arise when filtering even a mildly
Viscosity Control
incompatible fuel since the increased sludge volume can re-
quire the filter to back flush u p to 400 times a day. This can The automatic viscometer continuously samples and mea-
cause increased wear on back flushing components and on sures the viscosity of the fuel and controls the steam to the
the screen, as well as produce a Icirge volume of sludge for heaters to maintain a preset injection viscosity to the engine's
disposal. fuel injection system. This is critical since viscosity control is
There are two t3rpes of replaceable, cjirtridge-type fuel fil- a major factor in efficient fuel injection into the diesel engine.
ters: the surface type a n d the depth type. Surface elements Real time, accurate viscosity measurement is very important
are similar to metal screens that have a limited thickness. because of the low viscosity index of m o d e m , highly cracked
They can be made from cellulose, fiberglass, felt, or metal. residual fuels. Since the viscometer is critical to correct fuel
Surface filter elements are frequently pleated to increase the viscosity control, the units should be checked and ccdibrated
filtration surface area within a given space and to increase periodically. A valved bj^Dass line, together with isolation
the element's life. A problem with surface filters is that or- vEdves before and after the viscometer, can provide the means
ganic sludge and/or asphtdtenes, together with solids, cEin ac- to service the unit without a main engine shutdown.
cumulate on the surface of the filter and seal the surface. This
results in rapidly increasing pressure across the filter, which,
Fuel Supply Flowmeter
in turn, limits the useful filter life.
A depth filter is designed so that the entire depth of the el- To accurately measure the engine's fuel consumption, a fuel
ement works as a progressive filter. This allows the contami- supply flowmeter is needed. A mass flowmeter or a positive
nants to be controlled throughout the element's depth Eind re- displacement type of meter that is reliable and accurate is
duces the buildup of contaminants on the surface that can recommended. A corrosion resistant material should be used
reduce filter life. This feature is especially important for fuels on EJI oil wetted internal surfaces. Some fuel system arrange-
with residual components that can cause problems for sur- ments require the use of a second fuel flowmeter to measure
face filtration. the return fuel from the engine's injection system. In these
systems, the return flow must be subtracted from the fuel
flow to determine the fuel used by the engine. The return
Boost Systems and Deaeration flowmeter should be the same type a n d model as the fuel
flowmeter.
The boost or service system consists of two p u m p s (one run-
ning, one standby) providing fuel to the boost heater sets, the
viscometer, the homogenizer, the final filter, and to the diesel Fuel Final Filter
engine injection system. Duplex strainers of 20 to 40 mesh Since the high pressure injection p u m p s are sensitive to any
protect the boost p u m p s from tank and piping debris. debris, the boost system should be fitted with a final simplex
Modern fuel systems use deaeration units t h a t remove 10 micron filter located just before the supply to the fuel in-
gaseous bubbles from the return fuel from the engine. These jectors. This filter should be fitted with a differential pressure
systems are closed and pressurized to prevent fociming and indicator. Some operators opt to use self-cleaning final filters
frothing of the hot residual fuel. Older systems were open to to minimize manpower.
the atmosphere in the mixing t a n k where the r e t u r n fuel
mixed with the incoming fuel and the gaseous bubbles were
intended to dissipate within the tank. All older/boost systems B a c k Pressure Control
should be upgraded to closed, pressurized systems at a con- To minimize foaming, cavitation, and vapor formation in the
venient yard period. Closed, pressurized systems should use fuel returning from the fuel injections pumps, a positive pres-
sure of 350 kPa will be needed for high viscosity residucil fuel engines operate at sustained metcJ temperatures over twice
that requires a high preheat for proper injection viscosity. those found in diesel engines, the cleanliness requirements of
the fuel are much more severe than those for diesel engines.
Homogenizer In gas turbine engines, it is criticcJ to control metallic com-
pounds, insoluble and soluble fuel contaminants, dissolved
As residual fuels become more dense with a higher viscosity water soluble metallic contaminants, fire water, solids, and
and higher carbon and asphaltene contents, homogenizers sometimes microbial contaminants [16,17].
will become more important to aid in the preparation of the The gas turbine fuel treatment system is similar to the
fuel for injection, complete combustion, and the reduction of diesel engine system except for the more intensive treatment
exhaust peirticulates cmd opacity (smoke). Very simply, a ho- needed to all but eliminate metallic contamination in the
mogenizer disperses insoluble hydrocarbon clusters in the fuel. Where some metallics, such as vanadium and nickel
residual fuel, completely disperses all free water and cem pro- cannot be (practically) removed by fuel treatment, they can
duce a stable, water-in-fuel emulsion (when potable water is be neutralized using fuel additives. For example, marine
added to the fuel prior to the homogenizer). The homoge- diesel engines can operate well at hundreds of parts-per-mil-
nizer breaks up the insoluble hydrocarbon materials and lion of metallic contaminants, whereas gas turbines must
sludges into very fine particles that aid ignition and burnout have metallic contaminants in the single digit parts-per-mil-
of the high boiling range, high molecular weight materials. lion range, or less. This critical requirement places great em-
There are several different types of homogenizers available, phasis on all aspects of fuel purchase, sampling, delivery,
but the most effective operate on cavitation and shear princi- storage, and treatment. The fuel treatment system must con-
ples, and require significant power to operate. Other units sistently and reliably control fuel contaminzmts without up-
operate on some ultrasoniccJly. As fuels become more heav- sets or malfunctions. Additioneilly, most gas turbine manu-
ily cracked, the use of homogenizers will increase. When facturers strongly recommend that starting, warming up, and
used regularly, homogenizers can reduce the unbumed fuel shutting down be done with a clean, contaminant-free, light
particles that cause waste heat boiler fires (from unbumed distillate fuel. Once the engine has been warmed up and sta-
fuel particles). bilized, the residual/crude oil can then be introduced into the
fuel system.
Emulsifiers
Emulsifiers are units that produce a controlled, stable, water- Tankage
in-fuel emulsion of residucd fuel. Emulsifiers can be homog-
enizers with the addition of potable water. The IMO has con- The fuel treatment system actually begins with the fuel tamks,
sidered water-in-fuel emulsions as the most cost-effective since the initial settlement for free water and solids occurs in
storage. Gas turbine fuel tanks should be fitted with floating
method to reduce NOx exhaust emissions for existing marine
suctions and fill line diffusers. The floating suctions draw the
diesel engines. If marine diesel NOx reductions ever mandate
cleanest fuel from the top of the tank continuously, allowing
the control of NOx on existing ships, water emulsion retrofits
more time for the settlement of contaminants in the mid and
will be the primary technology utilized.
lower regions of the tanks. A fill line diffuser reduces the ve-
locity of the fuel and redirects it during tank filling to prevent
Waste Heat Economizers reentrainment of tank bottom settlement. Also, it all but elim-
As diesel engines become more efficient and slower ship inates currents in the tank that hinder settling.
speeds result in reduced diesel engine loads, the heavily Since metallic contamincmts are to be minimized, coating
cracked fuels are not completely burned out in the diesel en- the inside tank surfaces with an inert, non-metallic coating,
gines. The residue of unbumed cylinder lube oil added to the such as an epoxy, is recommended. Under no circumstances
organic fuel residue causes the waste heat economizer to ex- should a zinc type coating be considered.
perience a greater rate of tube fouling, soot fires, and major
economizer (iron or hydrogen) fires. Since the mid 1980s, the Fuel Treatment
incidence of economizer fires has steadily increased. The ho-
mogenizer Ccm minimize the unbumed residual fuel residues As with all marine fuel treatment systems, the centrifugal
and, if potable water is added to produce water in fuel emul- separator is the foundation and keystone of the system. But,
sions, the economizer can be maintained in a cleaner condi- with gas turbine systems, this separator system becomes
tion. Chemical additives used in the residucd fuel can also much more comprehensive and complicated [18]. A modem
benefit the cleanliness of the economizer. residual fuel or crude oil burning gas turbine usually requires
As a minimal precaution, waste heat boilers should instcJl two stages of water washing, centrifuging at reduced flow
cind monitor the economizer exit temperature and the pres- rates, the use of demulsifying chemical additives, and the use
sure drop across the unit to warn the engineers about an im- of metallic neutralizing fuel additives (see Fig. 14). Demulsi-
pending fire. fying chemicals reduce the tendency of residual fuels to read-
ily emulsify with water. Since these emulsions are difficult to
break in the sepjirator, the use of a demulsifier is recom-
GAS TURBINE FUEL SYSTEM mended to prevent a problem during water washing of the
gas turbine fuel.
Gas turbine engines can operate on gaseous and liquid fuels, Figure 14 shows a typical two-stage water washing gas tur-
including limited residual fuels and crude oils. Since these bine system using a demulsifying additive. The staged water
o washing system is used to reduce the sodium level to below

one part-per-million. The system operates by use of a meter-
P^^ X ing pump that adds a demulsifying additive to the untreated
XQUJ. » 1 — ^ 00
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perature up to 97-99°C. The demulsifier and heated residual
1 LJJ
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o O Q: 3 fuel are thoroughly mixed with 98°C recycled wash water in
h- 1— Q LiJ _ |
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o ^ <L^ separator. Five to ten percent clean water wash water at 98°F
(/) 5Ld
is then metered into the discharge of the first centrifuge and
mixed in the second mixing tank. The residual and water
mixture then flow to the .second centrifugal separator for fi-
nal water and solids removal.
To maintain an effective gas turbine treatment system, all
treated fuel must pass through a monitor that reads the wa-
ter content in the residual fuel after the second separator.
The separators must also remove solid contaminants such
as catalyst particles, sand, rust, and debris from the fuel to
prevent damage and wear to the gas turbine fuel nozzles. Ad-
ditionally, these aggressive solids can cause severe erosion to
I the turbine blades and turbine nozzles.

The final step in the gas turbine fuel treatment process is to
inhibit/neutralize the vanadium and nickel with a chemical
additive. These additives are metered into the clean fuel
stream just prior to gas turbine usage. Oil soluble additives,
which are the easiest to use, are cost effective for vanadium
I and nickel levels below 150 PPM.

Above 150 PPM, additive cost dictates more economical
I water soluble or oil dispersable magnesium additives as an
alternative. These alternative additives have low operating
costs but higher capital costs.
(0
a Heater sets for gas turbine residual fuels should be low
density designs to prevent heater deposits and to prevent
2 destabilizing of any additives used with these fuels.
(5 Gas turbine treatment systems require filtration to remove
all solids above five microns. This level of filtration of resid-
ual fuel requires a specialized filtration medium that is an all
organic, depth type, system. This is critical since gas turbines
have a lower tolerance than diesel systems for solid contam-
inants.
Lastly, a final filter, not necessarily a five micron unit,
should protect the gas turbine from any piping or system re-
lated debris.
In addition to using a clean distillate for starting and stop-
ping the gas turbine engine, a fast acting bypass system
should be installed to allow the distillate to purge out the
residual fuel from the gas turbine's lines in case of an emer-
gency shutdown, stall, or trip. If residual fuel solidifies in the
piping of the gas turbine, the engine will require disassembly
prior to restart.
CONSTRUCTION MATERIALS
In a typical gas turbine treatment system, iron-based materi-

als, steel, and stainless steel are all valid material choices. It
is important that no copper, copper alloys, zinc or any of its
alloys (such as galvanized) be allowed to come into direct
contact with the fuel. Copper and zinc alloys or coating must
never be used in tubes or coils within heaters nor in any coat-
ing or cladding for fuel storage tanks. It is essential to avoid
the use of any galvanized piping or tank plating, as well as the
popular zinc-rich tank coatings. The preferred tank coating D396 Fuel Oils (Steam Plant Spec)
would be an epoxy type coating. D2880 Gas Turbine Fuel Oils (G.T. Spec.)
(also see D 4418)
Conclusions
The supply of marine residual fuels will experience pressure OTHER STANDARDS
from three eireas. Refineries will receive heavier crude oils,
which will result in higher density, higher carbon content ISO
marine residual fuels. Then as refineries upgrade, there is ISO 8217, Annex B for Residuals: Calculated Carbon Aro-
more pressure to increase the intensity of cracking that will maticity Index Calculation
result in fuels with more ignition problems and higher car-
ISO10478, Cat Fines: Digestion & Analysis of Catalyst Parti-
b o n contents. Lastly, the shore side (and to a lesser extent
cles
marine) environmental regulations will require cleaner burn-
ISO 10307-2, Compatibility: Total Sediment Potential of
ing fuels with less sulfur and less aromatics. This will divert
Petroleum Fuels
more difficult, heavier fuels into the marine market. The net
ISO 14597,Vanadium and Nickel: Determination of Vana-
result will be that more difficult fuels will increase in the ma-
dium and Nickel in Liquid Fuels—^Wavelength Dispersive
rine market.
X-Ray Fluorescence Spectrometry
Then, from the engine manufacturers, come new diesel en- ISO 10478, Sodium: Sodium Content of Petroleum Fuels
gines with higher Brake Mean Effective Pressure (BMEP), ISO 3735, Storage Oxidation: Storage Oxidation of
higher fuel injection pressures, that are more demanding of Petroleum Fuels
ignition quality and are more sensitive to fuel contaminants. ISO 3735/10307-1, Sediment: Total Sediment Existent of
The combustion of the residual fuel supply quality and the Petroleum Fuels
trend in m o d e m diesel engine design will demand larger, ISO 8217, Petroleum Products—Fuels (Class F): Specifica-
more efficient fuel treatment equipment to be assembled into tions of Marine Fuels
more comprehensive fuel treatment systems to preclude op-
erating problems and schedule interruptions. Older diesel
ships should upgrade fuel treatment systems to prevent prob- Military F u e l Specifications
lems caused when older fuel treatment equipment/systems
MIL-F-16844: All Purpose Marine Distillate Fuel
try to cope with m o d e m cracked fuels.
As gas turbine engines continue to grow in the military ma-
rine and in cruise ships, their fuel treatment systems must REFERENCES
maintain the highest fuel quality and least contamination of
any marine engine. Since gas turbine engines use only 100% [1] Winkler, M. F., Residual Fuel Oil User's Guidebook, Volume 4,
distillate fuels, the problems are initially easier, but one load Diesels; and Volume 3, Gas Turbines; Southwest Research In-
of contaminated fuel can cause severe hot corrosion damage, stitute for Electric Power Research Institute, May 1988. EPRI-
so continued vigilance is needed to prevent fuel related prob- AP-5826.
lems. [2] Leigh-Jones, C, A Practical Guide to Marine Fuel Oil Handling,
The Institute of Marine Engineers, London, 1998.
[3] Winkler, M. F., The Influence of Fuel Quality on the Performance,
Operation, and Maintenance of Diesel Propulsion Engines, Mar-
ASTM STANDARDS itime Administration, U.S. Dept. of Commerce, March 1979.
[4] Winkler, M. F., Relationship of Fuel Quality to Marine Boilers and
No. Title Diesel Engine Performance, The Society for Marine Port Engi-
D 445 Kinematic Viscosity of Transparent & neers, NY, January 1978.
Opaque Liquids [5] Barnes, G. K., Liddy, J. P., and Marshall, E. G., "The Ignition
D 1298 Density by Hydrometer Quality of Residual Fuels," CIMAC Paper 25, International
Council of Combustion Engines, 1 Birdcage Walk, Westminster,
D 613 for Distillates Cetane N u m b e r of Diesel Fuels London SW1H911, UK, June 1987.
D 4868 Estimation of Net and Gross Heat of [6] The Flammability Hazards Associated with the Handling, Storage
Combustion of Petroleum Fuels and Carriage of Residual Fuel Oil, Oil Companies International
D 93 Flash Point by Pensky-Martens Closed Marine Forum (OCIMF), 27 Queen Anne's Gate, London,
Cup SWIH, 9BU, December 1989.
D 97 Pour Point of Petroleum Products [7] Winkler, M. F., "Coping with Today's Fuels—Distillate and
D 482 Ash from Petroleum Products Residual—Diesel and Steam," Society of Naval Architects and
D 95 Water by Distillation Marine Engineers, Jersey City, NJ. Presented at the SNAME
D 4176 Free Water and Particulate Contami- Chesapeake Marine Engineering Symposium, Washington,
D.C., January 1984; Society of Marine Port Engineers, NY,
nation in Distillate Fuels
March 1982; National Maritime Show, Baltimore, March 1982.
D 4294 Sulfur in Petroleum Products by En-
[8] Winkler, M. F., "Fuel Management: Coping With Future Fuels,"
ergy-Dispersive X-ray Fluorescence Marine Engineering/Log Magazine, March 1983.
Spectroscopy [9] Newbery, P. J., Davies, T. A. C, and Chomske, K. M., "Heavier
D 524 Carbon Residue, Conradson, Residual Fuels for Marine Diesel Engines," MotorShip Magazine,
of Petroleum Fuels West Sussex RH16 3DH, UK. Presented at the 6th International
D 2069-98 Marine Fuel Specifications Motorship Conference, London, March 1984.
[10] Winkler, M. F., Systems Design for Future Fuels-Steam and [14] Winkler, M. F., "Diesel Fuel Systems to Prevent Operational
Diesel, Society of Marine Port Engineers, Avenel, NJ, 1983. Problems," presented at the S.A.E. Marine Propulsion Technol-
[11] Winkler, M. F., "Operational Problems and Marine Fuel Oils," ogy Conference, 14 May 1986, Washington, D.C.
Presented at the International Conference and Long-Term Stor- [15] ISO 8216-0: Petroleum Products - Fuels (Class F) - Classification
age Stabilities, San Antonio, TX, Jixly 1986; Society of Automo- - Part 0: General, International Organization for Standardiza-
tive Engineers Conference, Washington, D.C., May 1986. tion, Geneva, Switzerland, 1986.
[12] Winkler, M. F., "Shipboard Fuel Handling and Treatment For [16] Winkler, M. F., "Management of Gas Turbine Fuel Systems,"
Diesel Engines," presented at the ASTM International SjTnpo- Gas Turbine International Magazine, March-April 1977.
sium on Marine Fuels, Miami, FL, December, 1983; Society of [17] Winkler, M. F., "Management of Residual Fuel Systems for Gas
Maritime Arbitrators, NY, October 1983; Fort Schuyler Forum Turbines," Gas Turbine International Magazine, May-June 1977.
sponsored by Society of Marine Port Engineers, NY, March 1981. [18] Winkler, M. F., "Management of the Gas Turbine Fuel Systems,"
[13] Fisher, C. and Lux, J., BUNKERS: An Analysis of the Practical. ASTM International, October 1973; Society of Automotive En-
Technical and Legal Issues, Second Edition, 1994, Lloyd's of Lon- gineers, Canada, August 1971; Society of Automotive Engineers,
don Press, NY, 1994. Philadelphia, November 1970.
Section III: Hydrocarbons and Synthetic Lubricants:
Properties and Performance
Rajesh J. Shah, Section Editor

MNL37-EB/Jun. 2003
Hydrocarbon Base Oil

Chemistry
Arthur J. Stipanovic^
HYDROCARBON BASE FLUIDS COMMONLY USED in the formulation chemistry:

of engine oils, industrial lubricants, greases, and other prod- • provide a brief overview of the base oil market and identify
ucts, are composed of a broad spectrum of molecular species emerging trends,
including aromatic, paraffinic, a n d cycloparaffinic (naph- • outline the refinery processing scenzirios typical of current
thenic) molecules [1-4]. Over the past severeil decades, new base oil production in the United States,
separation methods and analytical techniques have made it • review the chromatographic and spectroscopic techniques
possible t o accurately characterize and quantify the hydro- most commonly used to characterize base oil composition,
carbon t5ês that exist in base oil while relating these com- • provide a comparison of hydrocarbon tjrpe distributions
positional pEirameters to crude oil source and refining condi- for base oils obtained by several different refinery pro-
tions. F o r example, ASTM test m e t h o d D 2549 exploits cesses, including re-refined oils,
column chromatography to separate a base oil into saturate • review important chemical mechanisms leading to the ox-
and aromatic fractions while D 2786 and D 3239, mass spec- idation and degradation of base oils,
trometry techniques, further sub-divide each fraction into a
• outline composition/performance relationships for base oils
group of molecular types. As a result, the physical and chem-
in various automotive and industrial lubricant applications.
ical properties of base fluids are now m u c h better understood
and, in some cases, it has become possible to predict the per-
formance of a formulated lubricant directly from base oil
LUBRICANT B A S E OIL M A R K E T
composition using statistical m e t h o d s o r neural network
modeling [3-8]. Refining Capacity i n the United States
From the perspective of lubricant applications, among the
Since most lubricants typically contain in excess of 80% base
most important properties that depend directly on base oil
oil by volume, their physical and chemical properties play a
composition include viscosity index (VI), oxidative/thermaJ
key role in defining the ultimate performance profile of a lu-
stability, low temperature fluidity, a n d additive solubility.
bricant and the additive technology that must be employed in
Other significant parameters such as kinematic viscosity and
formulation. In addition, the marketplace availability, cost,
volatility are influenced primarily by molecular size although
and qucdity of base oil are critical considerations in defining
composition may play a role as well. As will be discussed in
the economics and performance of a finished product. As a
this chapter, each of these performance parameters is influ-
result, lubricant development requires a n understanding of
enced differently by subtle changes in the hydrocarbon type
both the base oil meirket and the techniccil issues surround-
distribution of the base oil and, as a result, they are sensitive
ing specific product requirements.
to crude oil source and refinery processes. Further, since base
oil refining technology is changing at a revolutionary pace, it On a global basis, the market for hydrocarbon-based min-
is increasingly important that lubricant formulators appreci- eral oils a n d wax exceeds 10 billion gallons per year [10]
ate the impact of base oil chemistry on product performance. while annual U.S. production is approximately 3.5 billion
gallons [11], of which about 20% is designated as "naph-
Although synthetic fluids such as polyalphaolefins a n d
thenic" and 80% "paraffinic" (these terms will be defined be-
polyesters have grown in their importance in many lubri-
low). A profile for the eleven largest base oil refiners in the
cants, this chapter will focus on mineral oil base fluids de-
U.S. is provided in Table 1.
rived from crude oil via a n u m b e r of refinery processes. For
most lubricant product lines such as engine oils and indus- Petro-Canada, a major base oil producer in Canada, pro-
trial process oils, mineral basestocks account for greater than vides a n additional 230 MM gallons/year from its Missis-
90% of the commercieJ product volume, although the mar- sauga, Ontario plant while Imperial Oil in Samia, Ontario re-
ketplace penetration of S5rnthetics is increasing modestly [9]. fines a n additional 92 MM gallons/year. Annual base oil
The organization of this chapter will focus on the following re-refining capacity in the U.S. and Camada is estimated to be
issues in base oil technology a n d hydrocarbon lubricant approximately 62 MM gallons and 32 MM gallons, respec-
tively, as outlined in Table 2 [11].
' Director, Analytical and Technical Services, Faculty of Chemistry, B a s e Oil M a r k e t P r i c e s

State University of New York, College of Environmental Science and
Forestry, 123 Jahn Laboratory, One Forestry Drive, Syracuse, NY Although the market price of base oil varies dynamically over
13210. time in response to crude cost and availability as well as re-
169
TABLE 1—Production of lubricating oils and waxes—1999 [11]. ing capacity in North America has decreased by approxi-
Capacity mately 8% from 1980 to 1995 [10].
Refiner Location (mm GallonsA'ear)
Exxon Baton Rouge, LA 577
and Baytown, TX BASE OIL REFINING AND PROCESSING
Equilon" Deer Park, TX, 298 TECHNOLOGY
Martinez, CA and
Wood River, IL'
Sun Tulsa, OK and 271 Crude oil sources from which lubricant-grade mineral oils
Yabucoa, PR are refined contain thousands of molecular species differing
Motiva* Port Arthur, TX 269 in chemical constitution and size [14]. Base oil manufacture
Excel Paralubes" Westlake, LA 269 is, therefore, a very complex process that fractionates
Chevron Richmond, CA 214
Pennzoil-Quaker State Rouseville, PA and 199 molecules based on molecular weight (size) and composi-
Shreveport, LA tion to yield a product with appropriate viscosity and chem-
Mobil Beaumont, TX 180 ical stability. At least five processing stages may be employed
Valero Energy Corp.'* Paulsboro, NJ 176 to produce a lubricant base oil: 1) crude distillation; 2) dea-
Cit-Con Lake Charles, LA 146 sphalting to remove very heavy fractions of the crude; 3) sol-
Marathon—Ashland Catlettsburg, KY 130
vent extraction or hydrogen refining to remove undesirable
"Shell/Texaco joint venture. Formerly Shell base oil refineries. aromatics and heteroaromatic species; 4) solvent or catalytic
^Shell/Texaco/Star Enterprise joint venture. Formerly a Star Enterprise
refinery. dewaxing to remove linear paraffins (wax), which can crys-
"Conoco/Pennzoil joint venture. tallize, causing poor flow properties at low temperatures;
''Formerly a Mobil refinery.
'Since the 1999 NPRA report, the Wood River facility no longer produces and 5) hydrogen finishing or clay treatment to remove trace
lubricants. quantities of heteroaromatic species, olefins, or other
molecules that could cause stability problems [10]. In addi-
tion to removing undesirable molecular species, refining
generally increases the viscosity index (VI) of a distillate. VI
TABLE 2—Re-refined base oil production in the U.S. reflects the relationship between base oil viscosity and tem-
and Canada [11].
perature and is calculated from kinematic viscosities
Capacity recorded at 40°C and 100°C (ASTM D 445) using an empiri-
Refiner Location (mm GallonsATear)
cally derived procedure defined in ASTM D 2270. All hydro-
Evergreen Oil Inc. Newark, CA 12.3 carbon-based mineral oils decrease in viscosity with in-
Safety-KUeen Corp. East Chicago, IL 50.6
Hub Oil Company Calgary, Alberta 3.1
creasing temperature as shown in Table 4. Comparing two
Mohawk Lubricants Ltd. N. Vancouver, BC 6.1 oils that have an identical viscosity at 100°C (4 cSt), a lower
Safety-Kleen Corp. Breslau, Ontario 23.0 VI oil will have a lower viscosity above 100°C and a higher
Total 95.0 viscosity below 100°C than a higher VI oil. In general, higher
VI products are considered more desirable because they
maintain a greater fraction of their viscosity and lubricating
properties at high temperatures (100-150°C) while exhibit-
gional refinery supply/demand issues, Table 3 provides a gen- ing lower viscosity, better fluidity, and improved pumpabil-
eral reflection of base oil prices in early 1999, when crude oil ity at very low temperatures (0°C and lower) when treated
averaged less than $20/bbl compared to 2000 when crude with pour point depressant additives. The specific molecular
cost climbed above $25/bbl [12 A,B]. Table 3 also illustrates components of base oil responsible for high VI will be dis-
that base oil prices generally increase with increasing viscos- cussed below.
ity grade due to several factors including: the "natural"
molecular weight range of the crude sources used for lubri-
cant manufacture and the extra refining required for heavier
distillate streams, since they are t3rpically richer in aromatics TABLE 3—Market prices of paraffinic base oil in the U.S. ($/g£d).
and sulfur-containing molecules. Based on an average price Average Cost Range of Prices
of $1.00 per gallon, domestic base oil refiners generate rev- Base Oil Viscosity ('99/'00) ('99/'00)
enues in excess of $3.5 billion annually. Low (90-150iV) 0.85/1.17 0.79-1.04/1.07-1.23
Medium (200-250yV) 0.86/1.18 0.80-1.04/1.07-1.27
Heavy (500-600A^) 1.00/1.27 0.94-1.17/1.20-1.37
Future Refining Trends Bright Stock (Very Heavy) 1.19/1.52 1.16-1.31/1.41-1.53
Although basestock demand is growing only modestly in

North America at less than 3% per year [9], other regions of
the world are expanding more quickly [10]. Specifically, cer-
tain South and Central American and Asian countries are ex- TABLE 4—VI: The effect of temperature on viscosity.
periencing lubricant growth demand in excess of 5% per Temperature
year. In all cases, an evolution to higher quality base stocks, Oil VI CC 40°C 100°C 150°C
such as Group II and III oils, defined below, is evident on a 75 192 21.0 4 1.87
worldwide basis [13]. As a result of extreme competition to 100 155 19.5 4 1.91
produce and utilize Group II base stocks and an overall re- 125 117 17.7 4 1.97
duction in demand for naphthenic stocks, the base oil refin- 150 92 16.3 4 2.03
CHAPTER 7: HYDROCARBON BASE OIL CHEMISTRY 171
Distillation TABLE 6—Relationship of SUS to

kinematic viscosities for a 100 VI
Two distillation units are typically required to effectively base oil.
fractionate crude oil for use in lubricants [10]. First, an at- Kinematic Viscosity SUS Viscosity
mospheric still is employed to selectively remove gases and at 100°C (cSt) at 100°F
other light products such as gasoline and naphtha from the 3 70
lube distillate stream. Secondly, the remaining stock is dis- 4 100
tilled under reduced pressure in a vacuum distillation unit 6 200
yielding a number of viscosity fractions appropriate for vari- 8 310
10 430
ous applications. Typical boiling points for each crude oil 12 560
fraction are shown in Table 5. The distillation cut corre- 14 710
sponding to lubricating oils typically consists of molecules 16 870
that range in size from 20-40 carbon atoms per molecule. 18 1000
Most refineries fractionate the distillate into 3-5 distinct vis-
cosity grades, historically called "neutrals," for which 100°C
kinematic viscosity values range from 3-5 cSt for so-called
"light neutral oils," 6-9 cSt for "medium neutrals" and > 10 thenic molecules are insoluble in the extraction solvent while
cSt for "heavy neutrals." In commercial practice, the viscos- multi-ring aromatics (polynuclear aromatics), sulfur and ni-
ity grade designation for base oils, such as 100 Neutral trogen compounds, olefins, and other undesirable species are
(lOON), was based on the Saybolt Universal Second (SUS) dissolved in the polar solvent phase. After phase separation,
system of measuring viscosity that is no longer widely uti- the non-polar phase containing the base oil is stripped of
lized. Table 6 illustrates the relationship between "historic" residual polsir solvent and is usually hydrogen treated as dis-
SUS viscosity grades and kinematic viscosities obtained from cussed below. Furfural, phenol, and N-methyl-2-pyrolidone
ASTM D 445. (NMP) are commonly used as extraction solvents [10,11].
Propane Deasphalting Hydrogen Refining/Hydrocracking

For certain heavy distillates and vacuum residua, base oils of Although solvent refining is effective in improving the qual-
very high viscosity (Bright Stocks) can be refined through ity of distillates in the manufacture of base oils, a significant
propane deasphalting [10]. In this process, liquefied propane yield loss is normally associated with the extraction process.
under relatively high pressure is used to precipitate insoluble, This loss can be economically unacceptable for distillates de-
high molecular weight aromatic hydrocarbons such as as- rived from relatively poor crude oils that contain high con-
phaltenes and to extract other compounds (typically termed centrations of heavy aromatic compounds. Fortunately, it is
"resins"), which could be deleterious to the performance of also possible to improve the quality of a raffinate through
the base oil being refined. Sulfur and nitrogen compounds as various catalytic processes in which high-pressure hydrogen
well as certain metals can also be removed by propane deas- (1500 - 4000-1- psi) is employed to saturate aromatic
phalting. molecules while cracking other large molecules to smaller
compounds of molecular weight appropriate for base oils
[10]. Olefins as well as sulfur and nitrogen containing com-
Solvent Refining pounds are also reacted and removed by hydrogen process-
For basestocks of low to moderately high viscosity, solvent ing. Because aromatics are converted to saturated com-
refining has been employed extensively and on a worldwide pounds, hydrogen processing normally increases VI.
basis; this refining technology is probably the most popular
method. Solvent refining removes undesirable polar and Dewaxing
highly condensed aromatic molecules from the distillate and,
in doing so, significantly increases VI. In this process, distil- Essentially, all crude oil and base oil distillates contain a
late is mixed with an insoluble polar solvent that creates a small fraction of linear paraffins (wax) [14] that can crystal-
two-phase system. Ideally, desirable paraffinic and naph- lize at low temperatures. For engine oils, transmission fluids,
and other lubricants that must remain liquid and pumpable
to temperatures approaching -40°C, it is necessary to re-
TABLE 5—Distillation cuts of crude oil [14, 15]. move as much wax as possible from the basestock. To ac-
Fraction Boiling Range (°C)
complish this task, at least two techniques are commonly
used to remove wax: solvent dewaxing (SDW) and catalytic
Ethane, butane, propane gases <0
dewaxing (CDW). For SDW, the base oil is first diluted in a
Light naphtha to 150
Heavy n a p h t h a 150-205 solvent (toluene, for example) and then the mixture is added
Gasoline to 180 to a wax non-solvent (typically ketones such as methyl ethyl
Kerosine 205-260 ketone-MEK). The mixture is then chilled to low tempera-
Stove oil 205-290 tures to precipitate wax as a solid and is then collected by fil-
Lights gas oil 260-315
tration. SDW is a batch process. In the CDW procedure, a
Heavy gas oil 315-425
Lubricating oils >400 shape selective catalyst is exploited to "crack" the paraffins
Vacuum gas oil 425-600 into smaller, volatile segments that can be fractionated by
Resid >600 distillation. CDW is a continuous process and, as a result, en-
joys m a n y advantages over SDW. However, since CDW is system, crude fractions that boil in the range typical of base
more efficient in removing wzix and other branched pEiraffins oils (250-275°C and 275-300°C; at 1 atm) are naphthenic if
than is SDW, the resulting base oil VI is usually reduced since they have a n API gravities of < 3 3 a n d < 2 0 , respectively.
paraffins contribute to high VI. More recently, several pro- Paraffinic oils for the same boiling ranges provide API gravi-
cesses have been developed that isomerize wax to brsmched ties of > 4 0 and > 3 0 . API gravity (ASTM D 287) is sensitive to
isomers that do not crystallize as readily as linear peiraffins. the relative ratio of paraffins, cycloparaffins, and aromatics
As a result, VI is preserved by the hydroisomerization process in a crude or base oil. Higher paraffinic cheiracter increases
cind very high VI oils (>120 VI) can be made directly from API gravity. A significant feature that distinguishes most
wax as a feedstock. Several API Group III base oils, to be de- naphthenic crudes is a very low natural level of linear paraf-
fined below, are synthesized from a pEiraffin hydroisomeriza- fins or wax, which enables the production of base oils with
tion procedure. very low pour points and excellent low temperature fluidity,
essential in some applications such as refrigeration oils.
Naphthenic base oils also have a relatively high aromatic
Hyfinishing (Hydrofinishing)
content, which has limited their use in other applications
At the conclusion of the refining steps detailed above, base where higher toxicity is a concern. Due to improvements in
oils still may contain small quantities of sulfur, nitrogen, or- dewaxing methodology and concern over the potenticd ad-
ganic acids, and partially hydrogenated aromatics that can verse health effects of naphthenic base oils, the market share
cause the base oil to exhibit poor color stability and an in- of these stocks has steadily decreased over the past decade
creased tendency to form sludge or other insolubles [10]. His- (see Ref 11 and earlier issues of the annual NPRA survey).
torically, base oils were "finished" using either a sulfuric acid
procedure or clay contacting. Unfortunately, both of these
procedures jield potentially hazardous byproducts that re- B A S E OIL CHARACTERIZATION
quire careful disposal to avoid environmental contamination.
As a result, most m o d e m refineries use a catal3îc hydro- Hydrocarbon Type Analysis
genation process called hyfinishing to remove trace levels of
impurities from base oil. Hydrogen pressures are typically The chemiCcd composition of lubricant base oil is strongly
500-1000 psi, which are below the levels required for hydro- dependent o n a n u m b e r of factors. These include crude oil
cracking. Hyfinishing decreases the aromatic content of a source, molecular weight range (generally higher molecular
base oil slightly while significantly lowering sulfur and nitro- weight crudes are richer in multi-ring aromatics), the refin-
gen levels. Byproducts of hyfinishing include H2S, NH3, and ing process (solvent vs. hydroprocessing), the degree of refin-
CO2, which result from the cracking and hydrogenation of ing, and the effectiveness of the finishing process.
undesirable organic molecules containing S, N, or O het- Determining the chemical compositional profile of base
eroatoms. oil is usually initiated with a chromatographic separation
procedure to isolate the aromatic and saturate fractions
of the sample. ASTM method D 2549 involves an open col-
B a s e Oil R e - r e f l n i n g u m n procedure using a bauxite column packing with polar
The reclamation of base oil from used engine oils and indus- and non-polar organic solvents to elute the aromatic and sat-
trial lubricants has become a n important process from both urate fractions, respectively. In this procedure a sample of
an environmental protection and economic perspective. In base oil is applied to the top of the column, which is then
the U.S., a Presidential Executive Order spurred the develop- flushed sequentially with solvents of increasing polarity. Sat-
ment of re-processing technology in October 1993, requiring urated molecules, including both paraffins and naphthenic
that all federal agencies establish procedures to purchase lu- molecules, bind to the column less strongly than ciromatic
bricants containing at least 2 5 % re-refined base oil. Many compounds and, as a result, they elute from the column with
municipalities have adopted this requirement for contract n-pentane (non-polar) while the aromatics require "stronger"
purchases of lubricants as well. Although a n u m b e r of pro- polar solvents (chloroform/ethyl alcohol) to be eluted. Typi-
cessing m e t h o d s can be used to recycle spent lubricants, cal aromatic and saturate levels determined by D2549 for a
most commercial re-refiners utilize at least three stages: series of base oils, refined by different methods, are given in
heating to remove water and residual low molecular weight Table 7. It may generally be concluded that base oils contain
hydrocarbons (fuels), distillation to separate hydrocarbons a preponderance of saturate compounds and that the level of
from polar oxidation products (sludge, varnish, other insol- aromatics for a solvent refined base oil increases with viscos-
ubles), residual fuel components, organometallic additives, ity grade largely because heavier distillates contain higher
etc., followed by hydrotreating to reduce sulfur, nitrogen,
and polynuclear (multi-ring) aromatic levels. In at least one
commercial re-refining process, a p r o p a n e deasphalting TABLE 7—Composition of base oils.
stage is employed to remove undesirable by-products etnd ad- Refining Process - SUS
ditives prior to re-distillation. Viscosity Grade % Saturates % Aromatics
Solvent Refining (SR)—lOOA? 70-90 10-30
SR Medium Viscosity—320N 65-75 25-35
N a p h t h e n i c vs. Paraffinic B a s e Oils SR High Viscosity—850A^ 60-70 30-40
Bright Stock 50-60 40-50
The widely used term "naphthenic" base oils represents those Hydrocracked 100 90-100 0-10
stocks produced from naphthenic crude as defined by the Hydroisomerized 100 95-100 0-5
U.S. Bureau of Mines Classification of Crude Oils [16]. In this SR—Naphthenic Crude 60-70 30^0
levels of aromatics. Further, hydroprocessing techniques, TABLE 10—Typical aromatic distribution of lOON (4 cSt)
specifically hydrocracking and hydroisomerization, drasti- base oils.
cally reduce aromatic level. In addition, base oils processed Relative Volume %
from naphthenic crudes typically exhibit a high aromatic Hydrocarbon Type Group I Group II Group III
content and a very low level of paraffins (<8%). Monoaromatics 11.7 0.9 4.0
A related column chromatography method, ASTM D 2007, Diaromatics 3.1 0.6 0.9
is based on a clay-silica gel adsorption procedure that re- Triaromatics 1.1 0.2 0.2
solves a base oil sample into aromatic, saturate, and polar Tetraaromatics 0.8 0 0.1
Pentaaromatics 0.4 0 0.1
fractions. In this procedure, the following solvents are used Thiophenaromatics 1.6 0.1 0.4
to elute the hydrocarbon fractions: n-pentane (elutes satu- Unidentified Aromatics 2.7 0.2 0.6
rates), toluene (elutes aromatics), and toluene/acetone Total 21.4 2.0 6.3
(elutes polars). ASTM D 2007 was chosen as the preferred
method for base oil characterization in the so-called
"Base Oil Interchangeability Guidelines" established by the TABLE 11—Typical aromatic sub-categories for a 70A^
American Petroleum Institute (API) in API Publication group I base oil.
1509 - Engine Oil Licensing and Certification System (API Hydrocarbon Type Volume % Total
Address: 1220 L Street NW, Washington, DC 20005-4070, Monoaromatics 13.2
www.api.org). In this publication, the API concludes Alkylbenzenes 6.94
that "Not all base oils have similar physical or chemical Naphthenebenzenes 3.37
properties or provide equivalent engine performance in en- Dinaphthenebenzenes 2.92
gine testing The API Base Oil Guidelines were developed Diaromatics 2.6
to ensure that the performance of engine oil products is not Naphthalenes 0.91
Acenaphthenes, dibenzofurans 0.89
adversely affected when different base oils are used inter- 0.77
Flourenes
changeably by engine oil blenders" (API 1509). Under these Triaromatics 0.7
guidelines base oils are grouped into three categories accord-
Phenanthrenes 0.45
ing to composition, VI, and sulfur content as shown in Table Napthenephenanthrenes 0.22
8. Group IV is reserved for polyalphaolefins and Group V in- Tetraaromatics 0.3
cludes other basestocks not included in Groups I-IV. 0.08
Pyrenes
API Publication 1509 also defines which engine tests are Chrysenes 0.17
required when interchanging a base oil in an approved gaso- Pentaaromatics 0.1
line or diesel engine oil formulation using the base oil defini- Perylenes 0.06
tions above. Currently in the U.S., approximately 1.76 billion Dibenzanthracenes 0.03
gallons of annual production of paraffinic base oil is Group I Thiophenoaromatics 0.7
while 870 million gallons/year is Group II [11]. The ratio of Benzothiophenes 0.23
Group II to Group I has increased significantly since the early Dibenzothiophenes 0.50
1990s and most new base oil plants utilize refining technol- Naphthobenzothiophenes 0.0
Unidentified Aromatics 1.5
ogy that provides Group II stocks.
In reference to the ASTM D 2007 procedure, it should be Total Aromatics 19.0
noted that a hydrocarbon analysis technique based on Thin-
Layer Chromatography with Flame-Ionization Detection has
demonstrated that "the ASTM method does not always yield
pure fractions of each hydrocarbon type and cross contamina-
TABLE 8 --API lubricant base stock categories tion introduces considerable inaccuracies in the results" [17].
API Group % Saturates % Aromatics VI (1) % Sulfur (2) These deviations are attributed to column overloading, in-
I <90 >10 <120 >0.03 complete separation, and incomplete recovery of fractions
II >90 <10 >80, <120 <0.03 from the column for D 2007.
III >90 <10 >120 <0.03
"Viscosity Index by ASTM D 2270.
^Sulfur content by any of the following: ASTM D 2622, D 4294, D 4927, Spectrometric Identification of Base Oils
D3120. Components
TABLE 9—Typical saturates distribution of lOON (4 cSt) Although Nuclear Magnetic Resonance (NMR) [18,19], Ultra
base oils. Violet (UV; ASTM D 2008), and Infrared Red (IR) spectro-
Relative Volume % scopies [20], along with a number of chromatographic tech-
Hydrocarbon Type Group I Group II Group III
niques [21] have been successfully employed to characterize
the compositional profile of lubricant base oils, several mass
Paraffins 23.9 22.0 70.2
14.7 23.1 11.8
spectrometry (MS) techniques have evolved into standard
Monocycloparafflns
DlcyloparafHns 11.3 19.2 5.3 ASTM methods suitable for base oil analysis. Once base oil
Tricycloparafflns 8.1 11.7 1.8 saturate and aromatic fractions are isolated by the column
TetracycloparafHns 9.9 9.3 1.6 chromatography procedures discussed above, each fraction
Pentacycloparafflns 6.6 7.2 0.6 can be subjected to further analysis and sub-catergorization
Hexacycloparaffins 4.2 5.6 2.5
by mass spectrometry using ASTM Methods D 2786 and D
Total 78.7 98.0 93.7 3239. Tables 9-11 contain the major sub-categories of satu-
rated and aromatic molecular groups resulting from these papers by Sarpal [18,23] and Sahoo [24] demonstrate the po-
MS techniques for typical Group I, II, and III base oil types. tential of this method in characterizing base oil. Aromatic
Representative molecular structures for the hydrocarbon carbon atoms exhibit resonances at chemiced shifts ranging
types outlined in Tables 9 and 10 eire given in Tables 12 and from 100-160 while saturated carbons (paraffins and naph-
13. It should be noted that actual "base oil" molecular struc- thenes) provide shifts in the range of 10-60 ppm [24]. From
tures would contain a greater number of carbon atoms than the information in Table 14, it is also possible to estimate the
shown in Tables 12 and 13. The structures shown are illus- average peiraffinic chain length of base oils by developing ra-
trative of the chemical functionality of base oil, however. A tios of chain ends (-CH3 groups) to -CH2- groups well sepa-
more general discussion on the characterization of rated from chain ends.
petroleum fractions by MS is the subject of an excellent re- A relatively new pulse protocol called DEPT expands the
view article by Altgelt and Boduszynski [22]. utility of ^^C-NMR for base oils in that it provides individual
ASTM D 3239 further subdivides the aromatic fraction de- spectra for each carbon atom t3?pe CH„ where n = 0-3
tailed in Table 10 into sub-categories as illustrated in Table thereby increasing resolution and the ability to quantify car-
11 for a Group I base oil. bon species [23]. In using NMR to study base oils, care must
be taken, however. '^C-NMR is inherently non-quantitative
since each carbon atom relaxes at a rate depending on its sur-
NMR Spectroscopy of Base Oils roundings and complete relaxation is required for integra-
Although a detailed review of NMR spectroscopy as applied tion data to be quantitative. Since carbon nuclei relaxation
to base oil characterization is beyond the scope of this chap- times can be on the order of seconds, total relaxation be-
ter, it should be emphasized that '^C-NMR spectroscopy is an tween NMR pulses is not typically achieved. As a result, the
extremely useful method to distinguish aromatic from satu- use of a so-called relaxation agent, such as chromium acety-
rated carbon atoms in base oil while quantifying the length lacetonate, is essential with base oils to ensure complete re-
and degree of branching for peiraffinic components. Recent laxation enabling quantitative integration.
TABLE 12—Molecular structure of base oil hydrocarbon types.

Hydrocarbon
Types Structures
Paraffins (inclndes isoparaffins) \A/^/\
Mononaphthenes
-0-
Dinaphthenes oCc;r
VÂÂ^-JY^
Trinaohthenes
Monoaromatics
^<y^
Indanes:
Aromatic / Naphthene "Hybrid"

^
Diaromatics
/lL^js*^j,,Jk^
TABLE 13—Molecular structure of base of hydrocarbon types (Continued).

Hydrocarbon Stmctures
Types
Triaromatics
^
Tetraaromatics
-o^
Thiophene 0
Benzothiophene CO
Dibenzothiophene 0:p
Napthobenzothiophene
s
TABLE 14—Structural parameters derived from '^C-NMR. cellent reviews and texts [2,25-31 ], it is worthwhile to discuss
Typical Chemical several key mechanisms. As shown in Fig. 1, hydrocarbon ox-
R-Group Description (1) Shift (ppm) idation proceeds through a number of steps involving free
CHa Short Branch E n d 11.4 radicals:
CH3 Long Branch E n d (a) 14.1 The initiation stage can be triggered by peroxide or hy-
CH2 Adjacent to Long Chain E n d (p) 22.7
CH2 Near Chain End (7) 32.0
droperoxide impurities in the oil [32] or by the thermal crack-
CH2 Adjacent to Long Chain CH2 (8) 30.1 ing of hydrocarbons on hot metal surfaces in cin engine, for
CH2 Middle of Long Chain (e) 29.7 example. Once a radiceJ is formed it can readily extract a hy-
drogen atom from hydrocarbon molecule (R-H), which is
subsequently very reactive toward oxygen (O2) 3rielding a per-
oxide radical (R02»). Table 15 compares the relative hydro-
B A S E OIL C H E M I S T R Y gen atom abstraction reaction rates for primary, secondary,
and tertiary carbon atoms when attacked by a peroxy radical
Oxidation Reactions (sec-alkyl- COO») and a t-butoxy radical ((CH3)3CO») [33].
Hydroccirbon oxidation chemistry is of great importance in These data show that hydrogen atoms cffe removed more
the ukimate appHcation of base oils and lubricants, since at easily (faster reaction rate) in the order tertiary > secondary
the high temperatures typical of most lubricating environ- > primEiry, which is directly related to the stability of the rad-
ments, oxidation can lead to undesirable oil thickening, the ical that is formed. This observation suggests that molecular
formation of insoluble sludge and varnish deposits, and the structures such as linear parafBns will have greater resis-
creation of potentially corrosive organoacid compounds. Al- tance to oxidation compared to other branched paraffins or
though this subject has been extensively covered in many ex- cycloloparafKns that contain a relatively greater proportion
Initiation: I-I I* and B', respectively, which can Hmit further reactivity by
evaporation from the hquid phase system. As oxidation con-
R-H + !• ^ I-H + R* tinues, B undergoes condensation-type polymerization reac-
tions to yield molecule P that has a high molecular weight but
Propagation: -> R02* is still soluble in the hydrocarbon liquid phase. As a result, P
is capable of significantly increasing the viscosity of the lu-
R02» + R-H • ROOH + R* bricant being oxidized. As a polymer, P is not volatile and re-
mains in bulk solution and in contact with the metal surface.
Termination: R« + R02» " -> ROOR Through further oxidation and thermal decomposition, P be-
comes an insoluble deposit of very high molecular weight on
2R02» -•R-O4-R metal surfaces. This model has been effective in predicting
deposits in both gasoline and diesel engine tests as well as
R-O4-R -p. O2 +Non-Radical high temperature oxidative oil thickening in many applica-
tions.
Products
Although hydrocarbon oxidation can have a profound ef-
FIG. 1—Hydrocarbon oxidation by free radicals. fect on the properties of a lubricant, this process can, fortu-
nately, be controlled by the use of antioxidant additives.
These molecules will be discussed more extensively in an-
TABLE 15-—Relative hydrogen abstraction rates. other chapter of this manual. Very generally, antioxidants
Molecule
function either by scavenging radical species or by decom-
posing peroxides to unreactive products. Radical scavengers
Radical CeHs CH3 Cj6^5^'l2^H3 C6H5CH-(CH3)2
include hindered phenols such as t-butylphenol, quinines,
sec-alkyl-COO« 1 9 14 and certain amines. Zinc dialkyldithiophosphate, a common
R-CH3 R2CH2 R3CH
(CH3)3CO. 12
antiwear compound, also serves in a peroxide decomposing
1 44
capacity as well.
TABLE 16—Reactivity of substrate molecules I m p a c t o f S u l f u r C o m p o u n d s o n B a s e Oil

toward the phenyl radical. Chemistry
Relative Reactivity
Substrate Molecule per a-Hydrogen Throughout the evolution of base oil refining and processing
technology, sulfur content has been employed as an indicator
Primary Aliphatic 1
Cyclopentane 10 of product quality and a predictor of lubricant performance.
Cyclohexane 9 In this context, the t e r m "sulfur" relates to soluble,
Indane (See Table 12) 72 organosulfur compounds that occur naturally in crude oil in
Acenapthalene 92 contrast to elemental, yellow sulfur. Current domestic base
oil sulfur concentrations typically range from <0.05 wt% to
0.4% for light base stocks and u p to 0.8-1.0% for heavier vis-
of secondary or tertiary hydrogen atoms. The rate of free rad- cosity grades. In other regions of the world, it is not uncom-
ical propagation is Eilso very dependent on ring geometry and m o n to observe sulfur levels in excess of 1.5-2.0%. From the
adjacent function groups as shown in Table 16 for phenyl perspective of base oil chemistry, how the organosulfur con-
radicals [33]. tent impacts lubricant performance is very complex and de-
As oxidation proceeds, propagation reactions involving pends, to a large extent, on the ultimate application and the
peroxy radical addition to other hydrocarbon molecules typ- nature of the additives used in the formulation. Although cur-
ically result in the formation of polar compounds and higher rent manufacturing trends suggest that a very low sulfur con-
molecular weight species, which may ultimately increase the tent is most desirable for base oil, it has historically been
viscosity of the oil. The combination of oligomeric and poly- thought that higher sulfur levels directionally improve base
meric radicals during the termination phase of oxidation can oil oxidation stability as well as friction a n d wear perfor-
also cause a molecular weight increase and viscosity en- mance.
hancement. Studies on the autoxidation of n- hexadecane The pioneering work of Dennison and Conduit [37] in the
(linear CI8 paraffin) at temperatures of 160-180°C have il- 1940s concluded that "the oxidation stability of refined
lustrated that Ccirboxylic acids, hydroperoxides, ketones, al- petroleum lubricating oils is the result of small quantities of
cohols, and esters Eire all formed over a period of hours. It is natural sulfur compounds and not of any inherent stability of
interesting to note, however, that this "model system" exhib- the hydrocarbon fraction itself. In the absence of the natural
ited a significant increase in viscosity while only a "modest" sulfur compounds the hydrocarbon fraction oxidizes rapidly
increase in molecular weight was observed [31]. and, in the initial stages of the reaction, autocatalytically."
A useful oxidation model for thin hydrocarbon films on This work clearly illustrated that certain sulfur containing
metal surfaces has been developed by Professor E.E. Klaus compounds, specifically monothioethers containing at least
a n d his co-workers at the Pennsylvania State University one aliphatic or cycloaliphatic group attached to the sulfur
[34-36]. They have shown that if Molecule A is oxidized it atom (sulfides), were very potent antioxidants in lubricants.
forms Molecule B that initially has the same molecular These authors were successful in selectively removing the
weight as A. At this stage, both A and B can volatilize to A' sulfur compounds from a mineral oil while keeping other
TABLE 17—Oxygen uptake of base oil—impact of sulfur compounds.

Oxygen Uptake at 1 h, 171°C
Base Fluid Sulfur Compound Added (cm^ per 100 g oil)
Base Oil E (102 VI, 0.1% S) 0.1% Natural Organosulfur 100
Desulfurized Base Oil E None >2000
Desulfurized Base Oil E +1.4% cetyl phenyl sulfide 190
Desulfurized Base Oil E + 1% bis(phenylethyl) sulfide 50
Base Oil A (8 VI, 0.53%S) 0.53% Organosulfur 170
Desulfurized Base Oil A None >5000
Desulfurized Base Oil A 1% dicetyl sulfide 90
Desulfurized Base Oil A 2% dicetyl sulfide <10
Desulfurized Base Oil A 3% dibenzothiophene >5000
compositional variables constant. They observed that the TABLE 18—Relative reactivity of hydrocarbon radicals.
high temperature oxidation rate of the sulfur-free oil was Substrate Species: Relative Reaction Rate
m u c h higher than the original sulfur-containing base fluid. Radical CH3 - X X = per Hydrogen Atom
In these experiments oxygen uptake by base oil was moni- Phenyl* Alkyl 1
tored over time (hours) at 171 °C under atmospheric pressure. Phenyl* Phenyl 9
Typical data are provided in Table 17. Phenyl* Benzothiophene 14
Phenyl* 2-Thiophene 15
Table 17 illustrates that desulfurized base oils exhibit very
poor oxidation inhibition compared to the original base oil RCH2* Phenyl 65
RCH2* 2-Thiophene 210
and that certain sulfur compounds, specifically organosul-
fides, can significantly reduce the rate of oxidation at high
temperature. Sulfur-containing aromatic molecules, how-
ever, such as dibenzothiophene, did not appear to act as an- TABLE 19—Impact of basic nitrogen compounds on the oxidation
tioxidants and may actually increase the rate of oxidation of hexadecane (Cu catalyst, 0.6% butylated hydroxy toluene
slightly (data not shown). Further work reviewed by Harpp (BHT) added as an antioxidant).
et. al. [32] revealed that sulfides in themselves are not an- Effective Nitrogen RBOT Lifetime
tioxidants but rather they become active when oxidized to Compound Concentration (ppm) (min.)
— SO2, — SO3 and related organo-sulfonic acids. These au- Hexadecane (HD) 596
thors also report that thiophenes (or thioaromatics) have "no HD + 3-n-butylpyridine 10 216
stabilizing effect on hydrocarbon oil oxidation" and they 5 248
2 296
were not able to identify a molecular mechanism through
HD -1- 2,4-dimethylquinoline 9 306
which antioxidation could occur. 4.5 324
More recently, using both statistical and neured network 2 405
HD + 2-methylindole 11 501
modeling techniques, Stipanovic, Smith, and co-workers
6 516
[3,4] have shown that base oil thioaromatic content can be 0.2 578
directly correlated to an increase in oxidation and deposit HD + Carbazole 10 576
formation level observed for crankcase engine oils in the HD + Phenanthridine 10 440
ASTM Sequence HIE and VE gasoline engine tests. These ob-
servations were attributed to an increase in the rate of free
radical propagation in the engine oil at high temperature
based on data reported by Russel [33]. As shown in Table 18, Nitrogen C o m p o u n d Reactivity
the free radical hydrogen a t o m abstraction rate is m u c h Nitrogen containing molecules found in base oils can also ac-
higher for thiophenes than other hydrocarbons for at least celerate oxidation and deteriorate the useful lifetime of lu-
two types of radicals that could occur in hydrocarbon sys- bricants. More specifically, "basic nitrogen" compounds (so-
tems. As a result, it is reasonable to conclude that propaga- called proton acceptors) such as various pyridine derivatives,
tion reactions can be accelerated by the presence of thioaro- can act at very low concentrations (below 10 p p m based on
matic molecules, such as benzothiophene, although data N) in deteriorating oxidative stability [6,38,39]. Oxidation
specific to alkylperoxy radicals, of significance in hydrocar- lifetime for the straight chain paraffin hexadecane, a base oil
bon oxidation, are not readily available. "model compound," in the presence of small quantities of
The role of sulfur compounds as natureJly occurring base "basic nitrogen" are shown Table 19. The data clearly illus-
oil stabilizers has some very interesting implications. It is trate that such species can promote oxidation rate in the
well known that untreated, sulfur-free synthetic base oils, ASTM D 2272 RBOT procedure. These results illustrate that
such a polyalphaolefins, oxidize more readily in tests such as the molecular structure of the "basic nitrogen" compound in-
the Rotary Bomb Oxidation Test (RBOT;ASTM D 2272) than fluences the oxidation reaction. More specifically, Yoshida
conventional mineral oils that contain sulfur compounds. et. al [38] have found that reducing the pKb of the nitrogen
However, if appropriate antioxidants are added to both t5ês group enhances the overall rate of oxidation.
of base fluids, the PAOs typically respond with better long- In addition to these model compound studies, statistical
term oxidation stability. Severely hydrocracked, low sulfur and neural network modeling methods have demonstrated
Group II and III base oils exhibit similar behavior. that RBOT lifetimes for prototype industrial oils (hydraulic
fluids and turbine oils) also decrease with increasing base oil In engine oils, poor cold temperature fluidity can reduce
basic nitrogen content. Further, thermal sludge formation pumpability to the extent that oil stcirvation causes catas-
and oxidation onset determined by a high pressure differen- trophic engine failure. To protect against this occurrence, the
tial scanning calorimetry technique indicated a deterioration SAE J300 Engine Oil Viscosity Classification specifications
with higher levels of basic nitrogen [6]. include two ASTM tests, D 3829 and D 5293, which measure
both the high shear viscosity and pumpability, respectively,
of engine oils to assure that a motor will start and have suffi-
Olefins cient oil fluidity to assure good lubrication. A low tempera-
Although crude oils Eire generally relatively low in olefin con- ture viscosity limit is also included in the specifications for
tent [10], base oil processing techniques can introduce many geeir oils and transmission fluids. This viscosity is de-
olefins, especially at high temperatures, due to "cracking" re- termined using a very low shecir Brookfield Viscometer oper-
actions. In the presence of heat or UV light, olefins can poly- ating at —5 to —40°C, depending o n viscosity grade. The spe-
merize to form higher molecular weight products that can cific test method is described in ASTM D 2983.
color the base oil or actually cause sediment. In general,
olefins can be removed during the process of hydrofinishing
Composition/Performance Correlations for
or by clay treatment discussed above [10].
Engine Oils
Gasoline cind heavy duty diesel engine oils probably repre-
CHEMICAL COMPOSITION/LUBRICANT sent the most sophisticated lubricant formulations in terms
PERFORMANCE CORRELATIONS of physical a n d chemical requirements and, subsequently,
their additive packages are very complex. Engine oils must
As previously discussed, base oils contain a broad spectrum of provide a fluid lubricating film for sliding metal-to-metal
paraffinic, cycloparaffinic, and aromatic molecules, the dis- interfaces at high t e m p e r a t u r e s while neutralizing acidic
tribution of which varies with crude source and refinery pro- combustion gases; minimizing oxidation and corrosion; sus-
cessing. More importantly to the lubricant chemist and engi- pending insoluble combustion a n d lubricant oxidation by-
neer, each of these hydrocarbon types can exert a different products; reducing wccir and the tendency to foam; etc. Since
effect on the ultimate physical and chemical properties of the each of these characteristics can be influenced by base oil
base oil and, ultimately, the lubricant from which it is formu- composition, considerable attention has been focused on re-
lated. Table 20 illustrates the relationship between hydrocar- lating specific molecular components to engine performance.
bon type and performance for several important properties. Murtay and co-workers [1,2] were among the first to use
base oil compositional data derived from mass spectrometry
to develop statistical correlations between oxidation in the
B a s e Oil R h e o l o g y a n d C o m p o s i t i o n ASTM Sequence IIIC and HID oxidation engine tests and
The flow properties, or rheology, of a lubriccint strongly re- base oil hydrocarbon type distribution. These authors ob-
flect the composition of the base oil used in its formulation. served that a regression function including saturate content
Comparing hydrocarbons of similar molecular weight, paraf- plus total sulfur concentration predicted viscosity increase
fins (especially linear paraffins) provide the highest positive very well for a series of engine oils formulated to be API SE
contribution to base oil VI while aromatics and naphthenes, quality. In this function, higher levels of saturates and sul-
particulcirly multi-ring structures, strongly decrease VI. Base fur enhance performance. Viscosity Index edone was not
oils of high VI Eire generally preferred for lubricants because found to be a good predictor of performance for oils origi-
they provide higher viscosity at high temperatures and lower nating from different crude, sources, but it did correlate rea-
viscosities at low temperatures, provided they are properly sonably well for samples derived from a single crude. Mur-
treated to inhibit wax crystallization. In the absence of effec- ray also demonstrated that during the course of oxidation
tive pour point depression, higher VI oils containing elevated reactions, the level of both saturates and aromatics de-
levels of wax display poor low temperature fluidity as wax creased while the concentration of polcir compounds in-
crystals form network structures that Eire resistant to flow. In creased significantly. For example, in the ASTM Sequence
most cases, polymeric pour point depressant additives elimi- IIIC engine test, a SAE lOW-30 oil that was originally 74.1%
nate wax crystallization and, u n d e r these circumstances, saturates, 13.6 % aromatics, and 4.9% polars exhibited an
base oils rich in paraffins can exhibit excellent rheological end-of-test composition of 46.1% saturates, 7.9% aromatics,
properties at low temperatures. cind 33% polars.
TABLE 20—Performance characteristics of base oil components.

Base Oil Proprety ParaiBns Naphthenes Aromatics
Viscosity Index (VI) Excellent Poor-Good Poor
Low Temperature Fluidity" Poor Good Good
Low Temperature Fluidity* Excellent Good Good
Pour Point Poor Good Excellent
Oxidation/Thermal Stability Excellent Poor-Good Poor
Solvent for Additives Poor Good Excellent
"Unadditized.
''Treated with a pour point depressant.
Roby and co-workers were also successful in developing TABLE 21—Predicted engine test results for a re-refined
statistical correlations between base oil composition and per- and virgin base oils in formulated engine oils.
formance in the ASTM Sequence HID and VD gasoline en- High Average Low
gine tests [40]. For high temperature oxidation in the HID Result Result Result
Test Rating (VO/RR) (VO/RR) (VO/RR)
procedure, it was learned that no single base oil parameter
Sequence HIE
provided a good correlation to viscosity increase but a re-
Piston skirt varnish 9.21/9.34 8.92/8.95 8.63/8.7
gression equation including nitrogen content (ASTM D (10 = "Clean";
4629), olefin n u m b e r (ASTM D 460), sulfur content (ASTM D 8.9 = "Passing")
1552) and saturates (column gradient elution chromatogra- % Viscosity increase 283/219 192/163 73/65
phy) provided an excellent fit (R-squared = 0.97) to the ob- ( < 3 7 5 % = "Pass")
Sequence VE
served data. For oxidation control, high levels of saturates
Average engine varnish 5.45/5.51 4.93/5.08 4.32/4.8
and sulfur compounds were beneficial while elevated olefin (10 = "Clean";
and nitrogen levels contributed to poor performance. In the 5 = "Passing")
Sequence VD gasoline engine test, which eveJuates deposit
formation at relatively low levels of oil oxidation, the individ-
ual variables discussed above all showed good correlations measures engine oil viscosity increase as a function of soot
(R-squared values > 0.79) to varnish formation with higher level under conditions that result in very little oil oxidation,
nitrogen, olefin, and sulfur content being detrimental. Aver- and it is very sensitive to the chemical nature of the disper-
age engine varnish ratings in the Sequence VD improved with sant used in the additive package. It has been speculated that
increasing base oil saturates content, however. the strong base oil effect could be due to the impact of base
More recently, base oil effects in the Sequence HIE and VE oil solvency on the dispersant and its ability to interact with
engine tests have been studied [3,4] using Partial Least and stabilize soot particles from aggregation. Base oils with
Squares (PLS) and neural network modeling methods. These high aromatic concentration strongly solvate the dispersant
authors evaluated the engine test performance of a group of molecule and perhaps, the solvation shell inhibits the disper-
different base oils (approx. 12 oils) formulated into engine sant from properly interacting with soot. For oil ringland de-
oils using similar additive technology. For the Sequence HIE posits, evidence suggests that base oils high in saturates con-
oxidation test, viscosity increase and piston skirt varnish rat- tent are not effective in washing away deposit precursors in
ings generally improved with paraffin content while reacting the ring belt region of the piston and, as a result, deposits
negatively to high levels of multi-ring naphthenes, multi-ring form more readily. Since this mechanism could be very de-
aromatics, and thioaromatics. Total sulfur content was found pendant on additive chemistry, its universality has not been
to reduce viscosity increase and piston deposits in the Se- established. API document 1509 also details the relationship
quence HIE, consistent with its antioxidant effect discussed between base oil group and the engine testing required when
earlier. For the Sequence VE test, total sulfur, thioaromatics, base oils are interchanged in heavy duty diesel engine oil for-
and multi-ring aromatics all enhanced the formation of var- mulations. A more detailed analysis of the impact of base oil
nish deposits. composition on the performance of heavy duty diesel engine
Using the PLS modeling protocol described in Ref 3, it is oils has recently been published by Cherrillo and Huang [41].
possible to predict the engine test performance of lubricants,
assuming a c o m m o n passenger car engine oil additive tech-
B a s e Oil E f f e c t s i n I n d u s t r i a l L u b r i c a n t s
nology, using base oil compositional features as input. In this
fashion, the potential Sequence VE varnish ratings for engine Although base oil composition can play an important role in
oils formulated from a population of base oils representing defining the performance of engine oils, additive chemistry
typical U.S. production were predicted. Ratings are based on and concentration can largely overcome potential deficien-
a visual examination of a n u m b e r of engine pairts where 10.0 cies of a pEirticular basestock. Typically a 10-15% treat level
corresponds to a totally clean part, 5.0 is the m i n i m u m "pass- of dispersant/inhibitor package is added to a motor oil to con-
ing" rating, and <4.0 corresponds to a very poor engine oil trol oxidation, deposits, etc. In industrial lubricants, how-
formulation. API Group I oils gave varnish values of 5.0 or ever, formulation economics dictate very low additive treat
less. Group II oils exhibited improved varnish ratings in the levels, usually less than 2% for products such as hydraulic
range of 5.5-5.8, while Group III and IV oils provided ratings fluids, turbine oils, quenching oils, and other process fluids.
of 6-6.5. As a result, product quality is linked more directly to base oil
In a separate study, a group of re-refined oils (RR) were composition.
evaluated and, on average, predictions suggested that they The work of Murray cited above [1] also demonstrates that
would perform at levels comparable to "virgin" oils (VO) as- industrial oil oxidation lifetimes in the D 943 oxidation test
suming normeJ test-to-test vEiriability. These results are sum- a n d the D 2272 Rotary B o m b Oxidation Test (RBOT) in-
marized in Table 2 1 . creased with increasing saturate levels for 150 N oils con-
Several generalizations can be made about the role of base taining an oxidation inhibitor. Sulfur content played a minor
oil composition in heavy duty diesel engine oils where oil role, however, presumably because the inhibitor effectively
thickening due to the accumulation of soot cind piston ring- controlled oxidation. For the D 943 test, Firmstone and co-
land deposits are important considerations in several indus- workers [4] showed, using Partial Least Squares models, that
try standard tests. Base oils of comparatively high saturates increases in base oil peiraffin content, sulfur concentration,
content have been found to perform better in the Mack T-8 VI, and aniline point enhance oxidation lifetime, while cy-
engine test than oils of higher aromatic content. This test cloparafHns, multi-ring aromatics, and nitrogen content have
a negative impact. In a study by Mooken on the stability of cal device from high friction and premature weeir is depen-
turbine oils, D 943 eind D 2272 results improved with higher dent on the high shear viscosity of the lubricant and its vis-
levels of saturates and sulfur while lower concentrations of cosity-pressure coefficient [45]. Thicker lubricant films are,
aromatics and basic nitrogen were most beneficial [39]. therefore, produced by fluids exhibiting a higher a value.
The impact of evolving base oil quality toward Group II However, in the design of many fuel economy enhancing "en-
and III stocks on the performance of greases and other in- ergy conserving" lubricants, a less viscous film is desired
dustrial oils has been recently reviewed [42]. For base oils since mechanical energy can be wasted if the film is too ro-
containing only negligible quantities of aromatic compounds bust. In these cases, lubricants of lower a are favored. In
and essentially no heteroatomic species, oxidation stability other applications such as Continuously Variable Transmis-
was found to be influenced positively by paraffin content and sions (CVTs), where the fluid must provide high levels of trac-
negatively by polycyclic naphthenes. tion, a very high a is needed [46].
Based on the importance of a in the design and application
of lubricants, effort has been focused on determining the re-
Influence of Base Oil Composition o n the lationship between base oil structure and its response to high
Viscosity-Pressure Coefficient pressure [44]. Figure 2 illustrates the magnitude of viscosity
increase that can be expected for typical lubricant base oils,
Most organic fluids, including lubricant base oils, exhibit a over pressure ranges not uncommon in certain mechanical
reversible viscosity increase with the application of high devices, plotted by API base oil groups. These data were
pressure due to the molecular mobility restrictions imposed recorded using a falling body viscometer [47].
by the forces being exerted [43]. This phenomenon is espe-
In general, Group IV (polyalphaolefin) fluids provide the
cially important for lubricants, since in most mechanical ap-
lowest increase in viscosity with increasing pressure, fol-
plications, films of fluid are compressed between sliding sur-
lowed by Group III, Group I, Group II, and finally napthenic
faces under very high loads. The degree to which a fluid
base oils. In this specific example, a statistical analysis [48]
thickens under high pressure is given by the following ex-
revealed that the Group III and IV oils provided the lowest a
pression [43,44]:
values because these products were very high in paraffin con-
log Tjl 7)0 = P a where: T) = Viscosity at pressure P tent (>60%), while Group I and II products provided inter-
mediate performance because they contained less paraffins
Tjo = Viscosity at atmospheric and higher levels of naphthenic ring compounds (>40%).
pressure Since the cycloparaffin ring structure is sterically very bulky,
P = Pressure it is especially sensitive to applied forces and contributes sig-
nificantly to increasing the viscosity-pressure coefficient for
a = Viscosity — Pressure base oils. Planar aromatic rings appear to pack with less dif-
Coefficient ficulty. Under pressure, paraffins are easily compressed and
In this expression, if pressure is given in MPa (megaPascals), can actually be induced to crystallize if pressures are suffi-
the viscosity-pressure coefficient for a base oil is t5îcally ciently high. In the design of CVT fluids, molecules are syn-
9-15 GPa~'' The importance of a in the process of lubrication thesized to optimize their steric bulkiness [46].
is multifold. In the so-called hydrodynamic regime of lubri- A number of other procedures are also available to calcu-
cation, the film thickness of fluid that protects the mechani- late the viscosity-pressure coefficient for base oils from com-
Group I -*- Group 11 -A- Group III -¥r Group IV —- Naphthene
100 200 300 400 500 600

Pressure (MPa)
FIG. 2—Viscosity - pressure relationships for base oils at 100°C (nominaiiy 4 est at
100°C, 1 atmosphere pressure).
positional data and/or other bulk fluid properties [44,49]. and solubilize this plasticizer is an important consideration.
Roelands [44] has shown that the viscosity-pressure relation- In other cases, certain base oil molecular fractions can actu-
ship for base oil can be predicted solely from atmospheric ally dissolve into the rubber matrix causing it to swell. Al-
viscosity (TJO) a n d a knowledge of the percentage of though most lubricant base oils are relatively inert in their
carbon atoms in a aromatic ring structure (CA) and the per- ability to deleteriously interact with a variety of elastomeric
centage of naphthenic (cycloparaffinc) carbons (Cn). John- materials commonly in use, high aniline point products, such
ston determined that the pressure-viscosity coefficient could as Group IV polyalphaolefin (PAO), can cause elastomer
be calculated from ambient pressure fluid density and the cracking after long periods of exposure at high temperatures
viscosity/temperature relationship (specifically viscosity at due to a loss in plasticity. In many cases, a so-called seal swell
two temperatures is needed) [49]. More recently, Spikes and agent can be successfully added to PAO to maintain good seal
co-workers have shown that the thickness of a lubricant film characteristics. At the other extreme, low aniline point naph-
under conditions of elastohydrodynamic lubrication (EHD) thenic base stocks can cause seals to swell excessively also
can be related to a by the following expression obtained from creating operational problems. As a result, for any base oil
a high-speed ultrathin film interferometry technique [45]: system, rubber compatibility should be evaluated carefully in
formulating a lubricant product.
h oc U 0-*^ 7, 0*" a 0 "
where: h = film thickness measured by interferometry, U is

the mean entrainment speed, and TJ is the low pressure dy- Biological P r o p e r t i e s of B a s e Oils
namic viscosity.
Since lubricants can come in direct contact with humans in
some applications, the biological toxicity of base oils is a con-
B a s e Oil S o l v e n c y E f f e c t s cern especially for those products containing high concen-
trations of polycyclic aromatic hydrocarbons (PAHs). These
In any lubricajit formulation, base oils are required to dis- compounds have been found to be mutagenec and carcino-
solve polar additive compounds and to ultimately disperse genic axid the International Agency for Research on Cancer
polar oxidation products that are formed during use. For this has classified 18 PAHs as cancer causing [50 and references
reason, the so-called aniline point of a base oil can be a criti- therein]. From a molecular structure perspective, these 18
cal parameter in defining its compatibility with additives and molecules each have in common a 4-6 fused aromatic ring
the byproducts of use. Aniline point is determined by ASTM system and a so-called 3-sided concave "bay region" similar
D 611 a n d represents the t e m p e r a t u r e at which aniline, in structure to the geometries shown for triaromatic and ter-
(C6H5MNH2), a polar aromatic compound, becomes miscible taaromatic molecules shown in Table 13.
with a hydrocarbon base oil. At low temperatures, base oil Probably the most well established method to assess the
and aniline are not miscible but as temperature is raised they potential mutagenicity/carcinogenicity of base oils is the IP
become a single phase at the aniline point, commonly ex- 346 Method that uses dimethylsulfoxide (DMSO) extraction
pressed in °F. In general, base oils of low aromatic/high satu- to isolate PAHs. By correlation to mouse skin painting stud-
rates content have high aniline points (>230°F, 110°C), con- ies, it was determined that base oils exhibiting DMSO-ex-
ventional solvent refined base oils have m o d e r a t e aniline tractable levels exceeding 3 wt % should be considered car-
points (200-215°F, 93-102°C) and naphthenic base oils have cinogenic [50]. F u r t h e r work by Nessel a n d co-workers
a very low aniline point (<150°F, 65°C). As a result, aniline indicated that a level of 5% IP 346 extractables might be a
point can be viewed as a sensitive index of the "solvent more appropriate target [50]. This group also developed a
power" of a base oil t o w a r d polymeric VI improvers, NMR-based method to characterize the concentration of hy-
organometallic friction modifiers and anti-wear agents, de- drogen atoms in the so-called "bay region" of PAHs and they
tergents, anti-oxidants, and other molecules. In severe cases, have compared these data to IP 346 results and t u m o r inci-
additives soluble in low to medium aniline point base oils dence results obtained from skin painting studies as shown in
might experience limited solubility in high aniline point Table 22. Based on these results, Nessel proposes that a limit
products. In these cases, improved solubility can be attained of 1500 p p m of bay region hydrogen atoms be established as
by adding a small fraction of a very polar synthetic basestock a limit of carcinogenicity [50]. NMR enjoys the advantage of
such as polyolester or an alkylbenzene to the high aniline being much faster and less expensive than other methods of
point base oil thereby increasing its "solvent power." assessing the toxicological effects of base oils.
Due to concerns over the potential toxicity of aniline, some Unpublished results generated by the author indicate that
effort has been devoted to eliminating this procedure. It has the IP 346 method correlates reasonably well to the multi-
been found using chemometric techniques that proton and ring aromatic content obtained from ASTM D 3239 for rela-
'^C-NMR spectral data can be correlated to aniline point with tively light to m e d i u m viscosity base oils (70-150N or 3-5 cSt
a high degree of accuracy, possibly creating an opportunity at 100°C). However, it underestimates the aromatic content
to use NMR directly as an index of base oil solvency [48]. of m e d i u m to heavy grades (320-850N). Presumably the
DMSO extraction procedure of IP 346 is not effective in solu-
bilizing higher molecular weight aromatics. It was not estab-
Rubber Compatibility lished, however, if these heavier aromatics promoted a mu-
In many service applications, lubricant products come in tagenic or carcinogenic response in animal tests. It is
contact with rubber (elastomer) seals, gaskets, o-rings, and possible that their relatively large size restricts their molecu-
other components. Since most elastomers include a plasti- lar mobility and ability to be adsorbed into the tissue of ani-
cizer to soften the material, the ability of a base oil to remove mals.
TABLE 22—Base Oil Carcinogenicity: A comparison of techniques.

NMR - Bay Region IP 346 - % DMSO Tumor
Base Oil/Petroleum Stream Hydrogens (ppm) Extractables Incidence - %
Extracted/Hydrotreated paraiEnic oil Up to 39 <1.0 0
Extracted/Nonhydrotreated paraffinic oil Up to 86 <1.4 0
Hydrotreated naphthenic oil 100-600 2.5-6 0
Straight-run hydrotreated gas oil 100-200 5-6 0
Processed paraffinic blend 1500 5-6 36-54
Unrefined vacuum distillate 1500-3200 5-12 20-60
Vacuum distillate aromatic extract 3800-9000 12-15 60-90
Catalytically cracked gas oil 3800-5600 16-43 4-40+
TABLE 23—Joint ASTM/IP lubricant test methods. are: Institute of Petroleum: www.petroleum.co.uk, ASTM In-
ASTM Test IP Test ternational: www.astm.org
Number Number Method Description
D 445-97 71 Kinematic viscosity cmd
cal'c of dynamic viscosity CONCLUDING REMARKS
D 611-82 2 Aniline point determination
D 2270-93 226 Cal'c of viscosity index from
kinematic viscosity It was the objective of this chapter to demonstrate that hy-
D 4629-96 379 Organically bound nitrogen drocarbon base oils are a complex collection of molecules
whose diverse individual properties combine to determine
the performance characteristics of a formulated lubricant.
Biodegradability Examples and references have been provided that support
this objective and serve to highlight the overall importance
The ability of a lubricant to degrade naturally in the environ- and complexity of base oil technology as an integral part of
ment is becoming an increasingly important property that is the lubricant industry.
directly related to the composition and molecular weight of In addition, an effort was made to highlight those anal34i-
the base oil employed in its formulation [52,53]. Currently, cal techniques and predictive modeling procedures that en-
several standcird experimental protocols are widely utilized able the chemical composition of a base oil to be determined
to evaluate the biodegradability of a lubricant: ASTM D 5864 and then exploited to predict how it will behave in actual
(fully formulated lubricants), D 6006 (hydraulic fluids), and product applications. Although further research and method
the European method CEC-L-33-T-82. Voltz has shown that development is still needed, a future can be envisioned where
hydraulic fluids based on hydrocarbon mineral oils only de- actual engine tests, bench oxidation tests, or biological assays
grade to an extent of 40% after 25 days in the CEC test while are not needed to confirm the quality/toxicology of a base oil
synthetic, ester-based fluids are degraded almost entirely relying, instead, on predictive modeling.
(>90%) [53]. Synthetic hydrocarbons and polyethylene gly-
cols were found to display intermediate behavior with maxi-
m u m degradation levels of 70% and 55%, respectively.
STANDARDS
In addition to composition, the size of a base oil molecule
can influence its biodegradability. Weller has reported using ASTM IP
the CEC protocol, that 2 and 4 cSt PAOs degrade at reason- No. No. Method Description
ably high levels, 75% and 65% respectively, while 6, 10, and D 92-01 36 Flash and Fire Points by Cleveland
100 cSt PAO samples degraded less than 20% [54]. Similar re- Open Cup
sults have been reported for other types of base oil suggesting D 93-00 34 Flash Point by Pensky-Martens
a limiting molecular size exists above which an organism Closed Cup Tester
cannot adsorb and biodegrade hydrocarbon molecules. D 97-96a 15 Pour Point of Petroleum Products
D 189-01 Conradson Carbon Residue
D 297-92 API Gravity
INTERNATIONAL STANDARDS D 445-97 71 Kinematic Viscosity and Cal'c of
Dynamic Viscosity
As shown in Table 23, many of the ASTM experimental test D 482-00 Ash in Petroleum Products
procedures outlined in this chapter have analogs in the Insti- D 524-00 Ramsbottom Carbon Residue
tute of Petroleum (IP) Standard Test Methods published in D 611-82 2 Aniline Point Determination
the UK. Several examples are given below where the ASTM D 892-01 146 Lubricant Foaming
and IP organizations share a single test method: in m a n y D 943-99 157 Oxidation of Inhibited Oils
other cases, the ASTM and IP have developed methods to de- D 1492-96 Bromine Index
termine the same lubricant property (sulfur content, low D 1500-98 ASTM Color
temperature viscosity, base oil aromatics, etc) through the D 2007-01 Aromatics, Saturates, Polars in
application of somewhat different procedures. Each organi- Base Oil
zation maintains an web site with extensive capabilities of D 2008-91 UV Absorbance of Petroleum
searching for specific methods. The addresses for each site Products
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Lubricant Base Oils: Correlations to Sequence VE and IIIE
tion
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D 2622-98 Sulfur by X-Ray Fluorescence
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D 3829-93 Borderline Pumping Temperature
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D 4530-00 Carbon Residue-Micro Method plications," SAE Publication 981405, Society of Automotive En-
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MNL37-EB/Jun. 2003
Hydrocarbons for Chemical

and Specialty Uses
Dennis W. Brunett, ^ George E. Totten, ^
and Paul M. Mattlock^
ETHYLENE (C2), PROPYLENE (C3), AND THE C4 PRODUCTS (butene- DISCUSSION

1, butene-2, isobutylene and 1,3-butadiene) are monomers of
enormous industrial importance. Among the numerous uses Commercial Production of Synthetic
of ethylene are the synthesis of ethylene glycol, which is used Hydrocarbons
for antifreeze formulation, and the production of polyethy-
lene terephthalate. Ethylene is also used for polyethylene Basestocks for Synthetic Hydrocarbon Production
manufacture and as a co-monomer in the production of var- The unsaturated synthetic hydrocarbons such as ethylene,
ious synthetic rubbers. propylene a n d butenes m a y be produced either by steam
The primary method for the production of ethylene and cracking saturated hydrocarbons (ethane, propane, Eind bu-
other light olefins is steam cracking. Steam cracking is per- tane), or by steam cracking feedstocks such as virgin crude
formed both on liquefied petroleum gases (LPGs) and on liq- oil fractions (naphtha, kerosine, and gas oil). In addition,
uid feedstocks. LPGs include ethane, propane, and/or butane. ethylene may also be produced from crude oil directly [1].
Liquid feedstocks are generally paraffinic or naphthenic and Different types of feedstocks may be used for the produc-
include n a p h t h a and petroleum condensates. When these tion of synthetic hydrocarbons. The primary feedstocks are
feedstocks are thermally "cracked," the resulting product the "gas liquids." Gas liquids include ethane, propane, and
stream contains a complex mixture of hydrocarbon com- butane, all sepeiration products from natural gas. The second
p o u n d s . The process challenge is to separate the various class of feedstocks is the refinery off-gases. Refinery off-gases
product components at the desired purity. are mixtures of hydrogen, m e t h a n e , ethylene, ethane,
The purity of the individual products is set by their ulti- propane, a n d others. A typical off-gas contains approxi-
mate use. For example, some polymerization processes are mately 20 mol% ethane, 16 mol% ethylene, 3.6 mol% C3
especially sensitive to particular contaminsLnts in monomer/ derivatives, with the remaining components being hydrogen,
co-monomer feeds. Some of these impurities poison cata- methane, and acid gases. Off-gases are obtained from refin-
lysts or reduce their efficiency. Others may degrade the ery operations.
physical or performance properties of the polymer prod- Liquid feedstocks include various petroleum fractions de-
ucts. Because olefin purity is so important to downstream rived from crude oil processing (naphtha, kerosine, atmo-
processing, it is essential that producers and consumers spheric gas oil and vacuum gas oil) as well as liquid conden-
alike utilize a standard set of well-tested and widely ac- sates from natural gas processing (natural gasolines) and
cepted antdytical procedures to measure and control the natural gas condensates such as Algerian and Brega conden-
quality of these chemicals. The ASTM D.02.0D Subcommit- sates. They are defined by their boiling points. The approxi-
tee on Hydrocarbons for Chemical and Specialty Uses has mate boiling ranges of the petroleum fractions are provided
developed such a series of analytical standards for the in Table 1 [2].
petrochemical industry. Raffinates are residues from extraction processes such as
In this chapter, a brief overview of the most common infor aromatics recovery. These feedstocks t3îcally possess a
dustrieJ production methods of C2, C3, and C4 synthetic hy- broad range of compositions and boiling ranges.
drocarbons is provided. Typical purity standards and com- The composition of the crude oil fractions varies with the
m o n classes of impurities are also discussed. The chapter source as shown in Table 2 [1]. The type of feedstocks will
also includes various types of ASTM analytical procedures affect the composition of the product being produced. Gen-
and the separation principles involved. erally, the heavier the feedstock, the greater the amount of
by-products. In addition to feedstock composition, the com-
position of the product stream resulting from steam cracking
is also d e p e n d e n t on t e m p e r a t u r e , residence time, and
steam/hydrocarbon ratio. The optimization of the residence
time, coil outlet temperature and coil outlet pressure (crack-
' The Dow Chemical Company, 2501 North Brazosport Blvd., ing severity) for a given feedstock are the most critical vari-
Freeport.TX 77541. ables in determining the product mix.
^ G. E. Totten & Associates, LLC, PO Box 30108, Seattle, WA 98103.
^ The Dow Chemical Company, 771 Old Saw Mill River Road, Tarry- The second most frequently used method of ethylene pro-
town, NY 10591. duction is recovery from refinery gas. Alternate methods are
185
TABLE 1—Approximate boiling point mined based on the product mix required. Table 3 provides a
ranges for different liquid feedstocks. list of the different types of feedstocks typically used in steam
Boiling Range crackers for the production of ethylene.
Liquid Feedstock (°F)
Naphtha Ethylene Production
Full range 80-430
Light 80-300 Dependency of Reaction Product and By-Product Complexity
Heavy 250-430 on Feedstock Structure—Ethylene may be produced commer-
Kerosine 400-500 cially by thermal cracking of hydrocarbons, recovery from re-
Atmospheric gas oil fineiy off-gas, recovery from coke-oven gas, or dehydration
Light 400-680
of ethanol. In practice, almost all of the high purity ethylene
Heavy 600-800
Vacuum gas oil 800-1100 produced in the U.S. is the result of steam cracking. Table 4
Gas condensates 80-530 [3] lists various ethylene manufacturing facilities a n d the
method of ethylene generation.
In the steam cracking process, steam is added to the hy-
TABLE 2—Typical composition of feedstocks used for drocarbon feed stream to:
synthetic hydrocEirbon production. 1. Reduce the partial pressure of the hydrocarbon
Component Naptha Kerosine Gas Oil 2. Reduce the high-temperature residence time
Origin Kuwait North Sea Kuwait, 3. Reduce coke formation in the reactor. (Carbon monoxide
North Sea and hydrogen are formed by reaction of steam with carbon
Density (g/mL) 0.724 0.801 0.839
at the high temperatures encountered in the reactor. This
Sulfur content (mass %) 0.04 0.03 0.1
ASTM boiling range (°F) is the famous "water-gas" reaction.)
IBP 28 180 220 Ethylene product yield, like that of other synthetic hydro-
50% 121 206 290 carbons, correlates with the carbon/hydrogen ratio of the
EP 175 242 380
BMCI 29.7 27.7 components in the feedstock being steam cracked. Generally,
PONA analysis (mass %) as the feedstock becomes heavier (which is typically accom-
Paraffins 72.3 50.9 41.8 panied by increasing amounts of naphthenes and aromatics
Olefins and a corresponding lowering of the C/H ratio), the reaction
Monocyclic naphthenes 16.7 15.8 19.2 products become heavier and more aromatic, while conver-
Polycyclic naphthenes 10.5 14.1
Monocyclic aromatics 11.0 14.9 20.9
sion yields to lighter olefins decrease.
Polycyclic aromatics 7.9 4.0 E t h a n e m a y be produced by Ci chemistry by thermal
cracking of methane at 1000°C as shown in Scheme 1 [4].
This is not the preferred commercial route to ethane, how-
ever, because the bond dissociation energy of a C—H bond of
known using feed streams from coal, ethanol, coke oven gas 93.3 kcal/mol is considerably higher than a C—C bond-disso-
and other sources, but these are rarely used. Therefore, S5T1- ciation process of 71.0 kcal/mol [9], making this an energy in-
thetic hydrocarbon p r o d u c t i o n from these alternative efficient process.
sources will not be discussed in detail here.
The value of BMCI shown in Table 2 refers to the Bureau CH4 -» CHs*
of Mines Correlation Index. BMCI is used to estimate the
2CH3* -^ CH3 - CH3
amount of ethylene in feedstocks. Higher numbers indicate
m o r e aromatic character. BMCI is calculated from the S c h e m e 1—Formation of ethane from methane.
following equation:
Ethylene m a y be produced by the dehydrogenation of
48640 ethane as shown in Scheme 2. This reaction process, like all
BMCI = VABP + 456.8 [1] thermal cracking processes, is accompanied by side reac-
473.7(^.5)
tions, which lead to the formation of aromatic and naph-
Where: VABP is the volume average boiling point (°K) and dis thenic hydrocarbon ring structures.
is the density in g/mL at 15°C.
The BMCI value estimates the extent of naphthenic and aro- CH3 - CH3 ^ CH2 = CH2 + H2
matic content of a hydrocarbon feedstock emd is calibrated for S c h e m e 2—Ethylene formation by dehydrogenation of
hexane to yield 0% and pure benzene to yield 100%. ethane.
Synthetic hydrocarbon feedstocks are typically low in sul-
fur content. High sulfur feedstocks may be used, but these
TABLE 3—Selected feedstocks for synthetic hydrocarbon
materials produce larger quantities of acid gases, which must
production.
be removed from the resulting products. Low chloride feed-
stocks should be used as chlorides may cause irreparable Gases or Gas Liquid Products Liquid Feedstock
damage in the furnace tubes due to chloride stress cracking Ethane Naphtha
and corrosion. Propane Kerosine
Butane Raffinates from extraction processes
It is possible to obtain any of the synthetic hydrocarbons Refinery off-gases Atmospheric gas oil
from any feedstock by steam cracking. Higher paraffinic con- Vacuum gas oil
tent materials yield higher conversion to short-chain olefins. Natural gasoline
The choice of feedstock for a steam cracker is typically deter- Gas condensates
CHAPTER 8: HYDROCARBONS FOR CHEMICAL AND SPECIALTY USES 187
T A B L E 4 — S u m m a r y o f ethylene process m e t h o d s u s e d ;in t h e U n i t e d States.
PRODUCT COUNTRY COMPANY SITE ROUTE TECHNOLOQY LICENSOR START
ETHYLENE USA BPCHEM. AVJimx HYD-CARBON STCRACKIN NA. 1975
ETHYLENE USA BP CHEM. ALVIN/TX HYD-CARBON ST CRACKIN BRAUN 1977
ETHYLENE USA COND.VISTA LAKECWLA HYD-CARBON ST CRACKIN N.A. 1^8
ETHYLENE USA CPCHEM OEDAR BAYO HYD-CARBON STCRACKIN LUMMUS 1977
ETHYLENE USA CPCHEM PORTAR/TX HYD-CARBOI ST CRACKIN LUMMUS 1970
ETHYLENE USA CPCHEM SWEENY/TX HYD-CARK)N STCRACKIN N.A. • 1957
ETHYLENE USA CPCHEM SWEENYm( HYD-CARBON STCRACKIN N.A. 1967
ETHYLENE USA CPCHEM SWEENY/TX HYD-CARBON STCRACKIN BRAUN 1978
ETHYLfeNE USA CPCHEM SWEENY/TX HYD-CARBON STCRACKIN BRAUN 1991
ETHYLENE USA DOW FREEPORT/T HYD-CARBON STCRACKIN DOW 1972
ETHYLENE USA DOW FREEPORT/T HYD-CARBON ST CRACKIN BRAUN 1994
ETHYLENE USA DOW PLAQUEMINE HYD-CARBON ST CRACKIN HA. 1972
ETHYLENE USA DOW PUQUEMINE HYD-CARBON ST CRACKIN DOW 1980
ETHYLENE USA DOW SEADRIFT/TX HYD-CARBON STCRACKIN N.A. 1957
ETHYLENE USA DOW TAFT/U HYD-CARBON STCRACKIN LUMMUS• 1967
ETHYLENE USA DOW TAFT/U HYD-CARBON STCRACKIN LUMMUS 1978
ETHYLENE USA DOW TEXAS CITY/rx HYD-CARBON STCRACKIN N.A. 1969
ETHYLENE USA DUPONT ORANGE/TX HYD-CARBON STCRACKIN LUMMUS 1967
ETHYLENE USA EQUISTAR CHANNELVIE HYD-CARBON STCRACKIN UMIMUS 1976
ETHYLENE USA EQUISTAR CHANNELVIE HYD-CARODN ST CRACKIN LUMMUS 1977
ETHYLENE USA EQUISTAR CHOC.BAYOU HYD-CARBON ST CRACKIN N.A. 1980
ETHYLENE USA EQUISTAR CLINTON/IA HYD-CARBON ST CRACKIN KELLOGG 1^8
ETHYLENE USA EQUISTAR CORPUS/TX HYD-CARBON STCRACKIN S&W 1980
ETHYLENE USA EQUISTAR LfiPORJEfTX HYD-CARBON ST CRACKIN KELLOGG 1991
ETHYLENE USA EQUISTAR LAKECH/LA HYD-CARBON STCRACKIN N.A. 1971
ETHYLENE USA EQUISTAR MORRIS/IL HYD-CARBON STCRACKIN LUMMUS 1972
ETHYLENE USA EXXONMO.CH BATON R/LA HYD-CARBON STCRACKIN LUMMUS 1972
ETHYLENE USA EXXONMO.CH BAYTOWN/TX HYD-CARBON STCRACKIN KELLOGG 1979
ETHYLENE USA EXXONMO.CH BAYTOWN/TX HYD-CARBON STCRACKIN EXXON 1997
ETHYLENE USA EXXONMO.CH BEAUMON/TX HYD-CARBON STCRACKIN N.A. 1961
ETHYLENE USA EXXONMO.CH HOUSTOWrX HYD-CARBON ST CRACKIN N.A. 1978
ETHYLENE USA FORMOSA PL POINT CX5MF/TX HYD-CARBON ST CRACKIN KELLOGG 1994
ETHYLENE USA FORMOSA PL POINT C»MF/TX HYD-CARBON ST CRACKIN KEUOGG 2001
ETHYLENE USA HUNTSMANC ODESSAAJS HYD-CARBON STCRACKIN N.A. 1965
ETHYLENE USA HUNTSMANC PORTAR/TX HYD-CARBON STCRACKIN S&W 1979
ETHYLENE USA HUNTSMAN C PORTNECHE HYD-CARBON STCRACKIN N.A. 1978
ETHYLENE USA JAVELINAC CORPU^TX RFRY-QAS ETH RECOV N.A. 0
ETHYLENE USA SHELL CHEM DEER PA/rX HYD-CARBON ST CRACKIN KELLOGG 1978
ETHYLENE USA SHELL CHEM DEER PA/rX RFRY-GAS N.A. N.A. 0
ETHYLENE USA SHELL CHEM NORCO/LA HYD-CARBON STCRACKIN KELLOGG 1975
ETHYLENE USA SHELL CHEM NORCO/U HYD-CARBON STCRACKIN KELLOGG 1981
ETHYLENE USA SHELL CHEM NORCO/LA HYD-CARBON STCRACKIN N.A. 2000
ETHYLENE USA SUNOCO CH. BRANDENBUR HYD-CARBON STCRACKIN N.A. 1952
ETHYLENE USA SUNOCO CH. CLAYMONT/D HYD-CARBON ST CRACKIN N.A. 1961
ETHYLENE USA TEXAS EAST LONGVIE/TX HYD-CARBON STCRACKIN KELLOGG 1974
ETHYLENE USA WESTLAKECA CALVERT CI HYD-CARBON STCRACKIN BRAUN 1964
ETHYLENE USA WESTLAKEPC LAKECHAA HYD-CARBON ST CRACKIN KELLOGG 1991
ETHYLENE USA WESTLAKEPC LAKECHflJ^ HYD-CARBON STCRACKIN LUMMUS 1997
ETHYLENE USA WILLIAMS 0 GEISMAR/LA HYD-CARBON ST CRACKIN LUMMUS 1968
The structural complexity of the product stream increases Additional reaction processes shown in Scheme 6 were
with the carbon chain length of the feedstock. This is illus- proposed for temperatures greater than 800°C [11].
trated by the thermal cracking of propane to jdeld ethylene
a n d propylene shown in Scheme 3 [15]. The first two reac- C2H3* -> C2H2 + H»
tions in Scheme 3 yield the primary products [5,6]. Fair pro- C2H4 <-> C2H2 + H2
posed that butenes and methane were the most probable de-
composition products [15]. C2H2 + C2H4 —> condensation products + CH4
C3H8 -^ C2H4 + CH4 40% C2H4 -^ carbon black + H2

S c h e m e 6—Âdditional ethane thermal decomposition re-
C3H8 -^ C3H6 + H2 36%
action processes occurring above 800°C.
C3H8 -^ 14C4H8 + CH4 10%
Laidler determined the reaction mechanism for the forma-
C3H8 -^ VzCjUe + Yi C3H6 + ^CH4 14%
tion of ethane from the thermal decomposition of propane
S c h e m e 3—Ethylene formation from propane. shown in Scheme 7 [12]. Laidler proposed that only the H»,
CH3» and CsH?* radicals are involved in the chain propagation
The primary thermal cracking reaction products from n- steps and that C2H5», formed by ethane decomposition, is not
butane and i-butane are shown in Scheme 4 [8]. It was shown regenerated. Termination occurs by methyl and propyl radical
by Fair that no ethylene is formed from the branched sub- recombination or by the recombination of two methyl radicals.
strate, t'-butane [8].
n - C4H10 -^ CH4 + C3H6 C3H8 -> CH3» + C2H5»
n - C4H10 -^ C2H6 + C2H4 C2H5' + CjHg ^ C2H6 + C3H7*
n — C4H10 —> H2 + n — C4H8 H» + C3H8 ^ H2 + C3H7»
n - C4H10 ^ H2 + 2C2H4 CH3» + CjHg ^ CH4 + C3H7*
i - C4H10 -^ CH4 + C3H6 C3H7* -^ CH3» + C2H4
/ - C4H10 -^ H2 + i - C4H8 C3H7« ^ H» + C3H6
S c h e m e 4—Primary reaction products formed by thermal CH3* + C3H7* -^ CH4 + C3H8 or CH3» + CH3* -^ C2H6
cracking of n-butane and i-butane. C3H7* + C3H7* -^ C S H M or C2H6 + CjHg
Thermal Cracking Reaction Mechanism—Hydrocarbon ther- S c h e m e 7—Laidler mechanism of the thermal decomposi-
mal cracking reactions have been studied in detail for many tion of propane.
years [5,7,9-13]. The Kalinenko cmd Brodski reaction mech-
anism for the thermal decomposition of ethane below 800°C The mechanism of formation of ethane from the thermal
is provided in Scheme 5. decomposition of butane [13] and higher alkanes [15] have
also been studied but will not be discussed here.
C2H6 ^ 2CH3» There are n u m e r o u s reactions involved in hydrocarbon
H» + [C2H6, CH4, C2H4, C3H8, C4H10] -> H2 thermal decomposition. In the absence of equilibrium pro-
cesses, the initial chain scission reaction of the hydrocarbon
+ [C2H5», CH3», CzHj*, C3H7», C4H9*} substrate is unimolecular. The primary decomposition prod-
CH3» + [C2H6, H2, C2H4] -^ CH4 + [C2H5», H», CzHj*] ucts lead to olefins and by-products. Activation energies for
thermal decomposition of hydrocarbons vary from 70-79
CjHs* + [H2, CH4, C2H4] ^ C2H6 + [ H», CH3», C2H3»] cal/g-mol at 500-1000°C [16].
C2H3* + [H2, CH4, C2H6} ^ C2H4 + [ H», CH3», CzHs*] Thermal decomposition of propylene is also unimolecular
with reported activation energies varying from approxi-
CH3» + C2H5* <-> C3H8 mately 59-67 cal/g-mol [5,7,17-19]. Reaction mechanisms
2C2H5* <-> C4H10 and kinetics have been reported for other potential ethylene
feedstocks including; propylene [17,20], n-butene [17], n-bu-
C2H3« + [C2H5», CH3», C2H3»] ^ [C4H8, C3H6, C4H6 } tane [8,17,20,21], j-butane [8,17,20], n-butylene [20], and i-
C2Hs» -^ C2H4 + H» butene [17].
Commercial Production of Ethylene—Steam cracking is the
C2H5* -t- C2H4 O C4H9*
most common method used to produce ethylene. The desired
C4H9» <^ C3H6 + CHj* feedstock is diluted with steam and passed through a high-tem-
perature furnace. There are numerous patented designs em-
C2H3» + C2H4 ^ C4H7*
ploying vertical or horizontal gas-fired tubes (direct heating),
C4H7* -^ H» + C4H6 fluidized bed heated tubes (indirect heating), and other heat
sources. Figure 1 provides a schematic illustration of a steam
C4H10 -> CH3» + C3H7* cracking unit used to produce ethylene. The reaction products
S c h e m e 5-Kalinenko and Brodski ethane thermal decom- and yields are controlled by the feedstock, cracking tempera-
position reaction mechanism (less than 800°C). ture, residence time, and other plant-specific variables.
Example of Front End Depropanizer/Front End Reactor Process
Compression Acid Gas

> Quench • Dryers
Removal
r: Fuel Oil Product

*• Pyrogasoline Product H2. CH4.
Chilling Secondary Acetylene

Train Dryers Compression Depropanizer
Reactors
C-4+
(H2, CH4)
Ethylene Ethylene Ethylene
_w Off-Gas Refiigeration " Product
Recovery
Demethanizer Deethanizer I C-2 Splitter

Propylene
Product
r prude C-4
Product
C-2's, C-3's C3,C3=,MA, PD

-*\ C-3 Splitter T} Pyrogasoline
Product
Ethane Propane
Recycle Recycle
FIG. 1—Schematic illustration of a steam-cracking unit used for the production

of ethylene.
The reaction is quenched (stopped) by cooling the product from the propylene in the same reactor as acetylene if the
stream rapidly to about 600°F (315°C), a temperature where cracked gas is first "depropanized" rather than "de-etha-
olefinic products are typically stable. The cooling process is nized." The stream containing Cj to C3 hydrocarbons is then
performed through a heat exchanger or by coinjection with sent to the reactors, followed by various distillations for pu-
water or oil. rification of both ethylene and propylene. The C4 and heav-
The by-products formed during ethylene synthesis by ier material is generally not hydrogenated, but simply dis-
steam cracking include: tilled after the C3 and lighter material is removed. There are,
1. Acetylene—The a m o u n t of acetylene that is formed de- however, some facilities that hydrogenate the raw gas stream
pends on the feedstock a n d cracking severity. Although after removal of the heavier components in the quench sys-
acetylene can be isolated in high purity, it is usually con- tem. Methylacetylene and propadiene are typically of very
verted to ethylene. This is performed over a catalyst. Cata- low concentrations and are typically not isolated. However,
lyst selectivity is very important. If the catalyst is too active they can be isolated and sold as welding gases.
ethane will be produced not only from the hydrogenation 4. Butadiene andButenes—1,3-Butadiene is produced by dis-
of the acetylene but also some of the ethylene (negative se- tillation of the crude C4 material from the mixture fol-
lectivity) yielding a net loss of ethylene production. Be- lowed by solvent extraction of the m o n o m e r . In North
cause acetylene cannot be distilled out of the ethylene, hy- America, butadiene is derived from the steam cracking of
drogenation is the preferred technique for removal. LPGs or liquid feeds, followed by extractive distillation of
During the hydrogenation process, a liquid product, green the crude C4 cut of the cracked gas.
oil, is produced composed of hydrocetrbons increasing in 5. Pyrogasoline—In ethylene production, one of the by-prod-
chain length by multiples of 2. This material must be re- ucts is called pyrogasoline, which is commonly known as
moved because of the possibility of downstream fouling in "pyrolysis gasoline" or "pygas." The lightest components in
low temperature portions of the distillation process (de- this stream are the C5 compounds, which include isoprene
methanizer, C2 splitter, and cold train). This green oil is and piperylene. Cyclopentadiene is dimerized in this pro-
typically returned to the process mixed with the fuel oil cess and later recovered as dicyclopentadiene. Pyrolysis
stream also produced in the cracking process. gasoline is used as a feedstock in C5 S3Tithetic hydrocarbon
2. Propylene—Propylene is also produced by hydrocarbon py- production. (The subject material for this chapter is limited
rolysis (steam cracking or catalytic cracking). Other meth- to C2, C3, and C4 synthetic hydrocarbons.) Pjrolysis gasoline
ods are used reirely. Some processes upgrade refinery ma- is also the primary feedstock for the extraction of benzene.
terial to a more pure, polymer grade, but the production The total product stream from the cracking process is pu-
process still occurs in a refinery. The third m e t h o d is rified before distillation by multi-step treatments, which may
propane dehydrogenation, but this is currently not being include:
used to any appreciable extent in North America or South • Oil and/or aqueous quenching of the hot cracked gas for re-
America. Some dehydrogenation is being done in Western moval of heavier components (C5 and heavier),
Europe and Southeast Asia. There is a very small amount • Compression of the remaining cracked gas to remove the
of propylene being produced in South Africa from coal. remainder of the heavier hydrocarbons,
3. Methylacetylene and Propadiene—^Depending on the plant, • Conversion of residual sulfur to hydrogen sulfide Eind sub-
methylacetylene and propadiene (allene) can be removed sequent removal by zeolite absorption,
• Acid gases removal by caustic extraction or amine absorp- Propylene Production

tion, Propylene is most often produced by either steam cracking or
• Carbon dioxide removal by absorption or extraction, cataljrtic cracking. Propylene is a major by-product from ethy-
• Drying to remove residual water after compression, lene production when feedstocks heavier than ethane are
• Acetylenic materials removal by selective hydrogenation or used. In steam cracking, generally, the heavier the feedstock,
extraction, the greater the a m o u n t of propylene produced relative to ethy-
• Methane removal by low temperature fractionation or se- lene. It is not unusual for propylene production to amount to
lective adsorption or selective absorption. 40-70% of ethylene production [1]. It should be noted, how-
The process challenge in the production of ethylene, like ever, propane and low boiling liquid feedstocks may not con-
other synthetic hydrocarbons, is obtaining pure ethylene form to this pattern if the cracking severity is low. This is why
from the complex reaction mixture after cracking. This is ac- such plants are more often called "olefin plants." Since ethy-
complished primarily by distillation after the product stream lene and propylene are co-produced in the same units, propy-
has been treated. Table 5 provides a listing of typical specifi- lene production will not be detailed separately here.
cations for ethylene produced in this way. Table 6 summarizes Table 7 provides a summary of typical product specifica-
the typical physical properties of ethylene and other synthetic tions for polymer grade propylene. The physical properties of
hydrocarbons. propylene are summarized in Table 6.
Butylene and Butadiene Production

Reaction Chemistry and Mechanism—Butadiene may be syn-
thesized by dehydrogenation of n-butenes at 1100-1250°F
TABLE 5—Typical product specification (593-677°C) over a metal catalyst as shown in Scheme 8 [21].
for ethylene.
However, due to the relatively high temperatures required for
Component Composition conversion, the reaction selectivity is often poor. Reaction
Ethylene 99.9 mol% min
Methane and ethane 0.1 mol%max C4H8 O C4H6 + H2
Hydrogen 1 mol ppm max
Acetylene 1 mol ppm max Scheme 8—Butadiene synthesis by butene dehydrogena-
Propylene and propane 10 mol ppm max tion.
Oxygen 1 mol ppm max
Carbon monoxide 1 mol ppm max temperatures may be reduced to 750-1100°F (399-593°C),
Carbon dioxide 1 mol ppm max thus permitting improved selectivity, by introducing air
Water 2 mol ppm max (steam + oxygen) into the reaction (oxidative dehydrogena-
Methanol 1 mol ppm msix tion) as shown in Scheme 9. Catalysts that have been reported
Total sulfur 1 mass ppm max
to produce good yields include: bismuth molybdate, mixed ox-
TABLE 6—Thermophysical properties of C2, C3 and C4 hydrocarbons."

Property Ethylene [1] Propylene 1-Butene Cis-2-Butene Trans-2-Butene 1,3-Butadiene
Molecular weight 28.05 42.08 56.11 56.11 56.11 54.09
Triple point
Temperature, °C -169.19° -185.26 -185.35 -138.91 -105.55 -108.92
Pressure, kPa 0.11 9.54 X 10"^
Latent heat of fusion, J/mol 3350 3003 3848 7309 9757 7980
(at melting point)
Normal boiling point
Temperature, °C -103.71 -47.6 -6.25 3.72 0.88 -4.4
Latent heat of vaporization, J/mol 13 540 18 420 21 917 23 349 22 757 22 597
Density of the liquid, mol/dm^ 20.27 14.47 11.15 11.43 11.17 12.03
Specific heat of the liquid, J m o l ^ ' K " ' 67.4 118 127 123.6
Viscosity of the liquid, Pa«s 1.61 X 10"" 1.92 X lO""* 1.98 X lO"'* 1.73 X 10"'' 1.79 X 10"^ 1.98 X 10"^
Surface tension of the liquid, N/m 0.0164 .0167 .0160 .0156 .0160 .0176
Specific heat of the ideal gas (25°C), 42.84 62.49 88.49 76.89 86.00 77.13
Jmor^K"'
Critical point
Temperature, °C 9.2 91.8 146.4 162.4 155.5 151.9
Pressure, MPa 5.042 4.62 4.02 4.21 4.10 4.33
Density, mol/dm^ 7.635 5.52 4.153 4.277 4.207 4.525
Compressibility factor 0.2813 0.2750 0.2760 0.2720 0.2740 0.2700
Gross heat of combustion of the gas 1.411 2.058 2.719 2.712 2.707 2.541
(25X), MJ/mol
Limits of flammability of atmospheric
pressure at 25°C
Lower limit in air, mol% 2.7 1.9 1.6 1.6 1.6 2.0
Upper limit in air, mol% 36 11.1 10.0 9.7 9.7 11.5
Autoignition temperature in air at 490 455 385 325 324 420
atmospheric pressure, "C
Vapor pressure at 25°C, kPa 7065 1156 297.1 213.7 234.1 281.1
"Values from a variety of sources and are believed accurate.
TABLE 7—Typical product specification stream is quenched by cooling, washed in a wash tower to re-
for propylene. move oxygenated bjrproducts, and finally scrubbed with an
Component Concentration oil to extract the organic products from nitrogen and carbon
Propylene 99.5 mol% min dioxide. The hydrocarbons Eire removed by stripping them
Paraffins 0.4 inol% max from the oil a n d then using extractive distillation to recover
Hydrogen 5 mol ppm max the butadiene.
Ethylene 100 mol ppm max
Acetylene 1 mol ppm max Most of the butadiene production in the world today is ob-
Methylacetylene 5 mol ppm max tained as a by-product of ethylene manufacture (see Table 8).
Propadiene 5 mol ppm max When there is excess capacity, butadiene may be selectively
C-4 Hydrocarbons 5 mol ppm max hydrogenated to butenes. Alternatively, excess butadiene
Carbon dioxide 5 mol ppm max
Carbon monoxide 5 mol ppm max
Methanol 5 mol ppni max
POSSIBLE MODIFICATION OF EXISTING COMMERCIAL OPERATIONS
Oxygen 2 mol ppm max TO INCLUDE OXIDATIVE DEHYDROGENATION OF BUTENES
Water 10 mass ppm max
Sulfur 1 mass ppm max
PHILLIPS PETROLEUM COMPANY PETRO-TEX CHEMICAL COMPANY
ides of tin and antimony, mixed oxides of molybdenum and n-BUTANE n-BUTANE
tellurium and nickel, calcium and chromium phosphates [27].
C4H8 + 1^02 ^> C4H6 + H2O BUTANE CATALYTIC
i
BUTANE CATALYTIC
DEHYDROGENATION DEHYDROGENATION
(HOUDRY)
S c h e m e 9—Butadiene synthesis by oxidative dehydro- BUTANE
genation of n-butane and n-butenes. BUTANE AND BUTENES
BUTENES SEPARATION
Shchukin studied the mechanism and reaction kinetics of (FURFURAL EXT. DIST.) ; BUTANE ONLY ;
butadiene synthesis by oxidative dehydrogenation and re- '-—in
ported the mechanism illustrated in Scheme 10 [24]. K ( 0 ) BUTADIENE SEPARATION
and K ( ) represent the oxidized and reduced state of the cat- 1 BUTENES SEPARATION i
alyst respectively. The values xj, X2, Vi, and V2 are reactant (FURFURAL EXT. DIST.)
and product coefficients. The reaction order was reported to

be approximately 0.5 with respect to 1-butene and oxygen BUTADIENE
[25]. I BUTENES i
BUTENE DEHYDROGENATION 1 *
K ( 0 ) + C4H8 -^ K(OC4H8) ^ CAT^kYTIC

r 'o)(YDiHYDROGENATibNi j f STEAM
K(OC4H8) -^ K(C4H8) + H2O -^ C4H6 + K ( ) I I AIR
K(OC4H8) + xiK(O) -^ V1CO2 + V1H2O + (xi + 1)K( ) i.-i *.

BUTENE
BUTADIENE SEPARATION OXYDEHYDROGENATION
K(0) -f- C4H68 <-> K(OC4H6) (FURFURAL EXT. DIST) CATALYTIC
K(OC4H6) + X2K(0) -^ V2CO2 + y4V2H20 + (X2 + 1)K( )

• 4 . . — I BUTADIENE SEPARATION
K ( ) + O2 ^ K ( 0 2 ) + K ( ) ^ 2 K ( 0 )
BUTADIENE
S c h e m e 10—Mechanism of butylenes synthesis by oxida-
tive dehydrogenation. Note: BROKEN LINES INDICATE AN ENLARGEMENT OF AN EXISTING
OPERATION OR THE ADDITION OF A NEW OPERATION.
The first reaction in Scheme 10 can act to isomerize 1-
butene into cis- and trans-2-butene [26]. The reactivity of the FIG. 2—Comparative illustration of Butadiene production by
butene isomers on an aluminum oxide catalyst decreases in the Phillips and the Petro-Tex processes.
the following order: 1-butene > cis-2-butene > trans-2-
b u t e n e [27]. Unsaturated carbonyl c o m p o u n d s can b e
TABLE 8—Typical product composition
formed as byproducts. Adzhamov reports that these carbonyl for C4 Hydrocarbon product stream.
compounds inhibit the oxidative dehydrogenation process
and butene isomerization [28]. Other by-products that are Component Composition
possible include furan, acetaldehyde, acetone, acrolein, C3 Hydrocarbons 0.1 mol% max
1,3 Butadiene 35-75 mol%
formaldehyde, methyl ethyl ketone, methyl vinyl ketone, and Ethyl acetylene 0.2-0.5 mol%
other carbonyl compounds and carbon dioxide [27]. Vinylacetylene 0.7-1.4 mol%
Commercial Butadiene Production Processes—^Two industrial cis-Butene-2 4-5 mol%
processes for butadiene production by oxidative dehydro- fran5-Butene-2 4.5-6.5 mol%
Isobutene 20-30 mol%
genation are the Phillips Petroleum Company Process [24,25] 1-Butene 15-25 mol%
and the Petro-Tex Chemical Company Process [22]. These n-Butane 5-15 mol%
two processes are illustrated schematically in Fig. 2 [30,31]. Isobutane 0.5-1 mol%
The butene feed stream is typiccJly mixed with steam and air C5 Hydrocarbons 0.1 mol% max
Total Sulfur 5 mass ppm max
and passed through a fixed-bed reactor. The reaction product
may be completely hydrogenated to butanes. In recent years, determine carbon dioxide, methane, ethane, acetylene and
many of the dedicated butadiene production units have been other hydrocarbons in high-purity ethylene. Hydrogen, nitro-
shut down. gen, oxygen, and carbon monoxide are determined in accor-
Butadiene separation from an oxidative dehydrogenation dcince with Test Method 2504. Ethylene concentration is de-
product stream or from the product stream of an ethylene termined by subtracting the sum of the percentages of
steam cracker is typically performed by an extractive distilla- hydrocarbon and non-hydrocarbon impurities from 100%.
tion. The butadiene boiling point is too close to other prod- This method is applicable over the range of impurities from
ucts to permit effective separation by fractionation in a con- 1-500 parts per million by volume.
ventional distillation process. There is no consensus on the In this method, the sample is sepetrated in a gas chromato-
best solvent system but extractive distillation systems that graph utilizing four different packed columns with helium as
have been reported include N-methylpyrrolidone, dimethyl- a carrier gas. Methane and ethane are determined using a
formamide, furfural, acetonitrile and dimethylacetamide silica gel column. Propylene and heavier hydrocarbons are
[32-34]. determined using a hexamethylphosphoramide (HMPA) col-
umn. Acetylene is determined by using, in series, a hexade-
cane and a squalene column. Carbon dioxide is determined
Analytical Test Methods using a column packed with activated charcoal impregnated
The above discussion has provided a general overview of the with a solution of silver nitrate in /3,/3'-oxydipropionitrile.
production of ethylene, propylene and C4 hydrocarbons in- Calibration data are obtained using standard samples con-
cluding butanes and 1,3-butadiene. Included in this discus- taining the impurities, carbon dioxide, methane, and ethane
sion is the generation of various by-products, many of which in the range expected to be encountered. Calibration data for
exhibit deleterious effects on downstream processes. This acetylene are obtained assuming that acetylene has the same
section provides a review of the ASTM procedures for prod- peak area response on a weight basis as methane. Calcula-
uct characterization. This will be done by dividing these tions for carbon dioxide, methane, and ethane are conducted
methods into those that are applicable for ethylene, propy- using the peak-height measurement.
lene, C4 hydrocarbons, and other related methods.
Propylene Characterization
Ethylene Characterization
Guide for Analysis of Propylene Concentrates (Guide D 5273)—
Guide for Analysis of Ethylene (Guide D 5234)—^When various Standard Guide D 5273 lists the major grades of propylene
producers and users of ethylene deal with anal3rtical results, produced in North America. Standard Guide D 5273 is in-
inconsistency of units and test methods may cause major er- tended to provide information on the likely composition of
rors. D5234 provides an overview of the typical concentra- propylene concentrates and on probable ways to test them.
tions of possible components found in ethylene, analytical Since there are currently no ASTM test methods for deter-
methods, and units of measure. Although this guide cannot mining all components of interest. Standard Guide D 5273
be used as a specification, it can provide a starting point for provides information on other potentially available test
specification development. It can also be used as a starting methods. This guide is not intended to be used as a standard
point for identifying suitable test methods for ethylene prod- for any grade of propylene concentrate.
uct characterization. Method for Liquefied Petroleum (LP) Gases and Propylene Con-
Determination of Hydrocarbon Impurities in Ethylene (Test centrates (Test Method D 2163)—D-2163 determines the com-
Method D 6159)—This method determines the amounts of position of LP gases and propylene concentrates. The com-
certain impurities that could impair the performance of high ponents measured are ethane, propane, propylene, n-butane,
purity ethylene. Test Method D 6159 is used for the determi- isobutane, butylene, and isopentane. The components can be
nation of methane, ethane, propane, propylene, acetylene, measured so long as their concentration is above 0.1%. This
iso-butane, propadiene, butane, trans-2-butene, 1-butene, information is useful when the product is to be sold either as
iso-butene, cis-2-butene, methyl acetylene and 1,3 butadiene a chemical intermediate or as a fuel. The component distri-
by a gas chromatographic procedure. This test method does bution data of LP gases and propylene concentrates can be
not determine all possible impurities. Carbon monoxide, car- used to calculate physical properties such as relative density,
bon dioxide, water, alcohols, nitrogen oxides, carbon disul- vapor pressure, and motor octane.
fide, and hydrocarbons higher than decane are not deter- Test Method D 2163 involves the separation of the compo-
mined by D 6159. These products must be determined by nents of LP gas by gas chromatography emd comparing them
other procedures. to corresponding components separated under identical op-
This test is conducted by injecting the as-received ethylene erating conditions from a reference standard or from pure
sample into a capillary gas chromatograph that is equipped hydrocarbons. The chromatogram of the sample is inter-
with a 6-port sampling valve and two wide bore capillary preted by comparing peak heights or areas with those ob-
columns connected in series. The columns are a dimethyl sil- tained on a reference standard mixture or pure hydrocarbon
icone column and a porous layer open tubular (PLOT) of interest.
AI2O3/KCI column. A flame ionization detector is used. The Determination of Trace Hydrocarbon Impurities in Propylene
hydrocarbon impurities are determined and the total impuri- Concentrates (Test Method D 2712)—Test Method D 2712 is
ties are used to calculate the ethylene content. used to determine ethylene, total butylenes, acetylene,
Determination of Ethylene, Other Hydrocarbons and Carbon methyl acetylene, propadiene, and butadiene at levels of
Dioxide (Test Method D 2505)—Test Method D 2505 is used to 5-500 ppm each in propylene concentrates. Trace levels of
these components may affect the commercial use of propy- This guide is not intended to be used as a specification for bu-
lene concentrates. tadiene products.
In Test Method D 2712, a relatively large volume of sample Butylene Analysis by Gas Chromatography (Test Method D
is charged to a gas partition chromatograph equipped with a 4424)—This is a gas chromatographic analysis of commer-
column that will separate trace hydrocarbon constituents cial butylenes, butylene concentrates, and butane-butylene
from the major components. Any column or combination of mixtures. This test method is designed to determine:
columns may be used providing that they exhibit the neces- propane, propylene, isobutane, n-butane, 1-butene, iso-
sary resolution. Various columns that have been used suc- butene, trans-2-butene, cis-2-butene, 1,3-butadiene, iso-pen-
cessfully are provided in Table 1 of Test Method 2712. tane and n-pentane at concentrations of about 0.05% or
Determination of Trace Methanol in Propylene Concentrates greater. It does not cover high-purity 1-butene or high-purity
(Test Method D 4864)—Methanol is a common impurity in isobutene streams.
propylene. It can have a deleterious effect on various pro- Test Method D 4424 involves the gas chromatographic sep-
cesses that use propylene as a feedstock. Test Method D 4864 aration of a sample on a packed column with either helium
determines methanol in propylene concentrates in the range or hydrogen carrier gas. The separated components are de-
of 4 ^ 0 parts per million by weight. tected using a thermal conductivity detector or a flame ion-
For Test Method D 4864, a known weight of water is mea- ization detector. Calibration data are obtained using either
sured into a sample cylinder containing a known amount of relative response factors or by using a standard ceJibration
liquefied propylene. The contents in the cylinder are shaken blend.
and the water/methanol phase is withdrawn. A reproducible
Determination of Butadiene Purity and Hydrocarbon Impuri-
volume of the extract is then injected into a gas chromato-
ties (Test Method D 2593)—Test Method D 2593 determines
graph equipped with either a thermal conductivity or a flame
1,3-butadiene impurities such as propane, propylene, iso-bu-
ionization detector. The methanol concentration is calcu-
tane, n-butane, 1-butene, isobutylene, propadiene, trans-2-
lated from the area of the methanol peak using calibration
butene, cis-2-butene, 1,2-butadiene, 1,4-pentadiene, methyl-,
and extraction factors obtained from synthetic blends of dimethyl-, ethyl-, and vinyl-acetylene in polymerization
known methanol content. grade butadiene by gas chromatography. Impurities includ-
Determination of Trace Carbonyl Sulfide (COS) in Propylene ing butadiene dimer, carbonyls, inhibitor, and residue are
(Test Method D 5303)—This test method measures traces of measured by other procedures, and can be used with this pro-
COS in propylene in the range of 0.5-4.0 parts per million by cedure to give a complete composition of the butadiene.
mass. In propylene producing processes, COS usually re-
mains with the C3 and must be removed since it affects prod- Determination of Butadiene Dimer and Styrene in Butadiene
uct quality. COS acts as a poison to commercial polymeriza- Concentrate (Test Method D 2426)—Test Method D 2426 mea-
tion processes, resulting in deactivation and costly process sures butadiene dimer (4-vinylcyclohexene-l) and styrene in
downtime. Accurate gas chromatographic determination of "recycle" and specification grade butadiene concentrates by
trace COS in propylene involves unique analyticcJ problems gas chromatography. This is done by injecting the sample
because of the nature of COS and idiosyncrasies of trace level into a gas chromatograph equipped with either a thermal
analyses. These problems result from the reactive and ad- conductivity or flame ionization detector with sensitivity suf-
sorptive nature of COS, the low concentrations being mea- ficient to detect 0.01% of butadiene dimer. Any packed col-
sured, the tjê of detector needed, and interferences from the umn may be used that is capable of resolving the butadiene
propylene sample matrix. Test Method D 5303 addresses dimer and styrene as discrete peaks. The quantity of the com-
these analytical problems and ways to properly handle them ponents of interest is determined from the chromatogram by
to assure accurate and precise analysis. comparing their peak areas or heights with those of a syn-
thetic sample.
Separation of the COS from propylene is accomplished by
gas chromatography. A relatively large volume of sample is Determination of Nonvolatile Residue in Polymerization Grade
injected onto a gas chromatograph equipped with a single Butadiene (Test Method D 1025)—This method covers the de-
packed column and flame photometric detector. The separa- termination of nonvolatile material in polymerization grade
tion is achieved isothermally at 10-50°C. Calibration data, butadiene. Test Method D 1025 involves taking a measured
based on peaJi areas, are obtained using a known gas stan- volume of liquid butadiene and allowing it to evaporate at
dard blend of COS in the range expected for the sample. The room temperature from a small glass evaporating dish until
COS peak area in the sample is measured and the concentra- only a residue remains. Heating the dish to a constant weight
tion of COS is calculated. completes the evaporation. The weight gain in the evapora-
tion dish is the nonvolatile residue.
C-4 Product Characterization
Determination of Peroxides in Butadiene (Test Method D
Guide for Analysis of 1,3-Butadiene (Standard Guide D 5799)—Butadiene polyperoxide is a very dangerous reaction
5274)—Standard Guide D 5274 covers the analysis of I,3-bu- product of butadiene and oxygen. This peroxide has been re-
tadiene products produced in North America. Standard ported to cause violent explosions in vessels that are used to
Guide D 5274 is intended to provide information on the likely store butadiene. Due to the inherent dangers of peroxides in
composition of 1,3-butadiene products and possible ways to butadiene, specification limits are usually set for their pres-
test them. Since there are currently no ASTM test methods ence. Test Method D 5799 determines the peroxide content of
for determining all components of interest. Standard Guide a sample of commercial butadiene in the concentration range
D 5274 provides information on other available test methods. of 1-10 ppm by mass.
For this method, a known mass of butadiene sample is perometrically with standard silver nitrate solution, using a
placed in a flask and evaporated. The residue is then refluxed standard saturated calomel electrode as the reference elec-
with acetic acid and sodium iodide. The peroxides oxidize io- trode. The diffusion currents are plotted against the corre-
dide to iodine, which is then titrated with standard sodium sponding volumes of silver nitrate solution used and the end
thiosulfate solution using visual end-point detection. Inter- point is taken as the intersection of the straight-line portions
fering traces of iron are complexed with sodium fluoride. of the curve. This method is not directly applicable in the
Determination of Carbonyls in CA Hydrocarbons (Test Method presence of other substances that combine with silver ion or
4423)—Test Method D 4423 covers the determination of car- oxidize chloride ion in dilute acid solution.
bonyls (ketones and aldehydes) in butadiene. The presence of The chloride ion concentration may also be obtained spec-
carbonyl species can have a deleterious effect upon butadi- trophotometriccilly by reaction of the chloride ion in the ab-
ene polymer properties or on the butadiene polymerization sorber solution with mercuric thiocyanate to release thio-
reaction. Test D 4423 measures carbonyl in the range of 0-50 cyanate, which forms a reddish-orange complex with Fe^^.
ppm, calculated as acetaldehyde. The intensity of the color is measured at 460 n m with a spec-
A measured a m o u n t of the sample is added to an alcoholic trophotometer or filter photometer. Bromides, sulfides, am-
hydroxylamine hydrochloride solution t h a t has been ad- monia, tobacco smoke, and more than 25 fx,goi hydrogen per-
justed to a given p H indicator coloration using either alco- oxide in the test solution interfere in the spectrophotometric
holic acid or base. The carbonyls will react with the hydrox- procedure.
ylamine hydrochloride releasing an equivalent a m o u n t of ASTM Butadiene Measurement Tables (Standard D 1550)—
hydrochloric acid. The solution is then titrated with standard ASTM D 1550 consists of a series of tables allowing the spe-
base to the original coloration. A blank containing only cific gravity of butadiene or concentrated butadiene (60% bu-
methanol and sample is titrated and the sample's results are tadiene or greater) at 15.6/15.6°C to be calculated from the
calculated using the blank adjustment. Results are reported density measured at a different temperature. The density is
as mg/kg carbonyls as acetaldehyde. measured by means of a hygrometer.
Determination of Total Inhibitor Content (Test Method D
1157)—Test D 1157 measures p-?ert-butylcatechol (TBC) in General Methods
pol3mierization or recycle grades of butadiene or other C4 hy-
Microcoulometric Determination of Sulfur in Petroleum Gas
drocarbon mixtures. TBC is commonly added to commercial
(Test Method D 3246)—Test Method D 3246 determines sul-
butadiene in amounts of 50-150 mg/kg as an oxidation in-
fur in petroleum gas. Trace quantities of sulfur in hydrocar-
hibitor. It is important that the sample not contain other phe-
bon products can be harmful to many catalytic chemical pro-
nolic material, as they will be measured as catechol. In gen-
cesses. M a x i m u m permissible levels of total sulfur are
eral, all phenols and their quinone oxidation products are
normally included in specifications for such hydrocarbons. It
included in the calculated catechol content. Small amounts
is recommended that this test method be used to provide a
of polymer do not interfere. This test method is applicable
basis for agreement between two laboratories when the de-
over the range of TBC from 50-500 mg/kg.
termination of sulfur in hydrocarbon gases is important. For
The catechol is separated from butadiene in Test Method liquefied petroleum gas, total volatile sulfur is measured on
D 1157 by evaporation. The residue is dissolved in water an injected gas sample. For such a material, a liquid sample
and an excess of ferric chloride is added. The intensity of must be used to measure total sulfur. Test Method D 3246
the yellow-colored complex is compared in a photoelectric covers the determination of sulfur in the range of 1.5-100
colorimeter with that produced by a known concentration p p m by mass in hydrocarbon products that are gaseous at
of the catechol. normal room temperature and pressure.
Determination of Trace Volatile Chlorides in Butane-Butene
The test procedure involves injecting a sample of the hy-
Mixtures (Test Method D 2384)—Test Method D 2384 is used
drocarbon into a c o m b u s t i o n tube m a i n t a i n e d at a b o u t
to determine trace amounts of volatile chlorides in butane-
800°C having a flowing stream of gas consisting of 80% oxy-
butene mixtures. Such information is valuable in cases where
gen and 20% inert gas. Oxidative pyrolysis converts the sul-
the chloride is deleterious in the use of this product. Chloride
fur to sulfur dioxide which then flows into a titration cell
contributes to corrosion problems in processing units in in-
where it reacts with triiodide ion present in the electrolyte.
stances where further processing of this material is involved.
The triiodide is reduced by the sulfur dioxide, and is coulo-
The test methods included in Test Method D 2384 cover the
metrically replaced. The toted current required to replace the
determination of the total volatile organic chlorides in con-
triiodide is a measure of the sulfur present in the sample in-
centrations from 10-100 p p m in buteine-butene mixtures.
jected.
The sample is first combusted in one of two ways. In lamp
The reaction occurring in the titration cell as sulfur dioxide
combustion, the sample is burned in an atmosphere of car-
enters is:
bon dioxide and oxygen or in purified air. The halogen-con-
taining combustion products are absorbed in dilute sodium li" + SO2 + H2O -^ SO3 + 3I~ + 2H+
carbonate solution. In oxy-hydrogen combustion, the sample
is burned in an oxy-hydrogen atomizer burner, and the com- The triiodide consumed is generated coulometrically from:
bustion products are absorbed in a dilute solution of sodium
31" ^ 1 3 + 2 e '
carbonate.
Chloride determination may be performed by amperomet- These microequivalents of triiodide (iodine) are equal to the
ric titration or spectrophotometrically. For amperometric number of microequivalents of titratable sample ion entering
titration, the chloride ion in aqueous solution is titrated am- the titration cell. A liquid blend containing a known amount
of sulfur is used for calibration. This is the same chemistry as This is a complicated gas chromatography method. Molec-
is used in the well-known Karl Fisher water titration. ular size is determined by using boiling point columns or
Gas Chromatographic Determination of Noncondensahle molecular sieve columns. Polar columns separate by polarity.
Gases in C2 and Lighter Hydrocarbon Products (Test Method D Hydrogenation is done on column using a platinum lined
2504)—Test Method D 2504 covers the determination of hy- column a n d hydrogen gas. In addition, t e m p e r a t u r e pro-
drogen, nitrogen, oxygen, and carbon monoxide in parts per gramming is used for separation.
million by volume range in C2 and lighter hydrocarbon prod- Determination of Boiling Range (Test Methods D 2892 and D
ucts. In this test, the sample is separated in a gas-solid chro- 2887)—Test Method D 2892 details procedures for the pro-
matographic system using molecular sieves as the solid ad- duction of a liquefied gas, distillate fractions, and residuum
sorbant. The concentration of the gases to b e analyzed is of' standardized quality o n which analytical data can be ob-
calculated from peak heights or areas. Argon can be used as tained, and the determination of yields of the above frac-
a carrier gas for the determination of hydrogen concentrations by b o t h mass and volume. From the above informa-
tions below 100 p p m by volume. Argon, if present in the sam- tion, a graph of temperature versus mass-percent distilled
ple, interferes with oxygen determination. can be produced. This distillation curve corresponds to a
Determination of Organic Hydrogen in Petroleum Fractions laboratory technique, which is defined at 15/5 (15 theoreti-
(Test Methods D 1018 and D 4808)—Test D 1018 determines cal plate column, 5:1 reflux ratio) or TBP (true boiling
the percent organic hydrogen contained by a sample. Knowl- point). This test m e t h o d can also be applied to any
edge of the organic hydrogen content of petroleum products petroleum mixture except liquefied petroleum gases, very
can be helpful in assessing performance characteristics. For light naphthas and fractions having initial boiling points
Test Method D1018, the petroleum product is burned from a above 400°C.
cotton wick in an a t m o s p h e r e of purified air. The water Alternatively, the boiling range distribution of petroleum
formed is collected from the combustion gases by a desiccant fractions may be determined by gas chromatography using
(CaCli) and weighed. The a m o u n t of organic hydrogen can be Test Method D 2887. This test m e t h o d is applicable to
calculated based on the water formed during combustion. petroleum products and fractions having a final boiling point
of 538°C (1000°F) or lower at atmospheric pressure and is
Continuous wave, low-resolution nuclear magnetic reso-
limited to samples having a boiling range greater than 55°C
nance spectroscopy provides a simpler, more precise alterna-
(100°F) and having a vapor pressure sufficiently low enough
tive method for determination of organic hydrogen content
to p e r m i t sampling at a m b i e n t t e m p e r a t u r e . For m o r e
of petroleum products. It is described in Test Method D4808.
volatile p e t r o l e u m fractions, including oxygenated com-
The NMR spectrum of the petroleum oil to be analyzed is
pounds. Test Method D 3710 should b e used.
compared to a reference. The spectrometer nondestructively
records the absolute concentration of hydrogen atoms in the
reference and test sample. The result is expressed as hydro-
gen content (on a mass basis) of the sample. Table 9 summa- ASTM STANDARDS
rizes which test variants that eire typically used with different
petroleum products within D 4808. No. Title
Determination of Paraffin, Naphthene and Aromatic Hydrocar- D 1018 Standard Test Method for Hydrogen in Petroleum
bons (Test Method D 5443)—Test Method D 5443 provides for Fractions
the determination of paraffins, naphthenes, and aromatics in D 1025 Test Method for Nonvolatile Residue of Polymer-
low olefinic hydrocarbon streams having final boiling points ization Grade Butadiene
of 200°C or less. The m e t h o d uses multi-dimensional gas D 1157 Test Method for Total Inhibitor Content (TBC) of
chromatography. Hydrocarbons with boiling points greater Light Hydrocarbons
t h a n 200°C and less t h a n 270°C are reported as a single D 1550 ASTM Butadiene Measurement Tables
group. Olefins, if present, are hydrogenated and resultant sat- D 2163 Test Method for Liquefied Petroleum (LP) Gases
urates are included in the paraffin and naphthene distribu- and Propylene Concentrates by Gas Chromatog-
tion. Aromatics boiling at C9 and above are reported as a sin- raphy
gle a r o m a t i c group. This test m e t h o d is not intended to D 2384 Test Methods for Traces of Volatile Chlorides in
determine individual components except for benzene and Butane-Butene Mixtures
toluene that Eire only Cg and C7 aromatics, respectively, and D 2426 Test Method for Butadiene Dimer and Styrene in
cyclopentane, that is the only C5 naphthene. The lower limit Butadiene Concentrates by Gas Chromatography
of detection for a single h y d r o c a r b o n c o m p o n e n t is 0.05 D 2504 Test Method for Noncondensahle Gases in C2 and
mass %. Lighter H y d r o c a r b o n Products by Gas Chro-
matography
D 2505 Test Method for Ethylene, Other Hydrocarbons,
TABLE 9—ASTM D 4808 test procedures available for and Carbon Dioxide in High-Purity Ethylene by
different petroleum products. Gas Chromatography
Approximate Boiling Range D 2593 Test Method for Butadiene Purity a n d Hydrocar-
Test Method Petroleum Products "C (-F) bon Impurities by Gas Chromatography
A Light distillates 15-260(60-500) D 2712 Test Method for Hydrocarbon Traces in Propy-
B Middle distillates 200-370 (400-700) lene Concentrates by Gas Chromatography
B Gas oil 370-510(700-950) D 2887 Test Method for Boiling Range Distribution of
C Residual 510+ (950+) Petroleum Fractions by Gas Chromatography
196 MANUAL 3 7; FUELS AND LUBRICANTS HANDBOOK
D 2892 Test Method for Distillation of Crude Petroleum Use—Determination of Traces of Car-
(15-Theoretical Plate Column) bon Monoxide and Carbon Dioxide—
D 3246 Test Method for Sulfur in Petroleum Gas by Ox- Gas Chromatographic Method
idative Microcoulometry ISO 6684:1982 Butadiene for Industrial Use—Deter-
D 3710 Test Method for Boiling Range Distribution of mination of tert-butyl-catechol (TBC)
Gasoline a n d Gasoline Fractions by Gas Chro- (4-( 1,1 - d i m e t h y l e t h y l ) - 1 , 2 - b e n z e n e -
matography diol)—Spectrometric method
D 4423 Test Method for Determination of Carbonyls in C4 ISO 6792:1982 Butadiene for Industrial Use—Deter-
Hydrocarbons mination of Oxygen and Argon in the
D 4424 Test Method for Butylene Analysis by Gas Chro- Gaseous Phase Above Liquid Butadi-
matography ene—Gas Chromatographic Method
D4808 Test Method for Hydrogen Content of Light Dis- 150 7381:1986 Butadiene for Industrial Use—Deter-
tillates, Middle Distillates. Gas Oils, and Residua m i n a t i o n of Oligomers—Gas Chro-
by Low-Resolution Nuclear Magnetic Resonance matographic Method
Spectroscopy ISO 7382:1986 Ethylene for Industrial Use—Determi-
D 4864 Test Method for Determination of Traces of nation of Traces of Polar Com-
Methanol in Propylene Concentrates by Gas Chro- p o u n d s — P r e p a r a t i o n of Condensate
matography Samples by Low-temperature Tech-
D 5234 Guide for Analysis of Ethylene Product nique
D 5273 Guide for Analysis of Propylene Concentrates ISO 8174:1986 Ethylene and Propylene for Industrial
D 5274 Guide for Analysis of 1,3-Butadiene Product Use—Determination of Acetone, Ace-
D 5303 Test Method for Trace Carbonyl Sulfide in Propy- tonitrile, Propan-2-ol, and Methanol—
lene by Gas Chromatography Gas Chromatographic Method
D5443 Test Method for Paraffin, Naphthene, and Aro- ISO 8175:1986 Propylene for Industrial Use—Deter-
matic Hydrocarbon type Analysis in Petroleum m i n a t i o n of Oligomers—Gas Chro-
Distillates Through 200°C by Multidimensional matographic Method
Gas Chromatography ISO 8176:1986 Butadiene for Industrial Use—Deter-
D 5799 Test Method for Determination of Peroxides in mination of Active tert-butyl-catechol
Butadiene (TBC)(4-(1,1 -dimethylethyl)-! ,2-ben-
D 6159 Test Method for Determination of Hydrocarbon zenediol)- High Performance Liquid
Impurities in Ethylene by Gas Chromatography Chromatography Method
OTHER STANDARDS UOP

UOP 212-77 Hydrogen Sulfide, Mercaptan Sulfur
D e u t s c h e s I n s t i t u t fur N o r m u n g ( D I N )
and Carbonyl Sulfide in Hydroccirbon
DIN 51872-4 (1990) Testing of gaseous fuels and other Gases by Potentiometric Titration
gases; determination of the compo- UOP 344-87 Moisture in Hydrocarbon Streams Us-
nents; gas Chromatographic procedure ing a n On-line Analyzer
DIN 51872-5 (1996) Testing of gaseous fuels and other UOP 496-63T Carbonyl Compounds in Light Hydro-
gases; determination of the compo- carbon Gases
nents - Part 5; capillary gas chromato- UOP 542-88 Trace Diolefins, Acetylenes, and Non-
graphic procedure condensable Hydrocarbons in LPG by
Gas Chromatography
UOP 569-79 Methanol in Petroleum Distillates and
International Organization for Standardization
LPG by Gas Chromatography
(ISO)
UOP 603-88 Trace Carbon Monoxide and Carbon
ISO 6377:1981 Light Olefins for Industrial Use—De- Dioxide in Hydrogen and Light
termination of Impurities by Gas Chro- Gaseous Hydrocarbons by Gas Chro-
matography—General Considerations matography
ISO 6378:1981 Butadiene for Industrial Use—Deter- UOP 772-77 Mercaptan Sulfur in LPG by Micro-
mination of Hydrocarbon Impurities— coulometry
Gas Chromatographic Method UOP 791-94 Sulfur Components in LPG or C5 Mi-
ISO 6379:1981 Ethylene for Industrial Use—Determi- nus Hydrocarbon Fractions by GC-
nation of H y d r o c a r b o n Impurities— SCD
Gas Chromatographic Method UOP 834-82 Arsine in Ethylene by Electrothermal
ISO 6380:1981 Propylene for Industrial Use—Deter- Atomic Absorption Spectrophotome-
mination of Hydrocarbon Impurities— try
Gas Chromatographic Method UOP 845-90 Trace Alcohols in LPG by Gas Chro-
ISO 6381:1981 Ethylene and Propylene for Industrial matography
REFERENCES [17] Fair, J. R. and Rase, H. F., "Process Design of Light Hydrocar-
bon Cracking Units," Chemical Engineering Progress, 1954, Vol.
[1] Kniel, L., Winter, O. and Stork, K., Ethylene: Keystone to the 50, No. 8, pp. 415-420.
Petrochemical Industry, Marcel Dekker Inc., NY, 1980. [18] Schutt, H. C , "Optimum Temperature Profile for Endothermic
[2] Ma, J. J. and Scheeline, H. W., "Ethylene," Process Economics Conversions in Tubular Reactors," Zeitschrift fuer Elektro-
Program, Report No. 28B, Stanford Research Institute, Menlo chemie. Vol. 65, 1961, pp. 245-255.
Park, CA, March 1978. [19] Buell, C. K. and Weber, L. J., "Ethylene Production by Cracking
[3] World Light Olefins Analysis, Vol II, Chemical Market Associ- of Ethylene-Propylene Mixtures," Petroleum Processing, Vol. 5,
ates, Inc., Houston, TX, December 2000, pp. 8-11. March 1950, pp. 266-272.
[4] Germain, E. and Maurel, R., "Thermal Decomposition of Pure [20] Kamptner, H. K., Krause, W. R., and Shilken, H. P., "High-Tem-
Methane at 1000°C in a Pipe Still," Genie Chimique, Vol. 88, perature Cracking," Chemical Engineering, Feb. 28 1966, pp.
1962, pp. 122-127 93-98.
[5] Sherwood, P. W., "Production of Ethylene from Petroleum [21] Schutt, H. C. and Zdonik, S. B., "Processing Scheme-Pyrolysis
Sources, Part I.," Petroleum Refiner, Vol. 30, No. 9, 1951, pp. Methods," Oiland Gas Journal, Vol. 54,2 April 1956, pp. 99-103.
220-225. [22] Haddeland, G. E., "Butadiene," Process Economics Program,
[6] Sherwood, P. W., "New Advances in Ethylene Production-I," Report No. 35, Stanford Research Institute, Menlo Park, CA,
Petroleum, Vol. 19, May, 1956, pp. 161-164. March 1968.
[7] Martin, R., Dzierzynski, M., and Niclause, M., "Thermal De- [23] Anonymous, "New Plants and Facilities, CE Construction
composition of Propane, 1. Introduction a n d Experimental Alert," Chemical Engineering, April 5 1971, pp. 111-116.
Study of the Pyrolysis of Pure Propane," Journal of Chemie [24] Nolan G. J., Hogan R. J., and Farba F., Jr., "2-Butene Dehydro-
Physique, Vol. 61, No. 3, 1964, pp. 286-297. genation Catalyst," U.S. Patent 3,501,547, 17 March 1970.
[8] Fair, J. R., Perkins, T. K., and Rice, H. F., "Comparing Olefin [25] Friedman, L., Womeldorph, D. E., a n d Stevenson, D. H.,
Unit Feedstocks," Petroleum Refiner, Vol. 34, No. 11, 1955, pp. "Houdry Dehydrogenation for Olefin Production," Proceedings
185-189. of the American Petroleum Institute, Sect. Ill, Vol. 38, 1958, pp.
[9] Rice, F. O., "The Thermal Decomposition of Organic Com- 203-212.
pounds from the Standpoint of Free Radicals. I. Saturated Hy- [26] Shchukin, V. P., Ven'yaminov, S. A., and Boreskov, G. K. "Iron-
drocarbons," Journal of the American Chemical Society, Vol. 53, Antimony Oxide Catalysts of Partial Oxidation. III. Kinetics and
May 1931, pp. 1959-1972. Mechanism of the Oxidative Dehydrogenation of Butylenes,"
[10] Davis, H. G. and Williamson, K. D., "The Kinetics of Pyrolysis Kinetika I Kataliz, Vol. 11, No. 5, 1970, p p . 1236-1242.
of E t h a n e and Related Hydrocarbons," World Petroleum [27] Echigoya, E., Watanabe, T., and Sano, H., "Studies on Oxidative
Congress Proceedings, Vth, Section 4, Paper 4, New York, 1959, Dehydrogenation of Butylenes over Bismuth Molybdate Cata-
pp. 1-17. lyst," Journal of the Chemical Society of Japan, Industrial Chem-
[11] Kalinenko, R. A. and Brodskii, A. M., "A Kinetic Scheme istry Section, Vol. 73, No. 5, 1970, pp. 933-937.
for E t h a n e Pyrolysis as an Aid to Optimization of Processes [28] Skarchenko, V. K., "Oxidative Dehydrogenation of Hydrocar-
Yielding Ethane," Kinetika I Kataliz, Vol. 6, No. 5, 1965, p p . bons," International Chemical Engineering, Vol. 9, No.l, 1969,
826-830. pp. 1-23.
[12] Laidler, K. J., Sagert, N. H., and Wojciechowski, B. W., "Kinet- [29] Adzhamov, K. Y., Alkhazov, T. G., Belen'kii, M. S., and Lisovskii,
ics and Mechanisms of the ThermjJ Decomposition of Propane. A. E., "Effect of Carbonyl Compounds on the Oxidative Dehy-
1. The Uninhibited Reaction," Proceedings of the Royal Society of drogenation of Butenes," Kinetika i Kataliz, Vol. 9, No. 6, 1968,
London, Series A, 1962, London, Vol. 270, pp. 242-266. pp. 1279-1284.
[13] Pumell, J. H. and Quinn, C. P., "The Pyrolysis of n-Butane," Pro- [30] Newman, F. C , "Process for Butadiene Manufacture by Oxyde-
ceedings of the Royal Society of London, Series A, Vol. 270, Lon- hydrogenation of Butenes," Industrial and Engineering Chem-
don, pp. 267-284. istry, Vol. 62, No. 5, 1970, p p . 42-47.
[14] Greensfelder, B. S., Voge, H. H., and Good, G. M., "Catalytic and [31] Husen, P. C , Deel, K. R., and Peters, W. D., "Phillips Butadiene
Thermal Cracking of Pure Hydrocarbons," Industrial and Engi- Process is Success," Oil and Gas Journal, 2 Aug 1971, pp. 60-61.
neering Chemistry, Vol. 4 1 , No. 11, 1949, pp. 2573-2584. [32] Reis, T., "Compare Butadiene Recovery Methods Processes, Sol-
[15] Fair, J. R., Mayers, J. W., and Lane, W. H. "Commercial Ethy- vents and Economics," Petro/Chem Engineer, August 1969, pp.
lene Production by Propane Pyrolysis in a Molten Lead Bath," 12-22.
Chemical Engineering Progress, Vol. 53, No. 9, 1957, p p . [33] Reis, T., "Butadiene Extraction," Chemical and Process Engi-
433^38. neering, March 1970, pp. 65-69, 72-76.
[16] Bartlit, J. R. and Bliss, H., "ICinetics of Ethane Pyrolysis," Amer- [34] Baron, T., "Precise Separations and Selective Extractions are
ican Institute of Chemical Engineers Journal, Vol. 11, No. 3, Keys to Petrochemicals," Oil and Gas Journal, 1971, July 5, Vol.
1965, p p . 562-572. 67, No. 27, p p . 100-102.
MNL37-EB/Jun. 2003
Additives and Additive

Chemistry
Syed Q. A. Rizvi^
M O S T UNTREATED OR NON-FORMULATED LUBRICANTS, i.e., mineral erated contaminants, and water separation or demulsibility.
base oils and synthetic basestocks, do not possess the prop- While some of these functions are common to all lubricants,
erties necessary to perform effectively in today's demanding others are more specific to the equipment being serviced.
lubricating environments. To function in such environments M o d e m lubricants are formulated from a range of base flu-
properly, base fluids need the help of chemicals called addi- ids and chemical additives. The primary function of the base
tives. Additives improve the lubricating ability of base oils, ei- fluid is to facilitate lubrication; that is, to provide a fluid layer
ther by enhancing the desirable properties already present or between moving surfaces to minimize friction, hence heat
by adding n e w properties. Such properties include suitable and wear. The base fluid in addition functions as a carrier of
viscosity, slipperiness, high film-strength, low corrosivity, additives; hence, it must be able to keep them in solution un-
low pour point, good cleansing and dispersing ability, low der normal operating conditions.
toxicity and low flammability [1]. Most of today's lubricants The base fluid can be of mineral origin, synthetic chemi-
are formulated lubricants, and additives are their integral cal origin, or biological origin. While mineral oil basestocks
part. The 1998 world consumption of lubricant additives is are obtained directly from petroleum fractionation, syn-
estimated at 2.588 million metric tons, of which North Amer- thetic basestocks are manufactured through transforma-
ica a n d Western Europe consumed 67%. This estimate is tions of petroleum-derived organic chemicals. Partly syn-
based on 1995 SRI data [2] and the estimated growth rate. thetic (semisynthetic) basestocks are compatible mixtures
of mineral oil and synthetic basestocks. Recently, a great
deal of interest has surfaced regarding the use of basestocks
LUBRICANT COMPOSITION of biological origin (vegetable a n d animal oils). Their
biodegradable nature and non-petroleum origin are two ma-
A formulated lubricant comprises a base fluid and a perfor- jor reasons for this impetus. For some industrial applica-
mance package, and in the case of multigrade oils, an additions, such as metalworking, even water is used to deliver
tional viscosity modifier. The performance package contains chemicals to parts that need protection. Section 2 of the
a n u m b e r of additives, the quantity of which is a function of ASTM Manual contains discussion on basestocks.
their quality (the ability to deliver the necessary perfor- Although many base fluid properties are modified or en-
mance), the quality of the base fluid (governed by its physical hanced by the use of additives, knowledge of such properties
and chemical properties), and the lubricant's intended use. is critical to the formulator. These include density, viscosity
The performance package can make u p to 30%, and some- (both at low and high temperatures), foaming characteristics,
times even higher, of the total lubricant composition, de- seal compatibility, oxidation resistance, corrosivity, the vis-
pending upon the desired performance level and the severity cosity-temperature relationship (VI), low-temperature prop-
of the end-use requirements [3]. In general, poor-quality base erties (such as cloud point and pour point), and high-temper-
fluids need better additives a n d in larger amounts than base ature properties (such as volatility and flash point) [4a].
fluids of good quality. Likewise, applications such as engine Viscosity, defined as an oil's resistance to flow, is critical to
oils a n d automotive gear oils, which place a higher demand its function as a lubricant. Inappropriate viscosity leads to in-
on the lubricant, require superior additives than those that effective lubrication and can lead to equipment damage. A
are less demanding. Engine oils account for the largest shaire n u m b e r of parameters, such as temperature, pressure, and
of the additive use. shear forces, affect viscosity. Of these, temperature has the
most profound effect; therefore, knowledge of viscosity-tem-
perature relationship or VI of an oil is important to a formu-
LUBRICANT BASESTOCKS lator.
The low-temperature properties of a lubricant include
Lubricants perform a variety of functions to prolong the life cloud point and pour point. When a sample of oil is cooled,
of the equipment. These include lubrication (reduction of its viscosity increases in a predictable manner until wax crys-
friction and wear), dissipation of heat, corrosion control, pre- tals start to form. On further cooling, the matrix of wax crys-
vention of excessive deposit formation, dispersion of use-gen- tals becomes sufficiently dense to cause an apparent solidifi-
cation of oil. Although this oil does not p o u r u n d e r the
' Research and Development Manager, Lubricant Additives Divi- influence of gravity, it can be moved if sufficient force is ap-
sion, King Industries, Inc., Science Road, Norwalk, CT 06852. plied: for example, by applying torque to a rotor that is sus-
199
pended in oil. Cloud point is the temperature at which the (OEMs), and the end-users. In Europe, ACEA (Association
first signs of wax formation (haziness) can be detected. Pour des Constructeurs Europeens de I'Automobiles), CEC (Con-
point is the lowest temperature at which the sample of oil seil Europeens de Coordination pour les Developments des
flows by gravity alone. High viscosity oils may cease to flow Essais de Performance des Lubrifiants et des Combustibles
at low temperatures because of further increase in viscosity pour Moteurs), ATC (Technical Committee of Petroleum Ad-
rather than because of wax formation. Pour points may be ditive Manufacturers), and ATIEL (Association Technique de
higher thsin cloud points. rindustries Europeenne des Lubrifiants) have collaborated
The high-temperature properties, such as volatility and in a m a n n e r similar to their American counterparts to come
flash point, of a base oil are governed by its distillation tem- u p with their own engine oil classification system, called the
perature, or the boiling range. Volatility is important because E u r o p e a n Engine Lubricant Quality Management System
it is a n indication of the oil's tendency to be lost during ser- (EELQMS). The system does include some individual OEM
vice due to vaporization, for example, in a hot engine. The requirements. In Japan, the Japanese Automobile Standards
methods used to determine volatility include ASTM Distilla- Organization (JASO) and, in India, Bureau of Indicin Stan-
tion Curves, thermogravimetric analysis (ASTM D 6375), Eind dards perform these functions.
Noack volatility (ASTM D 5800). Flash point is the lowest The performance package contains many classes of addi-
temperature at which auto-ignition of the vapor above the tives [5,6]. The primary functions of each class are briefly de-
heated sample occurs. Flash point of an oil is important from scribed below.
a safety point of view and is used to classify flammable liq- Stabilizers/Deposit Control Agents—Minimize the amount of
uids into hazard grades. deposit formation. Oxidation Inhibitors control oxidative de-
Density is important because oils may be formulated by composition of lubricant and additives. Dispersants keep nor-
weight but measured by volume. Demulsibility is the ability mally insoluble c o n t a m i n a n t s dispersed in the lubricant.
of a n oil to separate water. Foaming characteristics deter- Detergents prevent metal attack by acidic byproducts of com-
mine the tendency of the oil to form foam and the stability of bustion and oxidation and keep metal surfaces free of de-
the foam once it is formed. Seal compatibility of the oil is also posits.
important because the oil in most applications comes in con-
Film-Forming Agents—Either increase durability of the lubri-
tact with elastomer seals. If seals are damaged, the lubricant
cant film or form chemical films on metal surfaces. Friction
will be lost and the equipment will be left unprotected.
modifiers generally lower the coefficient of friction, thereby
Oxidative resistance of the base oil depends largely upon leading to improved fuel economy and wear control. Anti-
the structure of the hydrocarbons present. Lubricants that do wear a n d extreme pressure agents protect metal surfaces
not contain aromatic structures, or structures with unsatura- against wear and equipment seizure. Rust and corrosion in-
tion, have better oxidative stability than those that do. Oxi- hibitors prevent corrosion and rusting of metal parts that
dation of the base oil results in the formation of polar com- come in contact with the lubricant.
pounds that are either corrosive or lead to the formation of
resin, deposits, and sludge, which can impair proper func- Polymeric Additives—Âlter physical properties, such as vis-
tioning of the equipment. Previously, sulfur content of base cosity and pour point, of lubricants. Viscosity modifiers min-
oils was used as an indicator of their natural resistance to ox- imize the rate of viscosity decrease with an increase in tem-
idation. This is because many naturally occurring organosul- perature. Pour point depressants enable a lubricant to flow at
fur compounds in crude oils are moderately effective in de- low temperatures. Emulsifiers promote mixing of water and
stroying organic peroxides and breaking the oxidation chain oil to form an emulsion. Some hydraulic and metalworking
mechanism. However, m o d e m refining processes, used to lubricants are of emulsion type. Demulsifiers enhance water
enhance other desirable properties of base oils, result in the separation from oil c o n t a m i n a t e d with water. Foam in-
removal of these beneficial compounds. hibitors prevent the lubricant from forming persistent foam.
Other Additives—Perform miscellaneous other functions.
The base oil should not contain components that promote
corrosion. Corrosion tests usually involve bringing the oil Seal swell agents swell elastomer seals. Dyes are used to color
sample in contact with a metal, such as iron, copper, or sil- code lubricants and fuels. Biocides prevent degradation of
ver, u n d e r controlled conditions. Discoloration of metal, high water-based lubricants due to microbial attack. Cou-
changes in its surface condition, or weight loss reflect corro- plers help stabilize water/organic microemulsions.
sive tendency of the oil. Most lubricant additives, except perhaps some viscosity
modifiers and p o u r point depressants, comprise a n
oleophilic ("hydrocarbon-loving") hydrocarbon group and a
PERFORMANCE PACKAGE polar functionality [7]. The polar functionality typically con-
tains oxygen, nitrogen, sulfur, and or phosphorus. Figure 1
Lubricant additives are usually supplied as performance identifies polar and non-polar portions in the oleic acid
packages that are blended in basestocks to yield formulated molecule. All additives must initially be oil soluble; hence, the
lubricants. This is not the case in some applications, such as presence of a hydrocarbon group of sufficient carbon chain
metalworking fluids, where the end user may purchase the length is essential.
individual additives and blend them in base oil prior to use. Lubricant additives perform their function either in the
In the U.S., foixaulated lubricants are expected to meet per- bulk lubricant or on surfaces. The former type includes oxi-
formance requirements generally established by the Society dation inhibitors, detergents, and dispersants and the latter
of Automotive Engineers (SAE), American Petroleum Insti- type includes rust inhibitors, antiwear agents, and extreme
tute (API), U.S. Military, Original Equipment Manufacturers pressure (EP) agents. Additives may be designed either by al-
CHAPTER 9: ADDITIVES AND ADDITIVE CHEMISTRY 201
that make up the lubricant. The reaction sites, in order of de-

creasing ease of attack, are benzylic, allylic, tertiary alkyl, sec-
ondary alkyl, cind primary alkyl hydrogens. The result is the
formation of hydroperoxides and peroxy or other radicals.
POLAR MOIETY NON-POLAR MOIETY The rate of oxidation of hydrocarbons in addition depends
Surface Active Group Oleophilic Group
Contains oxygen, nitrogen, Consistsof a hydrocaibon upon the amount of oxygen, presence or absence of nitrogen
sulfur, or plK^honis chain oxides (NOx, a general term used for NO and NO2), ambient
temperature, and the presence or absence of metal ions.
Hydrocarbon oxidation is a three-step process, and com-
prises initiation, propagation, emd termination (Fig. 2). Initi-
NONPOLAR GROUP POLAR GROUP
ation involves the attack of atmospheric oxygen or of nitrogen
Oil-solubllizing Surface-active
oxides (NOx) on hydrocarbon molecules. The result is the for-
H H H H H . H H H H HH H H HH H!
mation of hydroperoxides (ROOH) and alkyl (R*) and peroxy
(ROO') radicals. During the propagation stage, hydroperox-
H3C' X X X W >^ >^ '>^ î ^^°" ides decompose either on their own or in the presence of metal
HHHHHH|!,,!,HHHHHH ;o
ions to alkoxy (RO') and peroxy radicals. These react with the
lubricant hydrocarbons to form a variety of additional radi-
Oleic Acid cals and oxygen containing compounds, such as alcohols,
aldehydes, ketones, and carboxylic acids [see the chapter on
FIG. 1—A general representation of a typical additive Oxidation]. Aldehydes and ketones are highly reactive and can
molecule. form polymers in the presence of acids, such as nitric and sul-
tering the strength of the polar functionahty or by changing furic acids. These acids result from the interaction of nitrogen
the size of the hydrocarbon chain. Changing the strength of oxides and sulfur oxides, products of combustion, with water.
the polar functionality alone is difficult and has its limita- Carboxylic acids attack iron, copper, and lead, present in the
tions. Changing the size of the hydrocarbon group, on the mechanical equipment, to form metal carboxylates that fur-
other hand, is much easier. In practice, both strategies are ther increase the rate of oxidation. During the termination
used. Whether an additive performs its function on the sur- stage, the radicals either self-terminate or terminate by react-
face or in the bulk lubricant depends on its polar to non-polar ing with oxidation inhibitors [8]. Oxidation inhibitors (InH)
ratio. With the strength of the polar moiety constant, addi- circumvent the radical chain mechanism by promoting de-
tives with small hydrocarbon groups have higher polar to
non-polar ratio than those with large hydrocarbon groups. As RH + O2 ROOH
a consequence, EP agents and rust inhibitors, which require
more surface activity, have small hydrocarbon groups; and RH + O2 ROO-+H ' Initiation
dispersants and detergents, which require a higher solubility RH +-NO, R- + HNOx
in oil, contain large hydrocarbon groups. Except in very few
cases, a connecting group or a link is necessary to connect
("tie") the two functionalities together. The importance of ROOH RO- + OH- >v
such a group is described in detail in the dispersants section.

ROOH + Fe+2 -*- RO- •»• OH' + Fe+3
ROOH + Fe*' -*• ROO- + Fe*^ + H*

StabilizersADeposit Control Agents
ROO - ••• RH -*• ROOH ••• R- > Propagation
This class of additives controls deposit formation. These ad-
ditives do so by inhibiting oxidative breakdown of the lubri- ROO- -*- R- ••• O2
cant to deposit precursors and by suspending those already
formed in the bulk lubricant. Oxidation inhibitors intercept RO - •!• RH -*• R O H -I- R-
the oxidation mechanism and dispersants and detergents do
OH- + RH •*- H2O + R- y
the suspending part.
Oxidation Inhibitors
ROO- + ROO- •*- RR + 2O2
All lubricants, by virtue of being hydrocarbon based, are sus-
ceptible to oxidation [7,8]. Many lubricants contain three ROO- + InH •*- ROOH + In-
major components: base oil, additives, and viscosity modi- >- Termination
fier, all of which have the susceptibility to oxidize. Each tjê RO- + InH -^ ROH + In-
of basestock, mineral, vegetable, or synthetic, has a stable
threshold beyond which stabilizers or oxidation inhibitors R- + InH -*• R H ••• I n -
are needed to retard oxidation. In terms of oxidative stability,

synthetic oils eire the most stable and vegetable oils are the RH = Hydrocarbon ROOH = Hydroperoxide
least stable. The oxidative stability of mineral oils is interme- RO- = Alkoxy Radical R - = Alkyl Radical
diate between the two.
InH = Inhibitor In- = Inhibitor Radical
Most lubrication applications expose lubricants to oxygen
in some manner. Oxygen reacts with hydrocarbon molecules FIG. 2—Oxidation mechanism.
composition of hydroperoxides and taking reactive radicals are provided in Fig. 3. Synthetic methods for polysulfides,
out of the oxidation process by reacting with them. Oxidation phosphites, and dithiophosphoric acid and dithicarbamic
inhibitors can be classified as hydroperoxide decomposers, acid derivatives are described in the antiwear and extreme
radical scavengers, or metal deactivators, depending upon the pressure agents section. Those for synthesizing alkylphenols
mode of their controlling action. are provided in the detergents section. Hindered phenols,
Sulfur containing compounds, such as sulfides a n d dithio- such as 2,6-di-?-butyl-4-methylphenol (BHT), a n d diaryl-
carbamates, and phosphorus containing compounds, such as a m i n e are p r e p a r e d by reacting phenol, alkylphenol, or
phosphites and dithiophosphates, act as hydroperoxide de- diphenylamine with an olefin in the presence of a Lewis acid
composers. Nitrogen a n d oxygen containing c o m p o u n d s , catalyst. The salicylidene meted deactivator is a product of
such as arylamines and hindered phenols, act as radical scav- phenol, formaldehyde, and ethylenediamine.
engers [8,9]. These chemicals convert chain-propagating Some oxidation inhibitor combinations are synergistic.
hydroperoxides and radicals to innocuous products. Some That is, they reflect an effect greater than the additive effect
inhibitors, such as dithiophosphoric acid derivatives and of two or more inhibitors. Such combinations usually, but
dithiocarbamates are extremely potent oxidation control not always, consist of compounds that intercept oxidation by
agents. This is because they act both as hydroperoxide de- two different mechanisms. An example is the combination of
composers and as radical scavengers. They in addition pos- a sulfur compound with an arylamine or a hindered phenol
sess antiwear properties. [13].
Transition metals can act as both oxidation initiators (pro- Oxidation inhibitors cire used in almost all lubricants, with
moters) and oxidation inhibitors, depending upon their oxi- gasoline and diesel engine oils and automatic transmission
dation state [8]. They act as promoters if they facilitate the fluids accounting for ~ 60% of the total use. High tempera-
formation of free radicals, and they act as inhibitors if they ture and high air exposure applications require a higher level
remove free radicals from the oxidation process [10]. For ex- of oxidation protection. Zinc diaJkyl dithiophosphates are the
ample, heavy metals, such as iron and lead, and their salts are primary inhibitor tj^pe, followed by eiromatic amines, sulfur-
well known as oxidation promoters [11,12]. Metal deactiva- ized olefins, and phenols.
tors, another class of oxidation inhibitors, are used to control A n u m b e r of tests are used to assess a lubricant's oxidation
oxidation under such circumstances. These inhibitors, pri- stability under accelerated oxidation conditions. ASTM Se-
marily used in fuels, form complexes with metal ions via quence IIIE/IIIF (viscosity increase), ASTM Sequence VE/VG
chelation, thus taking t h e m out of the chain reaction. (sludge and varnish formation), and CRC L-38 (bearing cor-
Ethylenediaminetetraacetic acid derivatives and N,N-disali- rosion) tests are used for engine oils. The CRC L-60-1 test is
cylidene-l,2-propanediamine represent the m o s t p o p u l a r used for gear oils a n d the ASTM D 943 and ASTM D 2272
members of this class. The structures of common inhibitors tests are commonly used for turbine oils.
1. Hydroperoxide Decomposers
R-S-(S)rS-R X = 0 or 1; R = alkyl or functionalized alkyl
DialkyI polysulfide
RQ.,,S
(R0)2R,
H
RO'%
Zn :>-c' CHo
R
DialkyI hydrogen Alkylphenol Zinc dialkyi Methylene coupled
phosphite dithlophosphate dlthlocarbamate
2. Radical Scavengers 3. lUletal Deactivators
2,6-DI-f-butyl-4-methylphenol Alkylated diphenylamine

[BHT (Butylated hydroxytoiuene)]
N, N-Disalicylldene-1,2-propanediamine
FIG. 3—Commonly used oxidation inhibitors.

RCH2CH(CH3)2 + O2 Hydroperoxide
CH3
_,OH
R<hr^=S:,^~. + O2 »- '^"-X^-^*^^ Hydroperoxide
Alkene
RCH2CH(CH3)2 +• N O , *- RCH2CH(CH3)2 + HNO,
o-
R ^ ^ C H 3
R^^N^CHj + . OH
CH3
CH3
Hydroperoxide Alltoxy radlcai
.OH
O O-
+ • NO, R ^ x k , ^ ^ + MONO
Hydroperoxide Allyloxy radical
ONO o-
1 I
/ • RCH2CH(CH3)2 »• RCH2CH(CH3)2
Nitrite Ester
RCH2CH(CHi)2 +• NO2
V RCHiCHCCHjlj- RCH=CH(CH3)2
NO2
NItroalkane
O ONO2
+ • NO2 — * • ^<!x^;^^^/^
Aliyioxy radical Nitrate Ester
FIG. 4—Formation and decomposition of nitrite and nitrate esters.
Dispersants In gasoline-fueled engines, nitrogen and oxygen present in

Dispersants are additives that suspend oil-insoluble resinous the air-fuel mixture react at high temperatures to form NO
oxidation products and particulate contaminants in the bulk and NO2. These oxides can react with hydrocarbons of the
oil. By doing so, they minimize sludge formation, particulate- fuel and the lubricant to form nitroalkanes and nitrite and ni-
trate esters [14,15]. The mechanism of their formation is
related abrasive wear, viscosity increase, and oxidation-
shown in Fig. 4. These esters and the hydroperoxides gener-
related deposit formation. Dispersants perform these func-
ated from the direct oxidation of the lubricant either ther-
tions by:
mally or hydrolytically decompose to form highly oxygenated
• solubilizing polar contaminants in their micelles. monomeric species [14]. These can polymerize to a slight de-
• stabilizing colloidal dispersions in order to prevent aggre- gree under the influence of heat to form resin, varnish, lac-
gation of their particles and their separation out of oil. quer, deposits, and sludge (Figs. 5 and 6). Resin is made up
• suspending such products, if they form, in the bulk lubri- of oligomeric molecules with an approximate molecular
cant. weight of 500-700. Varnish, lacquer, and deposits comprise
• modifying soot to minimize its aggregation and oil thick- materials of much higher molecular weight. The sludge, de-
ening. pending upon the severity of the operation, can be watery in
• lowering surface/interfacial energy of dirt to decrease its consistency or thick like a semi-solid.
tendency to adhere to surfaces. In diesel-fueled engines, soot from the combustion cham-
Dirt is a generic term that describes undesirable materials ber is the key component of carbon and lacquer deposits that
that result from oxidative degradation of the lubricant, the occur on pistons, and sludge. These deposits result when soot
reaction of chemically reactive species (such as carboxylic combines with resin. In general, lacquer is rich in resin, and
acids) with the metal surfaces in the engine, or the decompo- carbon is rich in soot. Sludge results when soot combines
sition of thermally unstable lubricant additives, such as ex- with the oxygenated species, oil, and water [16]. Local piston
treme pressure agents. temperatures and the lubricant's ash-producing tendency
2 0 4 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK
Partially Combusted Fuel

Fuel
JNOx
Liquid Nitrated and Oxygenated lUlonomers
Oil Insoluble Products (Resin)

\ Carbon
Lubricant \ Water
\ Solids
/
Varnish »-Sludge
Resin -•" Varnish
Accumulate as
Resin-coated deposits in areas
Soot Particles of low oti velocity
Resin + Soot
Soot-coated -*- Lacquer
Resin Particles
Resin + Soot + Oil + Water Sludge

FIG. 5—Mechanism of deposit formation.
Because of low oil-solubility, resin tends to separate out as

amber lacquer on hot piston surfaces. If oil contains soot,
soot separates with resin to form "resin-coated soot particles,"
which appear as black lacquer. As the soot level increases,
more and more soot associates with resin to form "soot-
* coated resin particles." These events are shown in parts A and
B of Fig, 6. The size and the composition of these particles do
not allow them to adhere to metal surfaces. However, they
can collect in areas of low oil flow, such as piston grooves, as
deposits.
Dispersants suppress the interaction between resin and
soot particles, by preferentially associating with them and, at
the same time, keeping them suspended in the bulk lubricant.
Since both resin and soot particles are polar in character, ei-
ther by their very nature or due to adsorbed polar impurities,
the dispersant associates with these particles via its polar
end. As mentioned earlier, all additive tjês, except some vis-
cosity modifiers and pour-point depressants, contain a polar
^ functional group and a non-polar oleophilic hydrocarbon
A Soot ^ Resin o- Additive moiety. The polar group, which in dispersants is oxygen or
nitrogen-based, attaches itself to oxidation products, such as
FIG. 6—Mechanism of soot-resin-additive interaction. resin, soot, and sludge peirticles. The oleophilic hydrocarbon
group keeps them suspended in oil [16]. These situations are
depicted in parts C and D of Fig. 6.
(ASTM D 482) have a profound effect on the composition of The performance of dispersants can be explained by con-
carbon deposits. High temperatures and lubricants with high sidering the concepts of steric stabilization and electrostatic
metal content primarily produce deposits with high residue stabilization. According to steric stabilization, once the dis-
and low organic content [17]. Metals are the main source of persant molecules attach themselves to either resin or soot
ash. Basic detergents contain meted and therefore are con- particles, their long hydrocarbon chains prevent agglomera-
sidered to contribute towards ash. Zinc dialkyl dithiophos- tion of the particles [16]. This is depicted in Fig. 7. The elec-
phates also contribute, but only slightly. trostatic mechanism is based on repulsion between particles
Hydrocarbon Chains of with like charges, which minimizes agglomeration. The de-
Adsorbed Dispersant velopment of charged particles in a low-dielectric medium,
such as oil, can be explained in two ways [18]. According to
the first explanation, the dispersant is already ionized and
through adsorption imparts a chcirge to the particle (depicted
by mechanism A in Fig. 8). According to the second explana-
tion, the non-ionized dispersant adsorbs onto the surface of
the particle, an acid-base reaction involving the transfer of a
proton or another ion occurs, and the counter-ion desorbs re-
sulting in the formation of a charged particle. Particles with
like charges repel one another, thereby preventing agglomer-
ation. This is shown in part B of the exhibit. Neutral and high
soap detergents, discussed in next section, are believed to
perform via this mechanism. It is important to note that for
Separation certain classes of dispersants, both mechanisms might be op-
Distance erating simultaneously.
FiG. 7—iVIeclianism of steric stabiiization. Interestingly, empirical data suggest that the ionic mecha-
nism, although it seems unlikely due to the organic nature of
the lubricant medium, does operate [18].
The essential performance features in a dispersant are its
thermal and oxidative stability, its low-temperature proper-
ties, and above all its ability to disperse soot, deposits, and
deposit precursors. Poor thermeJ stability can impair a dis-
persant's ability to disperse polar oxidation and decomposi-
tion products in the bulk lubricant. Poor oxidative stability
can make a dispersant contribute towzirds deposit formation.
Low temperature properties of the modem lubricants are
c : ^ ^ { Particle ) ^ ^ gaining importance. The use of light base oils to meet low
temperature requirements in finished lubricants is no longer
possible because of the volatility specifications (ASTM D
5480 and D 5800). The use of pour point depressants for
paraffinic oils has limited utility because it only affects some
low temperature properties, such as pour point, but not oth-
ers, such as cold cranking. Base oil manufacturers therefore
use a number of strategies to develop base oils with good low
temperature properties. These include isomerization via hy-
drocracking and use of special synthetic oils as additives. Be-
cause dispersant is a major component in engine oil formu-
lations, its structure can antagonize low-temperature
properties of these oils. And of course soot and deposit con-
trol, or dispersancy, are the primary functions of a disper-
sant. If a dispersant does not possess these properties, it is
not effective as an additive.
A dispersant contains three structural features: a hydrocar-
bon group, a polar group, and a group that connects the two
cAi, c^^ together, the connecting group or a link. These are depicted
in Fig. 9 by a graphic representation of a disperscuit molecule.
FIG. 8—Tlie meclianism of eiectrostatic stabiiization. (a) by While each structured feature affects a different property or
ionized dispersant. (b) by un-ionized dispersant. properties in a dispersant, all three are essential to a disper-
sant's oversdl performance. The nature of the hydrocarbon
Connecting Group
Nitrogen or o)^gen _
Derived Functionality
FiG. 9—Graphiic representation of a dispersant molecule.

group impacts all key properties, namely, thermal and oxida- monly used polyalkylene) of molecular weight between 440
tive stability, low-temperature performance, and disper- and 5000 is reacted with maleic anhydride, either thermally
sancy. Its structure can influence a dispersant's thermal and or in the presence of chlorine, to yield a succinic anhydride.
oxidative stability and low-temperature properties. Its degree Reaction of the succinic anhydride with amines (polyalky-
of branching can improve or hurt the low temperature prop- lene-polyamines and heterocyclic polyamines) results in the
erties and compatibility with the additive package. Its molec- formation of succinimide dispersants. The corresponding re-
ular weight can affect dispersancy. The hydrocarbon radical action of the succinic anhydride with alcohols, especially
in dispersants is oligomeric or polymeric and is usually polyhydric alcohols, results in the formation of succinate es-
aliphatic in nature. It contains 70 to 200 or more carbon ter dispersants. Figure 10 summarizes the syntheses of
atoms to ensure good oil solubility. A polyisobutenyl alkyl alkenylsuccinimides and alkenylsuccinates. Mannich disper-
group is the most commonly used hydrocarbon group. In sants are produced by the condensation of a high molecular
some dispersants, the hydrocarbon moiety is derived from a weight alkylphenol (polyisobutylphenol), an aldehyde, and
high molecular weight polymer, such as olefin copolymer, polyalkylene-polyamines. Phosphonic acid ester dispersants
polyacrylate, polymethacrylate, or styrene-ester polymer. are prepared by reacting phosphonic or thiophosphonic
Such dispersants can also function as viscosity modifiers and acids with ethylene oxide or propylene oxide. The starting
are appropriately called dispersant viscosity modifiers. acids are obtained from the hydrolysis of olefin-phosphorus
The link is the weakest portion of the dispersant molecule pentasulfide adducts. The preparation of Mannich products
because of its chemical structure. It can fall apart thermally and phosphonic esters is described in Fig. 11.
or chemically, making a dispersant ineffective. The most While in most cases starting polyalkylene has a molecular
commonly used polar groups are alcohol and amine derived. weight of 1000 or 2000, the resulting succinimide and succi-
They can oxidize, hydrolyze, and or thermally degrade and nate dispersants have molecular weights that are 3-7 times
make dispersant molecule lose its structural integrity. The higher. This is due to the bifunctionality of the alkenylsuc-
size and the nature of the polar group (whether it is oxygen cinic anhydride and the polyfunctionality of the alcohols and
or nitrogen-based) determine dispersancy. amines that are used to make dispersants. The result is the
Chemical classes suitable for use as dispersants include formation of bridged structures that increase a dispersant's
cilkenylsuccinimides, alkenylsuccinate esters, high molecular dirt-suspending ability via more extensive interaction. The
weight amines, Mannich bases, and phosphonic acid deriva- bridged structure of a dispersant is graphically depicted in
tives. Polyisobutenylsuccinic acid derivatives (succinimides Fig. 12.
and succinate esters) are commercially the most commonly Dispersants have major uses in gasoline engine oils, diesel
used dispersant types. engine (heavy-duty and railroad) oils, natural gas engine
Both succinimides and succinate esters are prepared from oils, and aviation piston engine oils. Dispersants are also
alkenylsuccinic anhydrides. Polyisobutylene (the most com- used in automatic transmission fluids and gear lubricants.
PIB
•<"
Polyisobutylene Maleic Anhydride Polyisobutenyl
Succinic Anhydride
PIB H2NCH2CH2NHCH2CH2N ""'^ ~ | ,NCH2CH2NHCH2CH2l<^

\
Alkylenepolyamlne
Polyisobutenyl Polyisobutenylsucclnlmlde
Succinic Anhydride
H2 R'
R'
PIB ,C /
I Y~CH20
PIB
R
HOH2C-C—CH2OH
I
R V o
Polyisobutenyl Polyol <j^^CH20-
Succinic Anhydride
R
Polylsobutenylsuccinate Ester
FIG. 10—Synthesis of alkenylsuccinimides and alkenylsuccinates.

MANNICH DISPERSANTS
?" H /
Js.,.CH2NCH2CH2NHCH2CH2Nv
CH2O + H2NCH2CH2NHCH2CH2N
R' Alkylenepolyamine '^ Polyaminomethylalkylphenol
Alkylphenol
R=Polyisobutyl Group
PHOSPHONIC ACID DISPERSANTS
PIB + P2S5 *• Adduct — ? — • PIB—P-OH or PIB—P-OH

Polylsobutylene Phosphorus OH OH
Pentasulfide
Polyisobutylenethiophosphonic Acids
S S CH3
11 II I
PIB—P-OH + Pro - PIB—P—OCH2CH — O H Bis-hydroxypropyl
I I Alkenylthiophosphonate
OH
OCH2CH — O H
Alkenylphosphonic Propylene Oxide I
Acid CH,
FIG. 11—Synthesis of Mannich and phosphonic acid dispersants.
Aikenylsuccinic acid or Alkylphenol

Derived Connecting Group
Nitrogen or Oxygen Derived
Functtonallty \
Alkylene or Pdyalkyleneamine Hydrocarbon

Derived Bridging Group Groups
Nitrogen or Oxygen Derived

Functtonality Altenylsuccinic acid or Alkylphenol
Derived Connecting Group
FIG. 12—A representation of the bridged structure of a dispersant.

Gasoline a n d heavy-duty diesel engine oils account for low. The excess base per equivalent of acid in metal hydrox-
75-80% of the toted dispersant use. Succinimide and succi- ide-containing detergents is generally lower t h a n t h a t in
nate ester (pentaerythritol esters of polyisobutenylsuccinic metal carbonate-containing detergents. Detergents are de-
anhydride) dispersants are used in both gasoline and diesel scribed chemically in terms of their metal ratio, soap content,
engine oils. High molecular weight amines and Mannich sulfated ash (ASTM D 874), degree of overbasing or conver-
dispersants are used in gasoline engine oils only. Succin- sion, and total base n u m b e r (TBN) [5].
imide dispersants are often used in automatic transmission Let us represent a detergent, for example a basic calcium
fluids, power steering fluids, and, to a limited extent, in gear sulfonate, by the general formula (RS03)vCaw(C03)a:(OH)y ,
oils. Both types are also used as fuel additives. The use of where v, w, x, and y denote the n u m b e r of sulfonate groups,
phosphonate dispersants is generally restricted to non-en- the n u m b e r of calcium atoms, the n u m b e r of carbonate
gine lubricants. This is because engine oils have a phospho- groups, and the n u m b e r of hydroxyl groups, respectively. The
rus limit due to its adverse effect on catalj^tic converters. metal ratio is defined as the total equivalents of metaJ per
The formulators prefer to use zinc dialkyl dithiophosphates equivEdent of acid. Since calcium is a divalent metal, each
instead because they are potent oxidation inhibitors as well atom of calcium represents two equivedents. Hence, the metal
as good antiwear agents. ratio can be Ccilculated by the equation.
In gasoline and diesel engine oils, the effectiveness of a dis-
persant is determined by its ability to suspend oil-insoluble 2\v
Metal Ratio =
products of combustion, oxidation, and oil degradation. In
the laboratory screen tests, this is assessed by a dispersant's
The degree of overbasing describes the ratio of equivalents of
ability to either disperse lamp black or used engine oil sludge.
the metal base to equivalents of the acid substrate and is usu-
However, in the laboratory engine tests, such as the ASTM
ally expressed as conversion. Conversion indicates the
Sequence VEA'^G Test and various diesel engine tests (Cater-
a m o u n t of inorganic materied relative to that of the organic
pillar IK, IM-PC, IN, IP, and IR), a pass rating in varnish,
material and is expressed as the n u m b e r of equivalents of
sludge, and deposits is required.
base per equivalent of acid times 100.
Detergents N u m b e r of equivalents of base ^ . „ „

Conversion
Number of equivalents of acid
Detergents perform functions similar to those of dispersants; 2w
that is, they suspend oxidation products and sludge particles X 100
in the lubricant. Detergents, in addition, have the ability to
neutralize acidic combustion and oxidation products; there- In other words, conversion is the metal ratio times 100. Neu-
fore they control rust, corrosion, and resinous build-up in the tral detergents have a conversion of 100 because the ratio of
engine. Detergents, like dispersants, contain a surface-active equivalents of base to the equivalents of acid is 1. Soap con-
polar functionality a n d a n oleophilic hydrocarbon group tent refers to the a m o u n t of neutral organic acid salt and re-
with an appropriate n u m b e r of carbon atoms to ensure good flects a detergent's cleansing ability, or detergency, and dirt
oil solubility. Sulfonate, phenate, carboxylate, salicylate, and suspending ability. The soap content can be determined by
phosphonate are the common polar groups present in deter- the use of the following formula.
gent molecules.
Detergents eire metal salts of organic acids. Common acids Percent soap Formula weight [(RS03)2 Ca] X 100
that are used to sjrathesize these compounds include alkyl- Effective formula weight
benzenesulfonic acids, alkylphenols, carboxylic acids, and
Effective formula weight is the combined weight of all
alkenylphosphonic and alkenylthiophosphonic acids. The
atoms that make u p the formula (RS03)vCaw(C03);c(OH),
quantity of metal used may be equal to or in excess of the pre-
plus that of the diluent. The percent sulfate ash is the ash ob-
cise amount (stoichiometric amount) necessary to completely
tained after treating the detergent with sulfuric acid and ig-
neutralize the acid function. When the metal is present in the
nition. The knowledge of ash-producing tendency of a lu-
stoichiometric amount, the detergents are called "neutral."
bricant is important to the formulator (ASTM D 482). This
When it is present in excess, they are called "basic, overbased,
is because combustion of the lubricant results in ash that
or superbased." The general formulas for basic metal sul-
can contribute to deposits in those areas of the engine that
fonate, metal phenate, and metal carboxylate are given below.
are in close proximity to the combustion chamber, such as
the piston top land and the groove behind the top piston
(RS03)a M • xMfcCOs • yM(OUX
ring.
Basic Sulfonate
The total base number, or TBN, of the detergent indicates
(RPhO)aM • xMfcCOa • yM{OU)c its acid neutralizing ability and is expressed as mg KOH/g of
Basic Phenate additive. Both the acid n u m b e r and the base number are ex-
(RCOO)aM • xMbCOs • >'M(OH)<; pressed in this fashion. The convention regarding its use and
Basic Carboxylate the details on how to calculate acid and base numbers are de-
scribed in the ASTM Standard D 974. TBN can be calculated
Where a,b, and c = 1 or 2, depending upon if the metal M is from the number of equivalents of the excess metal after salt-
monovalent or divalent. ing the acid, that is (2w — v), as follows.
Detergents may contain the excess base as metal hydrox-
ide, metal carbonate, or both. For noncarbonate detergents, (2w - v) X 56100
TBN (mg KOH/gm)
X in the above formulas is zero. For carbonate detergents, y is Effective formula weight
For a monovalent metal, (w — v) will be used instead. In ad- in Group III. The ability to overbase is directly related to a
dition to the alkylbenzenesulfonic acids, alkylphenols, car- metal's base strength. For Group I metals, basicity increases
boxylic acids, and alkenylphosphonic acids that were men- from lithium to sodium to potassium. For Group II metals, it
tioned earlier, sulfur-coupled and methylene-coupled increases from magnesium to calcium to strontium to bar-
alkylphenols are also used as detergent substrates. The meth- ium. It is, therefore, most difficult to overbase lithium in
ods of synthesis of these substrates are presented in Fig. 13. Group I and magnesium in Group II.
Alkylbenzenesulfonic acids are obtained by sulfonating alkyl- Metals commonly used to make detergents are sodium,
benzenes. The products obtained by sulfonating alkylaro- magnesium, calcium, and barium. Of these, calcium and
matics from petroleum refining are referred to as "natural" magnesium are used most widely, with a clear preference for
sulfonates and those obtained by sulfonating cilkylaromatics calcium due to its lower cost. The use of barium is being lim-
from the catalytic alkylation process are referred to as "3501- ited due to both the toxicity and the economic concerns. The
thetic" sulfonates. bases of choice are caustic (sodium hydroxide) for sodium
Alkylphenols eire prepared from phenol and an olefin by the detergents; lime (calcium hydroxide) for calcium detergents;
use of an acid catalyst. These alkylphenols can be further re- magnesium oxide for magnesium detergents; and barium hy-
acted with sulfur, sulfur dichloride, or formaldehyde to form droxide for barium detergents. For basic detergents that con-
sulfur-bridged and methylene-bridged alkylphenols. Alkylsal- tain excess base, the base may be present as is or as metal car-
icylic acids are prepared by the use of the Kolbe process, bonate. In practice, virtually all commercial detergents are
which involves reacting an alkali metal phenate with carbon overbased to some extent. For example, commercial "neu-
dioxide. Alkenylphosphonic acids are the hydrolysis products tral" sulfonates have a TBN of 30 or less. "Basic" detergents
of polyisobutylene-phosphorus pentasulfide adducts. typically have a TBN of 200 to 500.
Detergents are prepared by reacting an organic acid with Sulfonate, salicylate, and carboxylate detergents are com-
an appropriate metal base in the presence of a polar pro- mercially available as calcium and magnesium salts. Phenate
moter. Overbasable metals that can be used to prepare basic detergents are available as calcium salts and phosphonate de-
detergents are lithium, sodium, and potassium in Group I tergents are available as barium salts only. Basic calcium sul-
and magnesium, calcium, strontium, and barium in Group II fonates make up ~ 65% of the total detergent market, fol-
of the periodic table. Aluminum is the only overbasable metal lowed by phenates at ~ 31%.
SO3H
SO,
!<
R
Alkylbenzene Alkylbenzenesulfonic
Acid
COOK
Olefin
Plienol
R=Alkyl Group
Sulfur CoupledAlkylphenol Methylene Coupled

or Phenol sulfide Alkylphenol
H,0
PIB P,S
2*»5 Adduct •• RIB—P-OH
I
Polyisobutylene Phosphorus OH
Pentasulfide
Polyisobutenylphosphonic
Acid
X = O or S
FIG. 13—Detergent substrates.
The method of preparation of neutral and basic detergents with these compounds and keep t h e m in solution. The mech-
is outhned in Fig. 14 and the general structures for neutral anism by which detergents perform is analogous to that of
detergents are shown in Fig. 15. Basic detergents can be con- dispersants, which is shown in Figs. 7 and 8. Depending upon
sidered neutral detergents that contain excess base in an as- the lubricant's end-use, insoluble by-products may be soot,
sociated form. The structure of detergents can be envisioned acidic decomposition products, or deposit-forming resinous
as a reverse micelle, with a n a m o r p h o u s metal carbonate species [14,16]. Detergents control the buildup of these un-
molecule encapsulated by metal soap molecules with their desirable contaminants by keeping equipment surfaces clean
non-polar ends extended into the oil. This is depicted in Fig. and neutralizing acidic products from lubricant oxidation
16. and decomposition. They keep surfaces clean by forming a
Detergents are used in lubricants to perform functions sim- protective film via adsorption and by suspending deposit-
ilar to those of dispersants: that is, to keep oil-insoluble by- forming species in the bulk oil through association [7].
p r o d u c t s of c o m b u s t i o n and oil oxidation in suspension. Detergents can also act as oxidation inhibitors, depending
These products, which are polar organic compounds, include u p o n the n a t u r e of their functional group. For example,
alkyl nitrites and nitrates, nitroalkanes, carbonyl compounds phenates, sulfurized phenates, and salicylates possess oxida-
(aldehydes, ketones, and carboxylic acids), and oligomers re- tion-inhibiting properties, primarily due to the presence of
sulting from their thermal reaction. Detergents associate the phenolic functional group.
Substrate + Metal Oxide or Hydroxide -*- Neutral Salt

M„0 M{OH)„
stoichiometric Amount
Substrate + IMetal Oxide or Hydroxide ^ ^ »• Basic or Overbased

M„0 iW{OH)„ No CO, Salt
Stoicliiometnc Excess
Basic Salts = Neutral Salts • M„0, M(OH)„ or MnCOs
R/l = Na, Mg, Ca, Ba n « 1 or 2

FIG. 14—Synthesis of detergents.
^?\.S03)xM 0)xlWI
0)xlWI
R R
Metal Sulfonate Metal Salicylate
or
Sulfur and Methylene Bridged Phenates
s o o X = 1 or 2
R—P-O r. n « II II
Y = S or CHa
I I R—P-O R_p_s-p-R
O-IW ' ' I I lUI = Na, lUlg, Ca
0-iw o^ .o
M
Metal Metal Metal
Phosphonate Thiophosphonate Thiopyrophosphonate
FIG. 15—Idealized structures for neutral detergents.

O
II
-s-o
'6 \
II /
-s-o
II
o
Sulfonate
Hydrocarbon Head Group Basic Sulfonate Inverse Micelle
Group
Structure — Size: 100-150A°
Neutral Calcium Sulfonate
FIG. 16—Micellar structure of detergents.
Mack T-6, T-7, T-8/E, T-9, and T-10). Detergents have addi-
tionEil use in automatic transmission fluids and tractor hy-
draulic fluids. However, their use in these applications is not
Additive It/lolecule Metal Surface to control deposits but to modify the fluid's frictional proper-
ties.
Film-Forming Agents
Lubrication is necessary to facilitate the counter-movement
Physisorption of two sliding surfaces. This function, which is usually per-
formed by the base oil, can be enhanced by using high vis-
cosity oils [19]. However, beyond a certain threshold temper-
ature, the lubricant fails to form an effective film, and
friction and wear can result. The lubricant's film-forming
ability under such circumstances can be made more efficient
Cliemisorption by using film-forming agents. Such agents can interact with
metal surfaces either through adsorption or chemical reac-
tion. PhysicaJ adsorption, or physisorption, is a weaker asso-
ciation of the additive with metal than chemical adsorption,
or chemisorption, which in turn is weaker than chemical re-
action. During adsorption, an additive molecule generally
o o o o o o keeps its structural integrity. In a chemical reaction, how-
ever, it has the tendency to lose it because it gets converted
o o o o o o into new molecules. The modes of interaction of additive
molecules with the surface [20] are depicted in Fig. 17.
Chemical Reaction
Friction Modifiers
FIG. 17—Modes of additive - surface interactions. Friction modifiers are agents that modify the frictional prop-
erties of a lubricant. These are long-chain molecules with a
polar end group and a non-polar linear hydrocarbon chain.
Detergents have major use in crankcase lubricants. Gaso- The polar end groups either physically adsorb onto the metal
line and diesel engine oils account for over 75% of the total surface or chemically react with it while the hydrocarbon
detergent consumption. Detergent treatment levels in engine chains extend into the lubricant. These chains associate with
lubricant formulations are fairly high, with marine diesel en- one another and the lubricant to form a strong lubricant film
gine lubricants containing the highest detergent concentra- [21]. This is shown in Fig. 18.
tions. Marine engines use high-sulfur fuel, which leads to These additives are used to decrease or increase friction,
acidic combustion products (sulfuric acid). Therefore, lubri- depending upon the application. In engine lubricants and
cants for these engines need the base reserve of the "basic" gear oils, their primary function is to reduce friction, mini-
detergents for neutralization. mize wear and noise, and improve fuel economy by lowering
Detergency in diesel engine oils is evaluated by using both the power loss. In transmission and hydraulic fluids, these
single cylinder engine tests (Caterpillar IK, IM, IN, IP, and additives are used to facilitate timely engagement and disen-
IR) and multicylinder engine tests (GM 6.2L and 6.5L; and gagement of clutches and bands to assure smooth and noise-
Cohesion or Association
with Lubncant
Ifl \ ^
\!* ^ " " ^ ^ ^ ^
" X ^ ^ " A ^ ^V^
H ^ ^ H HtOT fVSft<
HHZH" H^^HH ^ ^ H ^ » ^
QH^H H-4HQ „ H ^ Hfi^

o p
(A) Physisorption
(B) Chemisorption
FIG. 18—Adsorption of polar additives on the metal surface.
boundary lubrication. Figure 20 shows the friction-reducing

capability of these additives in automatic transmission flu-
ids. At low sliding speeds, where metal to metal contact is
likely; friction modifiers interact with surfaces in the manner
discussed above and minimize such contact, and the associ-
ated rough shifting. However, at high speeds, their effect is
not as dramatic because such speeds promote hydrodynamic
lubrication. These additives minimize brake chatter in trac-
tors in an analogous manner.
Due to government regulations, increasing fuel costs, and
efforts to conserve resources, lubricants that can provide bet-
ter fuel economy are becoming more desirable. Energy Con-
serving engine lubricants are designated as Energy Conserv-
ing I (EC-I) or Energy Conserving 11 (EC-II), depending upon
Crankcase Temperature (°C) the extent of fuel conservation [23]. While the use of friction
FIG. 19—The effect of friction-modified lubricant on engine modifiers helps, other factors such as the lubricant viscosity
power loss. grade, the type of viscosity modifier used, and the nature of
the other additives present in the lubricant, all play an im-
portant role [24].
Frictional properties of transmission and hydraulic fluids
free operation. The effect of friction modifiers on the engine are extremely important. The frictional compatibility of the
power loss [22] is depicted in Fig. 19. At low ambient tem- fluid with the functioning parts of transmissions and wet
peratures, where lubricant viscosity is high enough to form brakes and wet clutches in tractors assures their smooth and
an effective lubricating film, friction modifiers have little ef- noise-free (chatter-free) operation. Frictional properties play
fect in minimizing power loss due to friction. However, at an equally important role in gear oils. In standard applica-
high temperatures, friction modifiers become more effective tions, friction-modified gear oils not only protect gears and
because of the loss of lubricant viscosity, which may lead to axles against frictional damage but they also contribute to-
0.16 TABLE 1—The effect of friction modifiers in gear oils.

LFW-1 Machine Coefficient of Friction
GL-5 gear oil (80W-90) 0.057
GL-5 gear oil (80W-90) 0.054
+ 1% friction modifier
GL-5 gear oil (75W) 0.055
GL-5 gear oil (75W) 0.052
Coefficient of Friction
LVFA Machine Static Dynamic
GL-5 gear oil (75W) 0.070 0.052
GL-5 gear oil (75W) 0.050 0.042
20 30 40 50 60 GL-5 gear oil (75W) 0.052 0.043
Sliding Speed (cm/s) + 1% oleic acid
GL-5 gear oil (75W) 0.062 0.050
FIG. 20—Friction reducing ability of an automatic transmission + l%ArmeenHT
fluid.
O SAE 7SW Oil + Friction Modifier
• SAE 75W Semi-syntlietic Oli
wards fuel economy. For limited-slip axles, which contain

friction clutches and cones, friction-modified gear lubricants
minimize noise arising from stick-slip. LFW-1 (Alfa Laval
Load, Friction, and Wear Test) and LVFA (Low-Velocity Fric-
tion Apparatus) data for gear oils showing the effect of fric-
tion modifiers on friction [25] are presented in Table 1. As
can be seen from the table, friction modifiers decrease static
and dynamic coefficient of friction in both the single grade
and the multigrade oils. In general, friction-modified gear
oils show an increase in axle-efficiency relative to normal
gear oils. This is shown in Fig. 21. Axle efficiency is better 110
both for urban and highway driving. Axle efficiency is be- Sump Temperature (°C)
lieved to have a positive correlation with fuel economy.
Under heavy loads, the EP agent replaces the friction mod- FIG. 21—The effect of a friction modifier on axle efficiency of
a gear oil.
ifier and takes over the function of preventing damage. As the
load decreases, friction modifiers again come into action.
Friction modifiers have a finite life, which is related to their
oxidative and thermal stability. These additives are com- modifiers. Graphite presents problems when used in conven-
monly used in gasoline engine oils, automatic transmission tional lubricants; hence, at present, its use is limited to
fluids, tractor hydraulic fluids, power steering fluids, shock greases.
absorber fluids, and metalworking fluids. In passenger car The effectiveness of friction modifiers and antisquawk
applications, these additives help in meeting federal govern- agents is judged by the lubricant's performance in LVFA and
ment-mandated fuel economy requirements. In ATFs and SAE # 2 tests. Their load-carrying capacity is determined by
limited slip axle lubricants, friction modifiers are used to the film strength tests, such as the Timken test.
control clutch and band engagement. Antisquawk additives,
which are functionally similar to friction modifiers, are used Antiwear and Extreme Pressure Agents
to reduce objectionable mechanical noise, such as squawk Wear occurs in all equipment that has moving parts in con-
and chatter. Antisquawks are primarily used in automatic tact. Three conditions that can lead to wear are surface-to-
transmission and tractor hydraulic fluids, automotive gear surface contact, surface contact with foreign matter, and ero-
oils, and some industrial oils. sion due to corrosive materials. Wear resulting from
This class of additives includes fatty alcohols, fatty acids, surface-to-surface contact is frictional or adhesive wear,
fatty amides, molybdenum compounds, and graphite. For the from contact with foreign matter is abrasive wear, and from
fatty alcohol and fatty acid families, friction-modifying prop- contact with corrosive materials is corrosive wear. Fatigue
erties are a function of the length and the structure of the hy- wear is an additional tjrpe of wear that is common in equip-
drocarbon chain and the nature of the functional group. ment where surfaces are not only in contact but also experi-
Long and linear-chain materials reduce friction more effec- ence repeated stresses for prolonged periods. Abrasive wear
tively than short and branched-chain materials. Also, fatty can be prevented by installing an efficient filtration mecha-
acids are better than fatty amides, which in turn are better nism to remove the offending debris. Corrosive wear can be
than fatty alcohols. Saturated acids, containing a 13 to 18 controlled by using additives that neutralize the reactive
carbon chain, are generally preferred. Lower molecular species that attack the metal surfaces. The control of adhe-
weight fatty acids are avoided because of their corrosivity. sive wear requires the use of additives called antiwear and ex-
Fatty acid derivatives are the most commonly used friction treme pressure (EP) agents.
Under normal conditions of speed and load, two metal suring fluids. For GF-2 and API SH and SJ quality engine oils, ASTM
faces are effectively separated by a lubricant film; a condition Sequence IIIE and VE engine tests are used to determine the ef-
identified as hydrodynamic lubrication. An increase in load or fectiveness of antiwear agents. However, for API SL and ILSAC
a decrease in speed promotes metal-to-metal contact. This GF-3 categories (approved in 2001), ASTM Sequence IIIF, IVA,
causes a temperature rise in the contact zone due to frictional and VG engine tests are used. To determine the performance of
heat, which results in the loss of lubricant viscosity a n d EP agents in gear oils, the CRC L-37 and CRC L-42 axle tests are
hence its film-forming ability. With a progressive increase in used. The general effectiveness of these additives in metalwork-
load and/or a decrease in viscosity, the nature of lubrication ing fluids is determined by Timken, Four-Ball, and Falex tests.
changes from hydrodynamic to mixed-film to boundary lubri- Extreme pressure additives are usually supplemented with anti-
cation. Antiwear additives and EP agents offer protection un- wear additives to make the formulations effective at lower tem-
der mixed-film andboundary lubrication conditions [26]. This peratures and under milder loading conditions as well.
is shown in Fig. 22, Part B [27]. Most antiwear and extreme pressure agents contain sulfur,
Antiwear and EP additives both provide protection by a chlorine, phosphorus, boron, or combinations thereof. The
similar mechanism, except that EP additives typically require classes of compounds that inhibit adhesive wear include alkyl
higher activation temperatures and load than the antiwear and aryl disulfides and polysulfides, dithiocarbamates, chlo-
additives. Simply stated, antiwear additives perform under rinated hydrocarbons, and phosphorus compounds such as
mild conditions and EP additives perform under severe con- alkyl phosphites, phosphates, dithiophosphates, and
ditions. The severity of conditions is determined by the "load alkenylphosphonates.
factor" experienced by the additive and the temperature at Both antiwear and extreme pressure additives function by
which the additive functions. Load is a function of equip- thermal decomposition and by forming products that react
ment speed and service. Heavy loading requires the use of ex- with the metal surface to form a solid protective layer. This
treme pressure agents and mild loading requires the use of solid metal film fills the surface cavities (asperities) and fa-
antiwear agents. Thus, it is important to consider both the cilitates effective film formation, thereby reducing friction
load and the temperatures that the equipment is likely to ex- and preventing welding and surface wear. The meted films
perience before selecting these additives. consist of iron halides, sulfides, or phosphates, depending
Antiwear agents are commonly used in engine oils, automatic upon the antiwear and EP agents used. Friction modifiers
transmission fluids, power steering fluids, and tractor hydraulic differ from antiwear and extreme pressure agents in that they
fluids. Extreme pressure agents are used in other power-transform the protective film via physical Eind chemical adsorp-
mitting fluids, gear oils, shock-absorber fluids, and metalwork- tion instead of chemical reaction.
Lubricant-
Film
FLUID-FILM LUBRICATION
Surfaces well separated by
the bulk lubricant film
A 1 1 Lubricant
Film
.. * J 1 Boundary Lubrication
MIXED-FILM LUBRICATION
c ! \ / - ^ Mixed-film Lubrication Both the bulk lubricant and
the boundary film play a
role
u.
"5
c
a>
8 —- » Fluid-film Lubrication BOUNDARY LUBRICATION

o Performance essentially
depends upon the quality of
.ZN. the boundary film
P
(A) RELATIONSHIP OF VISCOSITY (2), (B) GRAPHIC REPRESENTATION OF
LUBRICANT FILM THICKNESS IN
SPEED (AO, AND LOAD (P) TO
DIFFERENT LUBRICATION REGIMES
FRICTION AND FILM THICKNESS
FIG. 22—Types of lubrication.

.^'
4R0H + P2S5 - • 2 (R0)2P, + H2S
\
SH
DialkyI Dtttiiophosphoric
Acid
.^' Zn + H2O
2 (RO)2P. + ZnO (R0)2P-
\ .
SH
DiaikyI Dithjophosphoric Zinc DialkyI
Acid Dithioptiosphate
Activated
2 CH2=CH—<
Olefin
OR
2 (ROhP,
i^°l< Zn
J2
5 Cn2 CH2 C. Zinc Diaryl
OR Oithiophosptiate
DialkyI Ditliiophosphate
Ester
THERMAL STABILITY:
Aryl > Primary Alkyl > Secondary Alkyl
ANTIWEAR ACTION:
Secondary Alkyl > Primary Alkyl > Aryl
FIG. 23—Syntiiesis of dialkyi dithiophosphoric acid derivatives.
The film-formation by these additives is a two-step process. Dithiophosphoric acid derivatives decompose, generally
The adsorption of the chemical onto the metal surface occurs below 200°C, to form thiols, olefins, polymeric alkyl thio-
first. It is followed by the formation of chemically reactive phosphates, and hydrogen sulfide [28,29]. The antiwear per-
species due to thermal decomposition or hydrolysis. formance of these derivatives depends upon their thermal
Antiwear Agents—Zinc salts of dithiophosphoric acids are the stability, which in turn depends upon whether the alkyl
most widely used antiwear agents. These salts, in addition to groups are primary or secondary. Primary dialkyi dithio-
providing antiwear protection, act as oxidation and corro- phosphates decompose via an alkyl transfer mechanism to
sion inhibitors. They find major use in gasoline and diesel en- form zinc monoalkyl dithiophosphate and an alkyl thiophos-
gine oils and industrial lubricants. phate ester. Through a series of steps, these materials are
Zinc dialkyi dithiophosphates or zinc diaryl dithiophos- converted into zinc phosphate and trialkyl tetrathiophos-
phates cire S3aithesized by reacting the respective dithiophosphate, along with a variety of other products [28]. Trialkyl
phoric acids with zinc oxide. The dithiophosphoric acid tetrathiophosphate appears to be the major thermal decom-
derivatives that do not produce ash on combustion (ashless) position product, as shown by ^'P nuclear magnetic reso-
can be prepared by reacting the dithiophosphoric acids with nance (NMR) spectroscopy.
alkylene oxides, such as ethylene oxide or propylene oxide, or Secondary alkyl zinc dithiophosphates lose an olefin via ;8-
with materials that contain activated double bonds, such as elimination to form a product with free dithiophosphoric
cilkyl acrylates and methacrylates. The synthetic scheme to acid functionality. This product can further decompose by
prepare these materials is shown in Fig. 23. Dithiophospho- the loss of hydrogen sulfide or another olefin to form a
ric acids are products of reaction of an alcohol or a phenol thioanhydride and a variety of other products. Trialkyl
with phosphorus pentasulfide. tetrathiophosphate is again the major product. The aromatic
Thermal and hydrolytic stability of these products depends zinc dithiophosphates are believed to decompose by a free
upon the nature of the organic group. Dialkyi dithiophos- radical mechanism to phenol and a number of phosphorus
phates derived from primary alcohols are more thermally sta- and sulfur-containing products. Besides the thermal mecha-
ble than those derived from secondary alcohols, and are used nism described above, these additives can also decompose
extensively in formulating gasoline and automotive diesel en- oxidatively to form products that are potent oxidation in-
gine oils. Diaryl dithiophosphates, although thermally the hibitors. The details of their oxidation-inhibiting properties
most stable in this family, are hydrolytically the least stable were discussed in the oxidation inhibitors section and the ox-
and, with some exceptions, are not very effective antiwear idation chapter of this manusil. It is important to note that
agents. Therefore, they do not get much use. the oxidation inhibiting action of these additives is indepen-
dent of the nature of the alkyl group, but their antiwear ac- the former generates higher temperatures as a consequence
tion is not. Aliphatic zinc dialkyl dithiophosphates have bet- of the increased friction.
ter antiwear performance t h a n a r o m a t i c derivatives. And Disulfides and polysulfides decompose o n metal surfaces
among ahphatics, the secondary alcohol derived are better at t e m p e r a t u r e s above 200°C to form a protective sulfide
than those that are primary alcohol derived. layer. The thickness of this layer depends on the quantity and
Extreme Pressure Agents—Âlkyl and aryl disulfides and poly- the lability of sulfur in the additive. Sulfurized fatty oils and
sulfides, dithiocarbamates, chlorinated hydrocarbons, di- sulfurized olefins are the most commonly used products in
alkyl hydrogen phosphites, a n d salts of alkyl p h o s p h o r i c this class.
acids are the c o m m o n extreme pressure (EP) agents. Chlorine-containing compounds provide protection under
Polysulfides are synthesized from olefins either by reacting boundary lubrication conditions, via the formation of a metal
with sulfur or sulfur halides, followed by dehydrohalogena- chloride film. A detrimental aspect of chlorine-based E P
tion. Sulfurization of olefins with elemental sulfur, or sulfur agents is the formation of hydrogen chloride in the presence
and hydrogen sulfide, yields organic sulfides and polysulfides of moisture, which can cause severe corrosion problems.
[28,30]. Dialkyldithiocarbamates are prepared either by neu- Chlorinated paraffins with 40-70% chlorine by weight were
tralizing dithiocarbamic acid (resulting from the low-tem- once popular. However, environmental concerns about the
perature reaction of a dialkylamine and carbon disulfide) negative effects of chlorine are limiting the use of these addi-
with bases, such as zinc oxide or antimony oxide, or by its ad- tives.
dition to activated olefins, such as alkyl acrylates [31]. The Phosphorus c o m p o u n d s react with the metal surface to
synthesis of these materials is described in Fig. 24 and Fig. make a metal phosphite or a metal phosphate protective film.
25, respectively. Such a film forms at a m u c h higher temperature than that
Alkyl and aryl phosphites are obtained by reacting an alco- formed by sulfur EP agents. Tricresyl phosphate is the best-
hol or a phenol with phosphorus trichloride or by a transes- known phosphorus EP agent. Dialkyl hydrogen phosphites
terification reaction [32]. Alcohols a n d phenols react with [35] and phosphonic and phosphoric acid salts are other ex-
phosphorus pentoxide to yield a mixture of an alkyl (aryl) amples of such EP agents.
phosphoric acid and a dialkyl (diaryl) phosphoric acid [33]. As mentioned earlier, the EP mechanism can be consid-
These acids, when treated with bases, form salts. Alkyl phos- ered a two-step process. The first step involves adsorption of
phates can also be prepared by the oxidation of phosphites. the EP agent onto the metal surface and the second step in-
The preparation of eJkyl phosphites is outlined in Fig. 26 a n d volves its chemical reaction with metal to form the EP film.
of alkyl phosphates is outlined in Fig. 27. After being adsorbed on the surface, these materials ther-
The extent of EP protection in equipment depends upon mally decompose to reactive m e r c a p t a n s or p h o s p h o r u s
the conjunction temperature of the two metal surfaces in compounds that form the EP film. Probable mechanisms by
contact [34]. Figure 28 shows a direct correlation between which zinc dialkyl dithiophosphates form EP films is de-
the conjunction temperature and the degree of EP protection picted in Fig. 29. Organic halides, often not used in m o d e m
needed. The equipment that operates at low speeds and high formulations because of the environmental concerns, form
loads generally requires more EP protection than equipment an iron halide protective film, by reacting with the metal sur-
that operates at high speeds and low loads. This is because face via a similar mechanism [36]. Organic polysulfides are
R—CHa—CH=CH2 + Sg
Olefin I
Heat
R—CH=CH—CHa
R—CH=CH—CHz RCHz
I
Sx + Sa + R—CH2—CH—CH2
I I
R-CH2-CH-CH3 RCH
R—CH2—CH—CH3
f
Organic Poiysutfides
+
R
Dithiolethione
FIG. 24—Olefin sulfurization.
RjNH + CSj RzN —ct

SH
Oialkylamine Carbon
Disulfide Ditliiocarbamic
Acid
lUletai Oxide
or IHydroxidey CH2=CH—COOR
Activated
Olefin
/•/
M = Zn or Sb R2N — C ' R2N—C
M
X = 2 or 3 SCH2—CH5-COOR
Metal Dithiocarbamate Dithiocarbamate Ester
FIG. 25—Synthesis of dithiocarbamic acid derivatives.
PCI, P + 3 HCI
Triaryl Phosphite
.^
3 ROH PCI3 (R0)2P. + 2 H C I + RCI
Alcohol DialkyI Hydrogen

Phosphite
^
{PhO)3P + 2 ROH + H2O • (R0)2P. + 3PhOH
Triphenyl DialkyI Hydrogen Phenol

Phosphite Phosphite
(CH30)2P^ + 2 ROH (RO)2p^ + 2CH3OH

H
Diallcyl Hydrogen Methanol
Dimethyl Hydrogen
Phosphite Phosphite
FIG. 26—Synthesis of alkyl and aryl phosphites.
converted into dicJkyl disulfide, which reacts with the metal a function of the applied load [36]. When only disulfide is
to form the metcJ sulfide EP film [37,38]. used, weld occurs at a load of 250 kg, and the scar diameter
These inorganic films, which are only a few molecules is about 2.15 mm (Graph A). When a similar level of alkyl
thick, have low shear strength and are removed during the chloride is used, the weld load stays the same but the scar di-
movement of the surfaces in contact. This situation is repre- ameter improves to 1.74 mm (Graph B). Combining the two
sented in Fig. 30. Removal of the EP film can expose fresh types of EP agents to deliver an amount equal to that in the
metal, and the film-forming process is repeated. Each time previous cases increases the weld load to 350 kg and de-
the film is removed, the metal is removed with it. One way of creases the scar diameter to 1.6 mm (Graph C), thereby indi-
looking at the process of EP protection is the controlled wear cating a synergism between the two chemistries. A further in-
of rough surfaces, as shown in Fig. 31. crease in the amount of disulfide and chloride shows weld
In general, formulators use different tjrpes of EP agents in resistance beyond the load of 500 kg (Graph D). Similar sjoi-
combination because of the possible synergism [36,39]. The ergism exists between phosphorus and sulfur chemistries
synergism between sulfur and chlorine-containing EP agents [39]. The formation of active new compounds may be re-
is shown in Fig. 32, where average scar diameter is plotted as sponsible for the synergism.
o o
II II
3R0H + P2O5 — RO—P—OH + RO—P—OH
I
Alcohol Phosphorus OR OH
Pentoxide
DialkyI and MonoalkyI
Phosphoric Acids
Metai Base R'NHa

• /
Metal Salts Amine Salts
P=0
Triaryl Phosphite Triaryi Phosphate
FIG. 27—Synthesis of alkyl and aryl phosphates.
40C-
Many effective extreme pressure and antiwear additives
are corrosive to metals. Therefore, lubricants using them are
O typically formulated to optimize a balance between corrosiv-
S^35fl| ity and extreme-pressure and antiwear protection.
52
3 Rust and Corrosion Inhibitors
(B
a> 30C Corrosion is a general term used to describe the destructive
Q.
E alteration of metal by chemical or electrochemical action of
ffi its environment. It primarily involves a heterogeneous reac-
I-
I 25q lilHPIâ tion, which causes a metal to change from its nascent form
u
(metallic state) to an oxidized form (ionic state). All metals
c except noble metals are thermodynamically unstable under
5*200 atmospheric conditions and get converted into their oxidized
o form. On the other hand, noble metals, such as gold, plat-
u [ZESSIS inum, iridium, and palladium, are resistant to attack by the
environment and are therefore found in nature in the free
15a- form.
FIG. 28—Extreme pressure (EP) protection requirements vs There are many types of corrosion, but a lubricant supplier
conjunction temperature. is primarily concerned with corrosion in the presence of elec-
trolytes (electrochemical corrosion) and in the absence of
electrolytes (chemical corrosion). Common electrolytes that
Some additives in a formulation can diminish the effective- lead to electrochemical corrosion include water, acids, alka-
ness of EP/AW agents. These include surface-active additives, lis, and salts. Chemical substances that cause chemical cor-
such as certain friction modifiers, oxidation inhibitors, rust rosion include acids, alkalis, and sulfur. In alloys, corrosion
inhibitors, metal deactivators, detergents, and dispersants. can be selective or nonselective. It is selective if a particular
These components either irreversibly adsorb on the surface metal is corroded in preference to others. It is nonselective if
and interfere with the EP mechanism, or they form complexes all metals in the alloy are corroded at the same rate.
with EP agents, thereby rendering them inactive [40,41]. The Electrochemical corrosion involves the reaction of metals
same is true of some highly polar basestocks. This type of an- in the presence of electrically conducting solutions, or elec-
tagonism is quite common for some lubricants, such as gear trolytes, and occurs in two stages: the anodic process and the
oils, where EP agents form the core of the formulation. cathodic process. In the anodic process, metal goes into so-
Antiseize additives are a separate class of antiwear addi- lution as ions with extra electrons left over. The process can
tives, which perform independently of temperature. They im- be considered an oxidation. The cathodic process involves
prove boundary lubrication by forming the protective film the reaction of thus generated electrons with water and oxy-
through deposition. Molybdenum disulfide and graphite, gen to form the hydroxide ions. The process can be consid-
common additives of this type, are generally used in greases, ered a reduction. In solution, metal ions combine with hy-
some industrial oils, and various break-in lubricants. droxide ions to form metal hydroxides, or hydrated oxides.
S>>ii FeO Fe RS
RO.
V
J
OFe Fe
FeO Fe
OFe Fe OR
fFeO Fe I
RO sii„„ OFe Fe S=P—S—Zrw EP Film
I containing
K FeO Fe
OFe Fe
FeO Fe
-Olefin
O Sulfur and
Phosphorus
Compounds
RO. \^''''' OFe Fe
FeO Fe ^
K
Fe
s=p—s—ziw-X
Fe Fe
or RO or
Fe203 POLYMER Fe203
Adsorption Reaction
FIG. 29—The mechanism of boundary film formation by zinc dialkyi dithiophosphates.
FIG. 30—Protective boundary film vs shear.
Original Profile
Worn Profile
FIG. 31—Controlled wear of asperities to produce submicron
debris.
200 300
Applied Load (l<g)
A — 9.1% Di-t-Octyl Disulfide B — 8.52% t-Octyi Chloride
C — 4.55% Di-t-Octyi Disulfide + 4.36% t-Octyi Chloride
D — 9.1% Di-t-Octyl Disulfide + 8.52% t-Octyl Chloride
FIG. 32—Wear - load diagram, the ASTM procedure, showing

synergism between chlorine and sulfur extreme pressure (EP)
agents.
The rate of electrochemical corrosion depends upon the na- from the oxidation of the fuel sulfur and the basestock. Lu-
ture of the metal oxide film, the presence or absence of a po- bricant contains additive derived bases, both organic and in-
lar solvent such as water, the presence or absence of an elec- organic, which are usually weak a n d therefore pose little
trolyte (salts, acids, or bases), and the temperature. problem by themselves. However, the reaction between the
Chemical corrosion, on the other hand, does not need an acidic and the basic species results in salts, which can pro-
electrolyte and can occur both in aqueous and organic media. mote corrosion because they are electrolytes. The lubricant
It involves the attack of corrosive species, such as acids, also contains additives that can lead to acidic decomposition
bases, and sulfur, on metals. The damage occurs when the re- products. Some of these additives are sulfur and phosphorus
sulting compounds are removed. compounds that are added to the lubricant to improve its ox-
Factors that affect corrosion include internal factors and idative stability and antiwear performance. These can cor-
external factors [42]. Internal factors are directly related to rode metals either directly or by forming aggressive chemical
the metal itself, and include its composition, structure, sur- species via decomposition. Higher temperatures, which are
face condition, oxidation potential, a n d the presence of typically encountered in the internal combustion engines,
stresses. External factors pertain to the environment and in- can accelerate corrosion as well.
clude the nature of the oxide film, acidity, alkalinity, the pres- Metallurgy in automotive equipment commonly contains
ence of electrolytes, the presence and reactivity of the ag- iron (Fe), copper (Cu), lead (Pb), chromium (Cr), manganese
gressive species, and the temperature. While the role of these (Mn), antimony (Sb), a l u m i n u m (Al), vanadium (V), zinc
factors is considered elsewhere [42], we are especially inter- (Zn), nickel (Ni), and tin (Sn). Protecting four of these ele-
ested in the oxidation potential of various metals. ments against corrosion is of primary interest: iron, which is
Oxidation potentials of the elements that make u p the met- the principal metal used to forge the engine and the auxiliary
allurgy of m o d e m mechanical equipment are provided in Fig. equipment; copper, which is present in bearings and seals;
33. The elements that are primarily used to fabricate metal lead, which is also present in bearings; and aluminum that is
parts are shown by bold italic symbols. The potentials re- used in newer cars and trucks to make them lighter for better
ported in the table are relative to hydrogen with a value equal fuel economy.
to 0. Positive values indicate ease of oxidation and negative Protection against corrosion is necessary because it can
values indicate resistance to oxidation. Because of hydrogen lead to a loss of metal thereby lowering the integrity of the
being the reference point, we can directly compare these val- equipment and resulting in its malfunction. In addition, cor-
ues to assess the relative oxidative tendency of various met- rosion exposes fresh metal that can wear at an accelerated
als. The higher the oxidation potential, the easier it is for the rate and result in metal ions that can act as oxidation pro-
metal to oxidize. Metals in the left column of the table with moters.
smaller values are therefore less susceptible to oxidation, and Corrosion of iron and its alloys, sometimes referred to as
corrosion, than those in the right column. The values with ferrous corrosion or rust, is primarily electrochemical in na-
slash indicate a metal's first and second oxidation potentials. ture. It can occur b o t h in liquid and vapor phase and needs
For example, for iron, 0.44 represents the oxidation potential water, electrolyte, and oxygen. In an internal combustion en-
of the Fe° to Fe"^^ transition and 0.04 represents the oxidation gine, water results from fuel combustion, oxygen comes from
potential of the Fe° to Fe^^ transition. The same is true for the air, and electrol3?tes are metal salts that form by the reac-
copper. Of the metals of interest, aluminum is the easiest to tion of metals and certain additives with combustion and ox-
oxidize, followed by iron and lead. Copper with negative validation acids. This type of corrosion mainly occurs in engines
ues is the most resistant of the metals listed in the table. that are run in short cycles (stop-and-go driving). Rust initi-
Of the external factors listed above, acidity, alkalinity, the ates when water sets u p a localized electrochemical reaction
presence of the reactive species, and the temperature have between the surface iron and the iron oxide layer. Nascent
the largest impact. The presence of acids and bases can ac- iron acts as the anode, and the iron oxide layer acts as the cath-
celerate corrosion. In lubricant applications, acids result ode. Iron emits electrons and forms ferrous ions that are re-
Electrode Reaction
Lithium = Eo of +3.05
M *• M"* + nQ
Hydrogen = Eg of 0.00
Metal Eo Volts Metal Eo Volts
Lead(Pb) 0.13 Zinc (Zn) 0.76

Tin (Sn) 0.14 Chromium (Cr) 0.86/0.74
Nickel (Ni) 0.25 Manganese (Mn) 1.18/0.283
Iron (Fe) 0.44/0.04 Vanadium (V) 1.18
Copper (Cu) -0.S2l-O.34 Aluminum (Al) 1.66
FIG. 33—Oxidation potentials of common metals found In steel.

leased into the medium. The electrons migrate to the cathode

(oxide layer) and form hydroxide ions by reacting with oxygen PROBLEM
and water. Ferrous ions and hydroxide ions then combine to
form ferrous hydroxide, which is subsequently oxidized to fer- >- Lubricant
ric hydroxide, loses water, and becomes rust [12]. The mech-
Part A
anism of rust formation is depicted in Fig. 34, Part A.
Corrosion of copper and bronze, or yellow metal corrosion, Rust
is chemical in nature and occurs due to the attack of aggres-
sive species on metals. Such species result from the oxidation
and the combustion of hydrocarbon materials such as fuel,
base oil, and sulfur-containing additives. Yellow metal corro-
sion results when chemically reactive materials such as acids,
bases, or sulfur, attack copper or copper oxide. The result Cathodic Reaction (C)
is the formation of ionic copper compounds that are re- O2 + 2H20 + 4e ^ 40H"
moved, thereby causing metal damage. This is shown in Fig.
35, Part A. Anodic Reaction (A)
Lead corrosion involves a preferential removal of lead from Fe Fe^* + 2e
copper-lead beeirings, sometimes referred to as lead-leaching,
and primarily occurs in diesel engines. While its mechanism
is not well understood, it may partly be due to the attack of
SOLUTION
chemically aggressive species on metal. Certain classes of ad-
ditives, such as dispersants, appear to aggravate the situa- y Lubricant
tion. Aluminum corrosion is very slow because the aluminum
oxide film is tenacious and is not easy to remove. Parte
For protection, corrosion-inhibiting additives are used.
Protective
These additives are of two types: acid-neutralizers and film- Layer
formers. The acid neutralizing agents are additives that neu- Iron
' Metal
tralize aggressive acidic materieds and make them innocuous.
Film-formers attach themselves to metal surfaces to form an
impenetrable protective film [12]. Film formation can occur FIG. 34—The mechanism of rust Inhibition.
via physical adsorption or chemical adsorption. In the first
case, the resulting film is of a somewhat transient nature. In
the second case, however, it is more persistent. Film forma- S S S S Corrosive ss s s
PROBLEM
tion occurs when these additives interact with the metal sur- S S S S S Materials
sss s
face via their polsir ends and associate with the lubricant via
>- Lubricant
their non-polar ends, in a manner similar to that of the fric-
tion modifiers. Since these additives have high surface affin-
ity, they can compete with extreme-pressure and antiwear Part A
agents and impede their function. The rust-inhibiting mech-
mmxm
'^^•^^^^'^^^^^^^^^'î^^'^^^^^^'^^î^ Copper Oxide
anism and the corrosion-inhibiting mechanism via film-for-
mation are shown in Parts B of Figs. 34 and 35, respectively. . Copper
Metal
Figure 36 depicts the probable nature of the copper corro-
sion-inhibiting film. Part A shows copper inhibition by a
commercially available dimercaptothiadiazole (DMTD) SOLUTION s s s s Corrosive Ss s s
derivative and part B shows inhibition by tolyltriazole, an- SSSSS Materials
sss s
other commercial product. In the former case, it is the lubri- •^^ s "* Lubricant
cant associated with the hydrocarbon chain that acts as a
protective film and in the latter case, it is the adsorbed addi- Parte s '^ss <.• , s ^ \
^SSs
^§s^
tive that primarily acts as a protective film [12].
Deactivator
Chemical types used to inhibit corrosion of ferrous metals ^ ^ • ^ i * ^ ^ ^ ^ - ^ ^ " ^ ^ ' ^ ^ ' ^ ^ * ^ ^ ^ ^ ^ ^ ' ^ - ^ ' ^ ^ ^ ^ ^ Copper Oxide
www^
Film
include polyethoxylated alkylphenols, neutral and basic sul-
. Copper
fonates, alkenylsuccinic acids, alkyl phosphites and phos- Metal
phates, alkanolamines, and polymeric amines. Those used to
inhibit yellow metal corrosion mainly include oil-soluble het- FIG. 35—The mechanism of copper deactivation.
erocyclic compounds such as triazoles and dimercaptothia-
diazole (DMTD) derivatives. For lead corrosion, no effective
inhibitors are known. The only way to control lead-leaching nolamines, cire examples of physical adsorbers. Phosphoric
appears to be through proper balancing of the additive pack- acid, dithiophosphoric acid, and succinic acid derivatives are
age. examples of chemical film-formers. Basic detergents are ex-
Structures of the common corrosion inhibitors are shown cellent rust and corrosion inhibitors since they provide pro-
in Fig. 37. Long chain organic molecules, such as alka- tection both by neutralizing acids and by forming physically-
N-N
>-Lubricant
"SSR
Cu O Cu O Cu O Cu O Cu O Cu OCu O Cu O Cu O Cu O Cu O Cu
O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Oxide
Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu l^yer
O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O
(a)
vProtective
'^Film
Nc. JJ-R KyN-fl N>yN-R KyN-R
1 <
~Cu 0"Cu 0"Cu b'Cu <5 Cu'd Cii'dCu O'Cu'CJCu O Cu D Cii O Cu"
O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Oxide
Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu L^yer
O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O Cu O
(b)
FiG. 36—Copper passivators and mode of thieir action.
LCTÎ
^^\.0(CH2CH20)xCH2CH20H
Ca
Polyethoxyiated Ptienol Neutral Calcium Sulfonate

O
R—CH — C - O H
CH—C—OH
II
Lpr-] 2
Ca. xCaCOs
II
O Basic Calcium Sulfonate
Alltenylsuccinic Acid
0
II
) - - P - O H . R'N
.CH2CH2OH
1
R—N OR Aiitylammonlum
Phosphates
\H2CH2OH 0
Diethanolamine R O — P - O H . R'NHa^
I
OH
RSS^^^S SSR RS SH
\\ // N
N-N N-N X
Dimercaptothiadiazole Derivatives Alicylbenzotriazole
FIG. 37—Corrosion iniiibitors.

adsorbed films. For many applications such as gear oils, rust, the greater contribution of the higher molecular weight frac-
and corrosion, inhibitor systems are required to provide both tions in the molecular weight-determining process.
vapor-phase and liquid-phase protection, i.e., for surfaces The polydispersity index is a function of the polymerization
above and below the lubricant level. method. It is closer to 1 for polymers derived from anionic
Corrosion inhibitors have major uses in engine oils, gear polymerization, 1.5-2.0 for polymers derived from step
oils, metalworking fluids, and greases. Thiadiazole and tria- growth polymerization, between 2 and 5 for polymers de-
zole derivatives are especially useful in protecting against rived from radical polymerization, and above 5 for polymers
nonferrous or yellow metal corrosion. derived from polymerization using coordination catalysts.
Metal corrosion is measured by a variety of tests, depend-
ing upon the application. For GF-2 and API SH and SJ qual- Viscosity Modifiers
ity oils, CRC L-38 Test (copper/lead), the ASTM Sequence Mineral oils, which are effective lubricants at low tempera-
IID Rust Test (ASTM D 5844), and Cummins Bench Corro- tures, become less effective at high temperatures. At these
sion Test (copper/lead/tin) are used. For GF-3 and API SL t e m p e r a t u r e s , their film-forming ability (in the hydrody-
quality oils, ASTM Sequence VIII (unleaded L-38 Test; namic lubrication regime) diminishes due to a drop in vis-
ASTM D 6709) and Ball Rust Test (ASTM D 6557) are used. cosity. Prior to the use of viscosity modifiers, this problem
For gear oils, CRC L-13, L-21, and L-33 Tests are used for was partly overcome through seasonal oil changes. In winter,
rust and the ASTM D 130 Test is used for copper. For in- low-viscosity oils were used and in s u m m e r high-viscosity
dustrial products, the ASTM D 665 Test is used for rust and oils were used. The invention of viscosity modifiers led to the
the ASTM D 130 Test is used for copper. For hydraulic and introduction of multigrade oils thereby relieving the owner
metalworking fluids, a n u m b e r of ASTM specified tests are from seasonal oil changes.
utilized [3]. The principal function of a viscosity modifier is to mini-
mize viscosity variations with temperature. Previously, vis-
cosity index was used as a measure of an oil's response to
Polymeric Additives
temperature changes. Viscosity index (VI), which is derived
Materials with polymeric structures are the key components from the viscosity of the oil at 40°C and 100°C, is no longer
in high-performance lubricants. They can be used as lubri- meaningful. This is because most m o d e m equipment oper-
cant basestocks (see synthetic lubricants) or to enhance a lu- ates at extreme temperatures ( - 4 0 to +150°). At these tem-
bricant's inherent properties, such as viscosity and p o u r peratures, the viscosities do not conform to those predicted
point. They can also be used as starting materials to prepare by the viscosity index [4b,45].
certain classes of additives, such as dispersants and deter- Viscosity modifiers are polymers with average molecular
gents. The materials used for this p u r p o s e are m o r e oli- weights of 10000 to 150000; but those with molecular
gomeric than polymeric, i.e., their molecular weight is rela- weights between 10000 and 20000 are used most often. These
tively lower. Polymeric additives used in lubricants comprise chemicals are added to low-viscosity oils to improve their
viscosity modifiers, p o u r point depressants, emulsifiers and high-temperature lubricating characteristics. Viscosity mod-
demulsifiers, and foam inhibitors. ifiers minimize viscosity change with a change in tempera-
Most polymeric materials are compositions that consist of ture. This is a practical m e a n s of extending the operating
polymer chains of varying sizes. The bulk properties of these range of mineral oils to higher temperatures, without ad-
compositions depend upon the average molecular weight of versely affecting their low-temperature fluidity.
the polymer chains. The molecular weights of poljoneric ma- Viscosity modifiers cause an increase in oil's viscosity at cJl
terials are expressed as n u m b e r average, weight average, temperatures, except that thickening at lower temperatures
z-average, (z-l-1) average, and viscosity average molecular is less than that at higher temperatures. At low temperatures,
weights [43,44]. Of these, number-average (Mn), weight-av- the polymer molecules occupy a small volume and therefore
erage (Mw), and z-average (Mz) molecular weights are most have a m i n i m u m association with the bulk oil, or a small hy-
often used to describe polymer compositions. The number- drodynamic volume. Hydrodynamic volume is the volume of
average molecular weight (Mn) represents chemical stoi- the polymer and the associated oil. The effect is a marginal
chiometry cind is useful in carrying out chemical reactions in- viscosity increase. At high temperatures, however, the situa-
volving polymers. The weight-average molecular weight tion is reversed because the polymer chains extend or expand
(Mw) cortelates with mechanical properties, such as tensile as a consequence of the added thermal energy. This increases
strength and modulus in plastics, films, and fibers, and the polymer's association with the bulk oil due to an increase in
viscosity-improving behavior of the polymers. The z-average its surface area [7]. The result is an effective increase in vis-
molecular weight (Mz) largely influences the polymer's viscosity. Another way to describe this phenomenon is that at
coelastic properties, such as melt elasticity. While average higher t e m p e r a t u r e s the polymer becomes more soluble,
molecular weight information is important, it is the molecu- thereby causing viscosity to increase. The effect of a polymer
lar weight distribution that is more useful in understanding on the viscosity-temperature (VT) properties of an oil is de-
the polymer properties. The molecular weight distribution is picted in Fig. 38. Note that the VT line for the viscosity-mod-
m e a s u r e d by polydispersity index or heterogeneity index, ified oil has a lower (shallower) slope than that for the base
which is the ratio of the weight-average molecular weight to oil, thereby indicating a lower drop in viscosity with increas-
the number-average molecular weight, or Mw/Mn. For ing temperature. Figure 39 illustrates the mechanism of oil-
monodisperse polymers, which contain molecules of essen- thickening by viscosity modifiers.
tially the same chain length, the value of this index is close to
Variable thickening of oil by viscosity modifiers at low and
1. For polydisperse samples, it is greater than 1 because of
high temperatures allows the formulation of mutigrade oils.
The multigrade oils are designed to provide adequate viscos- persancy, fuel economy, and, indirectly, the extreme pressure
ity at high temperatures for engine protection and low viscos- performance.
ity at low temperatures for easy startability. Figure 40 shows Commercially available viscosity modifiers belong to two
the VT characteristics of single grade and multigrade oils. general classes: olefin-based polymers and ester polymers.
It is technically inaccurate to assess low-temperature vis- The olefin-based polymers include polyisobutylenes (PIBs),
cosities of the Vl-improved oils by linearly extrapolating the olefin copolymers (OCPs), and hydrogenated styrene-diene
VI (or VT) curves based on 40° and 100°C viscosities. This is (STDs) polymers. OCPs from ethylene-propylene mixtures
because such oils can show an inflection at low temperatures are called EPRs and those from ethylene-propylene-diene
thereby leading to erroneous viscosity estimates [4a]. The mixtures are called EPDMs. Ester polymers include poly-
low-temperature viscosities of the Vl-improved oils should be methacrylates (PMAs) and styrene ester polymers (SEs).
determined experimentally. It is also important to note that Viscosity modifiers find major use in multigrade engine
superior viscosity-temperature relationship of the multigrade oils and gear oils, transmission fluids, power steering fluids,
oils, as expressed by the viscosity index, is not solely due to a greases, and some hydraulic fluids. Olefin copolymers are of
greater preferential swelling of the polymer at higher tem- the most popular type, followed by polymethacrylates,
peratures. The use of low-viscosity oils with good viscosity- styrene-diene polymers, and styrene-ester polymers. OCPs,
temperature behavior to prepare these oils makes a substan- EPRs, and EPDMs find extensive use in engine lubricants.
tial contribution towards the overall effect [46]. In addition
to affecting the VT relationship, viscosity modifiers affect a Olefin-based Polymers
lubricant's other properties. These include pour point, dis-
These include polyisobutylenes, butyl rubbers, and olefin
copolymers. Polyisobutylenes (PIBs) and butyl rubbers are
both isobutylene-derived, except that PIBs are of somewhat
lower molecular weight than butyl rubbers. Unlike PIBs that
are derived from pure isobutylene, butyl rubbers Eire made
from isobutylene containing 3-8% diene in the monomer
mixture. Both types are manufactured by Lewis acid-cat-
alyzed polymerization.
Olefin copolymers (OCPs) are block polymers with rubber-
Viscosity-modified Oil like properties. They are prepared from olefin mixtures by
vanadium-based Ziegler-Natta catalysis. In ethylene-propy-
lene polymers (EPRs and EPDMs), the ethylene to propylene
ratio and their proper distribution in the backbone are criti-
cal to the polymer's low-temperature properties. OCPs are in-
Base Oil ferior to polymethacrylates in this regard and generally re-
quire pour point depressants to improve the low-temperature
performance of lubricants containing them. These polymers
find wide use in passenger Ccir motor oils and diesel engine lu-
bricants. Alpha-olefin copolymers, the lower molecular
weight analogues of OCPs, are prepared by polymerizing a-
olefins in the presence of a Lewis acid. These polymers find
use in lubricants, such as power steering pump lubricants and
Temperature
gear oils, which require enhanced shear stability. The PIBs of
FIG. 38—The effect of viscosity modifier on VT relationship 2000 to 3000 molecular weight are used as viscosity modifiers
of an oil. in gear lubricants, hydraulic fluids, and industrial oils.
Effective Volume in Oil Flow s Volume of Polymer Molecule +

(Hydrodynamic Volume) Volume of Associated Oil
Polymer
Molecule
Oil Associated
with Polymer
SOLUBILITY
Poor-4^ Good
TEMPERATURE
Low ' ^ High
FIG. 39—The mechanism of oil thickening by viscosity modifiers.

compatibility with a large number of refined and synthetic

basestocks and eire superior to olefin copolymers both in ox-
idative and thermal stability and in low-temperature proper-
ties. Because of these attributes, PMAs find extensive use in a
number of lubricants. Such lubricants include automotive en-
SAE30
gine oils, gear oils, automatic transmission fluids, hydraulic
fluids, industrial oils, and greases.
Styrene-ester polymers are prepared by first copolymeriz-
ing styrene and maleic anhydride and then esterifying the in-
SAE 10W-30 termediate alternating copolymer using a mixture of alco-
hols. Normally, the esterification step is taken to about 90%
or more, followed by post neutralization using a bifunctional
or polyfunctional amine. Because of the presence of the basic
nitrogen, these polymers function both as a dispersant and as
a viscosity modifier.
Figure 42 summarizes the methods of synthesis for poly-
acrylate and styrene ester type viscosity modifiers. Commer-
cially available ester polymers include Rohm and Haas's Acry-
loid series and Lubrizol's 3700 series products. Polymers
containing both OCP and ester based functionalities are also
-20 0 20 120 available. These are made either via grafting of an ester on to
Temperature (°C)- the OCP or by copolymeriztion of an alkyl acrylate and axi
olefin. Rohm GMBH's Viscoplex polymers belong to this class.
FIG. 40—Viscosity-temperature characteristics of single Thickening Efficiency—Thickening efficiency and shear sta-
grade and multigrade oils. bility are the two most important considerations for selecting
a polymer for use as a viscosity modifier. Thickening effi-
ciency is a direct function of a polymer's molecular weight.
Styrene-diene polymers (STDs) can be of the diblock or ran- More specifically, it is a function of the length of the pol5rmer
dom-block type and are produced by anionic polymerization backbone. Basically, the longer the backbone, the greater the
of stjrene and butadiene or isoprene. This type of poljrmer- thickening efficiency. On an equal weight basis, a high
ization produces polymers with a narrower molecular weight molecular weight polymer provides higher viscosity than a
distribution than those obtained by the use of Ziegler-Natta low molecular weight polymer, as long as structural features,
and Friedel-Crafts catalysts or the free radical initiators. That such as branching, are similar.
is, their Mw/Mn is closer to 1. Because of the narrow molecu- Since thickening efficiency of a polymer depends upon its
lar weight distribution, these polymers possess the best thick- molecular weight, different polymers must therefore be com-
ening power of the types discussed so far. However, the pres- pared on an equal molecular weight basis. For a given molec-
ence of the aromatic rings and the double bonds makes these ular weight, OCP has greater thickening power than styrene-
polymers more susceptible to oxidation. This problem is diene polymer, which in turn has greater thickening power
somewhat overcome by catalytically hydrogenating the dou- than polymethacrylate. The relationship between the poly-
ble bonds. Figure 41 schematically presents the synthesis of mer's molecular weight and the viscosity improving effect, or
these types of polymers. Recently, a different type of polymer, thickening, is presented in Fig. 43.
labeled a "star" polymer, also called radial isoprene, has be-
Shear-Related Viscosity Loss—The viscosity loss in a viscos-
come commercially available. It has thickening power similar
ity-modified lubricant can result from mechanical, thermal,
to that of the styrene-diene type, but has better shear stability.
and oxidative degradation of the polymer. Unlike mineral
A clustered polyanion prepared from divinylbenzene and
oils, which primarily exhibit Newtonian rheology, polymer-
styrene forms the center of the star, and the rays are made up
thickened oils exhibit viscoelastic rheology. That is, their vis-
of the polymerized diene monomer units. Commercial olefin-
cosity depends upon the degree of mechanical stress (shear).
based polymers include Exxon's Paratone series, Texaco's
When oils containing viscosity modifiers are subjected to
TLA products, and Shell's Shell Vis polymers.
moderate shear stress, viscosity decreases until it approaches
the viscosity of the polymer-free oil. The mechanical or shear
Ester Polymers viscosity loss is generally encountered in those equipment
These include polymethacrylates and styrene-ester polymers. parts that intermesh. Journal bearings, vane pumps, and gear
Polymethacrylates (PMAs) are produced by free radical poly- pumps are examples of such parts. The speed of the moving
merization of alkyl methacrylate. Since free radical polymer- surfaces also influences the shear rate and hence viscosity.
ization produces polymers with relatively broad molecular The viscosity loss of a lubricant is directly proportional to the
weight distribution, such polymers have low thickening effi- applied shear rate, as shown in Fig. 44. The higher the shear
ciency. Because of this, polymethacrylates have only moder- rate, the greater the loss in viscosity. Piston rings experience
ate viscosity-improving ability. However, the alkyl group in low shear rates; hence, the lubricant in this region experi-
the ester portion of the polymer can be altered to obtain prod- ences a low viscosity loss. Conversely, rod bearings cause
ucts that have the best oil solubility and optimum viscosity- high shear; hence the lubricant in this region undergoes a
improving properties. In addition, these polymers have good high viscosity loss. The viscosity loss in the regions of main
1. Polyolefin
CH3
'^3^N Acid
n C=CH2 -=SS». -CH2-C—
H3C CH3 J n
Polyisobutylene
Isobutylene
2. Olefin Copolymer
CH3
Ziegler
m CH2=CH2 + n CH3—CH=CH2 — • ~f~ CH2 CH2'~i CH—CH2-
\ 'm
Natta cat.
Ethylene Propylene Ethylene Propylene Copolymer
3. Styrene-Diene Poilymers
CH3
CH=CH2 -CH—CH2- CH—CH=C—CH2-
CH,
Anionic
m + n CH9—CH C-—CHo ^—1
Initiator
m
Styrene Isoprene Styrene-dlene Polymer
FIG. 41—Synthesis of olefln-based polymers.
CHa CH3
Radical
H2C=c—COOR -CH,—0-
Initiator I
Alkyl Methacrylate COOR
Alkyl Methacrylate Polymer
He=CH2
-CH-CHj—CH—CH-
Radical
Initiator II 'I o^ "o" ô
%
Styrene Maleic Styrene-maleic
Anhydride anhydride Polymer
1. ROH R'
/
2. H2NCH2(CH2)xNI
-CH-CH2—CH—CH-
\
0=C C=0
I I
NH OR
R R'
Styrene Ester Polymer
FIG. 42—Synthesis of alkyl methacrylate and styrene ester polymers.

bearings a n d cylinder walls that have intermediate shear specifically, it is the function of the size of the polymer back-
rates falls in between. bone. This relationship, which holds within a polymer type,
The viscosity loss can be temporary or permanent. If the is shown in Fig. 46.
viscosity bounces back to the original viscosity when the High molecular weight polymers generally lose viscosity at
stress is removed, it is termed as temporary viscosity loss. a higher rate u n d e r shear than low molecular weight poly-
This t j ^ e of loss is due to the reversible deformation of the mers. Hence, the lubricants thickened with low molecular
polymer u n d e r the influence of shear forces, which mini- weight polymers are more likely to maintain their viscosity in
mizes the association between the polymer and the lubricant. the desired viscosity range than the lubricants thickened with
Temporary viscosity loss, shown in Fig. 45, is desired in lu- high molecular weight polymers. Figures 47 and 48, respec-
bricants because it decreases the viscous drag at low temper- tively, depict the temporary and the permEinent viscosity loss
atures and therefore could contribute towards fuel economy in oils containing viscosity modifiers of two different molec-
[47]. ular weights [47]. As can be seen, in both cases the lower
The viscosity loss is considered p e r m a n e n t if after the molecular weight polymer experiences a lower viscosity loss.
shear forces are removed, the viscosity does not revert to its The problem of viscosity loss due to shear can be alleviated
prior value [47]. Permanent viscosity loss occurs when the by pre-shearing the high molecular weight polymer prior to
polymer in the viscosity-modified oil breaks down to the blending, or by choosing a more shear-stable polymer. Shear
lower molecular weight fragments u n d e r the influence of stability, which can be defined as the ability of a lubricant to
shear [48]. This type of viscosity loss is not desired because a resist viscosity loss under the influence of shear, primarily re-
formulated lubricant will not stay in its viscosity grade. lates to the permanent viscosity loss. Shear stability of a poly-
Whether temporary or p e r m a n e n t , viscosity loss depends m e r is inversely related to its molecular weight: the lower the
upon the shear stability of the polymeric viscosity modifier molecular weight, the higher the shear stability. The percent
used, which is a function of its molecular weight. More loss of viscosity in polymer-thickened oils is expressed in
terms of their shear stability index, SSI, which can be repre-
sented as follows.
nii-mf
SSIr^ X 100
mi-mo
m; = Initial viscosity of lubricant with the viscosity modi-
fier, cSt
mi = Final viscosity (viscosity after shear) of lubricant with
the viscosity modifier, cSt
rrio = Viscosity of the lubricant without the viscosity modi-
fier, cSt
T = Temperature in °C at which the viscosities are mea-
sured
Molecular Weight -
Shear stability requirements for different applications par-
allel the severity of the lubricating environment. Engine lu-
FIG. 43—Thickening as a function
of molecular weight. brication is mostly hydrodynamic in nature; hence, the lubri-
Shear Rate ^SZ.\
FIG. 44—The effect of shear rate on viscosity in different parts of an engine.

cants of low shear stability are adequate. Gear lubrication, on polymer molecules react with oxygen to form hydroperoxides
the other hand, is boundary in nature and therefore requires and peroxy radicals (see the oxidation inhibitor section).
lubricants of high shear stability. Transmission and hy- These species can disproportionate to form a n u m b e r of lower
draulic fluids fall in between the two in terms of these re- molecular weight oxygenated compounds. This type of degra-
quirements. This is shown in Fig. 49. dation not only causes a loss in viscosity but the resulting po-
The relationship between the polymer's molecular weight lar compounds also form varnish and coke deposits, in a
and its viscosity-improving effect, and the relationship be- manner similar to that of lubricants. The mechanism of ox-
tween the polymer's molecular weight and its shear stability idative degradation of pol5rmers is shown in Fig. 52.
are presented in Fig. 50 [4]. Specific viscosity TJ^^/C can be If one compares various classes of polymers in terms of de-
used as a measure of a polymer's molecular weight since the sirable properties, OCPs are the best with respect to treated
solution viscosity of the polymer-thickened lubricant is di- cost, but st5Tene-diene types (SB and SI polymers) are the
rectly related to the molecular weight of the polymer. Spe- best with respect to overall performance. OCP-g-PMA is the
cific viscosity is the absolute viscosity of a liquid relative to best choice if both the cost and the performance are consid-
that of water at the same temperature. As depicted in the ex- ered, which is usually the case.
hibit, both the polymer's viscosity-improving ability and the
shear sensitivity increase with an increase in its molecular Dispersant Viscosity Modifiers
weight (an increase in the specific viscosity). Higher shear
sensitivity implies lower shear stability. Dispersant polymers, or dispersant viscosity modifiers
(DVMs), are hydrocarbon polymers that have a dispersant
A n u m b e r of tests are available to measure the viscosity im- moiety attached to them. These materials are used as viscos-
proving properties and the shear stability of polymers in lu-
bricants. The shear stability of a lubricant is measured by the
CRC L-38 Test, FZG Shear Test, Sonic Shear Test (ASTM D
2603), Orbahn Shear Test, Bosch Injector Test, and the Ta-
pered Bearing Simulator Test (ASTM D 4683, D 4741, and D
6616). In terms of severity, the Tapered Bearing Test is the
most severe, followed by the FZG Test, Orbahn Test, and the
CRC L-38 Test.
Viscosity Loss Due to Polymer Degradation—In addition to me-
chanical breakdown (shear), polymers can undergo thermeJ
and oxidative degradation. Thermal degradation occurs when
the polymerization process is reversed under the influence of
heat. Polymers break down via chain scission to form lower
molecular-weight fragments. The consequence is a loss in vis-
cosity. This type of degradation, which is more prevalent in
aromatic polymers due to their ability to form more stable al- Molecutar Weight — — >•
lylic and benzylic radicals, is shown in Fig. 51. Oxidative

FIG. 46—Shear stability as a func-
degradation occurs when weak carbon hydrogen bonds in the tion of polymer molecular weight.
Vjvelogt^
- f ^ OH mm
Polvmer-containina • ^ ~ "
Oil
N. [Temporary
\ w Shear Loss
I
lU
Base
Oil
^ ^
1 1 1 1 1 .
102 10* 10« to* 106 107 108
Shear Rate,-=(3-1)
FIG. 45—Temporary viscosity loss due to shear.

1 1 1 or 4-vinylpyridine, imparts dispersancy directly. Grafting of

A ' maleic anhydride, on the other hand, leads to a substituted
succinic anhydride or succinic acid that must be reacted with
polyalkylene-polyamines to introduce a dispersant function-
ality. At present, no commercial products made in this man-
ner appear to be on the market. Antioxidant functionality can
\Mn=20,000 also be introduced in either of these two ways. Grafting is
common in the case of OCP and SD type polymers, but for
Mn=40,000\ PMAs, copolymerization is more prevalent.
Commercially available DVMs have two distinct function-
alities, a polymeric backbone (the VM portion) and a disper-
2" \ sant moiety. Thus, their physical, mechanical, and chemical
properties will depend upon both the inherent properties of
u Base Oil the VM portion of the molecule and the dispersant function-
> ality. In addition, some properties will depend upon both
1 1 1 1 t I
these functionalities, either due to synergism or antagonism.
io3 ^&^ io5 10^ io7 lo^ The properties that relate to the VM portion of the molecule
Shear Rate (s-i) are thickening efficiency, shear performance, thermal and
oxidative stability, and low temperature properties, and
FIG. 47—Temporary viscosity loss due to shear. those pertaining to the dispersant portion are oxidative and
chemical stability, and dispersancy. Considering the theo-
rized mechanism of the dispersant action, it is reasonable to
1 1
assume that the dispersancy will relate to both the basicity
and the molecular weight of the DVMs. Based on thepKa val-
^ ' ^=40,000 ues of the different functional groups, one would expect
r ^ ^ ^
dimethylamino group to be more basic than pyridyl group,
which in turn is expected to be more basic than 2-keto pyrro-
lidinyl group. Hence, one would anticipate dispersancy to fol-
1 low the same order.
f -
/
/
^
^
Mn=20,000 lOOT
n 1 1
10 20 30 80
Shear Time (min) Gear Oil
FIG. 48—Permanent viscosity loss due to shear.
•O .
C60
Tractor
Transmission
ity modifiers with added dispersancy. The molecular weights Fluids
of these materials are usually much higher than those of the
polymeric dispersants and can range 25000-500000. These
additives are derived from high molecular weight olefin |40|
copolymers (OCPs), polymethacrylates (PMAs), styrene- to
dienes polymers (SD) of linear or star configuration, and Automatic
styrene-ester polymers (SEs). Hydraulic Trimsmissiori
Dispersancy in these polymers is introduced by including Fluids Fluids
basic nitrogen or surfactant type oxygen-containing
20
monomers during the polymerization process. The mono-
mers that are commonly used for this purpose are shown in
Fig. 53. The dispersant functionality is introduced either by
grafting or through copolymerization. Grafting involves at- Engine
Oils '
taching a dispersant moiety, or its precursor, to an already
formed polymer. Copolymerization, on the other hand, in- 0.1 04 1 3 8
volves the use of a monomer, which can provide dispersancy Weight Average Molecular Weight (IMWxIO-^
during the formation of the polymer. Grafting of or copoly-
merization with a nitrogen-containing monomer, such as 2- FIG. 49—Shear stability requirements for various lubricants.
i2or
0.01 0.05 0.10 0.15 0.20 0.25

specific Viscosity % ^ c (cm^/g) ^ — > •
FIG. 50—The effect of specific viscosity on oil viscosity and shear stability.
Current practice favors mild dewaxing in combination with

the use of p o u r point depressants.
A good p o u r point depressant can lower the pour point of
a lubricant by as much as 40°C. These additives are com-
monly used in mineral oil-based lubricants that are designed
for applications with operating temperatures usually below
0°C. Pour point depressants have virtually n o effect on the
temperature where wax crystals start to precipitate (cloud
point) or the amount of wax that separates. They essentially
act as wax-crystal modifiers and function by altering crystal
shape and size. They do this either by absorption onto the
surface of the newly formed crystals or by co-crystallizing
with the precipitating wax. Both mechanisms inhibit lateral
crystal growth and keep the bulk oil fluid. Of the commercial
pour point depressants, edkylaromatics are believed to per-
form via the absorption mechanism and aliphatic polymers
FIG. 51—Mechanism of thermal degradation of via co-crystallization [45].
styrene-diene polymers. The molecular weight and the structure of the poljTneric
pour point depressants enable them to be effective over a
wider range than their low molecular weight counterparts.
The extended range of performance in the case of polymers is
Pour Point Depressants believed to be due to their limited solubility in petroleum
fractions. As the temperature decreases, different polymer
The p o u r point is the lowest temperature at which a fuel or
segments become successively co-crystallizable.
oil will pour when cooled under defined conditions. In gen-
eral, pour point is indicative of the a m o u n t of wax (straight- A good p o u r point depressant must possess one or more of
chain paraffins) in an oil. At low temperatures, wax tends to the following structural features.
separate as crystals with a lattice type structure. These crys- • Polymeric structure
tals can trap a substantial amount of oil via association, in- • Waxy and nonwaxy components
hibit oil flow, and ultimately hinder proper lubrication of the • Comb structure—comb structure meajis a short backbone
equipment. with long pendent groups
Base oil suppliers remove most of the wax during • Broad molecular weight distribution
petroleum refining. However, complete dewaxing of base oils Most commercial pour point depressants are organic poly-
is not practical because of process limitations, economics, mers, although some nonpolymeric substances have been
and the desirable presence of wax due to its high VI charac- shown to be effective. Tetra (long-chain)alkyl silicates,
ter [7]. For mineral oils to function effectively at low temper- phenyltristearyloxysilane, a n d pentaerythritol tetrastearate
atures, the additives called pour point depressants are used. are examples of the nonpolymeric t3rpe. Commercial pour
[-H-]
CH3
O2
.0-
Bond Cleavage
Other Oxidation Products

(Tliese include Carboxyiic Acids and Esters)
IHeat, Oj, and

Cataiysts
Varnish a n d C o k e Deposits
FIG. 52—Mechanism of oxidative degradation of polymers.
CH3 CH,
I /
CH2=C—C—OCH2CH2N ^
II ' " \
CH,
R R' R
1-Vinyl-2-pyrrolidinone Dimethylaminoethyl Alkylnaphthalene Alkylphenol

or N-Vinylpyrrolidinone Methacrylate
R, R' = Waxy Alkyl Groups
0\ CH3
I
CH2=C—C—OCH2CH2N
A-A
O
CH-CH2—OH—OH- CH3
2- or 4-Vinylpyridlne
Morpholinoethyl
°i r -OH,—0—
COOR
Methacrylate Alkyl Methacrylate

Styrene Ester
Polymer
CH, CH3 FIG. 54—Structures of c o m m o n pour point depressants.

CH2=C—C—0(CH2CH20|-[-CH2CHO-]R
O
modifiers and pour point depressants. When this chemistry
Polyether Ester of
Methacryllc Acid is used for viscosity improvement, the need for a pour point
depressant is minimized.
FIG. 53—Monomers used in synthesizing dispersant viscos- Pour point depressants are used at treatment levels of 1%
ity modifiers. or lower. In nearly all cases, there is an optimum concentra-
tion above and below which the pour point depressants be-
come less effective. The key structural difference between
point depressants include alkylated naphthalenes, poly(alkyl pour point depressants and viscosity improvers of the same
methacrylates), poly(alkyl fumarates), styrene esters, oligo- class is that viscosity improvers consist of long backbones
merized alkylphenols, phthalic acid esters, ethylene-vinyl ac- with short pendent groups and pour point depressants con-
etate copolymers, and other mixed hydrocarbon polymers. sist of short backbones with large pendent groups. This dif-
Figure 54 contains the structures of poly(alkyl methacry- ference is depicted in Fig. 55.
lates), alkylaromatics, and stjrene-ester polymers, which are Pour point depressants are used in engine oils, automatic
the most commonly used chemical types. High molecular and power transmission fluids, automotive gear oils, tractor
weight polymethacrylate derivatives can act both as viscosity and industrial hydraulic fluids, and circulating oils. The per-
be of sufficient chain length to provide proper solubility or

dispersibility in the oil phase.
Emulsifiers and demulsifiers can be classified as nonionic
or ionic, depending upon whether the polar part is uncharged
or charged. Ionic compounds can be subdivided further into
cationic if the charge is positive and anionic if the charge is
VISCOSITY MODIFIER— Long Backbone, Short Branches
negative [49]. It is important to note that only the charge on
the functional group attached to the carbon chain is used in
this classification. The charge on the counterion, which is
usually inorganic in origin, is ignored. The term amphoteric
applies to a group of additives that contain both the cationic
and the anionic groups of organic origin, preferably within
the same molecule. They possess the structural features and
the properties of both the cationic and the anionic materials
grouped together. Generalized structures for emulsifiers and
demulsifiers [50] are given in Fig. 56.
Emulsifiers reduce the surface tension of water and, there-
POUR POINT DEPRESSANT— Short Backbone, Long Branches
fore, facilitate thorough mixing of oil and water to form an
FIG. 55—Viscosity modifier vs pour point depressant - struc- emulsion. The efficiency of an emulsifier depends upon its
tural ditlerence. molecular weight (usually less than 2000), its HLB (hy-
drophile-lipophile balance) value, water pH and hardness,
the nature of the oil, and operating conditions, such as tem-
perature. Emulsifiers with an HLB value of 3-6 are suitable
for water-in-oil emulsions and those with an HLB value of
formance of a pour point depressant is determined in each 8-18 are suitable for oil-in-water emulsions. The manner in
basestock by one or more of the following tests: which these additives form emulsions is shown in Fig. 57.
• ASTM D 97—For pour point of petroleum oil. Water-in-oil emulsions form when these additives associate
• ASTM D 3829—Borderline pumping test. with water via their polar ends and with oil and other addi-
• ASTM D 2602—Âpparent viscosity at low temperature us- tive molecules via the non-polar ends. This is shown in part
ing cold-cranking simulation. A of the exhibit. The result is water miscibility in oil, or wa-
ter-in-oil emulsion. The mechanism of oil-in-water emulsion
• ASTM D 5949—Automatic Pressure Pulsing Method for
is similar, except that the additive molecules associate in the
pour point of petroleum products.
reverse manner. This situation is shown in part B of the ex-
• ASTM D 5950—Automatic Tilt Method for pour point of
hibit.
petroleum products.
• ASTM D 5985—Rotational Method for pour point of Demulsifiers perform the opposite function and enhance
petroleum products. water separation. Structurally, most demulsifiers are
oligomers or polymers with a molecular weight of up to
100 000 and contain 5-50% polyethylene oxide in a combined
form. They are commonly block copolymers of propylene ox-
Emulsifiers and Demulsifiers ide or ethylene oxide and initiators, such as glycerol, phenol-
Emulsifiers are chemical compounds that enable two immis- formaldehyde resins, siloxanes, polyamines, and polyols [51].
cible fluids to form an intimate raixture, known as an emul- For water-in-oil emulsions, polymers containing 20-50%
sion. Water-oil mixtures are often used as lubricants in many ethylene oxide are suitable. These materials concentrate at
industries and for a variety of applications. This is because the water-oil interface and create low viscosity zones, thereby
such lubricants are low cost, easier to dispose of, and have promoting droplet coalescence and gravity-driven phase sep-
fire retardant properties. Emulsions of water and mineral oil aration. Low molecular weight materials, such as alkali metal
have primary use in metalworking and hydraulic applica- or alkaline earth metal salts of dialkylnaphthalene sulfonic
tions. To be effective, emulsions must possess a number of acids, are also useful in some lubricant-related applications.
desirable properties. They should be stable over long periods As a general rule, nonionic emulsifiers are used in metal-
of time, possess good lubricating properties, not attack seals working fluids based on naphthenic stocks, and fatty acid
and metals, and be easy to demulsify for disposal. carboxylates are used in those based on paraffinic stocks.
In the presence of water, certain lubricant formulations Polyalkylene glycols (hydroxyalkyl ethers) are sometimes
have an increased tendency to form emulsions. This is due to avoided because their enhanced solubility in water does not
the presence of chemical additives that act as surfactants. allow clean separation for disposal. Polyethylene oxide
Demulsifiers are added to such formulations to enhance wa- derivatives and salts of carboxylic and sulfonic acids are the
ter separation and suppress foam formation. most commonly used emulsifiers, primarily in metalworking
Emulsifiers and demulsifiers are basically surfactants and fluids. Demulsifiers are used in applications where water
are made up of hydrophilic and hydrophobic moieties. The contamination of the lubricant is a problem and quick sepa-
hydrophilic moiety is nitrogen, oxygen, sulfur, or phosphorus ration of water is desired. Automatic transmission fluids, hy-
derived polar functional group, which is attached to a hydraulic fluids, industrial gear oils, and some engine oils, are
drophobic hydrocarbon group. The hydrocarbon group must examples of such lubricamts.
Foam Inhibitors OIL
Foam forms when a large a m o u n t of gas is entrained in a liq-

uid. While foaming is desirable in certain applications, such
as flotation, washing, and cleaning, it is undesirable in others,
such as distillation and pumping of fluids. In lubricant-related
applications, foam can act as an impediment and must be con-
trolled. Almost every lubricant application involves some kind
of agitation that encourages foam formation through air en- ^^(OCWÂ OIL
trainment. Excessive foaming will result in ineffective lubri-
cation and, over time, will cause oxidative degradation of the
lubricant. The viscosity and the surface tension of a lubricant
determine the stability of the foam. Low-viscosity oils pro-
duce foams with large bubbles, which tend to break quickly.
High-viscosity oils, on the other hand, generate stable foams
that contain fine bubbles and are difficult to break. The pres-
ence of surface-active materials, such as dispersants and de- (a)
tergents, further increases the lubricant's tendency to foam.
Foam inhibitors control foam formation by altering the
surface tension of the oil and by facilitating the separation of
air bubbles from the oil phase. In general, these additives
have limited solubility in oil, hence they are added as very
fine dispersions. Foam inhibitors are effective at very low lev-
els (3-150 parts per million).
Silicones (polysiloxanes), poly(alkyl acrylates), and
poly(alkyl methacrylates) are the commonly used foam in-
hibitors, with silicones being more popular. The ASTM D 892
H2O O^^^ v^«0 H2O
and D 6082 Tests are used to assess a lubricant's foaming ten-
dency. The structures of the two common types of additives
are shown in Fig. 58.
Other Additives
In addition to the major classes of additives described above,
lubricants contain a n u m b e r of other additives. These include
seal-swell agents, dyes, biocides, and couplers. Seals are used H2O (b)
in m o d e m machinery for a variety of reasons. In lubrication
FIG. 57—A representation of (a) water-in-oil emulsion,
systems, their functions are to: (b) oil-ln-water emulsion.
• Isolate various lubrication environments from harmful el-
ements.
Non-ionic
CH2CH2OH
RO{CH2CH20)xCH2CH20H R—N
NH(CH2CH20)xH CH2CH2OH
Poiyethoxylated Alcohol
N-Hydroxyalkylamide (HydroxyalkyI Ether) DIettianolamlne
R" R'
R—C R—N—CH2CH2 C,
1
^CpNa® 1 1
1
R" R"
Sodium Trialkylammonium Tetraalkylammonium
Carboxylate Salt Carboxylate
Anionic Cationic Amplioteric

FIG. 56—Emulsifiers and demulsifiers.
CHa CH3 MULTIFUNCTIONAL NATURE OF

CH, CH,
ADDITIVES
- 0 - S I - O—SI—0--SI -CH2- -C
I I A number of additives perform more than one function. Zinc
CH, CH, CHa COOR
dialkyl dithiophosphates, known mainly for their antiwear
Alkyl Methacrylate
action, are also potent oxidation and corrosion inhibitors.
DImethylslloxane Polyacrylates and styrene-ester polymers can act as viscosity
Polymer Polymer
modifiers, dispersants, and pour point depressants. Basic
FIG. 58—Common types of foam Inhibitors. sulfonates, in addition to acting as detergents, perform as
rust and corrosion inhibitors. They do so by forming protec-
tive surface films and by neutralizing acids that arise from
fuel combustion, lubricant oxidation, and additive degrada-
• Help maintain hydraulic pressure. tion.
• Allow removal and replacement of the malfunctioning
parts without the need to totally dismantle equipment.
ENVIRONMENTAL IMPACT OF ADDITIVES
• Minimize contamination and the loss of lubricant.
Seals are commonly made from polymeric materiails such ATC (the Technical Committee of Petroleum Additive Manu-
as fluoroelastomers, nitrile rubber, polyacrylates, and sili- facturers in Europe) carried out a study that traced engine oil
cones. Lubricants containing certain basestocks and additive additives across nineteen OECD (Organization for Economic
systems can cause shrinkage, brittleness, and deterioration of Cooperation and Development) countries from cradle to grave
seals, and impair the performance of the lubricating system. perspective. The objective was to assess the impact of addi-
Seal-swell agents are additives that maintain the integrity of tives on the consumer and the environment. The report [52]
these seals. Additives belonging to this class include reviews the nature, development, health and safety aspects,
polyesters, some phosphorus derivatives, and proprietary benefits to the consumer, and the ultimate fate of engine lu-
chemicals. Seal-swell agents are commonly used in transmis- bricant additives. An accompanying report [53] examines the
sion and hydraulic fluids. same for fuel additives.
Dyes are used to color-code lubricants to ensure their use
in the proper application and as a leak detection aid for the
consumer. ATFs contain a red dye, and the two-stroke cycle THE INTRODUCTION OF A NEW ADDITIVE
oils contain a blue or a purple dye. These dyes are oil-soluble
organic compounds, mostly with an azo structure (contains The development of a new additive is initiated after a new
nitrogen-nitrogen double bond). To a limited extent, dyes are product (lubricant) need is identified. The need for a new
also used to impart color or fluorescence to lubricants that product is usually expressed by the OEMs and the end-users
were historically perceived to indicate good performance. and relates either to the inadequate performance of the exist-
This is because today's refining processes remove coming products in the current equipment or the perceived needs
pounds that imparted this characteristic. of the equipment under development. To fulfill this need, var-
In general, mineral oil based lubricants resist microbial at- ious organizations, such as the SAE, API, ASTM, AGMA, and
tack because of their high-temperature operation and the OEMs, initiate the development of new performance specifi-
presence of additives, many of which have biocidal action. cations and test methods.
High water-based lubricants, such as certain metaJworking Additive companies, either alone or in collaboration with a
fluids and hydraulic fluids, are easily attacked by microbes lubricant supplier, try to satisfy the performance require-
and fungi. The control of bacterial and fungal growth is es- ments established for the new product. If the additive com-
sential to minimizing product deterioration and possible pany is unable to develop the additive system using their ex-
health hazards. This is done by the use of water-soluble tri- isting technology base, they initiate a project to develop and
azine, morpholine, imidazoline, and thiazoline derivatives, test a new additive.
which possess biocidal properties. Triazines, which owe their Newly developed additives are blended with other additives
biocidal action to their formaldehyde-releasing ability, find in a customer's base oil and are screened in a number of pro-
extensive use in this application. Couplers are additives used prietary bench tests. Bench tests, also called screen tests, are
in water-based lubricants to help stabilize microemulsions. accelerated tests that are devised to closely simulate condi-
Glycol and its derivatives are commonly used for this purpose. tions the lubricant is likely to experience in actual service. This
Metalworking fluids use a number of other additives. kind of testing is quite common because it allows the evalua-
These include alkalinity buffers, odor masks, and antimisting tion of a large number of additives quickly and inexpensively.
agents. Alkalinity agents and odor masks are used to control Once a lubricant satisfies the performance criteria of the
acidity and odor in water-based systems. Acidity and odor re- bench tests, full-fledged testing using actual equipment is car-
sults from the breakdown of oil and additives due to bacterial ried out. This may be done in a laboratory or in collaboration
and fungal attack. Amines and inorganic bases are used to with an end-user. For additives used in automotive products,
control acidity and natural and synthetic aromatic materials field trials may also be necessary. The costs associated with
are used to control odor. Antimisting agents are used to sup- the development and testing of the new additives can be phe-
press mist formation, primarily in oil-based fluids, which if nomenal. The performance package that has successfully met
not controlled can be harmful to workers. Polymers of vari- all the performance requirements is ready to be marketed ei-
ous types are used for this purpose. ther through factory-fill or service-fill lubricant blenders.
PERFORMANCE TESTING 1500), flash point (ASTM D 92 and D 93), volatility (ASTM D
1078 and D 5800), melting point, boiling point, odor, clarity
Reliable lubricant performance is a function of the quality of a n d water content (ASTM D 1744, D 4928, and D 4377).
its components. This implies both the base oil quality and While some ASTM standards are designed to analyze only
that of the performance package. Because most additives are low quantities of the described elements, in many instances
reactive components, their quality is assessed both individu- these methods can be used and are used to analyze larger
ally as well as in an additive package, which comprises a col- concentrations via dilution.
lection of additives.
Tests for F i n i s h e d F o r m u l a t i o n s
Tests for Individual Additives As mentioned earlier, lubricant additives are supplied as
The first and foremost concern after an additive is manufac- packages, especially for automotive applications, which are
tured is to establish its structural identity and purity. This is blended in mineral oil or synthetic basestocks to yield fin-
essential both from the perspective of conserving testing re- ished lubricants. The additives, being reactive chemicals, can
sources and for developing chemicals with optimal perfor- react with one another in the package either synergistically
mance. Structural identity can be established by the use of or antagonistically [55]. The formulator's challenge is to de-
analytical techniques available to a chemist. These include el- liver the intended performance by minimizing antagonistic
emental analysis, wet chemical methods, functional group effects and maximizing synergistic effects through careful
determination, molecular weight determination, and spec- balancing.
troscopic techniques. Some of the methods are provided in The viscosity modifier and the performance package are
the ASTM standards while others are not. Elemental analysis usually sold separately. This is because the two are not al-
is used to determine the amount of certain elements in the ways compatible in the concentrate form [45]. For applica-
additive, the finished lubricant, or the used lubricant. Such tions needing a viscosity modifier, the viscosity modifier is
elements include chlorine (CI), bromine (Br), nitrogen (N), blended in the base fluid, along with the performance pack-
sulfur (S), phosphorus (P), and boron (B), and metals, such age, to formulate the finished lubricant. Lubricant additive
as sodium (Na), potassium (K), calcium (Ca), magnesium suppliers develop general-purpose performance packages
(Mg), barium (Ba), zinc (Zn), copper (Cu), and molybdenum that meet industry specifications using widely available base-
(Mo). The m e t h o d s to analyze these are provided in the stocks and may fine tune them for an individual company's
ASTM Standards D 4951, D 5185, D 4927, D 5291, D 4047, use in its basestocks. Table 2 shows classes of additives used
D 1091, D 129, D 874, D 2622, D 808, D 4628, D 6443, and D to formulate engine lubricants, and Table 3 contains classes
6481. Functional group analysis involves the use of both the that are used to formulate non-engine lubricants. It is impor-
wet chemical m e t h o d s a n d the spectroscopic techniques. tant to note that all formulations do not contain all classes of
Commonly used wet chemical methods include neutraliza- additives identified in these tables.
tion n u m b e r determination (ASTM D 974, D664, D 3339, The quality of the additive package is determined by its
D4739, D2896), saponification n u m b e r (ASTM D 94), ability to meet established performance standards. Examples
bromine n u m b e r (ASTM D 1159 and D 2710), iodine value, of such standards include:
acetylation reaction, reaction with Grignard reagent, and • SAE's viscosity classification system
Kjeldahl method. The neutralization numbers and saponifi- • API's, ILSAC's, ACEA's, and U.S. Military's engine oil stan-
cation n u m b e r provide information on acidic functional dard for gasoline engine and diesel engine lubricajits
groups, such as sulfonic acid, carboxylic acid, and phospho- • GM's DEXRON® standard and Ford's MERCON® standard
ric acid. The neutralization numbers also provide informa- for automatic transmission fluids
tion on basic functional groups, such as amino groups and • API's standard for gear lubricants.
inorganic bases, and metal oxides, hydroxides, and carbon-
ates. Bromine n u m b e r and iodine value are used to assess un- The standards result from the joint efforts of many organi-
saturation in additives and lubricants. Acetylation and reac- zations. In the United States, such organizations include the
tion with Grignard reagent are used to determine the Society of Automotive Engineers (SAE), American Petroleum
hydroxyl content of additives. Grignard reagent is primarily Institute (API), American Society of Testing and Materials
used for situations, for example in the case of hindered phe- (ASTM), American Automobile Manufacturers Association
nols, where steric crowding does not allow a complete reac- (AAMA), Engine Manufacturers Association (EMA), U.S.
tion with the acetylation reagent. Kjeldahl method (ASTM D Original Equipment Manufacturers (OEMs), the U.S. Mili-
3228) is used to determine elemental nitrogen. Spectroscopic tary, and Chemical Manufacturers Association (CMA). In Eu-
methods include infrared (IR), nuclear magnetic resonance rope, the organizations include ACEA (Association des Con-
(NMR), and mass spectrometry (MS). These techniques are structeurs E u r o p e e n s de I'Automobiles), CEC (Conseil
well established and are aptly covered in many publications Europeens de Coordination pour les Developments des Es-
[54]. Purity is determined by gas liquid-phase chromatogra- sais de Performance des Lubrifiants et des Combustibles
phy (GLC or GC), thin layer chromatography (TLC), liquid pour Moteurs), ATC (Technical Committee of Petroleum Ad-
chromatography (LC), and gel permeation chromatography ditive Manufacturers), and ATIEL (Association Technique de
(GPC). Additional tests include molecular weight determina- I'lndustries Europeenne des lubrifiants). The ILSAC (Inter-
tion by vapor phase osmometer (VPO) and MS, oil solubil- national Lubricant Standardization and Approval Commit-
ity/package compatibility (ASTM D 501), copper strip activity tee) standard is a result of a collaborative effort of the Amer-
(ASTM D 130), viscosity (ASTM D 445), color (ASTM D ican Automobile Manufacturers Association of the United
States, Inc. (AAMA) and the Japan Automobile Manufactur-
ers Association, Inc. (JAMA). It is important to note that D 4741, and D 4684), emulsion-forming tendency, foaming
many OEMs and end-users have performance requirements characteristics (ASTM D 3427, ASTM D 892, and ASTM D
that are over and above those prescribed in these standards. 3825), refractive index (ASTM D 1218), flash point (ASTM D
The testing of packages involves prehminary testing and 3828, ASTM D 93, and ASTM D 92), cloud point (ASTM D
full scale testing. Preliminary tests include physical, chemi- 2500), pour point (ASTM D 97), volatility (ASTM D 6417),
cal, and machine tests. Full scale testing entails testing in a and evaporation loss (ASTM D 972). Standard ASTM test
laboratory via accelerated tests in real world equipment and procedures are used to evaluate these properties (See indi-
simulating actual service conditions. That is, the tests eire car- vidual additive testing section). Chemical tests, in conjunc-
ried out using actual engines, transmissions, axles, hydraulic tion with spectroscopic methods, are used to characterize the
pumps, and so on. These tests usually eveJuate more than one lubricant. Important chemical tests are:
lubricant property at a time. The equipment is disassembled • Structural analysis.
and its parts cire rated based on different criteria. Laboratory • Hydrolytic stability.
tests, performed under standard conditions, ascertain that • Tests to determine carbon residue, water content, sulfur,
lubricants meet the performance requirements established and ash content. The carbon residue test help determine
by various organizations. Standardized test methods for lu- the coke-forming tendency of the lubricants.
bricants are published in Federal Republic of Germany's DIN • Acidity, alkalinity, and alkaline residue.
standards, the USA's ASTM standards, the Britain's IP Stan- • Corrosion and corrosion protection tests.
dards, and the France's NF Standards. The equivalent test • Seal compatibility tests.
methods for important lubricant properties in different stan- • Tests to determine a lubricant's aging characteristics to
dards are available elsewhere [4c,56]. In the U.S., such tests predict its service life.
are run according to procedures prescribed by ASTM and Machine tests help assess a lubricant's performance in lab-
OEMs. The lubricants that pass these tests are sometimes oratory tests that are designed to simulate actual service con-
tested under field conditions as well. ditions. Machine tests, such as SAE #1, Four-Ball, Falex, FZG
Physical tests, commonly used for finished lubricants, in- (ASTM D 4998), and Ryder gear tests, evaluate a lubricant's
clude those relating to density (ASTM D 1298), viscosity effectiveness u n d e r mixed-film a n d b o u n d a r y lubrication
(ASTM D 445), viscosity index (ASTM D 2270), shear stabil- conditions [4a]. The details of the test are provided in Chap-
ity (ASTM D 1298, D 4624, D 5481, D 5133, D 2603, D 4683, ter 18, Metalworking and Machining Fluids.
TABLE 2 -- C o m m o n additive types for engine lubricants.

Two-stroke
Gasoline Diesel Engine Stationary Gas Aviation Cycle Engine
Additive Engine Oils Oils Engine Oils Engine Oils Oils
Dispersant k • • •
Detergent k • •
Antiwear/EP Agent k • •
•
Oxidation Inhibitor • • •
Corrosion Inhibitor/Metal Deactivator • • •
Friction Modifier
Pour Point Depressant » • • •
Foam Inhibitor
Viscosity Modifier
Other' •
'Other additive include couples, dyes, diluents, and emulsifiers.
TABLE 3—Common additive types used in non-engine lubricants.

Gear Oils Hydraulic Fluids
Automatic
Transmission Automotive Industrial Tractor Industrial Metalworking
Additive Fluids Gear Oils Gear Oils Hydraulic Fluids Hydraulic Fluids Fluids Greases
Dispersant
Detergent • • • •
Antiwear/EP Agent • • • « • •
Oxidation Inhibitor • • • • • •
Corrosion Inhibitor/ • • • • • •
Metal Deactivator
Friction Modifier • • •
Pour Point Depressant • • • •
Foam Inhibitor • • • • •
Viscosity Modifier • •
Other^ • • • •
'Other additives include couplers, dyes, diluents, and emulsifiers.
Viscosity Tests D 6616 methods, on the other hand, use tapered bearing sim-
ulator to determine HTHS viscosity. Two procedures that are
Viscosity plays a crucial role in forming effective lubricating used to measure grease viscosity are ASTM D 1092 and ASTM
films, which makes it one of the most important properties of D 4693. The first measures apparent viscosity and the second
a fluid [57]. Viscosity, defined as a fluid's resistance to flow, measures pumpability. The procedures ASTM D 2270 and D
is mainly a consequence of the internal friction of the fluid 2161 do not directly measure viscosity but are used for con-
[4]. Viscosity requirements or specifications are therefore version purposes. ASTM D 2270 or D 39 B is used to calculate
prescribed for almost all lubricants. Meeting these is abso- viscosity index (VI) from 40°C and 100°C kinematic viscosities
lutely critical for automotive lubricants, such as engine oils, and ASTM D 2161 is used to convert viscosities measured in
transmission fluids, and tractor hydraulic fluids. now obsolete units of Saybolt Universal Seconds (SUS) and
For automotive engine oils, viscosity requirements are de- Saybolt Furol Seconds (SFS) into centistokes (cSt).
scribed in the SAE Standards J300 [58] and J1536 [59]. The For two-stroke cycle SI engine oils, viscosity grades are
SAE Standard J300 deals with the viscosity of lubricants for based on miscibility with fuel and fluidity. This is to ensure
four-stroke cycle engines, of both compression ignition (CI) that the lubricant is miscible with fuel and that the blend
and spark ignition (SI) types, and two-stroke cycle CI engines. meets the low-temperature viscosity requirements. The ratio-
The SAE Standard J1536, on the other hand, specifies viscos- nale behind these requirements is that two-stroke cycle SI en-
ity of oils for two-stroke cycle SI engines only. The SAE Stan- gines usually do not have an oil sump, and the lubricant is
dard J1536 describes the miscibility and fluidity grades for mixed with the fuel in the fuel tank. The testing involves mix-
two-stroke cycle engine oils. The basic viscosity grade cate- ing lubricant with fuel and determining its pour point (ASTM
gories for engine oils are determined by the Crankcase Classi- D 4682). The performance of the new oil is compared with
fication System devised by the SAE, which uses test methods that of the reference oils to assign a viscosity grade. Trans-
approved by the ASTM. For transmission fluids and tractor mission and tractor hydraulic fluids, like engine oils, have
hydraulic fluids, the SAE grades are the same as those used low t e m p e r a t u r e and high t e m p e r a t u r e viscosity require-
for engine oils. However, for automotive gear oils, these are ments. Low temperature requirements are base upon ASTM
different and are described in the SAE Standard J306 [60]. D 2983 (Brookfield test) and ASTM D 445 is the basis for 40°C
Viscosity of non-automotive lubricants, such as industrial and 100°C kinematic viscosities.
gear lubricants and industrial oils, is described by the Ameri-
can Gear Manufacturers Association (AGMA) and Interna-
tional Standardization Organization (ISO) Standards, re- Performance Tests
spectively. As mentioned earlier, each tjrpe of lubricant must meet cer-
ACEA uses SAE viscosity classification system, described tain performance requirements prior to use. Such require-
in SAE J300. However, it has additional requirements relat- ments are described in service classifications or specifica-
ing to shear stability, evaporation loss, elastomer compatibil- tions (ASTM D 4485). The following section describes these
ity, sulfated ash, foaming tendency, and changes in viscosity based on the lubricant type.
due to high shear and high temperature. Special laboratory
test procedures are used to determine if a lubricant meets the Engine Oils
desired performance requirements in these areas. These pro- Engine oil performance requirements for North America are
cedures are described in the SAE J2227 report [61]. based on standard tests and are described by the API Engine
The ASTM D 445 method is used to determine kinematic Service Classification System, which was first introduced in
viscosity of a lubricant at 40°C and 100°C. This procedure em- 1969/1970 [62]. The system comprised separate performance
ploys a capillary viscometer. The ASTM methods D 2602, classes for gasoline engine lubricants and diesel engine lu-
D2983, D 3829, D 4684, and D5293 are used to determine low bricants. The system has been revised many times. At pre-
temperature viscosity of lubricants. ASTM D 2602 uses cold sent, classes for gasoline engine lubricants range from SA to
cranking simulator to determine apparent viscosity at 0 to SL and for diesel engine lubricants they range from CA to CI-
- 4 0 ° C range. The ASTM D 3829 and D 4684 procedures use 4. Of these, SA to SG categories for gasoline engine oils and
mini-rotary viscometer and are used to measure borderline CA to CE categories for diesel engine oils are obsolete and
pumping temperature (BPT) and apparent yield stress and ap- their r e q u i r e m e n t s are satisfied by API SH a n d CF (and
parent viscosity, respectively. ASTM D 5133 is scanning higher service classes), respectively [63]. However, at pre-
Brookfield technique that is used to measure gellation point, sent, the use of SH designation is limited to lubricants rec-
point at which sample viscosity reaches 30,000 cP. ASTM D ommended for both the heavy-duty diesel and the gasoline
2983 is also a Brookfield procedure that is used primarily for engines, such as those designated as CF/SH.
low temperature properties of automotive gear oils, auto- The ILSAC's performance categories, GF-1 and GF-2, is-
matic transmission fluids, torque and tractor fluids, and hy- sued in 1992 and 1996, use the API SH performance criteria
draulic fluids. The measurement is carried out at a constant but include a fuel economy ASTM Sequence VI Test. A new IL-
temperature in the range of 0 to —40°C. The ASTM procedures SAC category, ILSAC GF-3, was introduced in the year 2001.
D 5624, D 4683, D 4741, and D 5481 are used to measure high This category incorporated a n u m b e r of new tests that use en-
temperature/high shear viscosity (HTHS). The ASTM D 5624 gines of current design and operate on unleaded fuel, so as to
procedure uses a capillary viscometer where force is applied conform to the growing trend towards the use of unleaded
to a lubricant that is at 150°C to generate a high shear rate (10 gasoline. The tests include ASTM Sequence IIIF for oxidation,
s"'). The ASTM D 1092 procedure, used to measure viscosity ASTM Sequence IVA for valve train wear, ASTM Sequence VG
of greases, also uses pressure [57b]. The ASTM D 4683 and for sludge, varnish, and deposits, ASTM Sequence VII for
bearing corrosion, and ASTM Sequence VIII for rust and cor- marily pertain to frictioucJ characteristics, oxidation resis-
rosion [74]. API has stopped licensing GF-2 passenger car oils tance, deposit controlling ability, corrosion and wear prevent-
since April 2002 [64]. The work on the next ILSAC upgrade, ing ability, and fuel efficiency of the oil. The current engine
GF-4, has already started. The new category will require oils and bench tests for gasoline engine lubricants are as follows.
that are emission system catalyst compatible, have better fuel
economy, and provide better engine protection [65]. U.S. and European Tests
For diesel engine oils, API CF, CF-2, CF-4, CG-4, CH-4, and • Rust and corrosion—CRC L-38, ASTM Sequence VIII
CI-4 categories are active. API CF-2 is for severe-duty two- (ASTM D 6709), ASTM Sequence IID (ASTM D 5844), and
stroke cycle engines. API CF is for four-stroke cycle engines Ball Rust Test (ASTM 6557)
that are either turbocharged or use high sulfur fuel. Such en- • Oxidation—ASTM Sequences HIE (ASTM D 5844) and
gines are often for off-highway use. API CF-4 and CI-4 cate- IIIF, CRC L-38, and Peugeot TU-3M High-temperature
gories are for four-stroke cycle engines for on-highway use. • Thermal and Oxidative Stability—Thermo-oxidation En-
API CF-4 is for 1991 low emissions engines, API CG-4 is for gine Oil Simulation Test (TEOST; ASTM D 6335), High-
1994 low emissions engines, and API CH-4 is for 1998 low temperature Deposit Test
emissions engines. API CI-4, the 2002 upgrade of the diesel en- • Sludge, varnish, deposits, and v\;ear—CRC L-38, ASTM Se-
gine oil standard, is suitable for use in engines that are quence HIE (ASTM D 5533), ASTM Sequence VE (ASTM D
equipped with exhaust gas recirculation and other exhaust 5302), and VG (ASTM 6593), M-B Ml 11 Black Sludge, VW
emissions control mechanisms/components. Such engines are 1302, and Peugeot TU-3M High-temperature
designed to meet the 2004 exhaust emissions standard. In gen- • Valve Train Wear—ASTM Sequence IVA and Peugeot TU-
eral, oils meeting higher service requirements are suitable for 3M Wear
use in the lower service class within the same category. New • Fuel Efficiency—ASTM Sequence VI, VIA (ASTM D 6202),
proposed category, PC-8, for next generation heavy-duty and VIB (For GF-3), and M-B M i l l Fuel Economy
diesel engine oils has been under consideration for some time. • Extended drain capability—VW T-4
It is designed to address the Japanese OEM concerns over the
ability of the API CH-4/CI-4 qualified oils to protect their en- Japanese and Indian Tests
gines that use slider followers. The American engines use • Rust and corrosion—CRC L-38/Petter Wl, ASTM Sequence
roller followers. The CI-4 category includes eight fired engine IID (ASTM D 5844)
tests and seven bench tests [66]. The diesel engine tests include • Oxidation—Toyota. IG-FE, CRC L-38/PetterWl, and ASTM
Caterpillar IR, Cummins M i l , MackTSE (ASTM D 5967) and HID and HIE (ASTM D 5533)
T-10, and GM 6.5L Roller Follower Test (ASTM D 5966). This • Sludge, varnish, deposits, and wear—Toyota IG-FE, Nissan
category accommodated two major OEM specifications, VG-20E, Nissan SD22 (JASO 336-90), Nissan TD25 (JASO
Cummins CES 20076 and Mack EO-M Plus, both of which re- 336-97), CRC L-38/Petter Wl, CLR LTD, ASTM HID and
quire performance beyond that delivered by API CH-4. HIE, ASTM VD and VE (ASTM D 5302)
In addition to API, two other organizations actively partic- • Valve train wear—Toyota 3A, Toyota 3E, Nissan KA-24E
ipate in establishing engine oil performance. These are U.S. The current diesel engine tests are as follows. These tests
Military and original equipment manufacturers (OEMs). The are devised to measure protection against rust, varnish, de-
needs of the U.S. Military are different from those of the com- posits, sludge, wear, high-temperature oil-thickening, ring
mercial users. Its fleets consist of vehicles that not only vary sticking, fuel economy, and foaming tendency.
in size (ranging from 2 to over 1000-hp), but they also oper-
ate under a variety of conditions. U.S. Military specifications U.S. and European Tests
are designated by the prefix MIL. While largely similar to API • Piston deposits, ring sticking, oil consumption, and piston
service designations, there can be subtle differences. Simi- liner and ring distress—Caterpillar IK, IM-PC (ASTM D
larly, certain OEMs have additional requirements to qualify 6618), IN, IP (ASTM D 6681), and IR; Detroit Diesel 6V
oils for use in their equipment. Mack EO-M and Cummins 92TA (two-stroke cycle engine; ASTM D 5862)); Mack T-6;
CES 20076 specifications are examples of such requirements. VW 1.6TC Diesel Intercooler and VW Direct Injection; Peu-
ACEA establishes oil quality for use in Europe and JASO geot XUDl 1 ATE and XUDl IBTE; MAN 5305; and M-B OM
and Bureau of Indian Standards (BIS) establishes oil quality 364A/LA and M-B OM 441LA
for use in Japan and India, respectively. ACEA specifies the • Roller follower wear—Roller Follower (lifter pin wear), GM
use of tests developed by the ASTM and CEC (Conseil Eu- 6.2L and GM 6.5L (ASTM D 5966)
ropeen de Coordination pour les Developments des Essais de • Soot thickening—Mack T-6, T-7, T-8/T-8E (ASTM D 5967),
Performance des Lubrifiants et des Combustibles pour Mo- T-9 (ASTM D 6483), and T-10.
teurs; Coordinating European Council). ACEA 2002 Stan- • Engine oil corrosiveness—ÂSTM D 5968
dard consists of four lubricant classes for gasoline engines, • Oxidative stability/Viscosity increase—VW Direct Injection
Al-02, A2-96 (issue 3), A3-02 and A5-02; five lubricant classes and Peugeot XUDl lATE and XUDl IBTE
for light-duty diesel engines, Bl-02, B2-98 (Issue 2). B3-98 • Sludge, varnish, and wear/cleanliness—M-B OM 602A, M-B
(Issue 2), B4-02, and B5-02; and four lubricant classes for OM 364A/LA, M-B OM 441 LA, and Cummins M-11
commercial diesel engines, E2-96 (Issue 4), E2-96 (Issue 4), • Fuel Economy—M-B M i l l Fuel Economy
E4-99 (Issue 2), and E5-02. Current Japanese specifications • Foaming tendency—Navistar 7.3L EOAT [Hydraulically Ac-
include JIS K 2215 for gasoline engine oils and JASO DH-1 tuated Electronic Controlled Unit Injector (HEUI)]
for diesel engine oils. • Bore Polishing—MAH 5305, M-B OM 364A/LA, M-B OM
Each active category has associated tests. These tests pri- 441 LA
Indian Tests sion's clutch and band system is their most important fea-
• Piston deposits, sludge, varnish, and wear—Caterpillar ture. DEXRON® and MERCON® are the two major types of
1H2/MWM-B, Caterpillar 1G2/MWM-B, M-B OM 364A, M- a u t o m a t i c transmission fluids that are presently in use.
BOM616 DEXRON® fluids meet General Motors' performance speci-
• Soot Thickening—Mack T-7 fications and are primarily designed for use in their trans-
• Bore Polishing—M-B OM 616 missions. MERCON® fluids meet Ford's performance re-
quirements and are used in its transmissions. DEXRON®-III,
Service classifications for two-stroke cycle engine oils are MERCON® , and MERCON®-V fluids are the most current
described in the SAE Standard J2116 [67]. The API designa- specifications for transmission fluids. DEXRON®-III, intro-
tions for oils approved for use in two-stroke cycle engines are duced in 1994, is suitable for use in GM transmissions that
TA and TC, and NMMA (National Marine Manufacturers As- were designed to improve fuel economy and emissions [69].
sociation) designations are TC-W, TC-WII®, and TC-W3®. TA Design changes and operating environment for these trans-
oils are designed for use in low performance engines and TC missions called for fluids with good low-temperature proper-
oils are designed for use in high performance engines, except ties, good thermo-oxidative stability (ASTM D 5579), and
outboard engines (ASTM D 4859). TC-W, TC-WII®, and TC- frictional durability. DEXRON®-III specification was de-
W3® oils, on the other hand, are intended for use in water- signed to improve shift-feel smoothness, antiwear character-
cooled outboard engines. The quality of two-stroke cycle oils istics, low-temperature fluidity, and oxidation resistance of
is assessed on the basis of their ability to prevent piston scuff- the fluid. DEXRON®-IV specification, proposed but not yet
ing, exhaust system blocking, ring sticking, and deposit-in- in use, will require fluids of lower kinematic and Brookfield
duced pre-ignition ASTM D 4857 and D 4858). JASO and ISO viscosities so as to minimize energy losses and further im-
based two-stroke cycle categories are at present being devel- prove fuel efficiency. Tests and evaluation criteria for auto-
oped. These will be based upon oil's lubricity and detergency, matic transmission fluids are provided below.
and its ability to control exhaust smoke and exhaust system
blocking. The engine test requirements for NMMA's most re- • Friction and wear—ASTM D 2882, Band Clutch, Plate
cent category TC-W3® are listed below. Clutch Friction
• Thermo-oxidative stability—4L60 Transmission, ABOT Ox-
• Piston varnish, deposits, and ring sticking—OMC 40-hp, idation
OMC 70-hp • Frictional consistency and durability—Cycling (ASTM D
• Scuffing, bearing stickiness, and compression loss—Mer- 5579)
cury 15-hp • Smooth shifting of gears—Shift Feel
• Tightening and lubricity—Yamaha CE50S
• Preignition—^Yamaha CE50S Power Transmission Fluids—Power transmission fluids
(PTF) aire used in heavy-duty automatic transmissions and
Many changes have occurred for water-cooled engine spec-
torque converters in off-highway equipment. Such equip-
ifications since writing this article. NMMA's categories TC-
ment is commonly used in agriculture and construction in-
W, TC-WII®, and TC-W3® are now obsolete and a recertified
dustries. Viscosity and frictional properties of these fluids are
TC-W3® category was introduced. At present, the availability
critical to their performance. Just like ATFs, the SAE and
of the OMC 70-hp and OMC 40-hp engine test parts is in ques-
OEM performance specifications are used to describe these
tion. fluids [70]. Power transmission fluids are classified on the
Transmission Fluids basis of their performance in Allison C-4 and Caterpillar TO-
4 friction tests. Fluids meeting Allison C-4 requirements are
The important functions of these fluids are lubrication, cool- designed for equipment that has both torque conversion and
ing, and to act as a hydraulic medium to transmit power. automatic transmission features.
These fluids are of three types: automatic transmission flu-
ids, manual transmission fluids, and power transmission flu-
ids. There is no official API classification system for these flu- Gear Oils
ids. Performance requirements for transmission fluids are Gear oils are primarily formulated to provide extreme pres-
established by the OEMs [68]. The most important features sure protection for gears and axles to prevent fatigue, scor-
of these fluids are their frictional consistency (durability) and ing, and wear under boundary lubrication conditions. Gears
frictional compatibility with the transmission's components. are used in automobiles and industry to perform a number of
In a u t o m a t i c transmissions, such c o m p o n e n t s include diverse functions. Because of differences in design, each gear
clutches and bands; in manual transmissions and manual type places different demands on the lubricant.
transaxles, they include cone or plate type synchronizers. Un- Automotive Gear Oils—Performance specifications for auto-
like automatic transmissions, which use transmission fluids motive gear oils are established by the API, U.S. Military, and
recommended only by the OEMs, manual transmissions use the OEMs. The API service designations for automotive gear
a variety of fluids. Such fluids include automatic transmis- oils range from GL-1 to GL-6, specifying oils in increasing or-
sion fluids, engine oils (5W-30), some gear lubricants, and der of load-carrying capacity [71,72]. The abbreviation "GL"
specialty fluids. In addition to frictional properties, certain stands for gear lubricant. The GL-6 classification, which was
OEMs require transmission fluids for their equipment to
previously used to describe antiscoring performance over
have improved shear stability, low-temperature fluidity, and
and above that provided by the GL-5 lubricants, is technically
other specific characteristics.
obsolete. The GL-4 and GL-5 categories correspond to U.S.
Automatic Transmission Fluids—The frictional compatibility Military specifications MIL-L-2105 and MIL-L-2105D, re-
of automatic transmission fluids (ATFs) with the transmis- spectively, and define oils for service-fill only. The specifica-
tion MIL-PRF-2105E, issued in 1995, combines the GL-5 re- Industrial Gear Oils—Service requirements of industrial gear
quirements of MIL-L-2105D and thermal oxidation stabihty, oils are established by AGMA, DIN, and a variety of other or-
antiwear, and seal compatibility requirements of the newly ganizations, such as U.S. Steel, Cincinnati Milacron, and Al-
released API specification MT-1. The new specification de- coa [74]. The important function of these lubricants is to re-
fines lubricants for nonsynchronized manual transmissions duce friction and wear. Tests pertaining to these include
used in buses and heavy-duty trucks. Factory-fill oils are de- Timken (ASTM D 2782), Four-Ball EP (ASTM D 2783), Four-
fined by major car and truck manufacturers. Such oils have Ball Wear (ASTM D 4172), U.S. Steel S-205, and FZG
performance characteristics that are critical to the satisfac- (A/8.3/90). Additional tests deal with rust and yellow metal
tory operation of a particular drive train and may include corrosion protection (ASTM D 665, IP 135, and ASTM D 130),
break-in, bearing preload, and limited slip durability. Mack demulsibility (ASTM D 1401, IP19, and ASTM D 2711), oxi-
GO-G/S and GO-H/S are examples of such specifications. dation resistance (ASTM D 2893, U.S. Steel S-200), foaming
European OEMs use API GL-5 and MIL-L-2105D to define tendency (ASTM D 892 and IP 146), and air release time (DIN
minimum performance requirements for oils used in their 51381, IP313).
equipment. They have additioned requirements pertaining to
surface fatigue, component cleanliness, synchromesh dura- Hydraulic Fluids
bility, and viscometrics, depending upon their specific need/s.
The primary function of these fluids is to transmit power ef-
Japanese OEMs recommend API GL-5 lubricants for vehicles
ficiently and control wear. Hydraulic fluids are of two general
fitted with h3rpoid and spiral bevel axles and API GL-3 and GL-
4 lubricajits for cars and trucks equipped with manual trans- types: those used to lubricate tractor hydraulics and those
missions. Most modem cars use transaxle drive train ar- used to lubricate industrial hydraulic equipment.
rangement and hence do not need rear axle lubricants. A new Tractor Hydraulic Fluids—Tractor hydraulic fluids (THFs)
performance specification, PG-2, for automotive geetr oils is are multipurpose lubricants that are used to lubricate trans-
presently under consideration [73]. It is a temporary designa- missions, final drives, hydraulic systems, wet brakes, and wet
tion for axle lubricants to be used in heavy-duty truck and bus clutches [75]. To perform these functions properly, THFs
final drives that employ spiral bevel and hypoid gears. This must combine hydraulic and transmission properties with
category is designed to qualify lubricants with higher thermal extreme-pressure properties. Their function as a transmis-
durability, seal compatibility, and surface fatigue perfor- sion fluid and as a lubricant for wet brakes and wet clutches
mance than the existing GL-5 lubricants. requires them to possess proper frictional characteristics.
Tractor hydraulic fluids differ widely in performance re-
The API and the military specifications have associated
quirements because OEMs can not agree on common speci-
bench and axle tests [74]. These include tests to evaluate the
fications for a universal tractor hydraulic fluid. The specifi-
oil's ability to protect gears and axles against fatigue, scoring,
cations for these fluids, in general, deal with extreme
and wear. Additional tests deal with a gear oil's oxidative sta-
pressure (EP) and antiwear properties, and with matching
bility, foaming tendency, and the ability to protect against
rust and corrosion. Axle tests are run according to methods the frictional requirements of the equipment. The quality of
established by the American Coordinating Research Council these fluids is assessed on the basis of their ability to meet in-
(CRC). Bench and axle tests used to qualify automotive gear dividual OEM specifications as well as API GL-4 (for EP) and
oils (ASTM D 5760) are given below. Allison C-4 (for friction, oxidation, and wear) performance
requirements. There are eight major OEM specifications and
• Scoring resistance under high-speed shock load conditions— most tractor fluids are formulated to meet them. These spec-
CRC L-19 and FTM 6504T, CRC L-42, Vehicle Rear Axle ifications are:
Score
• Resistance to gear distress under high-torque low-speed con- • JI Case MS 1207
ditions—CRC L-20, CRC L-37 (ASTM D 6121) • John Deere J20C/D, and J27
• Antiwear properties—kSlU D 5182, FZG (A/8.3/90), and • New Holland FNHA-2-C-201.00 and M2C159B/C
(A/10/90) • AGCO Massey-Ferguson Ml 135, Ml 139, and Ml 141
• Gear surface fatigue—Mack Spalling Tests associated with these specifications include:
• High-temperature stability of lubricant—ASTM D 5763, • Wear and Extreme-pressure Tests—Denison T-50 Vane
Mack Transmission Test T-2180, CRC L-60, and CRC pump and P-46 Piston Pump; Vickers 35VQ-25 Vane and
L-60-1 Vickers V104C Vane Pump, Constant Volume Vane Pump
• Lubricant stability in motored axle test—Ford BJ 15-1 (ASTM D 2882); FZG EP/antiwear [DIN 51354 (Part 2)];
• Corrosion resistance in the presence of water—CRC L-13 or Four-Ball EP (ASTM D 2783); and Four-Ball Wear (ASTM
FTM 5313.1 and CRC L-21, CRC L-33 D4172)
• Copper corrosion—ÂSTM D 130 • Oxidation Tests—Tnrbme Oil (ASTM D 943); Sludge
• Oil seal compatibility—ASTM D 471, ASTM D 5662 (ASTM D 4310); and Rotary Bomb (ASTM D 2272); Uni-
• Foaming tendency—ASTM D 892, CRC L-12 versal Oxidation Test (ASTM D 5846)
• Transmission cyclic durability—ASTM D 5579 • Corrosion Tests—Turhins Oil Rust (ASTM D 665) and Cop-
• Material separated on centrifugation after 30 day storage at per Strip (ASTM D 130)
room temperature—FTM 3440, modified • Miscellaneous Tests—Turbine Oil Demulsibility (ASTM D
• Channeling characteristics of lubricant—FTM 3456.1, mod- 1401); Hydrolytic Stability (ASTM D 2619); Cincinnati Mi-
ified lacron Thermal Stability (ASTM D 2070); Denison TP
• Compatibility with existing gear lubricants—SS & C FED- 02100 Filterability; Foam ASTM D 892; Air Separation
STD-791 Method D 3430 and D 3440 (DIN 51381); and Seal Compatibility [DIN 53538 (Part 1)]
In addition to a hydraulic fluid, farm tractors and related every other aspect, they resemble soluble oils. Because of the
equipment need an engine oil and a transmission fluid. In or- lower oil content, these fluids appear clear. However, some
der to reduce the number of lubricants handled by the farmer, high semisynthetic fluids contain >3.0% oil and are translu-
the concepts of Universal Tractor Transmission Oil (UTTO) cent. Their appearance is a function of the particle size.
and Super Tractor Oil Universal (STOU) were developed. UT- The performance specifications of metalworking fluids are
TOs have the ability to lubricate transmissions, wet brakes, established by the OEMs and end-users. Test methods to
and hydraulic systems. STOUs have the additional ability to evaluate performance of these fluids are not well standard-
be used as engine oils and meet major performance criteria of ized. Tests that are presently used or can be used to judge the
the leading equipment manufacturers. Such oils must there- suitability of metalworking fluids include:
fore pass additional tests. For UTTO oils, these include L-20 • Corrosion Teste—Copper Strip (ASTM D 130), Turbine Oil
High Torque Low-speed Test, Vane and Piston Pump Test, Rust (ASTM D 665), Aqueous Cutting Fluid (IP125), Filter
and Vickers 35VQ25 Test. For STOU oils, these include engine Paper Chip Breakpoint (IP287), Aluminum Cup Stain, Hu-
oil tests, such as ASTM Sequence IID, HID, VD, CRC L-38, midity Cabinet Rust (ASTM D 1748), Salt Spray (MIL-B-
Mack T-6, and T-7; L-20 High Torque Low-speed Test; Vane 117-64), Cleveland Condensing Humidity Cabinet (ASTM
and Piston Pump Test; and Vickers 35VQ25 Test. D 2247)
Industrial Hydraulic Fluids—These lubricants help transmit •Extreme Pressure—Four-Ball Wear (ASTM D 4172),
and control power in equipment used in industries, such as Timken (ASTM D 2782), Four-Ball EP (ASTM D 2783),
automotive, manufacturing, material handling, construction, Falex EP (ASTM D 3233)
chemical, mining, textile, food, rubber, and agriculture. • Stability~¥oam Tendency/Stability (ASTM D 892, IP312),
These fluids fall under three categories: antiwear hydraulic Panel Coker, Demulsibility (ASTM D 1401), Emulsion Sta-
fluids, rust and oxidation-inhibited oils (R & O oils), and fire- bility (IP263), Aquarium Biostability
resistant fluids. Performance criteria for industrial hydraulic • Miscellaneous—Color (ASTM D 1500), GM Quenchometer
fluids are defined by OEMs. Each hydraulic pump manufac- (ASTM D 3520), Thread Tapping (Lubrizol test). Pipe
turer has its own performance requirements that pertain to Threading (Lubrizol test). Stick-slip (Cincinnati Milacron
lubricant viscosity, antiwear properties, demulsibility, and test), Bijur Filtration, Falex #8, SLT (Draw Bead Simula-
ability to inhibit rust, oxidation, corrosion, foam, and filter tor), Reichert Test, and Tapping Torque Test (ASTM D
plugging. Tests for these fluids include: 5619)
• Wear and Extreme-pressure Tests—Denison T-50 Vane Miscellaneous Industrial Oils
pump and P-46 Piston Pump; Vickers 35VQ-25 Vane and
Vickers V104C Vane Pump; FZG EP/antiwear [DIN 51354 Compressor oils, refrigeration oils, turbine oils, circulating
(Part 2)]; Four-Ball EP (ASTM D 2783); and Four-Ball oils, slideway lubricants, and rock drill lubricants make up
Wear (ASTM D 4172) this group. Compressor and refrigeration oils are used in com-
• Oxidation Jesfs—Turbine Oil (ASTM D 943); Sludge pressors to reduce friction and act as a seal separating low and
(ASTM D 4310); and Rotary Bomb (ASTM D 2272) high-pressure areas. Turbine and circulating system oils are
used to lubricate steam and gas turbines for marine and sta-
• Corrosion Tesfs—Turbine Oil Rust (ASTM D 665) and Cop-
tionary applications. Circulating oils are used in systems
per Strip (ASTM D 130)
where large quantities of heat must be removed and where
• Miscellaneous Tests—Turbine Oil Demulsibility (ASTM D
heavy contamination of oil occurs. As a result, these oils must
1401); Hydrolytic Stability (ASTM D 2619); Cincinnati Mi-
possess excellent air and water separation properties and
lacron Thermal Stabihty; Denison TP 02100 Filterabihty; good oxidative stability over the duration of their use. Slide-
Foam ASTM D 892; Air Separafion (DIN 51381); and Seal way and drill lubricants are used to lubricate guiding surfaces
Compatibility [DIN 53538 (Part 1)] on the bed of a machine along which a table or a carriage
moves and to lubricate pneumatic equipment. These oils must
Metalworking Fluids perform under extreme temperatures, high loads, moisture,
Metalworking fluids are used to convert metal into a compo- and poor ambient air quality. They therefore possess both the
nent or a piece. These fluids are of four basic t3ês, straight EP activity and the rust and corrosion-inhibiting properties.
oils, soluble oils, semisynthetic fluids, and synthetic fluids. Sol- ISO viscosity grades and U.S. Military and OEM performance
uble oils, semisynthetic fluids, and synthetic fluids are water- requirements usually specify these lubricants.
based and differ from one another, mainly in their oil content Turbine oils are classified as R & O oils, non-EP oils, and
and emulsion type [76]. Straight oils are devoid of water. EP oils. R & O oils are formulated to provide rust and oxida-
They are mineral oil-based (primarily hydrotreated naph- tion protection and EP oils are formulated to provide EP pro-
thenic basestocks) and usually contain sulfur, chlorine, and tection, depending upon the intended end use. EP oils con-
phosphorus-derived additives. Soluble oils are water emul- tain R & O packages enhanced with antiwear additives. R &
sions of mineral and/or fatty oils. An emulsifying agent or O oil performance specifications are established by OEMs,
surfactant is used to form these emulsions. Synthetic fluids such as U.S. Steel, Cincinnati Milacron, Denison, General
are oil-free and are simply solutions of additives in water. Electric, and organizations, such as U.S. Military, AFNOR
Since most organic materials are hard to dissolve in water, (Association Francais Petroles de Normalisation) and DIN
high polarity of the additives is necessary for solubility. (Deutsche Industrie Norm). Specifications for non-EP oils
Soaps or other surfactants are sometimes added to help in are established by General Electric, British Government, and
this regard. Semisynthetic fluids are in between soluble oils DIN and for EP oils the OEM Brown Boveri plays an active
and synthetic fluids as far as their oil content is concerned. In role [74]. Common tests for these oils are as follows.
R & O Oils serves to immobilize the lubricant until service application

• Wear Tests—Vane P u m p (ASTM D 2882), Denison P-46 Pis- causes it to be released. The lubricant contains additives
ton Pump, Four-Ball Wear (ASTM D 4172) which reduce friction and prevent wear. Greases perform
• Oxidation Tests—Rotary Bomb (ASTM D 2272), Turbine the same basic functions as their fluid counterparts but, in
Oil (ASTM D 943), 1000-hour Sludge (ASTM D 4310), view of their high viscosity, they do not perform cooling and
Cincinnati Milacron Heat, FTMS 5308.6 cleaning functions efficiently. Based on thickener, greases
can be classified as simple-soap, complex-soap, and non-
• Corrosion Tests—Rust (ASTM D 665), Copper Strip (ASTM
soap. Simple-soap greases contain lithium (Li), sodium
D 130)
(Na), calcium (Ca), barium (Ba), or aluminum (Al) fatty
• Miscellaneous Tests—Turbine Oil Demulsibility (ASTM D
acid carboxylates. Complex-soap greases contain metal salts
1401), Neutralization N u m b e r (ASTM D 974 and D 664),
of fatty and nonfatty acid mixtures. Nonsoap greases may
Foam (tendency/stability) (ASTM D 892), and Air Release
contain either inorganic compounds or orgeinic compounds
(DIN 51381, ASTM D 3427)
as thickeners.
Turbine Oils Greases are described by the National Lubricating Grease
• Oxidation Tesfs—Turbine Oil (ASTM D 943), 1000-hour Institute (NLGI) consistency grades and NLGI Service Clas-
Sludge (ASTM D 4310), IP280 TOP, IP280 Sludge, Rotary sification System for automotive use, first implemented in
Bomb (ASTM D 2272), FTMS 5308.6, and Universal Oxi- 1991 [77], Consistency grades are 000, 00, 0, and 1-6 and are
dation Test (ASTM D 5846) based on degree of hardness and ASTM Worked penetration
• Corrosion Tests—Rust (ASTM D 665), Copper Strip (ASTM rcinge @ 25°C. NLGI service classifications are LA and LB for
D130) chassis use and GA, GB, and GC for use in wheel bearings.
• Wear Test—FZG (A/8.3/90), a n d Four-Ball EP (ASTM D Prior to this classification, the SAE recommended practice,
2783), Falex (ASTM D 2670), Ryder gear tests to fulfil U.S. published in the SAE information report J310, was used for
Military requirements. this purpose. The report, first introduced in 1951, had several
• Miscellaneous Tests—Viscosity Index (ASTM D 2270), revisions, the most recent of which occurred in 1993 [78].
Tests associated with NLGI Service Classes, provided in the
Flash Point (ASTM D 93), Pour Point (ASTM D 97), Neu-
ASTM 4950 Automotive Grease Specification, are listed be-
tralization N u m b e r (ASTM D 974 and D 664), Air Release
low.
(DIN 51381, ASTM D 3427), F o a m (tendency/stability)
(ASTM D 892), Demulsibility (ASTM D 2711), and Turbine • Shear Stability—Mukistroke Penetration (ASTM D 217),
Oil Demulsibility (ASTM D 1401) Roll Stability (ASTM D 1831), Wheel Bearing Leakage
(ASTM D 4290 and D 1263)
Greases • Oxidation Resistance—Bomb Oxidation (ASTM D 942),
The use of this lubricant goes back to ancient times [62]. Lu- High Temperature Life (ASTM D 3527), High-Temperature
bricating grease is defined as a "solid-to-semifluid products Performance (ASTM D 3336)
of dispersion of a thickening agent in a liquid lubricant. • Water Resistance—Water Washout (ASTM D 1264), Water
Other ingredients imparting special properties may be added Spray-off (ASTM D 4049)
(ASTM D 288)." Such ingredients include additives that im- • Bleed Resistance—Oil Separation, static (FTM 321.3), Pres-
part other desirable properties, such as EP, water resistance, sure Oil Separation (ASTM D 1742)
etc. The lubrication function is carried out by the small • Extreme Pressure/ Antiwear—Four-ball EP (ASTM D 2596),
amount of oil that is released during equipment operation. Timken Method (ASTM D 2509), Four-ball Wear (ASTM D
Because of their semisolid nature, greases are used when 2266), Fretting Protection (ASTM D 4170), SRV Test
fluid lubricants are inefficient, the need for lubrication is in- (ASTM D 5706 and D 5707)
frequent, and/or the lubricant is required to maintain its orig- • Corrosion—Rust Test (ASTM D 1743), E m c o r (IP 220),
inal position in a mechanism. Copper Corrosion (ASTM D 4048)
Greases are formulated from both synthetic and mineral • Pumpability—Low-temperatu re Torque (ASTM D 4693)
oil basestocks by using a thickening agent and selected ad- Mobility (US Steel LT37)
ditive packages. The thickener, usually a metal soap (a car- • Msce/ZaneoMS—Elastomer Compatibility (ASTM D 4289)
boxylic acid salt) and sometimes a gelled basic sulfonate, Dropping Point (ASTM D 566 or D 2265)
ASTM AND OTHER STANDARDS
ASTM No. ISO No. IP No. Test

D 92-01 2592:1973 36/84 (89) Test Method for Flash and Fire Points by Cleveland Open Cup
D 93-00 2719:1988 34/88 Test Method for Flash Point by Pensky-Martens Closed Cup Tester
D 94-00 6293:1983 136/89 Test Method for Saponification N u m b e r of Petroleum Products
D 97-96a 3016:1994 15/95 Test Method for Pour Point of Petroleum Products
D 129-00 Test Method for Sulfur in Petroleum Products (General B o m b Method)
D 130-94(2000) 2160:1985 154/95 Test Method for Detection of Copper Corrosion from Petroleum Products by the
Copper Strip Tarnish Test
D 217-97 2137:1985 50/88 Test Method for Cone Penetration of Lubricating Grease
D 445-01 3104:1994 71/97 Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (the
Calculation of Dynamic Viscosity)
D 482-00 Test Method for Ash from Petroleum Products
D 566-97 2176:1995 132/96 Test Method for Dropping Point of Lubricating Grease
D 664-95 (2001) 6619:1988 177/96 Test Method for Acid Number of Petroleum Products by Potentiometric Titration
Method
D 665-99 7120:1987 135/93 Test Method for Rust Preventing Characteristics of Inhibited Mineral Oil in the
Presence of Water
D 808-00 Test Method for Chlorine in New and Used Petroleum Products (Bomb Method)
D 874-00 3987:1994 163/96 Test Method for Sulfated Ash from Lubricating Oils and Additives
D 892-01 6247:1998 146/82 (88) Test Method for Foaming Characteristics of Lubricating Oils
D 942-90 (1995) 142/85 (92) Test Method for Oxidation Stability of Lubricating Greases by the Oxygen B o m b
Method
D 943-99 4263:1986 280/96 Test Method for Oxidation Characteristics of Inhibited Mineral Oils
D 972-97 Test Method for Evaporation Loss of Lubricating Greases and Oils
D 974-01 6618:1997 139/93 Test Method for Acid and Base Number by Color-Indicator Titration
D 1078-95 195/90 Test Method for t h e Determination of Distillation Characteristics of Volatile
Organic Liquids (ASTM Procedure Now Obsolete)
D 1091-00 Test Method for Phosphorus in Lubricating Oils and Additives
D 1092-99 Test Method for Measuring Apparent Viscosity of Lubricating Greases
D 1159-01 3839:1978 130/92 Test Method for B r o m i n e N u m b e r s of Petroleum Distillates and Commercial
Aliphatic Olefins by Electrometric Titration
D 1218-99 Test Method for Refractive Index a n d Refractive Dispersion of Hydrocarbon
Liquids
D 1263-94 (1999) Test Method for Leakage Tendencies of Automotive Wheel Bearing Greases
D 1264-00 Test Method for Determining the Water Washout Characteristics of Lubricating
Greases
D 1298-99 3675:1993 160/96 Practice for Density, Relative Density (Specific Gravity), or API Gravity of Crude
Petroleum and Liquid Petroleum Products
D 1401-98 6614:1994 412/96 Test Method for Water Separability of Petroleum Oils and Synthetic Fluids
D 1500-98 2049-1996 196/97 Test Method for ASTM Color of Petroleum Products (ASTM Color Scale)
D 1742-94 (2000) Test Method for Oil Separation from Lubricating Grease During Storage
D 1743-01 Test Method for Determining Corrosion Preventive Properties of Lubricating
Greases
D 1744 Test Method for Determination of Water in Liquid Petroleum Products by Karl
Fischer Reagent (Discontinued 2000)
D 1748-00 366/84 Standard Test Method for Rust Protection by Metal Preservatives in the Humidity
Cabinet
D 1831-00 Test Method for Roll Stability of Lubricating Grease
D 2070-91 (2001) Test Method for Thermal Stability of Hydraulic Oils
D 2161-93 (1999) Practice for Conversion of Kinematic Viscosity to Saybolt Universal Viscosity or to
Saybolt Universal Viscosity
D 2265-00 Test Method for Dropping Point of Lubricating Grease Over Wide Temperature
Range
D 2266-91 (1996) 239/97 Test Method for Wear Preventive Characteristics of Lubricating Grease (Four-Ball
Method)
D 2270-93 (1998) 2909:1981 226/91 (95) Practice for Calculating Viscosity Index from Kinematic Viscosity at 40 and 100°C
D 2272-98 Test Method for Oxidation Stability of Steam Turbine Oils by Rotating Pressure
Vessel
D 2500-99 3015:1992 219/94 Test Method for Cloud Point of Petroleum Products
D 2509-93 (1998) 326/83 (88) Test Method for Measurement of Load-Carrying Capacity of Lubricating Grease
(Timken Method)
D 2596-97 Test Method for Measurement of Extreme-Pressure Properties of Lubricating
Grease (Four-Ball Method)
D 2602-86 Test Method for Apparent Viscosity of Engine Oils at Low Temperature Using
Cold-cranking Simulator (Replaced in 1993 with D 5293)
D 2603-01 Test Method for Sonic Shear Stability of Polymer-Containing Oils
(Continues)

D 2619-95 Test Method for Hydrolytic Stability of Hydraulic Fluids (Beverage Bottle Method)
D 2622-98 Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-Ray
Fluorescence Spectrometiy
D 2670-95 (1999) Test Method for Measuring Wear Properties of Fluid Lubricants (Falex Pin and Vee
Block Method)
D 2710-99 Test Method for Bromine Index of Petroleum Hydrocarbons by Electrometric
Titration
D2711-01a Test Method for Demusibility Characteristics of Lubricating Oils
D 2782-01 Test Method for Measurement of Extreme-Pressure Properties of Lubricating
Fluids (Timken Method)
D 2783-88 (1998) 293/97 Test Method for Measurement of Extreme-Pressure Properties of Lubricating
Fluids (Four-Ball Method)
D 2882-00 Test Method for Indicating Wear Characteristics of Petroleum and Non-Petroleum
Hydraulic Fluids in Constant Volume Vane Pump
D 2893-99 Test Method for Oxidation Characteristics of Extreme-Pressure Lubricating Oils
D 2896-01 3771:1994 276/95 Test Method for Base Number of Petroleum Products by Potentiometric Perchloric
Acid Titration
D 2983-01 267/84 Test Method for Low-Temperature Viscosity of Automotive Fluid Lubricants
Measured by Brookfield Viscometer
D 3228-96 Test Method for Total Nitrogen in Lubricating Oils and Fuel Oils by Modified
Kjeldahl Method
D 3233-93 (1998) Test Method for Measurement of Extreme Pressure Properties of Fluid Lubricants
(Falex Pin and Vee Block Methods)
D 3336-97 Test Method for Life of Lubricating Greases in Ball Bearings at Elevated
Temperatures
D 3339-95 (2000) 7537:1989 BS7393 Test Method for Acid Number of Petroleum Products by Semi-Micro Color Indica-
tor Titration
D 3427-99 Test Method for Air Release Properties of Petroleum Oils
D 3520-88 (1998) Test Method for Quenching Time of Heat-Treating Fluids (Magnetic Quench-
ometer Method)
D 3527-95 Test Method for Life Perforraance of Automotive Wheel Bearing Grease
D 3825-90 (2000) Test Method for Dynamic Surface Tension by the Fast Bubble Technique
D 3828-98 3679:1983 303/83 (88) Test Method for Flash Point by Small Scale Closed Tester
3680:1983
D 3829-93 (1998) Test Method for Predicting the Borderline Pumping Temperature of Engine Oil
D 4047-00 4265:1986 149/93 Test Method for Phosphorus in Lubricating Oils and Additives by Quinoline
Phosphomolybdate Method
D 4048-97 Test Method for Detection of Copper Corrosion from Lubricating Grease
D 4049-99 Test Method for Determining the Resistance of Lubricating Grease to Water Spray
D 4170-97 Test Method for Fretting Wear Protection by Lubricating Greases
D 4172-94 (1999) 293/97 Test Method for Wear Preventive Characteristics of Lubricating Fluid (Four-Ball
Method)
D 4289-97 Test Method for Elastomer Compatibility of Lubricating Greases and Fluids
D 4290-94 (1999) Test Method for Determining the Leaking Tendencies of Automotive Wheel
Bearing Grease Under Accelerated Conditions
D 4310-98 Test Method for Determination of the Sludging and Corrosion Tendencies of
Inhibited Mineral Oils
D 4377-00 356/93 Test Method for Water in Crude Oils by Potentiometric Karl Fischer Titration
D 4485-01 Specification for Performance of Engine Oils
D 4624-93 (1998) Test Method for Measuring Apparent Viscosity by Capillary Viscometer at High-
Temperature and High-Shear Rates
D 4627-92 287/94 Test Method for Iron Chip Corrosion for Water-Dilutable Metalworking Fluids
125/82
D 4628-97 Test Method for Analysis of Barium, Cadmium, Magnesium, and Zinc in Unused
Lubricating Oils by Atomic Absorption Spectrometry
D 4682-87 (1996) Specification for Miscibility with Gasoline and Fluidity of Two-Stroke Cycle Gaso-
line Engine Lubricants
D 4683-96 Test Method for Measuring Viscosity at High Shear Rate and High Temperature by
Tapered Bearing Simulator
D 4684-99 Test Method for Determination of Yield Stress and Apparent Viscosity of Engine
Oils at Low Temperature
D 4693-97 Test Method for Low-Temperature Torque of Grease-Lubricated Wheel Bearings
D 4739-96 276/95 Standard Test Method for Base Number Determination by Potentiometric
417/96 Titration
D 4741-00 Test Method for Measuring Viscosity at High Temperature and High Shear Rate by
Tapered-Plug Viscometer
D 4857-Ola Test Method for Determination of the Ability of Lubricants to Minimize Ring
Sticking and Piston Deposits in Two-Stroke-Cycle Gasoline Engines Other Than
Outboards
D 4858-00 Test Method for Determination of the Tendency of Lubricants to Promote Preigni-
tion in Two-Stroke-Cycle Gasoline Engines

D 4859-97 Specification for Lubricants for Two-Stroke-Cycle Spark-Ignition Gasoline
Engines-TC
D 4863-00 Test Method for Determination of Lubricity of Two-Stroke-Cycle Gasoline Engine
Lubricants
D 4927-96 Test Methods for Elemental Analysis of Lubricant and Additive Components—
B a r i u m , Calcium, P h o s p h o r u s , Sulfur, and Zinc by Wavelength-Dispersive
X-Ray Fluorescence Spectroscopy
D 4928-00 Test Methods for Water in Crude Oils by Coulometric Karl Fischer Titration
D 4950-95 (2000) Classification and Specification for Automotive Service Greases
D 4951-00 Test Method for Determination of Additive Elements in Lubricating Oils by Induc-
tively Coupled Plasma Atomic Emission Spectroscopy
D 4998-95 Test Method for Evaluating Wear Characteristics of Tractor Hydraulic Fluids
D 5133-99 Test Method for Low T e m p e r a t u r e , Low Shear Rate, Viscosity/Temperature
Dependence of Lubricating Oils Using a Temperature Scanning Technique
D 5182-97 334/93 Standard Test Method for Evaluating the Scuffing Load Capacity of Oils (FZG
Visual Method)
D 5185-97 Test Method for Determination of Additive Elements, Wear Metals, and Contami-
nants in Used Lubricating Oils and Determination of Selected Elements in Base
Oils by Inductively Coupled Plasma Emission Spectroscopy (ICP-AES)
D 5291-96 Test Methods for Instrumental Determination of Carbon, Hydrogen, and Nitrogen
in Petroleum Products and Lubricants
D 5293-99a Test Method for Apparent Viscosity of Engine Oils Between - 5 and — 35°C Using
the Cold Cranking Simulator
D 5302-01 Test Method for Eveduation of Automotive Engine Oils for Inhibition of Deposit
Formation and Wear in a Spark-Ignition Internal Combustion Engine Fueled
with Gasoline and Operated Under Low-Temperature, Light-Duty Conditions
(Sequence VE)
D 5480-•95 (1999) Test Method for Engine Oil Volatility by Gas Chromatography
D5481- 96 Test Method for Measuring Apparent Viscosity at High-Temperature and High-
Shear Rate by Multicell Capillary Viscometer
D 5533-•98 Test Method for Evaluation of Automotive Engine Oils in Sequence IIIE, Spark-
Ignition Engine
D 5579- 01 Test Method for Evaluating the Thermal Stability of Manual Transmission Lubri-
cants in a Cyclic Durability Test
D 5 6 1 9 00 Test Method for Comparing Metal Removal Fluids Using the Tapping Torque Test
Machine
D 5662 Test Method for Determining Automotive Gear Oil Compatibility with Typical Oil
Seal Elastomers
D 5706- 97 Test Method for Determining Extreme Pressure Properties of Lubricating Greases
Using a High-Frequency, Linear-Oscillation (SRV) Test Machine
D 5707. Test Method for Measuring Friction and Wear Properties of Lubricating Greases
Using a High-Frequency, Linear-Oscillation (SRV) Test Machine
D 5760- 95 Specification for Performance of Manual Transmission Gear Lubricants
D 5763- 95 Test Method for Oxidation and Thermal Stability Characteristics of Gear Oils
Using Universal Glassware
D 5800 00a Test Method for Evaporation Loss of Lubricating Oils by the Noack Method
D 5844. 98 Test Method for Evaluation of Automotive Engine Oils for Inhibition of Rusting
(Sequence IID)
D 5846- 99 Test Method for Universal Oxidation Test for Hydraulic and Turbine Oils Using the
Universal Oxidation Test Apparatus
D 5862- 99a Test Method for Evaluation of Engine Oils in Two-Stroke Cycle Turbo-Super-
Charged 6V92TA Diesel Engine
D 5949- 96 Test Method for Pour Point of Petroleum Products (Automatic Pressure Pulsing
Method)
D 5950- 96 Test Method for Pour Point of Petroleum Products (Automatic Tilt Method)
D 5966- 99 Test Method for Evaluation of Engine Oils for Roller Follower Wear in Light-Duty
Diesel Engine
D 5967- 99a The Method of Evaluation of Diesel Engine Oils in T-8 Engine
D 5968 00a Test Method for the Corrosiveness of Diesel Engine Oil
D 5985- 96 Test Method for Pour Point of Petroleum Products (Rotational Method)
D 6082- 00 Test Method for High Temperature Foaming Characteristics of Lubricating Oils
D6121- 01 Test Method for Evaluation of the Load Carrying Capacity of Lubricants Under
Conditions of Low Speed and High Torque Used for Final Hypoid Drive Axles
D 6202 -01 Test Method for Automotive Engine Oils on the Fuel Economy of Passenger Cars
and Light Duty Trucks in t h e Sequence VIA Spark Ignition Engine
D 6335 Test Method for Determination of High T e m p e r a t u r e Deposits by Thermo-
Oxidation Engine Oil Simulation Test
D 6375 99a Test Method for Evaporation Loss of Lubricating Oils by Thermogravimetric
Analyzer (TGA) Noack Method
D 6417 99 Test Method for Estimation of Engine Oil Volatility by Capillary Gas Chromatog-
raphy
(Continues)
D 6443-99 Test Method for Determination of Calcium, Chlorine, Copper, Magnesium, Phos-
phorus, Sulfur, and Zinc in Unused Oils and Additives by Wavelength Dispersive
X-ray Fluorescence Spectrometry (Mathematical Correction Method)
D 6481-99 Test Method for Determination of Phosphorus, Sulfur, Calcium, and Zinc in
Lubrication Oils by Energy Dispersive X-ray Fluorescence Spectrometry
D 6483-99 Test Method for Evaluation of Diesel Engine Oils in T-9 Engine
D 6557-00 Test Method for Evaluation of Rust Preventive Characteristics of Automotive
Engine Oils (Ball Rust Test)
D 6593-00 Test Method for Evaluation of Automotive Engine Oils for Inhibition of Deposit
Formation in a Spark-Ignition Internal Combustion Engine Fueled with
Gasoline and Operated Under Low-Temperature, Light Duty Conditions
(Sequence VG)
D 6616-01 Test Method for Measuring Viscosity at High Shear Rate by Tapered Bearing
Simulator Viscometer at 100°C
D 6618-00 Test Method for Evaluation of Engine Oils in Diesel Four-Stroke-Cycle Super-
Charged IM-PC Single Cylinder Oil Test Engine
D 6681-01 Test Method for Evaluation of Engine Oils in a High Speed, Single-Cylinder Diesel
Engine—Caterpillar IP Test Procedure
D 6709-01 Test Method for Evaluation of Automotive Engine Oils in the Sequence VIII Spark-
Ignition Engine (CLR Oil Test Engine)
REFERENCES [14] Kreuz, K. L., "Gasoline Engine Chemistry as Applied to Lubri-

cant Problems," Lubrication, Vol. 55, 1969, pp. 53-64.
[1] Obert, E. F., "Lubrication," Ch. 16, Internal Combustion Engines [15] Lachowicz, D. R. and Kreuz, K. L., "Peroxynitrates. The Unsta-
and Air Pollution, Intext Educational Publishing, NY, 1968, pp. ble Products of Olefin Nitration with Dinitrogen Tetroxide in
633-677. the Presence of Oxygen. A New Route to a-Nitroketones," Jour-
[2] Modler, R., Anderson E., and Yoshida Y., "Lubricant Oil Addi- nal of Organic Chemistry, Vol. 32, 1967, pp. 3885-3888.
tives," Specialty Chemicals, Strategies for Success, Vol. 9, SRI In- [16] Kreuz, K. L., "Diesel Engine Chemistry as Applied to Lubricant
ternational, December 1996. Problems," Lubrication, Vol. 56, 1970, pp. 77-88.
[3] Rizvi, S. Q. A., "Additives: Chemistry and Testing," Tribology [17] Covitch, M. J., Graf, R. T., and Gundic, D. T., "Microstructure of
Data Handbook—An Excellent Friction, Lubrication, and Wear Carbonaceous Diesel Engine Piston Deposits," Lubricant Engi-
Resource, CRC Press, Boca Raton, FL, 1997, pp. 117-137. neering, Vol. 44, 1988, p. 128. (b) Covitch, M. J., Richardson, J.
[4] Klamann, D., Lubricants and Related Products—Synthesis, Prop- P., and Graf, R. T., "Structural Aspects of European and Ameri-
erties, Applications, International Standards, Verlag Chemie, can Diesel Engine Piston Deposits," Lubrication Science, Vol. 2,
Hamburg, 1984. (a) "Analysis and Testing," Ch. 10, pp. 218-247. 1990, pp. 231-251.
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MNL37-EB/Jun. 2003
Synthetic Lubricants—
Non Aqueous
Thomas F. Buenemann, ^ Steve Boyde, ^ Steve Randies, ^
and Ian Thompson^
POLYOL AND DIESTERS Chemistry and Manufacturing

General Features and Product Groups
ALTHOUGH THE DEVELOPMENT OF SYNTHETIC ESTER LUBRICANTS is
relatively recent, the use of esters as lubricating fluids is as Esters are defined as the class of chemical compounds con-
old as h u m a n technology. Before suitable mineral oils be- taining the ester functional group. They are normally manu-
came widely available as a b3^roduct of the petroleum based factured by reaction of a carboxylic acid with an alcohol (Fig.
fuels industry, lubricants were based on natural fats or oils, 1), optionally in the presence of an esterification catalyst, and
which are either triesters of glycerine with natural fatty acids, with elimination of water [5].
e.g., tallow and olive oil, or long chain monoesters of fatty The properties of the product esters can be controlled by
acids with fatty alcohols, e.g., sperm whale oil. appropriate selection of the raw materials used. The final
The use of synthetic esters as high performance lubricat- product properties are mainly dependent on the molecular
ing fluids was originally driven by the development of the weight, the n u m b e r of ester groups per molecule, and the de-
gas turbine or jet engine in aviation. Aviation turbines have gree of branching in alkyl substituent groups. A mixture of
a higher operating temperature than the piston engines that raw materials may be used to deliver the precise combination
preceded them, and jet aircraft are capable of operation at of properties required.
m u c h higher altitudes, where the ambient temperature is There are three main classes of synthetic esters currently in
very low. Consequently, lubricants for aviation turbines are use as lubricant base fluids: aromatic esters, aliphatic diesters,
required to have both very good high temperature stability and polyol esters. Aromatic esters, shown in Fig. 2, are manu-
and good low temperature flow properties. It was found factured by the reaction of an aromatic di or poly acid or an-
that mineral oils and synthetic hydrocarbons did not deliver hydride, such as phthalic anhydride, tiimellitic anhydride, or
the required combination of properties, and diesters were pyromeUitic anhydride, with a monoalcohol or mixture of
adopted as the lubricant base fluid of choice for early avia- monoalcohols. Diesters, shown in Fig. 3, are manufactured by
tion turbines [1]. As gas turbine technology developed, the the reaction of an aliphatic alpha, omega diacid with a monoal-
operating temperatures increased further, and diesters have cohol or mixture of monoalcohols. Polyol esters, shown in Fig.
been largely substituted in aviation applications by polyol 4, are manufactured by reaction of a diol or polyol having the
esters, which have even better thermal stability [2]. Despite neopentyl structure, such as neopentyl glycol, trimethylol
intensive research into alternative chemistries, polyol esters propane or pentaerythritol, with a monoacid or mixture of
remain the base fluid of choice for aviation turbine lubri- monoacids. Oligomeric esters, generally known as complex es-
cants. ters, can be manufactured by reaction of a diol or polyol with
a di or polyacid/anhydride, with a monoacid or monoalcohol
In addition to their good properties at extreme tempera-
to act as capping reagent. This allows preparation of materials
tures, synthetic esters have other desirable characteristics in-
having higher average molecular weights and consequently
cluding good lubricity, high viscosity index, low volatility,
higher viscosities, than can be achieved with simple diesters or
and compatibility with s t a n d a r d lubricant additives a n d
polyol esters. However, complex esters also have a distribution
basefluids. The fundamental chemistry is flexible and a wide
of molecular weights, which means that their volatility char-
range of raw materials is available, which means that ester
acteristics are not as good as simple esters of the same number
base fluids can be designed having a wide raxige of viscosities.
average molecular weight.
Other key properties such as biodegradability can also be
controlled by molecular design [3]. Consequently, synthetic
esters have found use in many applications outside aviation. Raw Materials
Examples include automotive crankcase a n d gear oils, 2- The raw materials used in the manufacture of synthetic esters
stroke lubricants, industrial gear oils, hydraulic fluids, textile for lubricant applications are derived from a variety of sources,
yarn lubricants, metal cutting and rolling fluids, air com- both natural and synthetic. Aromatic acids or anhydrides are
pressor lubricants, and refrigeration compressor lubricants manufactured by the oxidation of the corresponding hydro-
[4]. carbons [6,7]. Alpha, omega diacids are also generally pro-
duced by oxidation. The diacids used most widely to synthe-
size ester lubricant fluids are adipic, azelaic, sebacic, and
' Senior Application Manager and ^ Technology Manager, Uniqema
Lubricants, P.O. Box 2, 2800 AA Gouda, Buurtje 1, Gouda, BE 2802, dodecanedioc acids, as well as C36 dimer acid. Adipic and do-
Netherlands. decanedioc acids are derived from petrochemical feedstocks.
249
whereas azelaic, sebacic, and C36 dimer acids are derived from
natural fatty acids [8]. The monoalcohols used in diesters are
mainly manufactured by carbonylation of olefin feedstocks. Polyol esters Q R = C4-C17linearor
branched aikyi
These alcohols are also used in the manufacture of plasticizers
R'" groups
and ethoxylate surfactants. They are generally commercially
available as a mixture of isomers and/or carbon chain num-
bers. Exceptions include 2-ethylhexanol, a derivative of bu-
I
R"- CK O ^ ^R
tanol, which is a single isomer, and the linear C-even alcohols
(eg Cg, Cio alcohol), which are manufactured by chemical re-
duction of naturally occurring fatty acids [9], R"
The mono acids (fatty acids) used in polyol esters may be
derived either from petrochemical or natural sources. Natu- PE; Pentaerythritol; R' = R" = R'" = CH20COR
rally occurring fatty acids are almost always linear and have TMP; Trimethylol propane; R"» R" = CH20C0R, R" = Et
an even number of carbon atoms. Lower carbon numbers NPG; Neopentyl glycol; R' = CH20C0R, R" = R" = Me
FIG. 4—Examples of polyolesters.

Acid ^ £st(^r:'
(Cs—Cift) are normally fully saturated, while higher carbon
OH Fsterififaqtion ^ ^ ' t ^ R' numbers (Cig—C22) have olefinic unsaturation. Petrochemi-
cal fatty acids may be either linear or branched. Linear
petrochemical acids are manufactured by the oxidative car-
n nWater bonylation of linear olefins, which are themselves derived
from ethylene and are therefore C-even (an even number of
C-atoms/molecules). Carbonylation adds a single carbon
FIG. 1—Chemistry of esteriflcatlon. atom, so linear petrochemical acids are normally C-odd (an
odd number of C-atoms/molecules) [8].
The neopentyl polyols used in polyol esters are manufac-
tured by reaction of an aldehyde with formaldehyde, fol-
lowed by chemical reduction [10]. As noted below, the
Aromatic esters neopentyl structure confers superior thermal and oxidative
o 0 0 stability as compared to other polyols, such as butane diol or
glycerol, and neopentyl polyol derived materials are pre-
I I ^ I ferred in lubricant applications for this reason.
The only significant exception to this rule is for glycerol es-
ters, which are also widely used in lubricating applications,
though only those where thermal and oxidative stability is not
II Trimellitate II a key performance requirement. Some of these glycerol esters
Phthalate O ° are simply purified vegetable oils, which are not normally
classified as synthetic esters. Others, known as mid-chain
R = C8 - CI8 linear or branched alkyl groups triglycerides (MCTs), are produced by chemical reaction of
purified short chain natural fatty acids with glycerol. The ox-
idative stability of MCTs is inferior to that of neopentyl polyol
FIG. 2—Examples of aromatic esters. esters, but they are used in applications where very high
biodegradability is required, or where products are required
to be manufactured only from renewable raw materials.
Diesters Manufacturing Technology
Esters are manufactured by reacting the desired acid and
ailcohol with an esterification catalyst, if required, and react-
% C — >^' ing at an elevated temperature [11]. The esterification reac-
( ^ " 2 > n - \ tion is reversible, and consequently it is necessary to drive the
. /
R' 0 ~ R ' equilibrium over to the desired product by removal of water.
The reaction temperature and pressure are therefore selected
so that water can be removed by distillation as it is formed.
n = 4 - adipates High temperatures also increase the rate of reaction, but very
n = 7 - azelates high temperatures may lead to undesirable side reactions or
n - 8 - sebacates discoloration. Esterification reactions are, therefore, nor-
n = 10 - dodecanedioates mally conducted at a temperature in the range 200-250°C.
R' - C8 - C13 linear or branched alkyl groups For diesters and aromatic esters, the reaction is generally
conducted in the presence of an excess of the monoalcohol.
FIG. 3—Examples of diesters. ASTM D 974-97 Standard Test Method for Acid and Base
CHAPTER 10: SYNTHETIC LUBRICANTS—NON AQUEOUS 251
Number by Colorimetric Titration (DIN 51 559 Part 1) is used Low Temperature Characteristics
to measure the acid value, and when the acid value of the re- The low temperature properties of esters, as for all lubricating
action mixture has reached the target value, implying that all fluids, depend on the VI, and on the tendency to form waxy
of the acid groups have reacted, the excess monoalcohol is re- solids [15], As noted above, the VI can be controlled by ap-
moved by distillation. propriate molecular design. Linear substituents are desirable
For polyol esters, the reaction is usually carried out in the to give a high VI and therefore control the increase in viscos-
presence of an excess of the monoacid. In this case, the ity with increasing temperature. Wax formation tendency is
progress of the reaction is controlled by monitoring the hy- dependent on the presence of saturated linear hydrocarbon
droxy] value according to ASTM E 326 Standard Test Method chains above a critical chain length. Linear saturated hydro-
for Hydroxyl Groups by Phthalate Esterification. When the carbon substituents containing approximately eight or more
target value is achieved, the excess monoacid is removed by carbon atoms will generally lead to tendency to wax formation
distillation. in the temperature region of interest, i.e., — 50°C to 0°C. Ester
Esterification catalysts are normally used to accelerate the base fluids intended for low temperature applications gener-
rate of the esterification reaction. Conventionally used ho- ally have a balance of linear and branched substituents to
mogeneous catalysts include complexes of transition metals, achieve both performance criteria which is measured by
especially titanium and tin, and strong acids, e.g., toluene- ASTM D 97-96a, Standard Test Method for Pour Point of
sulfonic acid. Heterogeneous catalysts such as acid ion ex- Petroleum Products (DIN 51 597).
change resins may also be used [11].
The fact that acids catalyze the esterification process can Volatility
be exploited in the manufacture of polyol esters, where the The ester group carries a permanent electric dipole. This
mono acid reagent, present in excess, may itself serve as the means that an intermolecular force due to dipolar interaction
catalyst. The crude ester produced by chemical reaction and exists between the ester molecules, in addition to the normal
distillation of excess raw materials normally requires further molecular van der Waals forces which are present between
processing to render it suitable for use as a lubricant base hydrocarbon groups. Consequently, intermolecular forces
fluid. It is particularly important to remove all traces of the are stronger in ester fluids, and esters have significantly
esterification catalyst, since the esterification catalyst is also lower vapour pressure, and therefore higher flash points than
capable of acting as a hydrolysis catalyst, which would have
hydrocarbons of similar molecular weight and viscosity [4]
a detrimental effect on the hydrolytic stability of the product.
determined by ASTM D 92-97, Standard Test Method for Fire
Where titanium catalysts are used it is normal to wash the
and Flash Point by Cleveland Open Cup (DIN 51 376).
crude ester with water, which hydrolyzes the catalyst to form
insoluble titanium oxide, which can be removed by subse-
quent filtration. Further treatments may be applied to reduce Chemical Characteristics
acid value; reduce water content, which is determined by
Thermal Stability
ASTM E 1064, Standard Test Method for Water in Organic
Liquids by Coulometric Karl-Fischer Titration (DIN 51 777 Sjmthetic esters all show very good thermal stability as com-
Part 1); or to remove color, which is measured by ASTM D pared to mineral oil, but diesters are significantly less stable
1209-97, Standard Test Method for color of clear liquids than polyol esters. This is because diesters can decompose
(Platinum-Cobalt scale) formed during reaction. Finally, the via a /3-elimination reaction, which forms an acid and an
product is filtered to remove particulate impurities. olefin. This pathway is not possible for polyol esters due to
the neopentyl structure, which has no hydrogen atoms, at-
tached to the /3 carbon of the alcohol residue [4].
Physical Properties
Hydrolytic Stability
Viscosity As noted above, the esterification reaction is reversible, and
Probably the most important characteristic of a lubricant esters can, in principle, react with water to regenerate the
base fluid is the viscosity measured by ASTM D 445-97, Stan- acid and alcohol raw materials. This reaction is known as hy-
dard Test Method for Kinematic Viscosity of Transparent and drolysis. The rate of hydrolysis under normal service or stor-
Opaque Liquids (DIN 51 550). The ester group does not sig- age conditions is very low, and hydrol3?tic stability is rarely an
nificantly increase viscosity as compared to a hydrocarbon issue in practice. However, it can be a cause of concern in
chain. Consequently, esters typically have viscosities similar some applications as the acids produced by hydrolysis could
to those of hydrocarbons of comparable molecular weight and potentially act as corrosive agents. Test methods have been
degree of branching [12]. The viscosity of ester fluids can be developed to characterize the rate of hydrolysis, i.e., ASTM D
controlled over a wide range by appropriate choice of molec- 2619, Standard Test Method for Hydrolytic Stability of Hy-
ular structure, and current commercially available materials draulic Fluids. In this test, 75 g of fluid and 25 g of water eire
cover the range of viscosities at 40°C from 5 cSt for simple di- sealed in a beverage bottle with a copper strip present for 48
esters up to >1000 cSt for complex esters [13,14]. h at 93°C (200°F). At the end of the test, the oil and water lay-
As for all fluids, the temperature dependence of viscosity ers are separated and insolubles are weighted. Viscosity and
(Viscosity Index, VI) is calculated by ASTM D 2270-93, Prac- acid numbers are also determined.
tice for Calculating Viscosity Index from Kinematic Viscosity However, these test methods must be used with caution as
at 40°C and 100°C (DIN/ISO 2909) which is a function of the the rate of hydrolysis depends on factors such as the
extent and type of branching in the molecule. VI can be con- structure and purity of the ester, reaction conditions, and the
trolled by molecular design as for viscosity [12], nature of additives present. An understanding of these rela-
tionships can be used to select appropriate ester lubricant and polyol esters are typically used. The more polar ester
formulations for a given application [16]. serves to enhance solubility of less polar additives in PAO,
and confer seal swelling properties, as well as superior ther-
Biodegradability mal stability. PhthaJate esters have been used where a low
Esters generally exhibit higher aerobic biodegradability than cost seal swellant is required.
corresponding hydrocarbons, because microorganisms pro- Diesters based on C36 dimer acid and polyol esters are fre-
duce lipase enzymes which catalyze ester hydrolysis. This quently used in two stroke cycle formulations to provide low
converts the ester into alcohol and acid, which have higher smoke properties and biodegradability for spilled or uncom-
water solubility and can be further degraded by enzyme cat- busted oil, particularly in marine applications.
alyzed oxidation reactions. The degree of initial biodegrad- Hydraulic fluids are formulated using synthetic polyol es-
ability of ester fluids is highly correlated with the hydrolytic ters or diesters where a combination of good oxidative sta-
stability. Ultimate biodegradability is also dependent on the bility and biodegradability is required. Organic esters also
linearity of the hydrocarbon subsituents. Esters derived from have better flame retardancy than mineral oils, although not
reactants containing fully linear alkyl substituents (and in as good as phosphate esters.
particular those containing olefinic unsaturation) such as As noted above, polyol esters remain the lubricant base fluid
polyol esters derived from natural fatty acids, e.g., trimethy- of choice for aviation turbine lubricants, even in military ap-
lolpropane oleate (TMPO), generally biodegrade particularly plications. Polyol ester- derived aviation turbine lubricants
rapidly. In contrast, a r o m a t i c esters, particularly those are generally formulated containing aminic antioxidants and
containing highly branched alkyl groups, biodegrade more ashless phosphate ester antiwear agents. There is continuing
slowly. However, even some branched aromatic esters can interest in increasing the upper temperature limit for aviation
meet the criteria for ready biodegradabilitiy according turbine lubricants, but the thrust of current research has
to OECD 301B [17]. OECD 301B is currently the most moved away from investigation of alternative base fluids to-
widely used test method for ready biodegradability of water- wards optimization of ester chemistry.
insoluble organic substances [18]. However, another closely The relatively recent development of hydrofluorocarbon
related test m e t h o d is ASTM D 5864-95, S t a n d a r d Test (HFC) compatible refrigeration compressor lubricants has
Method for Biodegradability of Organic Substances, which is led to increased demand for polyol esters [20].
less stringent in that the latter allows for preacclimation of Concern over the environmental impact of the ozone
the microbial inoculum, and therefore represents a less se- depleting chlorofluorocarbons (CFCs) previously used as re-
vere test regime. frigerant fluids has led to international legislation prohibiting
their use. This has resulted in a change to alternative refriger-
ants including the zero ozone depletion potential HFCs. The
Application and Performance Characteristics HFCs are not miscible with the hydrocarbon lubricants that
were generally used in CFC systems. Lubricant immiscibility
Although slightly more polar, most esters are fully miscible was found to cause poor oil return leading to lubricant star-
with mineral oils or synthetic hydrocarbons. Due to their vation in the compressor and fouling of low temperature heat
higher polarity, they are generally better solvents for polar exchange surfaces. Consequently, it has been necessary to de-
materials, such as many standard lubricant additives used in velop new HFC-miscible synthetic lubricants. Polyol esters
mineral oil based formulations. Consequently, esters are fre- have been generally adopted as the preferred basefluid for
quently used as a component of mixed base fluids containing most HFC compatible refrigeration applications.
polyalphaoleflns, which are poor solvents for polar additives.
However, the relatively higher solvency of esters may be a
disadvantage in formulations containing polar additives,
such as antiwear and EP agents which are required to adsorb POLYALKYLENE GLYCOLS
on the metal surface. The additive treat rate in an ester-based
fluid may need to be higher than in a mineral oil formulation Polyalkylene glycol (PAG) is a generic name used to describe
in order to ensure an effective surface concentration of the a family of products formed from the polymerization of one
additive [19]. or more alkylene oxides. Such products are also known as
The miscibility of esters with more polar materials also al- polyethers, polyoxyalkylene glycols, polyalkylene glycol
lows their use as mixtures with other polar synthetic base- ethers, polyglycols, and PAGs [21,22]. PAGs are an extremely
fluids, e.g., poly alkylene glycols, which are not generally versatile family of products, which can exhibit a wide range of
miscible with mineral oil. physical and chemical properties. They are excellent lubri-
The inherent oxidative stability of esters is similar to that cants in their own right [22-25], which makes them the fluid
of synthetic hydrocarbons. They therefore require the use of of choice for a large n u m b e r of engineering and lubricant
antioxidant additives to limit the rate of oxidation in service. applications.
However, esters generally show very good response to stan- The history of PAGs is a long one. The earliest reported
dard antioxidants and can easily be formulated to give good polymerization of ethylene oxide dates back to 1863 [26],
oxidative stability [4]. with the first commercial products (polyethylene glycols)
Four stroke cycle crankcase formulations require good available in 1939 [27]. The range of viscosities now covered
thermal and oxidative stability, low volatility, and good low by PAGs is vast, making these products suitable as lubricants
temperature pumpability. These requirements can be met by in their own right, but also as thickeners and lubricity im-
the use of mixed poly (alphaolefin)/ester base fluids. Diesters provers in water based systems.
CHAPTER 10: SYNTHETIC LUBRICANTS~NON AQUEOUS 253
The polyether section may contain one or more alkylene

oxides. Single oxide derived PAGs ("homopolymers") are
widely used and relatively simple to manufacture. When two
or more alkylene oxides are used—"copolymers"—these will
be incorporated as blocks ("block copolymers," e.g.,
EO—EO—PO—PO—EO—EO—EO, by sequential reaction
of the oxide), or r a n d o m l y ("random copolymers," e.g.,
PO—EO—EO—PO—EO—EO—PO—EO, by the reaction of a
mixture of oxides). These different polyether configurations
lead to somewhat different properties. For example, blocks
4 4.5 5 copolymers tend to have worse low temperature properties
log (molecular weight) than r a n d o m copolymers.
The principle benefits from including EO are increased wa-
FIG. 5—^Typical molecular weight distribution for a
ter solubility, reduced solubility with non-polar species (e.g.,
polyalkylene glycol.
hydrocarbons), and increased stability. The principle benefits
from including PO are improved low temperature perfor-
Chemistry and Manufacturing mance, reduced polarity, and thus increased solubility of lu-
bricant additives a n d nonpolar species.
PAGs are linear or branched chain polymers, which contain
ether linkages in their main polymer structure. They are pro- In most PAGs, the end group is a hydrogen atom, and this
duced by the polymerization of one or more alkylene oxides, is adequate for most applications. Reacting this active hy-
such as ethylene oxide (EO, C2H4O) cind propylene oxide (PO, drogen further (endcapping), by etherification or esterifica-
CsHgO), though butylene oxide (BO, C4H10O) and higher ox- tion, can yield beneficial effects. Typical end groups of this
ides can also be used. They can be considered to consist of form include aliphatic and aromatics (by etherification) and
three parts: the initiator, the alkylene oxide or polyether sec- alipathic ester groups [29].
tion, and the terminal or end group as shown below. Nuclear magnetic resonance (NMR) spectroscopy is a key
analytical technique for the chemical structural analysis of
initiator polyether section end group PAGs, including the determination of EO/PO ratio, initiator
(CH2-CH(R)-0)„ - R2 and end group analysis, polymerization sequencing (ran-
dom/block), and molecular weight [30,31].
(R is H or alkyl; R' and R^ are H, alkyl, acyl, etc; X is O, N, S,
etc; n is an integer 1, 2, 3, etc.) The three distinct parts of the Synthesis
polymer are variable, and it is therefore possible to produce
an infinite n u m b e r of different products, each with its own Most PAGs are manufactured via a three step process involv-
unique properties. The skill in making PAGs is to select the ing: catalyzation of the initiator; reaction with the alkylene
appropriate combination of initiator, polyether section and oxide(s) ('alkoxylation'); and post-treatment to remove the
terminal group to give the desired properties. Since the PAG catalyst or adjust the p H (see Fig. 6), the reaction of a n alco-
is in fact a "statistical polymer," the product will contain a se- hol (ROH) with EO.
ries of polymers w i t h a distribution of polyether chain The initiator is typically reacted with a catalytic amount of
lengths, centered around "n," and distribution of molecular a base, such as potassium hydroxide, to produce the alcoho-
weights, as shown in Fig. 5. The molecular weight distribu- late, RO — K + . The water produced may either be left in at this
tion is measured by the modified ASTM D 5296-97, Standcird stage, or may be removed under vacuum. The oxide addition
Test Method Gel Permeation Chromatography (GPC). As "n"
and the length of the polymer increases, so does the viscosity, Catalyzation:
thus giving access to a wide range of viscosity. The R group is
H for EO, CH3 for PO, etc. R-O-H + KOH- - * R-O-K+ + H2O
The initiator must be an "active hydrogen" containing com-
pound R ' X — H ; thus X must be an atom of the type O, N, S, etc. Reaction with oxide:
Alcohols are the most extensively used initiators, and include
monohydric alcohols (i.e., containing 1 OH group), such as bu-
R-OK* + CH2-CH2" •R-0-CH2-CH,-0-K+
tanol, or polyols (i.e., containing two or more OH groups), such
as ethylene glycol, glycerol—water can be considered as a di-
AK
hydric alcohol. Increasing the functionality of the initiator is R-O-CH2 - CH2 - O- K+ + n-1 (CHj - CH2 )
particularly useful when trying to build high molecular weight,
as there are more reactive OH ends for addition, and thus the Post-treatment:
reaction rate is increased. The higher OH concentration also
increases the polarity of the polymer, which is useful for par- R-(0-CH2 - CHj )„ - O - K+ + 'H+'
ticular applications; the OH value is typically measured using
ASTM E326, Standard Test Method for Hydroxyl Groups by
Phthalate Esterification. Lower polarity can be achieved by the
use of long chain aliphatic or aromatic alcohols; this is an op- R-(0-CH2-CH2)„-0-H
tion for achieving mineral oil miscibility of PAGs [28]. FIG. 6—Reaction scheme for PAG production.
reaction is normally carried out in a stainless steel reactor at PAGs show a broad viscosity range, from a few mm^/s at
elevated temperatures (tjrpically 80-150°C) and at high pres- 40°C up to a few hundred thousand, as a result of the build
sures (up to 10 bar). The alcoholate is a strong nucleophile, in molecular weight from a few hundred to several tens of
and this approaches the carbon adjacent to the ring oxygen of thousands. Over the wide range of PAG viscosity (for a con-
the alkylene oxide. An O—C bond is formed, and the epoxide sistent structural t3ê), the trends in the other physical
ring is opened; the ring oxygen then acts as the nucleophile for properties tend to vary in a fairly linear fashion. Their key
the next alkylene oxide addition. As the oxide is consumed in properties are water solubility, and excellent viscosity index
forming the polymer, more oxide is fed into the reactor, gen- (VT) determined by ASTM D 2270, Practice for Calculating
erally at a rate to maintain reactor pressure. Viscosity Index from Kinematic Viscosity at 40°C and 100°C
A key side reaction that occurs during propoxylation is the (DIN/ISO 2909) together with very good pour point and
formation of unsaturation by the isomerization of the PO flash point. The main route to adjusting the physical prop-
unit. This reaction limits the viscosity attainable with pure erties is by adjusting the initiator and the EO/PO ratio, as
propoxylates. In terms of reactivity, EO has a higher reaction shown in Table 1.
rate than PO and higher oxides, and reactivity is enhanced by For example, by changing the initiator from a diol, to a
the use of more basic catalysts. mono hydric alcohol (compare products a and b in Table 1),
Depending on the requirements of the final application, there is an increase in viscosity index. Likewise, increasing
when the poljTiierization reaction is complete, the final prod- the EO/PO ratio also results in an increase in VI. This is im-
uct may be subjected to a catalyst removal step. This is achieved portant in applications relying on little change in viscosity
by demineralization, using a magnesium silicate, and neutral- over a range of temperatures (e.g., worm gear lubrication).
ization with an acid, both of which are followed by filtration. Excellent pour and flash points are maintained across a wide
Both techniques work by replacing the metal ion (in this ex- viscosity range, but are again influenced by EO/PO ratio. In-
ample K"*") with a hydrogen ion (H"*"). Sometimes the catalyst is creasing the molecular weight leads to increased VI and flash
left in the product, and the product is treated with an acid to ad- point, but also increased pour point.
just its acid value, which is measured by ASTM D 974, Standard PAGs may be either water soluble or water insoluble de-
Test Method for Acid and Base Number by Colorimetric Titra- pending on their structure. Increasing the EO content in-
tion (DIN 51 559 Part 1); here, no filtration is then used. creases the water solubility. Linked with water solubility is
Typical quality control measurements, carried out during the so called "cloud point," (or inverse solubility tempera-
production of PAGs, include determination of viscosity by ture), which is measured by ASTM D 2024, Standard Test
ASTM D 445, Standard Test Method for Kinematic Viscosity Method for Cloud Point of Petroleum Products—PAGs show
of Transparent and Opaque Liquids (DIN 51 550), density by inverse solubility in water. Below the cloud point, normal sol-
ASTM D 70, Test Method for Density of Semi-Fluid Bitumi- ubility is observed, but at the cloud point, the PAGs come out
nous Materials (Pycnometer method), flash point by ASTM D of solution and eventually separate. The solubility and the
97, Standard Test Method for Fire and Flash Point by Cleve- cloud point increase as the EO content increases, and
land Open Cup (DIN 51 376), pour point by ASTM D 92, Stan- decrease with increasing molecular weight. PAGs tend to be
dard Test Method for Pour Point of Petroleum Products (DIN soluble in relatively polar materials and their excellent solu-
51 597), OH value by ASTM E326, Standard Test Method for bility in the ozone benign hydrofluorocarbons, such as Rl 34a
Hydroxyl Groups by Phthalate Esterification, and water con- (1,1,1,2-tetrafluoroethane), has considerably aided the tran-
tent by ASTM E 1064, Standard Test Method for Water in Or- sition from the chlorofluorocarbons in automotive air condi-
ganic Liquids by Coulometric Karl-Fischer Titration (DIN 51 tioning systems [32].
777, Part 1).
Chemical Characteristics
Physical Properties
Compared to mineral oils, PAGs have good thermal stability,
The physical properties of a selection of commercially avail- but poor oxidative stability as shown by thermal gravimetry
able PAGs are shown in Table 1, to illustrate the range of (23,25,28,30). However, one of the key characteristics of
physical properties. PAGs is that when they decompose, the final decomposition
TABLE 1—Typical physical properties of PAGs (with ASTM methods).

Flash Point
Viscosity Point
(mm?/s) Density Cloud Open Cup Pour
Functionality EO/PO Mol (g/cm^) Point ASTM D 92 Point
of Initiator Ratio 40°C 100°C VI Weight @20°C CC) (°C) CO
ASTM Method D445 D445 D2270 D70 D2024 D92-97 D97
Mono 0:1 11 3 103 350 0.9573 insol 80 -53
Mono (a) 0:1 126 22.5 204 1900 0.9940 insol 225 -36
Di(b) 0:1 142 22.2 184 2000 1.0035 insol 230 -36
Di 0:1 387 65 242 2600 1.0031 insol 232 -23
Tri (c) 3:1 127 18 157 1200 1.0951 >100 254 -28
Mono (d) 1:1 132 25 225 1650 1.0564 59 230 -42
Mono 1:1 1050 180 287 4500 1.0574 53 230 -28
Di 3:1 19500 2400 408 12500 1.0908 81 240 4
Tri 3:1 45000 6500 489 25000 1.0905 76 240 7
NOTE: the molecular weight is calculated from Mol Weight = functionality of initiator * 56100/OH value.
products are all volatile, with the result that there is no car- tive Characteristics of Inhibited Mineral Oil in the Presence
bonaceous solid or liquid residue, which can be proven by of Water. Anti-corrosion agents are available.
ASTM D 189-97, Standard Test Method for Conradson
Carbon Residue of Petroleum Products. This is a major ad-
vantage in many functional fluid applications such as high Application and Performance Characteristics
temperature chain oils and compressor fluids. Due to the flexibility in their chemical structure and proper-
In the absence of air, PAGs are stable up to around 250°C. ties, and their inherent lubricity, PAGs are used in a wide
At this point polymer chain scission occurs, which releases range of application areas, as illustrated by Fig. 7.
free radical ends, which further decompose by depolymer- Very high viscosity PAGs are used extensively in HFC (Hy-
ization to produce volatile components (eddehydes, ketones, draulic Fluid C type) water based fire resistant hydraulic flu-
alcohols, alkenes, alkanes, CO2) and lower molecular weight ids [36,37] where they perform the function of thickening the
polymers [30]. In the presence of air, PAGs are stable up to water, suppressing its pour point, and providing lubricity
around 180°C. Decomposition is initiated by an oxygen determined by ASTM D 2882, Standard Test Method for Indi-
molecule attaching itself randomly along the polymer chain. cating the Wear Characteristics of Petroleum and Non-
A radical is then formed, which rearranges, causing the poly- Petroleum Hydraulic Fluids in Constant Volume Vane
mer chain to break and lose its end group. This again leads to Pumps. The water provides the fire protection [38]. The key
a reduction in molecular weight and production of similar parameter is fire resistance and the performance standards
volatile components to the thermal breakdown. are developing apace [39,40].
By adjusting the chemical composition and by the use of A similar lubricity improving function is delivered by PAGs
antioxidants, the stability of the PAG can be improved signif- in water based metal working fluids, which additionally use
icantly. Increasing the EO content (compare the flash points the cloud point phenomenon of the PAG to boost lubricity: as
of product "c" and "d" in Table 1) and increasing the molec- lubricity of the fluid begins to fail, metal-metal contact
ular weight of the polymer tend to increase its stability. causes the temperature to increase, which heats the solution
Aminic and phenolic antioxidants, especially in combination, above the cloud point of the PAG, which is determined by
provide significant increase in stability to PAGs [33]. ASTM 2024-65, Standard Test Method for Cloud Point of
PAGs have good hydrolytic stability, which is measured by Nonionic Surfactants. This temperature rise results in the
ASTM D 2619-88, Standard Test Method for Hydrolytic Sta- PAG coming out of solution and being released into the con-
bility of Hydraulic Fluids, since they do not contain hy- tact to provide enhanced lubricity.
drolytically labile chemical groups. The low coefficient of friction and excellent viscosity/tem-
When released into the environment, PAGs tend to slowly perature or VI characteristics of the PAG lend it to the lubri-
biodegrade, helped by their affinity for water (and thus abil- cation of the gecirs and bearings, particularly to heavily loaded
ity to disperse in the environment) and their ability to oxidize worm gears used within the plastics, rubber and paper indus-
and fragment into smaller and more biodegradable struc- tries [41-43]. Tests for gear oil performance include the FZG
tures [22]. Rapid biodegradability of PAGs, as measured by Test [DIN 51 354] and ASTM D 2782-94, Standard Test
such tests as the OECD 301 and 302, is not inherent across Method for Measurement of Extreme-Pressure, better known
the range, but, is achievable by careful structural modifica- as the Timken Test. The efficiency of the worm gear is related
tion, especially towards the lower viscosity end of the range to the friction between the wohn drive and the gear wheel.
[34]. In general, biodegradability is favored by linear compo- Contact between these involves a high level of sliding result-
nents (i.e., EO rather than PO), and by reduction in molecu- ing in increases in operating temperatures—ideal operating
lar weight. conditions for the PAG. Combining this with their high level
In terms of general toxicity, PAGs are generally classified of tolerance for water ingress delivers excellent performance.
as low hazard, and some have approvals as indirect food con- The compression of process gases presents a unique tech-
tact lubricants [35]. nical challenge [44]. Due to the intimate contact between lu-
Due to their highly polar nature, which gives them a very bricant and gas, there can be dissolution of the gas into the lu-
strong affinity for metal surfaces, PAGs have excellent inher- bricant, resulting in a reduction in viscosity of the lubricant,
ent lubrication properties [23]. The lubricating film formed and as a worst case, washing of the lubricant from the metal
between moving metal parts remains intact even during very surfaces requiring lubrication. Owing to the polar nature of
difficult operating conditions, such as high temperatures and PAGs, they perform extremely well in the lubrication of com-
loads. pressors for low polarity process gases (e.g., methane, ethy-
However, their polar nature does require that care must be lene, nitrogen). Since there is very little dissolution of the gas
taken in the choice of compatible materials, particularly into the lubricant, the viscosity and lubricity is maintained
paints and some elastomers [25], which is determined by [44].
ASTM D 471-98el, Standard Test Method for Rubber Prop- PAGs are also suitable for use as air compressor lubricants,
erty-Effect of Liquids. Formulations using standard additive especially when combined with esters [46,47]. Since any
chemistry can also be hampered by solubility problems and build up of sludges or deposits in the compressor can lead to
potential reduction in activity—the PAG may compete for the ignition of the lubricant (for the proof of low carbon residues
metal surface with the additive. Increasing the molecular ASTM D 189-97 Standard Test Method for Conradson Car-
weight and the PO content does improve this situation by re- bon Residue of Petroleum Products can be used), the clean
ducing the polarity. Their hygroscopicity requires care to be decomposition characteristics of the PAG (ASTM D 189)
teiken regarding ferrous metal corrosion, which is measured make this a very attractive alternative to mineral oil based air
by ASTM D 665-99, Standard Test Method for Wear Preven- compressor lubricants.
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POLY (ALPHA-OLEFINS) /-I
Polyalphaolefiin fluids, or PAOs, are synthetic, saturated hy- Qimsr

drocarbons that are manufactured by a two-step process from
hnear alpha-olefins, that are themselves manufactured form
ethylene. These synthetic hydrocarbons are generically de-
scribed by their viscosity at 100°C. The most common com-
mercially used PAOs are 2, 4, 6, 8, and 10 cSt and the higher
viscosity grades 40 and 100 cSt. PAOs have excellent physical
properties when compared with conventional mineral oils, a
wide operating temperature range, including high flash and
firepoints, high viscosity indices and low volatilities. When
compared with certain natural and synthetic esters, PAO flu- FIG. 9—Typical PAO components [55].
ids have excellent thermal, oxidative, and hydrolytic stability.
Since the mid 1980s PAOs have quickly gained market share synthesis is ethylene as shown in Fig. 8. The reaction prod-
in the synthetic lubricant base fluid market, particularly in ucts of the first step are linear unsaturated alphaolefins
Europe [48]. The major application area was and continues to (LAO). These LAOs are used for the manufacture of a variety
be the automotive sector for crankcase oils answering the of chemicals, mainly as detergents. For the synthetic lubri-
quest for tighter specifications for lower oil volatility. Today, cant base fluids (PAOs 2-10 cSt), mainly 1-Decene is
automotive crankcase lubrication is still the main application oligomerized with the catalyst BF3 and a protic co-catalyst
area for PAOs globally. Other automotive application sectors such as water or an alcohol. For the higher viscosity PAO 40
are now two-stroke cycle engine oils, automatic transmission and PAO 100 Ziegler-Natta (Aluminium chloride based), cat-
oils, gear oils (multigrade), and greases. Industrial applica- alysts are used. The unsaturated oligomer mixture is hydro-
tions include: hydraulic oils, compressor oils, heat transfer genated using either Nickel or Palladium catalysts. Finally, a
fluids, and food grade oils and greases. distillation step is applied to remove unreacted monomers
The milestones of the technical history are marked by three and to separate the various product grades. Sometimes the
patents, one by Brennan [49] at Mobil Oil in 1968 and two by distillation step is carried out prior to hydrogenation [54].
Shubkin [50,51] of Ethyl Corporation in 1973. Brennan first The tjrpical molecular structures of a dimer, trimer and a
described a process for oligomerization of alpha-olefins tetramer of 1-decene are shown in Fig. 9. Every oligomer is
using a BF3—ROH catalyst system [49] whereby the combi- branched and is present as a number of different isomers.
nation of the selected process conditions and the catalyst sys- Though 1 -decene is the pre-dominantly used alphaolefine for
tem yielded a product consisting of a mixture of oligomers PAO manufacturing, shorter or longer chain length olefines
with a high concentration of trimers. Shubkin showed that may also be used. In particular, 1-dodecene has recently
instead of R—OH as a co-catalyst, H2O [50] or alcohols and gained importance for the synthesis of PAO 5 and PAO 9 [57].
carboxylic acids [51] could be also used in combination with Tailor made products can also be obtained by changing
BF3 to produce oligomers of uniform quality. reaction vsiriables such as temperature, time, catalyst con-
The U.S. Army and U.S. Navy took an early interest in this centration, co-catalyst t3ê, and concentration and distilla-
new synthetic base fluid. In July 1970 the MIL-H-83282 spection conditions [57].
ification for fire resistant hydraulic fluids based on PAOs was
established in cooperation with the industry [52].
Physical Properties
Chemistry and Meinufacturing The physical properties of the common commercially avail-
able PAOs are shown in Table 2. The given properties are typ-
As the name implies, Polyalphaolefines are synthesized up ical values and do not represent values for PAOs from a
from alphaolefines. The starting material of the chemical particular supplier. The low viscosity PAOs 2-10 have
excellent low temperature properties which make them very
suitable for applications in cold climate. The average viscos-
ity index (VI) calculated by ASTM D 2270, Practice for Calcu-
Catalyst BF3
DImer lating Viscosity Index from Kinematic Viscosity at 40°C and
Unsaturated Trimer
CH2 = CH2 >• R-CH=CH2 >•
Tetramer
lOOX (DIN/ISO 2909) for PAOs is 135. This has the advantage
ROH Oligomers that the viscosity changes much less with increasing temper-
Pentamer
Higher ature compared to a product with low VI. For PAO 2 no VI is
given because VI is undefined for fluids having a kinematic
NIorPd
Unsaturated Oligomers + H2 Saturated Paraffinic Hydrocarbons viscosity ofless than 2.0 cSt at 100°C. The advantage of a high
VI is that addition of viscosity index improvers is not required
Dimer for the formulation of lubricants for many applications. Also,
aigomeric Trimer DIstilatlon Viscosity the addition of pour point depressants is often not necessary
Tetramer
Mixture
Pentamer
Grades as the pour points for PAOs are very low. In Table 2 some other
Higher physical properties are given which are important to the lu-
bricant formulator. The flash point is important for safety rea-
FIG. 8—Chemistry of PAO manufacture [55]. sons and the given flash points in Table 2 are at least as high
TABLE 2—Properties of polyalphaolefines.

Parameter Test Method" PA0 2 PA0 4 PA0 6 PAO 10 PAO 40 PAO 100
KV @ 100 °C cSt ASTM D445 1.80 3.90 5.90 9.60 40.0 100
KV @ 40 °C cSt ASTM D445 5.5 16.8 31.0 45.8 395 1250
KV @ - 4 0 °C cSt ASTM D445 310 2540 7800 19000
Viscosity Index ASTM D2270 122 137 134 150 170
Pour Point, °C ASTM D79 -63 -69 -63 -54 -34 -20
Flash Point, °C ASTM D92 >155 215 225 264 280 290
Noack, % Loss DIN 51581 99 12.0 6.7 2.0 0.8 0.6
"ASTM D 6375 and D 5800 are alternate procedures.
TABLE 3—The oxidative stability of motor oil qualities studied Low toxicity in general, and biodegradability of the low
using High Pressure Differential Scanning Calorimetry (PDSC). viscous PAOs according to the CEC L-33-A-93 test, are
Additive-free Base Oils T (onset) [°C] other important benefits making these products versatile
Mineral oil based lube 187 for incidental food contact and environmentally acceptable
Synthetic lubricants lubricants
Polyalphaolefin 187
Polyolester 210
Diester 1 198
Blends of synthetic lubricants OTHER SYNTHETIC BASE STOCKS
Polyalphaolefin/polyolester 80/20 blend 196
Polyalphaolefin/diester 80/20 blend 196 Although mineral oils and the synthetic base fluids described
Base oils with additive in the sections above, together with solid lubricants, satisfy
Mineral oil based lube 254
Mineral oil/polyalphaolefin based lube the performance requirements of the majority of lubricating
55% mineral oil/22% PAO 260 applications, there r e m a i n m a n y applications where a
Mineral oil based diesel engine lube 262 different combination of properties would be desirable. A
Polyalphaolefin/esteroil 80/20 blend 274 wide variety of other chemical classes have been proposed as
candidate synthetic base fluids to cover the real or perceived
shortcomings of more established fluids. Many of these de-
velopments have been targeted towards high performance
as those of mineral oil of the same viscosity. Volatility is mea- aerospace applications, e.g., military aircraft and satellites,
sured by the standard NOACK volatility test at 250°C for 1 h. where satisfactory performance under extreme conditions of
Except for PAO 2, all other PAOs have very low volatility, t e m p e r a t u r e , high vaccuum, a n d high radiation m a y be
which makes them very suitable for high temperature appli- required, and unit cost is less significant [3]. Most of the pro-
cations and engine oils to reduce the need for "topping-up." posed chemistries, e.g., silicate esters, silahydrocarbons, ti-
Low volatility is also an important property for a fluid to re- tanate esters and phosphazines, appear not to have found any
tain the original viscosity during its working life. real application. However, others, in particular silicones, per-
The highly viscous PAO 40 and PAO 100 hsted in Table 2 fluoroalkyl ethers, polyphenyl ethers and cycloaliphatic hy-
are similar to low viscosity PAOs and have good viscometric drocarbons have found significant niche applications and are
properties and allow operation over a broad temperature discussed briefly in this section.
range. New PAOs with m e d i u m viscosity grades 5, 7, and 9
and very high viscosity grades, u p to 3000 cSt, and have re-
Silicones
cently been developed as custom-synthesized products [56].
Silicones are polymers containing the siloxane (Si—O—Si)
backbone structure with pendant alkyl side chains, normally
Chemical Properties and Performance
methyl groups. The chemistry is well established and silicone
Characteristics
fluids have been commercially available since the 1940s
Oxidation stability is one of the most important properties of [59,60]. They are manufactured by hydrolysis of di-
automotive lubricants, which are mainly responsible for the alkyldichlorosilane themselves p r e p a r e d by reaction of
oil renewal time. Essiger [57] investigated the oxidation sta- methyl chloride (or other alkyl chlorides) with silicon metal.
bility of different motor oil qualities with High Pressure Dif- Trialkyl monochlorosilanes are introduced into the reaction
ferential Scanning Calorimetry (PDSC) as shown in Table 3. in controlled stoichiometry to act as end capping reagents
PAO without anti-oxidants is as stable as mineral base oil, and control the molecular weight.
blends with synthetic ester, a n d shows superior oxidation Silicone fluids can be prepared with viscosities ranging
stability. In the presence of anti-oxidants, such blends were from < 1 to > 500 000 cSt. They are characterized by low pour
significantly more stable than mineral oil based engine lubes. points, low surface tension, high compressibility and little
The use of PAO is also c o m m o n today in high performance change in viscosity with temperature. The standard viscosity
greases. The lifetime of such greases is said to be three to five index calculation is not appropriate for silicones and other
fold c o m p a r e d to mineral oil based products. Wunsch materials with such low temperature coefficients of viscosity.
recommends operating temperatures of u p to 150-160°C for Methyl groups m a y be substituted by other functional
Lithium-12-hydroxystearate greases based on PAO [57]. groups to modify the inherent properties of the basefluid.
These substituents include phenyl groups (for improved ox- All types are manufactured as poly disperse polymers,
idative stability) and trifluoropropyl or tetrachlorophenyl which are then fractionated to give the molecular weight and
groups (for lubricity) viscosity ranges of interest.
Silicones are highly fire resistant and have very low PFAEs are available with viscosities ranging from about 5
volatility, good thermal stability, and very good chemical re- to about 500 cSt 40°C. Viscosity indices vary according to the
sistance. This makes them well suited to some highly de- chemical type, with the K and Y types having lower VT than
manding functional fluid applications, e.g., heat transfer oils the D and Z types. Pour points are generally low. High tem-
and transformer dielectric fluids. However, the load bearing perature volatilities depend on the molecular weight spread
characteristics of poly (dimethyl siloxane) Eire very poor and of the particular grade, but are generally low [60].
metal contacts lubricated by silicones tend to seize under The main chemical characteristic of PFAEs is outstanding
boundary lubrication conditions [59]. For this reason, simple resistance to oxidation by air. They are also resistant to
silicones are rarely used as base fluids, except in some spe- chemical attack by corrosive chemicals including strong
ciality greases where they serve as stable carriers for addi- acids and alkalis and oxidants such as fluorine and hydrogen
tives and solid lubricants. Such greases are used in aviation peroxide. As oxidative degradation is one of the most fre-
and automotive industries to lubricate linkages, bearings and quent limiting factors for lubricant life, this means that
bushings, and instrument components [3]. PFAEs can have very long lifetimes in service, and are well
Silicones are also used in textile applications as fibre, suited for sealed for life applications.
thread and yam lubricants, and modified silicones are used Like silicones, PFAEs have a tendency to exhibit seizure un-
as textile treatments for improved resistance to staining. der boundary conditions, and, also like silicones, they are not
Traditional lubrication applications of silicones are further miscible with standard lubricant additives, so the problem
limited by the fact that they are not generally miscible with cannot be alleviated by formulation with conventional
mineral oils, or other synthetic base fluids. This does, how- antiwear agents [3]. Thermal stability of PFAEs under ideal
ever, make them suitable for use as both profoaming and an- conditions in contact with glass is very good, but the benefit
tifoaming additives in more conventional base fluids. is often not realized in real life applications as thermal de-
Use of silicone fluids or additives in some manufacturing composition is catalyzed at lower temperatures by metcil flu-
environments where goods are painted or coated is discour- orides, particularly those of aluminium and ferrous metals.
aged because minute traces of silicones can interfere with the Metal fluorides are apparently produced by reaction of PFAEs
spreading and adhesion of paints. with metal oxides under conditions of tribological contact.
Silicone fluids are essentially non biodegradable and al- The same effect can lead to oxidative corrosion of some met-
though of low toxicity, they are likely to be persistent in the als by PFAEs under air. Both thermal decomposition and ox-
environment. Consequently, the environmental impact of idative corrosion are inhibited in the absence of oxygen [59].
dispersive applications is a cause of some concern. The very high cost of PFAEs has restricted their use to high
value applications where their properties are essential or
where greatly extended oil life can justify their use on eco-
Perfluoroalkyl Ethers (PFAEs) nomic grounds. The initial applications were in spacecraft,
where the very high chemical resistance of PFAEs was re-
PFAEs have structures basically similar to those of PAGs, but quired. The largest current application is in specialty vacuum
with all the hydrogen atoms replaced by fluorine. They were pump oils for use in contact with reactive chemicals in elec-
originally developed in the 1960s for aerospace applications tronics manufacture. PFAEs are cJso used in formulation of
and have subsequently found some use in other applications, greases for some sealed for life bearings.
particularly where resistance to oxidation or other chemi-
cally aggressive environments is required.
Four different classes of PFAEs have been commercialized,
Polyphenyl Ethers
for which the abbreviations D, K, Y, and Z have become gen-
erally accepted. These differ somewhat in their chemical Polypheny] ethers (PPEs) consist of benzene rings joined by
structure, and consequently show slight differences in per- ether links, with the ether links in bridging monomer units
formance, but all show broadly the same characteristics as being arranged in meta geometry. They were developed dur-
compared to other classes of base fluids. ing the 1950s for high thermal, oxidative, and radiation
PFAE-K and PFAE-Y have quite similar structures, consist- stability [61].
ing of a —(CFa—CF(CF3)—O—) repeat unit, although with PPEs are manufactured by reaction of phenols and halides.
different manufacturing routes, which lead to some The simplest member of the family is diphenyl oxide; longer
differences in properties. PFAE-K is prepared by anionic poly- chain analogues are available up to six benzene rings and are
merization of hexafluoropropylene oxide, whereas PFAE-Y is coded according to the number of benzene rings and ether
prepared by polymerization of hexafluoropropene in the pres- groups they contain; thus 5P4E contains five benzene rings
ence of oxygen. PFAE-Z contains a —(CF2—CF2)—O—) re- and four ether linkages.
peat unit and is prepared similarly to PFAE-Y, using tetraflu- PPEs have very high pour points and most are not liquids
oroethene, rather than hexafluoropropene. PFPE - D contains at room temperature. For example, the only example which
a —(CF2—CF2—CF2—O—) repeat unit, and is manufactured is currently commercially available, 5P4E, crystallizes at
by ring-opening polymerization of tetrafluorooxetane, fol- 43°C in the pure state, and therefore must be mixed with
lowed by exhaustive fluorination to convert the remaining other fluids to extend the liquid range and inhibit
C—H bonds to C—F bonds. crystallization, or used only in applications where it will re-
main at elevated temperature [62]. In addition, PPEs have SUJVIMARY

very low viscosity indices, so it is necessary to accept high vis-
cosity at lower temperatures in order to have adequate vis- Synthetic lubricants possess superior performance capabili-
cosity at the elevated temperatures of operation. [3] ties compared to mineral oils. There are three main reasons
PPEs are also characterized by high surface tension (ca. 50 why synthetic lubricants are selected in preference to mineral
dyn/cm, as compared to 30 dyn/cm for typical mineral oil). oils:
This means that they do not wet metal surfaces, or migrate
• improved stability, usually oxidative,
from the point of application. Thermal stability of PPEs is
• improved lubricity, usually at very high or very low tem-
good, but oxidative stability is not outstanding.
peratures and
PPEs have been used as aviation gas turbine lubricants for
• reduced environmental impact, usually high biodegrad-
supersonic military aircraft [61]. The main current applica-
ability or reduced toxicity.
tion for PPEs is as ultra-high vacuum diffusion pump fluids,
where lubricity is not important and the good high tempera- Oxidative Stability
ture characteristics can be exploited. They are also used in
formulation of radiation-resistant greases. The superior oxidative and thermal stability of synthetics
over mineral oil is historically the main reason why they are
used. It is very difficult to give precise figures for the exact
Alkylated Cyclopentanes temperature at which decomposition for a synthetic lubri-
cant occurs as this is affected by several variables, the main
Multiply-alkylated cyclopentanes (MACs) were introduced ones being:
as candidate lubricating fluids during the 1980s. MACs are
manufactured by reaction of cyclopentadiene, in the form of • exposure time
dicyclopentadiene, with an alcohol, followed by catalytic re- • tjê and amount of additives present (antioxidants, metal
duction of alkylated cyclopentadiene initial product [63,64]. passivators/chelators etc.)
A wide range of MACs have been reported, although • availability of oxygen (air)
apparently only one member of the class, tris(octyl dodecyl) • ability of the lubricant to remove heat
cyclopentane, has been commercialized. • which metals the lubricant is in contact with (catalysis and
Viscometric properties are typical for hydrocarbons and potential deposit formation at metal surfaces) and
similar to those of PAOs. The main distinguishing character- • the presence of system contaminants (e.g., acidic compo-
istic of MACs is that they are essentially monodisperse and nents)
their volatility is therefore substantially lower than mineral There are several different ways of measuring the oxidative
oil or PAO of similar viscosity. stability of a lubricant:
Viscosity and viscosity index can be adjusted by appropri- • Decomposition temperature as measured by a change in:
ate selection of the chain length and degree of branching of viscosity, acid value, hydroxyl value (ASTM D 943, Turbine
the alcohol raw material, and by the degree of substitution Oil Stability Test), amount of oxygen consumed (ASTM D
obtained. MACs are miscible with mineral oil and with stan- 2272, Rotary Bomb Oxidation Test), heat flow change (Dif-
dard lubricant additives. Tris(octyl dodecyl) cyclopentane ferential Scanning Calorimetery), etc., under specified -
has a particularly low pour point and low volatility, and is conditions
used in spacecraft applications [63]. • Temperature and nature of deposit formed on decomposi-
tion (e.g.. Panel Coker FTM3462 or Wolf strip tests UK 359,
ASTM D 189, Conradson Carbon Residue, DIN 51 551,
Cyclohexane Derivatives Pneurop DIN 51352-2)
The cyclohexane derivatives are a class of fluids which are • Volatility of a lubricant at set temperature and times (e.g.,
targeted, not at high temperature applications, but rather at ASTM D 5800, Noack test, Thermogravimetric Aneilysis)
automotive transmission applications requiring high trac- The life of oil at a particular temperature depends on the
tion. A range of such fluids were commercialized during the amount and type of degradation, which is acceptable,
1970s, although only one such material is currently available which in turn depends on how much performance can be
[65], namely 2,4-dicyclohexyl-2-methylpentane, which is allowed to deteriorate. Any chart comparing the relative
manufactured by catalytic hydrogenation of the linear dimer stability of synthetic lubricants will therefore be quite arbi-
of alpha methyl styrene [63]. trary and highly dependent on the specific oil, test condi-
In most respects, the cyclohexane derivatives behave simi- tions, and application [65]. For example, oxidation tests on
larly to other synthetic hydrocarbons of similar molecular pure basestocks can show that esters have an oxidative sta-
weight, but have the distinctive characteristic that they ex- bility similar or slightly worse than that of mineral oil. The
hibit high traction coefficients under the very high pressures reason for this is that mineral oil contains impurities that
experienced in an elastohydrodynamic (EHD) contact [63]. It can act as anti-oxidants. Esters tend to only show their re-
is believed that the rigid regular structure of the cyclohexyl markably better stability when compared to mineral oil,
component leads to a very high volume change on melting, provided the oils are formulated with antioxidants. Figure
and consequently a very strong pressure dependence of the 10 gives an indication of oil life versus temperature for a
temperature of solidification. Thus, under extreme pressure, range of formulated synthetic lubricants. Useful lifetimes
these fluids transiently solidify in the contact, forming a solid are based on filed experience from a range of applications
pad in the contact, which readily transmits lateral force and and should only be used as a crude approximation of actual
resists formation of shear slip planes. service life in a specific application. As the previous dis-
cussion has shown, oil hfe will change dependent on the ex- Their volatility is therefore highly dependent on the test tem-
act temperature regime. perature. The types of additives used also play an important
Table 4 gives a useful qualitative overview of the volatility role. Therefore, the table should only be used as a rough
a n d deposit forming tendencies of various oils. Deposit- guideline.
forming tendencies of synthetics can be highly dependent on The generation of heat from friction causes the tempera-
several p a r a m e t e r s not necessarily connected with chem- ture of the oil film to increase. This higher temperature re-
istry. For example, lubricants with a high polarity can help duces the viscosity of the oil. As the oil's ability to remove
solubilize and disperse decomposition products leading to heat is increased, this may lead t o lower operating
lower deposits. Polymers should have a narrow dispersion of temperatures. A lower temperature will reduce the decrease
molecular weight to avoid the lower molecular weight com- in viscosity of the lubricant and also reduce the oxidative
ponent volatilizing. Polymers such as Polyalkylene Glycols degradation of the lubricant, potentially increasing the life of
(PAGs) and Poly Iso Butylene (PIBs) tend to be very stable u p other components in the system. The heat transfer of various
to a certain t e m p e r a t u r e a n d then rapidly degrade. The lubricants can be compared by using a simplified version of
volatility and deposit forming tendencies can be highly de- the Sieder and Tate equation given below [69]. This equation
pendent on the presence of metals. Metals act as a catalyst is applicable to areas of turbulent flow. The equation can be
a n d therefore aid decomposition for specific chemistries. further simplified for areas of laminar flow.
LrO.bl pO.8^0.33
ha
snnHEtic HnmocAfaoNS
Where:
h = heat transfer coefficient of lubricant components
SUGON^ K = thermal conductivity
p = density
X= viscosity
Cp = specific heat capacity at constant pressure
Lubricants with good heat-transfer characteristics generally

have high specific heat capacity, high thermal conductivity,
high density, and a low working viscosity. T5rpical data for
several lubricant classes are given in Table 5. PAGs and
polyol esters, due to their polar nature and their superior lu-
bricity, should be able to lubricate the system at lower bulk
viscosities than their mineral oil equivalents, improving heat
too aoo 300
TEMPERA-niRE ' C transfer still further [69].
FIG. 10—A comparison of oil lifes for a range of synthetic lu- Lubrication
bricants [66].
As with oxidation, the lubricity of a synthetic lubricant is
highly dependent on the operating regime. Most wear tends
TABLE 4—An overview of the volatility and depo forming to occur during; start-up, slow-down to stop, overheating, or
tendencies of a range of synthetic lubricants evaluated using a overloading. Polar lubricants such as esters have greater
variety of tests. affinity for metal surfaces than mineral oil and are less likely
Volatility Deposit Formation to drain to the sump [69]. Such lubricants are therefore more
Lubricant at 250 "C at 250°C likely to maintain a lubricant film on start-up. Low tempera-
Mineral oil WON Poor Poor ture viscosity is also an important technical criterion. Cold
PA0 6 Good Fair starts, for instance, is the prime cause of engine wear and an
Alkyl benzene 150 Fair Fair effective lubricant film can be only be maintained by imme-
Esters Very good Excellent
PAGs Poor Very good diately effective lubrication circulation. Lubricants that have
PIBs Very poor Good poor low temperature flow properties can take a significant
Silicones Excellent Very good time to reach the parts that require lubrication. For automo-
Fluorocarbons Good to excellent Very good tive applications, this can be evaluated using the cold crank
TABLE 5-
Specific Heat Capacity
at100°C Thermal Conductivity Density at 100°C
Calg-' °C^' at 100°C gcni~^ Viscosity at 100°C in cPs Lube Heat
Lubricant Type (ASTM E 1269) m W m " ' °C"' (ASTM D 70) (ASTM D 445) Transfer Coeft.
Mineral Oil 0.52 127 0.82 6.49 7.33
PAO 6 [67] 0.55 144 0.77 4.54 9.14
Polyol ester [68] 0.55 150 0.93 5.58 9.91
PAG 0.46 185 1.02 7.75 9.21
simulator test (ASTM D 2602). An example of the benefits overview of the suitability of a variety of gases in a range of
synthetics can bring is given in Table 6. synthetic lubricants.
The viscosity of a lubricant has a marked effect on wear The polarity of the lubricant can also be very important.
(viscosity being related to film thickness). Viscosities of lu- Recent work suggests that when a small amount of a high
bricating oils are often quoted at 40°C (ISO grade) or 100°C viscosity polar lubricant (ester) is added to a low viscosity
(ASTM D 445). In reality the viscosity u n d e r operating non-polar base fluid (PAO), the polar component will prefer-
conditions is the controlling factor. Provided the stability of entially stick to the surface [76]. When the two metal surfaces
the lubricant is sufficient, the ability of the lubricant to resist are far apart, the bulk viscosity is controlled by the PAO.
viscosity dilution is dependent o n the Viscosity Index (ASTM When the surfaces come closer together, the PAO is squeezed
D 2270) and the ability of the lubricant to remove heat. The out of the contact zone. The polar ester sticks to the surface
viscosity index provides a measure of the rate of reduction of and stays in the contact area. As the ester has high viscosity,
viscosity with temperature. The viscosity pressure coefficient the bulk viscosity of the oil will increase as the surfaces come
measures the rate of viscosity increase with increased load. closer together.
The ability of the lubricant to resist overloading is therefore As viscosity of the lubricant is reduced, or if shear rate or
highly dependent on the viscosity pressure coeffecient of the load is increased, the chance of boundary lubrication is in-
lubricant. Table 7 gives an overview of the viscosity indices creased. This is especially true under conditions of start-up
and viscosity pressure coefficients for a range of synthetic lu- where the lubricant film may not yet have formed [77]. The
briccints. general properties of the lubricant that affect boundary lu-
In certain compressor applications, a proportion of the gas brication are: the degree of branching/aromaticity, molecular
u n d e r compression can become dissolved in the lubricant weight, polarity, a n d additives present in the lubricant.
(e.g., refrigerants, hydrocarbons), thereby reducing the lubri- Polar molecules are very effective boundary lubricants as
cant viscosity below the recommended viscosity required for they tend to form physical bonds with metal surfaces (i.e.,
lubrication. This problem can be solved to a certain degree by they stick to the surface better than mineral oil). Because of
using high viscosity grade lubricants (up to ISO 680 mineral these different interactions, the lubricity of a polar lubricant
oil). However, at low temperatures these lubricants are diffi- in a fully formulated fluid is not always easy to predict. Poleir
cult to p u m p . In addition, gas streams may wash the lubri- synthetics such as esters and PAGs can compete with anti-
cant off the cylinder walls, resulting in wear. PAGs and PIBs wear or EP agent for the metal surface. When polar base-
have been used in hydrocarbon applications because of their fluids are used they can cover metal surfaces in preference to
ability to resist this dilution. Where good solubility of the the antiwear additives. This can result in higher wear char-
lubricant is required, e.g., refrigeration applications, the ex- acteristics because, eJthough esters have superior lubricity
cellent lubricity of PAGs and polyol esters has been used to properties to mineral oil, under high load conditions they are
compensate for the reduction in viscosity. Table 8 gives Ein certainly less efficient than antiwear additives. It is therefore
very important to choose the cortect additive and to optimize
TABLE 6—Review of cold crank simulator viscosities for fluids its concentration to get the full lubricity benefit of using po-
with a viscosity of 4cSt fluids at 100°C. lar basestocks. Often, more polar antiwear agents or the same
Viscosity at 100°C Cold Crank Simulator antiwear agent at a higher dose rate is used to offset this fac-
icSt) Viscosity at -25°C (MPa.s) tor. Alternatively, the lubricant can be modified to decrease
(ASTM 445-97 (ASTM D 2602) its polarity.
Lubricant DIN 51550) DIN 51377)
Mineral Oil SN 100 3.8 1300
The use of bench tests is an attractive approach to wear
PA0 4 3.9 500 testing. Their low cost, short duration, and ease of operation
Polyol Ester 4.5 550 make them a desirable research tool. Many wear tests only
evaluate a particular wear regime. For example, the Shell
four ball (ASTM D 4172) and Falex (ASTM D 2670/D 3233)
TABLE 7—^Viscosity indices and viscosity pressure coefficients for tests measure the boundary weeir while the FZG (CEC L-07-
a range of synthetic lubricants.
1-71) and four ball (ASTM D 2783) tests look at failure load.
Viscosity Due to this narrow assessment, there has been justifiable re-
Type of Index Viscosity Pressure
Lubricant (ASTM 2270) Coefficients (GPa~" luctance to rely on lubricant performance data obtained from
Naphthenic Mineral oils 0-80 18.0™ -- 36.0^^" the use of bench wear tests. Nevertheless, they are useful as
Parafflnic Mineral oils 80-120 is.ot^" -- 23.0C72] an initial screening tool to spot crude trends that can later be
PAO 120-150 10.5^"] -- 12.6™ checked by system trials.
DI & Tri esters 50-150 5.3[™] -- 19.9™
Polyol esters 50-170 5.3^=5 _- 21.1™
PAGS 150-280 7 7[72] _- 19 jpo] Environmental Acceptability
Alkyl benzenes <0-110 11.8™-- 33.4™
In 1985, some 4.5 million tons of lubricants were used in the
EEC. Of these, some 2.5 million tons were consumed in ser-
TABLE 8—Field experience on the suitability of synthetic vice, leaving 2.0 million tons of waste oil. Of this waste oil, 0.7
lubricants with a variety of gases. million tons were re-used as a fuel supplement and 0.7 mil-
Lubricant Suitable Not Suitable lion tons were recycled, leaving 0.6 million tons or 13% un-
Mineral Oil Air, Hydrocarbons, CFC HFC/HFCs, CO2 accounted for [79]. This loss is the equivalent of one Exxon
PAOs Air, Hydrocarbons HFCs Valdez disaster per m o n t h [80]. Increasing interest is there-
Esters Air, CFC, HFC, HCFC, CO2 Ammonia fore being taken in the ultimate environmental impact of the
PAGs Air, Ammonia, HFC, CO2 Hydrocarbon lubricant.
Eco-labels for lubricant applications are starting to appear TABLE 11—Relative cost of synthetic lubricants
in both the United States and Europe. Initially these have versus mineral oil.
been focused a r o u n d hydraulic fluids (Blue Angel in Ger- Lubricant Relative Cost to Mineral Oil
many, Nordic Swan in Scandinavia, and ASTM D 6046 in the Mineral oil 1
U.S.) but this is likely to be extended to other application ar- PAOs 2-5
eas in the future. The schemes are voluntary and have been Esters 2-10
set u p to allow products to be differentiated using an agreed- PAGs 2-6
PIB 2-4
upon environmentally friendly labelling classification. The Alkyl benzene 2-3
biodegradability of the lubricant is an important part of the Silicones 10-50
legislation and can be measured by a variety of different test Polyphenylethers 50-250
methods (CEC-L-33-A-94, OECD 301B, ASTM D 5864, etc.). Fluorocarbons 75-300
The biodegradability of a variety of synthetic lubricants is
shown in Table 9. Even within a class of synthetics, the
biodegradability can cover a large range. Different
biodegradability tests can also give very different results for tions and transformations. Synthetics will therefore always
the same chemistry. Results can also be highly dependent on cost more than mineral oil. Their relative prices as opposed
where the activated sludge used in the tests is obtained from. to mineral oil are given in Table 11.
However, in general high viscosity, aromaticity, and a high Although more expensive than mineral oil, synthetics can
degree of branching all have a negative impact on biodegrad- lead to a major reduction in system production and running
ability. ASTM D 6006 and D 6384 are useful guidelines to costs and thereby quickly repay their initial costs. For exam-
biodegradability testing and the terminology used to describe ple, synthetics can lead to reduced lubricant consumption,
the results. lower maintenance and less plant downtime, reduced dis-
posal costs, and longer equipment lifetimes.
Food and Drug Administration (FDA) approved low toxic-
The growth of mineral oil has been stagnating over the last
ity lubricants are required increasingly for applications con-
few years. The higher performance, reduced environmental
nected to the food industry. The FDA food approval system is
impact, and the increasing potential to reduce costs using syn-
undergoing major changes and will be replaced shortly by a
thetics has allowed them to show strong year on year growth
new system. However, the old FDA classification system is
in many sectors. In short, the commercial importance of syn-
still being used. See Table 10. The cost of registration of a
thetic lubricants is set to increase significantly in the future.
new lubricant for food use can be considerable.
For many of the lubricants, several limitations of use are
listed, such as maximum dose rate or effect (e.g., can only be
used at a dose rate of bellow 0.5% in another FDA approved
ASTM STANDARDS
oil).
No. Subject
Relative Cost of Synthetics. D70 Density
D86 Distillation
Synthetic lubricants are made from a range of relatively ex-
D91 Precipitation n u m b e r (Sludge Forma-
pensive raw materials via a whole range of chemical interac-
tion)
D92 Flash Point - Cleveland Open Cup
TABLE 9—Biodegradability of synthetic lubricants. D93 Flash Point - Pensky-Martins
% Biodegradability % Biodegradability
D94 Saponification Number
by CEC-L-33-A-94 Test by OECD 301B Test D97 Pour Point
Lubricant Type After 21 Days After 28 Days D 130 Copper Strip Corrosion
Mineral oil 10-45 10-40 D 189 Carbon Residue - Conradson
PAOs 20-80 5-60 D445 Viscosity - Kinematic
Diesters 75-100 25-80 D471 Elastomer Seal Compatability
Aromatic Esters 0-95 5-45
Polyol Esters 0-100 0-80 D524 Carbon Residue - Ramsbottom
Alkyl Benzenes 5-20 0-20 D664 Acid Number, Potentiometric
PAGs 5-70 5-80 D665 Rust Prevention
Polybutenes 5-20 0-20 D873 Potential Residue
D892 Foaming Characteristics (Sequence I-
HI)
TABLE 10—An overview of FDA incidental food contact approval D 892 (Option A) Foaming Characteristics (Sequence I-
(CFR 178.3570).
III) (Option A)
Lubricant FDA Registered D943 Turbine Oil Stability Test (TOST)
Mineral oil No D972 Volatility - Evaporation loss
PAD Yes D974 Acid/ Base N u m b e r by Color Indicator
Ester Glycine ester (CAS No 110-25-8) and
Isopropyl oleate Titration
PAG Several water soluble and insoluble PAGs > D 1209 Color - APHA
RMM = 1000 D 1218 Refractive Index
Polybutene Hydrogenated polybutenes listed under D 1298 Density
178.3740 D 1401 Emulsion Characteristics
D 1500 Color - ASTM [4] Randies, S. J., "Refrigeration Lubes," Synthetic Lubricants and
D 1744 Water Content by Karl Fisher High Performance Functional Fluids, R. L. Rudnick and R, L.
D 1748 Rust Protection Shubkin, Eds., Marcel Dekker, NY, 1999, p . 563.
[5] Randies, S. J., "Esters," Synthetic Lubricants and High Perfor-
D2070 Thermal Stability
mance Functional Fluids, R. L. Rudnick and R. L. Shubkin, Eds.,
D2270 Viscosity Index
Marcel Dekker, NY, 1999, p . 63.
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D2500 Cloud Point Edition, John Wiley & Sons, Inc., NY, 1991, p. 991.
D2602 Cold Cranking Simulator [7] Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 18, 4th
D2619 Hydrolytic Stability (93°C) Edition, John Wiley & Sons, Inc., NY, 1991, p . 991.
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method W. Johnson and E. Fritz, Eds., Marcel Dekker, NY, 1982, p. 327.
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D2711 Demulsibility Characteristics Edition, John Wiley & Sons, Inc., NY, 1991, p . 893.
[10] Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 1, 4th
D2780 Gas Solubility
Edition, John Wiley, NY, 1991, p . 913
D2782 Timken OK Load
[11] Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 9, 4th
D2783 EP, 4-Ball E P Edition, John Wiley, NY, 1991, p . 755.
D2983 Viscosity -Brookfield [12] Briant, J., Denis, J., a n d Pare, G., Rheological Properties of
D3233 Falex Pin/Vee Lubricants, Editions Tecnip, Paris, 1989.
D3427 Air release [13] Emkarate Esters for Synthetic Lubricants, Product Brochure, ICI
D3827 Gas Solubility Performance Chemicals, Middlesbrough, UK, 1997.
D4052 Specific Gravity [14] Lubricant Esters, UnichemaBV, Gouda, Netherlands, 1997.
D4172 Four ball wear [15] Boyde, S., Journal of Synthetic Lubrication, Vol. 18, 2001, p . 99.
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D4742 [17] Scholz, N., Diefenbach, R., Rademacher, 1., and Linnemann, D.,
Thin Film Oxygen Uptake Test
"Biodegradation of DEHP DBF DINP," Bulletin of Environmen-
D5001 Ball on Cylinder Lubricity Evaluation
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D5133 Brookfield - Scanning
[18] OECD Guideline for t h e Testing of Chemicals, Ready
D5185 Elemental Analysis Biodegradability, OECD 301, Organisation for Economoic Co-
D5191 Vapour Pressure, Reid operation a n d Development (OECD), Paris, adopted 17 July
D5481 Viscosity - High T e m p e r a t u r e High 1992.
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D5800 Volatihty - NOACK at 250°C / TGA Structure on Boundary and Mixed Lubrication by Synthetic
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D6082 Foam, High Temperature
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D 6082 (Option A) Foam, High Temperature (Option A) -
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MNL37-EB/Jun. 2003
Environmentally Friendly Oils

Hubertus Murrenhoff^ and Andreas
Remmelmann^
Units environmental consciousness in the late 1980s, regulatory

,2 agencies began d e m a n d i n g that these fluids be rapidly
A m area
Cs J/(kgK) heat capacity biodegradable and nontoxic. This excluded mineral oil from
d mm diameter consideration. Currently vegetable oils, some synthetic esters,
FM N force and polyglycols are being used for these applications [1-10].
g m^/s gravity Since the properties of those base fluids differ substantially
P bar (lO^N/m^) pressure from those of conventional mineral oils, extensive testing is
Q m^/s flow required. To qualify the fluids for the intended applications,
T °C temperature special laboratory tests are required to ensure that they will
V m^ capacity withstand the pressures and t e m p e r a t u r e s encountered.
Ns/m^ dynamic viscosity Many of the chemical and physical test procedures were de-
V mm'^/s kinematic viscosity veloped for mineral oils and aren't applicable for these new
P kg/m^ density types of hydraulic fluids.
DIN Deutsches Institut fiir Normung Parallel to the development of base fluids, new additives
EP Extreme Pressure are being developed. This is necessary for two reasons:
HEES Hydraulic-Environmental group ES (synthetic 1. Existing additives used so far in mineral oil based pressure
ester) media lead to a deterioration of the performance proper-
HEPG Hydraulic-Environmental group PG (polyglycol) ties in rapidly biodegradable oils.
HETG Hydraulic-Environmental group TG (tri-glyc- 2. Existing additives contain toxic substances leading to a
erid) significant deterioration of the biodegradability of the
HFA Hydraulic-Fire-resistant group A (water-based) fluid [11,12-14].
HFC Hydraulic-Fire-Resistant group C (water glycol)
NZ Neutralization N u m b e r
ppm Parts-Per-Million Functions and Requirements
TMP tri-methylol-propan
VI Viscosity-Index In a hydraulic system, the pressure media has many func-
WGK Water Hazard Class tions. Fig. 1. Transmitting the hydraulic power is the main
C Carbon function. For this purpose, the pressure media connects the
CI Chlorine generator (pump) and the motor (cylinder) via the enclosed
CO2 Carbon Dioxide volume and carries the pressure that is determined by the
H Hydrogen load [15].
H2O Water This main function of a pressure media can be accom-
N Nitrogen plished in principle with any fluid; but additional require-
O Oxygen ments result in a substantial limitation of the fluids to be
VCI Verband Chemischer Ingenieure used. To ensure a long lifetime of the hydraulic components,
wear protection is of central importance. Moreover, the fluid
must protect the component surfaces against corrosion and
Pressure Media it must be compatible with the elastomers used as sealing
material.
In a variety of technical systems, hydraulic drives are the pre-
Based on the above-mentioned tasks, a variety of demands
ferred alternative because of their versatility and efficiency.
are m a d e on hydraulic fluids, see Fig. 2. To transmit hy-
To perform the drive functions over the life of the system, the
draulic power and guarantee high load stiffness, the fluid
hydraulic fluid must be considered as a system component
must exhibit a high bulk modulus. This is another prerequi-
during the design stage. Due to a societal increase in
site for optimal control in open and closed loop hydraulic
systems [14].
' Executive Director, Institute of Fluid Power Transmission and The task of protecting hydraulic components against wear
Control, IFAS, University of Teciinology Aachen, Steinbachstr. 53, D- and corrosion creates very high demands on the fluid [33]. It
52074 Aachen, Germany.
^ Product Engineering Hydraulics, John Deere Works Mannheim, must exhibit a high increase of viscosity vs. pressure, thus
Windeckstr. 90, 68163 Mannheim, Germany. producing a self-enhancing effect in the tribological contact
267
Copyright' 2003 by AS'I M International www.astm.org
FIG. 1—Functions of hydraulic fluids.
FIG. 2—Demands on hydraulic fluids.
for high loads [16]. In addition, the fluid must provide good ample, fluids used in underground mining or in steel mills
lubricating film wetting between surfaces moving relative to must be fire resistant to reduce the dcuiger of fire. An addi-
each other that reduce wear and stick slip. Materials used in tional requirement is environmental compatibility, which
hydraulic components such as bronze or other alloys are sus- has led to the development of another pressure media group
ceptible to corrosion. Consequently, the fluid should contain [19,22,35,38].
only a m i n i m u m a m o u n t of free acid, if any. The by-products
created by the aging process must be neutralized or adsorbed
Types of Pressure Media
by additives contained in the fluid to eliminate any acid
build-up. In addition, the fluid properties must vary only Different types of hydraulic fluids are shown in Fig. 3. Each
slightly over extended time [31]. one is developed for a specific application. The most com-
Elastomers and other non-metal components may also m o n type in use today is based on mineral oil.
be attacked by these by-products. Increased elastomer Fluids are blended with additives to inhibit aging, weeir and
swelling may result in complete decomposition and sealing to reduce friction and corrosion. For special application re-
failure. quirements, additives with detergent and dispersent charac-
Mechanical and volumetric losses in hydraulic units are re- teristics are used to suspend solid particles as well as water,
sponsible for heat generation. This heat is partially released in some cases u p to 5% water.
to the environment by convection. The pressure media itself, By utilizing special refining methods, it is possible to im-
however, accounts for the major part of the heat loss. To limit prove the viscosity t e m p e r a t u r e performance of the base
the temperature increase of the fluid, it must possess high stock. Group II API Base Oils can be blended to produce good
heat capacity and thermal conductivity. tribological characteristics and long-term stability. State of
These demands are directly related to the use of the pres- the art refining technology ensures constant production of
sure media in a hydraulic system. The development of fluids prime quality base stocks. The technology to develop addi-
is significantly influenced by external requirements. For ex- tives is readily available.
CHAPTER 11: ENVIRONMENTALLY FRIENDLY OILS 269
FIG. 3—Different types of hydraulic fluids [24,25].
TABLE 1—Groups of biologically fast degradable for the production of synthetic esters, a wide variety of tech-
pressure media. nical performance properties is possible. Early synthetic es-
Fluid Base Fluid Saturation Origin ters possessed a chemical structure similar to rapeseed oil.
HETG Native ester Unsaturated Native materials HEPG fluids is the third fluid type and is the only type that
HEES Synthetic ester Unsaturated Native materials is water-soluble. This can be an advantage for the biological
Saturated Chemical industry degradation in water. On the other hand, there is the danger
HEPG Poly-glycol Chemical industry
of fluid-contaminated water penetrating more deeply into the
soil layers, thus reaching ground water. For that reason, in
some countries, polyglycols are not considered environmen-
New groups of fluids have been developed to provide good tally friendly fluids.
fire resistance, rapid biodegradability, and low toxicity.
Mineral oils are classified based on their performance,
which is different from readily biodegradable pressure me-
CHEMICAL B A S E S O F N A T I V E A N D
dia, which are classified according to base fluid composition.
SYNTHETIC ESTERS
There are three groups of biodegradable fluids: natural esters
(type HETG), synthetic esters (type HEES), and poly-glycols
(type HEPG) as listed in Table 1. Functional Groups and Elementary Compound
HETG base stocks are derived from vegetable oils such as Pressure media based on native and synthetic esters consist
rapeseed and sunflower. These base fluids have a limited of carbon-hydrogen bonds as do mineral oils. However, the
temperature range. New additives have been developed to structure differs significantly from that of mineral oil, which
meet the expected application temperature ranges. Their explains the different properties and performance character-
poor thermal stability is due to the amount of unsaturated istics exhibited by these fluids. Examples of the different
carbon containing acids found in these natural esters. functional groups can be seen in Fig. 4.
HEES base stocks can be produced from various materials The characteristic group for an alcohol is the hydroxy
including natural esters. The use of natural esters usually group (OH-group). In a case where the OH-group of aliphatic
leads to unsaturated synthetic esters. Performance of the flu- alcohols is connected to a carbon-atom, the alcohol is de-
ids is superior to HETG fluids due to a more uniform molec- scribed as primary alcohol. In a case where the OH-group is
ular structure and the use of different alcohols. Using com- connected to a carbon-atom in the center of the molecule, it
pletely saturated esters, the resulting fluids exhibit very is considered secondary alcohol. Tertiary alcohols are those
stable aging characteristics. Additives used speciflcally for with an OH-group connected at a branch site in the molecule.
this type of fluid have also been developed. The hydroxy group of alcohols is responsible for their
Based on the many choices of acids and alcohols available higher boiling points compared to those of the comparable
carbonyl-group hydroxyl-group alkyl-group Mechanism of Esterification

0 H In Fig. 8, the general equation of a reaction for the produc-
tion of esters is shown. This chemical reaction produces es-
—c— OH C—H
ter and water. Water must be removed during reaction to
1
H achieve a complete conversion of the alcohol reaction with
the acid to produce a n ester (by shifting the equilibrium to
the right).
aldehyde carboxyl-group ketone
The equilibrium constant (K) for the ester producing reac-
O O 0 tion is [30]:
II [ester] • [water]
C—H C—OH R1-C—R2 K
[acid] • [alcohol]
carboxylic acid alcohol ester Where: "[ ]" indicates the concentration of the reactants (acid
and alcohol) or products (ester and water) in mole/liter. It is
O O desirable to maximize the concentration of ester and to min-
imize the concentration of acid and alcohol. One way to do
R 2 - C — OH R^-OH R^-O—C — R2
this is to remove water during the reaction. Thus, to maintain
FIG. 4—Important functional groups of organic chemistry. equilibrium, more water must be produced, which decreases
the concentration of acid and alcohol resulting in increased
water production. Similarly, increasing the alcohol concen-
-.1 -.1 tration will decrease the acid and increase the desired ester
R^ R' R'
\ \ \ -+\ - * content.
O—H + O—H O—H - - 0 — H
The rate of reaction is increased by the increasing temper-
FIG. 5—Hydrogen bond of alcohols, [22-30]. ature or by the addition of an acid catalyst such as H2SO4
(typically 5-10% based on the weight of the acid carboxylic).
Other, even stronger, acids may also be used. The rate of the
esterification reaction increases with increasing catalyst con-
alkanes, because of the shared hydrogen bond of the hy- centration
droxyl groups. A strong polarity of the OH-connection is The objective of ester production is to quantitatively com-
based on the electro-negativity of oxygen. The result is a pos- plete transition of acid into ester. This means that the con-
itive shifting of the hydrogen a t o m so that the hydrogen centration of ester should be as high as possible.
bonding connection shown in Fig. 5 becomes feasible.
The removal of water from the reaction mixture may be fa-
The possibility for hydrogen bonding is the reason for the cilitated by the addition of a solvent such as toluene. In this
still unlimited miscibility of simple alcohols with water. case, water is removed from the reaction mixture by
However, with increasing size of the non-polar organic alco- azeotropic distillation.
hol residue, this characteristic decreases.
The abbreviation R used in Fig. 5 represents a n alkyl-
group. This is a n acylic saturated carbon-hydrogen com- H —O ,0—H—O
pound, called an aJkane, from which a hydrogen molecule is R ' - Cy
. + C — R^ R^ - C C—R^
split off. According to their bonding capability, alcohols are O— H O
•^ O—H—O
considered to be monovalent, bivalent, or trivalent.
To produce a synthetic ester hydraulic fluid with good per- FIG. 6—Hydrogen bond of carbon acids.
formance properties, carboxylic acids are used. The carboxy
g r o u p COOH is the functional g r o u p of carbon acids. Its cis-configuration
nomenclature is based on the combination of the carbonyl
trans-configuration
and hydroxy group. Carboxylic acids with long-chain R-
groups attached are called fatty acids. The capability of car-
bon acids to hydrogen bond as with alcohols, is based on H H H
their chemical structure. This is the reason for their relatively
high boiling point, which is comparable to alcohols due to its I I I
dimeric structure resulting from the hydrogen bonds shown C=C
in Fig. 6.
Small carbon acids like the corresponding small alcohols H
are still soluble in water. However, the solubility diminishes FIG. 7—Isomers of carboxylic acids, cis and trans structure.
with increasing molecular size. When carboxylic acids con-
tain only single bonds, they are considered saturated.
Unsaturated acids contain at least one double bond. The carboxylic acid aicohd ester water
n u m b e r of double bonds influences chemical properties. Fur- O H
thermore, carboxylic acids are distinguished by different iso- I
R^-C — OH R} - O H ^ R' - O — C — R 2 O—H
mers resulting in different chemical and physical properties
(Fig. 7). FIG. 8—Chemical reaction of ester production.
The mechanism of the acid catalyzed production of ester 1. step: alcohol protonation
from carboxyhc acids and primary or secondary alcohols is
H
based on the addition of a proton to the oxygen of the carboxyl
group. Producing a mesomer-stabilized cation and the C-
atom of the carboxyl group becomes positive. By adding the
R3C-OH + H R3C-O
nucleophilic oxygen of the alcohol to this carbon atom, the es-
ter is finally produced by separation of water and protons; see
Figs. 9a and 9b.
Tertiary zJcohols are not esterified in this way because the 2. step: carbenium formation
hydroxyl group will undergo acid catalyzed elimination pro- H
ducing undesirable alkenes, as shown in Fig. 10.
R3C-0 - > R3C + H2O
3. step: electrophilic carboxyl group attack

1. step: carbonyl oxygen protonation
o OH' O o'^CRj
1 II ^ ^ 1 II R^ - C — O H "^ Rfi^ ~*' R^ - C — O H

R^ - C + H —*• R^ - C
I I
OH OH
4. step:proton migration
2. step: alcohol addition
0^—CR, O—CR3
OH* OH H R1^ - CII— O H -
Ri - C = 0 H " '
1 +
R^ - G + R 2 --OH ~* R^- - c — 0
5. step: proton removal

FIG. 9a—Ester synthesis with primary and secondary alco-
hols under acid conditions [22-30]. O—CR3 O—CR3
3. step: proton shifting R^-C=OH' R^-C=O + H

FIG. 10—Ester synthesis with tertiary-alcohols.
OH H OH
I / R^1 - CI — O — R 2
R^ - C — O * Alcohol Bonds
L V By variation of the acid and ester reagents, a vast array of

possible ester products and a wide variety of chemical prop-
4. step: water split off erties is achievable. These varieties, however, are limited by
OH the demand for a good biological degradability as well as by
O—R"" other technical requirements with regard to viscosity, viscos-
R1
^ - CI — O — R^ ity temperature dependence, and its stability under hydraulic
R,1' - C + H.O load. The different alcohols depicted in Fig. 11 are used for
II .
OH
the production of hydraulic fluids.
Trimethylolpropane is a colorless, crystalline substance
easily soluble in water. This is the stacking material used for
polyols by reaction with ethylene oxide and propylene oxide,
5. step: proton split off which are other reacted to form polyurethanes. By esterifica-
tion with carboxylic acids, ester lubricants with a high vis-
0 —R-" cosity index (VI) are produced.
1 // Glycerin is also a trifunctional alcohol and is very soluble
R' - C R^ - C + H in water. This is the main reason for its wide use in drugs and
\ cosmetics. When esterified with carboxylic acids, ester-based
OH O—R"
lubricants with a high VI are produced as well. These esters
FIG. 9b—Ester synthesis with primary and secondary alco- can also be produced from natural materials such as rape-
hols under acid conditions. seed oil through a pressing process.
trimethylolpropane glycerin ditives. Mono and glycerin esters, however, exhibit limited
OH OH
I I chemical stability at high temperatures and low temperature
H- C— H H—C — H performance.
H H H
High temperature stability and low temperature perfor-
I I I mance properties can easily be achieved with di-carboxylic
H-C—C -C — O H -OH acid and polyol ester. Carbon-6 to carbon-12 di-carboxylic
I I i acid esters are increasingly important as engine and com-
H H H
pressor lubricants. Polyol-esters are used in huge quantities
H—C—H H—C—H
I I as turbine oils for aviation applications where they are ex-
OH OH posed to extreme temperatures. Good oxidative stability is
trimethylolethane pentaerythritol
OH OH
I I vinegar acid stearic acid
H— C— H H—C — H
O H O
H H H
I I I H—0—C—C—H
II
-C — OH OH-C- -OH "*^17'^35
-c- I I I -c-
I H H
H H
neopentylglycol
-C—H
I
OH "T" oleic acid 1x unsaturated cis-configuration
O H H
OH
I
H—C—H OH-C—C^H,-^- "•^8^17
H H
I I linoleic acid 2x unsaturated cis-configuation
-C C C—H
O H H H H H
I I
H H
H — C—H OH-C—C,H; -C—C^C- '^5^n
I
OH H
FIG. 11—Survey of alcohols for lubricants. FIG. 12—Survey of acids for lubricants.
Pentaerythritol is a tetrafunctional alcohol with five carbon mono aster dicarboxylic acid ester
atoms. The four primary hydroxyl groups allow a relatively 0 O 0
easy esterification with different acids. These esters are very II II- II
stable against biological degradation in an aqueous solution. R1-0—C—R2 R1-0—C—R2-C—0—R3
polyol ester (TMP-ester) glycerin ester

Carboxylic Acids O 0
For esterification of those alcohols to lubricants, carboxylic II II

CHj-O—C—R1 CHj-O—C—R1
acids of vegetable and animal origin are used. Examples of the
different acids used in hydraulic fluids are illustrated in Fig. 12.
Ester basestocks, which are suitable as lubricants or pres- C,H,-C•* Q[_|__Q Q -R1 H—C
sure media typically possess a carbon number of about
18-30. These may be derived from natural sources. Achiev-
able viscosities are within the range of about 22-100 mm'^/s. CJ H j - O — C — R 1 CI H j - O — C — R 1
For this application, esters based on fatty acids are consid-
ered. They can be divided into five ester groups: mono, glyc- complex ester
erin, dicarboxylic, polyol, and complex, as shown in Fig. 13. 0 0
II
II
Mono-esters are prepared from linear monocarboxylic CH^-O—0—R1 C^riy - 0 - - C — R 2
acids, which are reacted with branched or linear alcohols.
The main applications of monoesters are in metaJ working 0
such as for lubricants for cold and hot rolling. Of special im- II
C,H,-( ; — C H j - o — c — -R1 C,Hg< -CH,- 0 — C — R 2
portance within the group of mono-esters are the unsatu-
rated methyl esters from which extreme pressure (EP) addi-
tives may be produced by reaction with sulfur or I
CH,-0—C—R1 - C — O — C H ,
sulfur-containing functionality. Glycerin esters of rapeseed II
oils, particularly when the rapeseed oil has a high iodine O
number (high unsaturation), are used to synthesize such ad- FIG. 13—Different ester types for lubricants [30].
achieved because of the unsubstituted beta-carbon atom and The position of the double bond within the fatty acid has
the primary hydroxyl groups. no significant influence on the pour point. However, slight
differences can be observed depending on the degree of dis-
tortion imparted by the double bond of the molecule. De-
CHEMICAL PROPERTIES OF NATURAL AND pending on the position of the double bond, the distance be-
SYNTHETIC ESTERS tween molecules increases, resulting in slightly different
pour points (Fig. 16).
Properties of esters are determined by the alcohol and acids Besides the number of double bonds, their steroconfigura-
from which they are derived. Various polyol-esters have been tion has a decisive influence on the viscosity properties. Es-
prepared by using alcohols for the production of lubricants ter with cis- double bonds will flow at low temperatures,
similar to the triglycerides of rapeseed oil. whereas fluids with trans- double bonds exhibit pour point at
comparable temperatures.
Branching exerts similar influence as double bonds. With
Viscosity and Viscosity Properties
increasing branching at a constant carbon number, the cold
Viscosity properties are important when esters are used as flow behavior of the ester increases and viscosity decreases.
lubricants. The acid being esterified does not only determine In contrast, an increased chain length with the same struc-
the viscosity of an ester molecule. The viscosity of esters ture results in an increase of viscosity.
products increases with increasing molecular weight of the Reduction of the pour point is also obtainable by using es-
alcohols or their number of hydroxyl groups. This is due to ters with acid mixtures. These mixtures do not crystallize as
the increasing structural possibilities for carboxylic acid readily thus leading to a decreased pour point.
components (Fig. 14). With the more complex esters there is no correlation be-
Pour points for these esters exhibit the same dependency tween viscosity and carbon number, since the viscosity in-
as observed with viscosity. Lowering the pour point requires crease is compensated by branching, due to increasing car-
a short-chain branching of the alcohol with tertiary carbon or bon number.
hydrogen-atoms. On the other hand, those molecular struc-
tures lead to a decreased oxidative stability of the alcohol.
Therefore, neo-pentyl-polyols are especially advantageous
for the production of lubricants, since they contain exclu-
sively primary hydroxyl groups and they are branched.
Acids used for the production of lubricants may also be the g 60-
same as those of natural oils and fats with 16-18 carbon
atoms, which produce the required classes of hydraulic fluid "o
Q.
viscosity ISO VG 22 to 68. To obtain high oxidation stability, 3 ziU
O
unsaturated acids are not desirable, since they represent a
preferred point of attack for reaction with oxygen. However,
double bonds also create a distortion of the ester molecule.
This distortion positively influences the cold flow properties
of the ester. The ester produced from acid with a monofunc- -40 -
tional alcohol and acids containing double bonds will still 6:0 8:0 10:0 12:0 14:0 16:0 18:0 18:1 18:2 18:3
flow at a temperature of 5°C, whereas completely saturated fatty acid
ester become solid at a temperature of 75°C (Fig. 15). [C-number: double bond]
FIG. 15—Pour-point of different esters with the same alcohol
[20].
45
40 " ^ 4*
'* — ^> <• - - ''
35
B cis j
O 30
.e 25
o
a.
S 20
o
°- 15
10
penta- tri- tri- tri- glycerin neo-

erithritol methylol- methylol- methylol- pentyl-
hexane propane ethane D5 D7 D9 D11 D13
glycol
position of the double bond
FIG. 14—Viscosity of different polyol-esters with the same
acid [46]. FIG. 16—Influence of double bonds on the Pour-point [20].
Hydrolysis drolytic stability. Only when using branched alcohols larger

than C8, does resistance increase to the level of saturated lin-
The chemical reaction for ester production is an equihbrium ear mono-alcohols. With glycerin esters, the saturated esters
reaction. Consequently, all esters-based fluids cleave into are more stable than unsaturated esters. Their stability can
their alcohol and acid components upon hydrolosis. This di- be compared to the stable mono-esters.
rectly influences the ester bond. This reaction, also called
In general, di-carboxylic acid esters are very stable against
"hydrolytic splitting," which continues until the chemical
hydrolysis. Their stability is almost independent of the chain
equilibrium is restored. Thus, hydrolytic stability of an ester
length, branching, and the alcohol components used. Satu-
is influenced by its chemical structure.
rated polyol-esters also achieve a comparably good stability.
Steric hindrance of the ester bond improves hydroljîc sta- The stability of unsaturated polyol-esters is comparable to
bility. This protection is due to the presence of methyl groups unsaturated glycerin esters. Figure 17 depicts hydrolytic sta-
instead of hydrogen atoms relative to the ester group. Those bilities of different ester structures. Low hydrolytic stability
methyl groups sterically protect the ester bond against water corresponds to a high acid n u m b e r in the figure.
attack. Depending on the n u m b e r of methyl groups posi-
Molecular features that improve hydrolytic stability also
tioned around the ester group, the reaction rate may be re-
reduce the biodegradability rate. This is of special impor-
duced many times. Table 2 provides a survey of the reaction
tance since hydrolosis is the starting reaction for biological
rate as a function of the amount of branching.
degradation. It follows that protecting an ester bond might be
With mono-esters, hydrolytic stability is primarily in- a disadvantage with regard to the ecotoxicologiccd properties.
creased using linear short-chain alcohols. Even short alkyl In any case, the formulation of rapidly biodegradable pres-
chains in these alcohols yield a significant increase of hy- sure media requires a confirmation of the ecotoxicologic
properties of the fluid.
Oxidation Stability
TABLE 2—Influence of a-carbon branching of
the oxygen ester on reaction speed [13]. Oxidation stability of synthetic esters is decisively influenced
Alkyl-substitution Relative Reaction Speed by their structure. With alcohols, especially short-chain
CH3 30 branched structures with tertiary H-molecules as they occur
CH3CH2 1 in rapeseed oil, which is a triglyceride, results in a significant
(CH3)2CH 0,03 decrease of oxidation stability. The degree saturation of the
(CH3)3C «0 ester molecule, however, has a much larger impact on oxida-
FIG. 17—Hydrolytic stability of different ester structure [15].

tion stability. As a rule, saturated alcohols are used for the amount of increased hydrolytic stability obtained. In addi-
production of lubricants and pressure media. For that rea- tion to the amount of unsaturated carboxylic acids (relative
son, the oxidative stability is mainly determined by the de- to s a t u r a t e d esters), the n u m b e r of double bonds in car-
gree saturation of the carboxylic acids. In general, the ten- boxylic acid also influences oxidative stability. In general, in-
dency of an ester molecule towards oxidation continually creasing the number of soluble bonds in a carboxylic acid (in-
increases with increasing amounts of unsaturated carboxylic creasing unsaturation) decreases oxidative stability.
acids. Figure 18 shows this for three different saturated The foregoing discussion provides only an overview of
polyol-esters a n d rapeseed oil. The oxidation stability of structure-performance consideration of ester base stock.
those fluids was determined by the viscosity increase after an However, the generalizations m a d e t h u s far will aid the
aging process according to the Baader-test (DIN 51587). reader in understanding lubricant formulation to provide
The dependency of the oxidation time for vegetable oils can high load capacity and good chemical and physical proper-
be taken from Fig. 19. These results were obtained by the ties. The summary of the effects is illustrated in Fig. 20.
R a n k i m a t method, which provides a significant improve-
m e n t in the precision of the test. Rapeseed oils, which are low
in euricic-acid content and sunflower oils, which are high in
oleic acid content were used as hydraulic fluids. Mixing those PRODUCTION OF ENVIRONMENTALLY
oils provided the required degrees of saturation. The strong FRIENDLY FLUIDS BASED ON NATURAL
dependency of the stability on the a m o u n t of double bonds is AND SYNTHETIC ESTERS
evident.
Oxidative stability may be enhanced by sterically protect- Native Esters
ing the double bond, e.g., by branchings. The effects of steric Oil is removed from rapeseeds by milling, pressing, or ex-
b r a n c h i n g on oxidative stability are comparable to the traction. These seeds contain approximately 40% oil and
8-10% water by weight. In the milling process the seeds are
fed into rollers to break down the cells so the oil can be re-
leased. Next, the milled seeds are conditioned by heating to
80-90°C to control the humidity to a m a x i m u m of 8% (Fig.
180 21). By this procedure, the vegetable oil becomes lighter and
•rapseed oil thinner. The seeds are then squeezed in a screw press under
160
•unsaturated polyol-ester a pressure of 200 bcir. This procedure yields between 40-60%
140 of oil. A higher yield can be obtained by either a finishing or
10 partial saturated polyol-
120 estsr by solvent extraction. The finishing process removes 90-96%
'1
F •saturated polyol-ester of the oil. For economic reasons the extraction method is the
10(1 procedure of choice.
>•
+ j
(A
O
O
an A higher oil yield can be obtained either by another press-
ID
60 ing process, the finish pressing, or by extracting the pre-
> pressed coarse-ground grain. By finish pressing, the oil con-
centration decreases to values between 4 and 10%. An
extraction reduces the residual oil contents to below 2% in
the seeds. The individual production steps are shown
schematically in Fig. 22.
2 3 4 5
For extraction, a solvent is used to dissolve the glycerides
aging time [days] from the seeds, not the undesirable accompanying sub-
stances like gums or resins, slime, and dye materials. More-
FIG. 18—Influence of saturation on oxidation stability [34].
over, the solvent must not contain any toxic substances that
are nonvolatile and thus unremovable. The solvent also must
^\l be separated from the extracted material. Aliphatic hydro-
carbons are used for this purpose, especially n-hexane, which
le" 1R can, due to its boiling point of 55-70°C, be separated easily
(1> 14 - from the coarse-ground grain. After those steps, the extracted
•—
•^
19 -
IZ -
raw material contains between 1 and 2% free fatty acids as
well as 300 p p m phosphatides and 0.35 to 0.5% sterines. To
o T" achieve the desired quality of the vegetable oil, a refining pro-
o o cess follows the extraction of the crude oil. Refining serves
5
•O fi0
.E 4 the purpose of reducing the contents of free fatty acids to
O 0.05% and that of the phosphatides to 0.02 ppm. The follow-
0- ing refining steps are necessary:
3 3.25 3.5 3.75 4 4.25 4.5 4.75 5 1. Precleaning to remove phosphatides (desliming).
2. Deacidizing and neutralization.
double compound amount [mmol/g]
3. Decolorization (bleaching) by means of absorbents, e.g.
FIG. 19—Oxidation stability vs. amount of double bonds with bleaching earth.
Rankimat method [34]. 4. Filtration and deodorization.
branching of branching of saturation of molecule linearity

alcohol acid acid weight
L
,\ 1 1 11 i
hydrolysis
staWlity
1, I L . I I
viscosity
i, i 1 i, I
low
temper-
ature
viscosity
1, I L n k
oxidation
stability
, 1 I 1 1 I I
viscosity
index
*
air release
It I 1 1 1 »
property
FIG. 20—Summarized table of the influence of structure on chemical and

physical properties.
Synthetic Esters is conducted in a slightly different way utilizing formalde-

Raw materiaJs for the production of synthetic esters are de- hyde and i-butanal. However, as a catalytic agent, sodium hy-
rived mainly from petro-chemistry. However, it is also possi- droxide is used (Fig. 24).
ble to use natural raw materials or their transformation prod- The production of carboxylic acids can be divided into two
ucts. In any case, this requires re-esterification or an major processes. On the one hand, from natural oils and fats
additional chemiced treatment, e.g., hydrogenation. Besides the corresponding fatty acids can be generated directly by hy-
the esterification procedure described previously, ester syn- drolysis. On the other hand, an alternative process is to direct
thesis can be subdivided into the production of different al- re-esterification of natural oils with synthetic alcohols. In addi-
cohols and acids. The great majority of those products origi- tion to those two possibilities, acids may also be produced us-
nate from other applications. The systematic production of ing chemical processes. Figure 25 shows this process for adipic
lubricants can be considered rather insignificant at this time. acids being used for the production of di-carboxylic acid esters.
Quantitatively, the largest portion of esters is the softener Large-scale production of synthetic esters are typically
sector. Long-chain alcohols and fatty acids cire mainly used batch processes. Depending on the desired degree of esterifi-
for the production of washing and cleaning agents, surfac- cation, different catalysts are added to the process, leading to
tants, and detergents. The fundamental path of synthesis will an accelerated conversion. During esterification, undesirable
be explained using a few examples. water is continuously removed from the alcohol and fatty acid
MultifunctioncJ alcohols are produced using the so-called reactants to optimize the conversion process. The reaction is
"aldol condensation". This is a catalytic addition of carban- stopped once the desired acid number, a measure for the com-
ions by bases to the carbonyl group of aldehydes or ketones. pleteness of the esterification, has been attained. To achieve
The carbanions are produced from activated methylene very low acid numbers (<0,5), another refining step is neces-
groups. After this reaction step, water is eliminated. Figure sary. Undesired substances are eliminated from the ester by a
23 shows this process for the alcohol pentaerythritol. The subsequent bleaching earth treatment. Finally, a filtration
production process for trimethylol propane is very simple ex- step is required to eliminate the bleaching earth from the es-
cept when formaldehyde and n-butanal are used. ter. A survey of the ester production process can be taken
For the production of neopentyl glycol, the aldol reaction from Fig. 26.
seeds
milling
f steam ^
u.1
conditioning
n-tiexane
squeezing
n
pellet-
9î:r^.':''i-'^'-''''-'• -.y'-^wl vaporization p
n-hexane
extraction Vi misceiia
J
j r • .•••i a
drying
1 filtration
"P filter
backlog
steam ^
L_n_
toasting D used n-hexane disposal
drying
1
n
cooling h' feeding stuff
FIG. 21—Production of rapeseed crude oils.
LOADS O N P R E S S U R E MEDIA IN very low temperatures as they occur in hydraulic systems.

OPERATION Moreover, autoxidation represents the initial stage for poly-
merization processes leading to surface films such as varnish
Oxidation or lacquer [27,28].
Autoxidation starts with an induction period where the
During operation, the pressure media goes through a continu- first carbon-radicals are initiated. To make this possible, ac-
ous change of its chemical properties due to the hydraulic load tivation is required, e.g., by mechanical supply of power
in the system. Over the long service life of the pressure media, through shearing or by a temperature increase. Furthermore,
its properties should change very slowly; this requires aging different catalytic agents, such as hydro-peroxides, peroxides
stability. During operation, the hydraulic load parameters or heavy-metal ions, accelerate this process, since these
such as pressure and temperature as well as shear stress affect molecules undergo bond scission to produce free radical ini-
the fluid. During operation, different types of contamination tiators. The necessity of a good fluid filtration is necessary be-
influence the service life of the pressure media. These can be cause heavy-metal ions produced from the metallic wear de-
liquids such as water or foreign oils, and solid particles such bris produce those free radicals. When hydro-peroxides are
as abrasive materials or environmental dust. Those loads can subsequently produced from peroxide and another car-
affect the fluid chemically as well as physically. boxylic acid, then a free C-radical is created. This radical re-
Of special importance for the stability of a pressure acts with the oxygen in the air to form peroxides, thus start-
medium is its resistance against oxidative attack. Oxidative ing a chain reaction (initiation). The hydro-peroxide
stability problems are aggravated by contact of the fluid with produced by this reaction is chemically unstable. It trans-
the ambient air in the tank of the system or with the air dis- forms easily into epoxides, keto-bonds, di-carboxylic acids,
solved in the fluid, leading to a change of the chemical and or other polymerization products. The reaction mechanism
physical properties. of autoxidation can be taken from Figs. 27 and 28. The au-
For the stability of lubricEints based on natural or sjmthetic toxidation mechanism stops once the radical concentration
esters, their resistance against the so-called autoxidation pro- exceeds a threshhold concentration, starting a reaction be-
cesses is of importance, since those reactions already start at tween the radicals (Fig. 28).
I NaOH ) neutralisation Jp^ slime removal

(90°C) K crude oil
, ik Tt.
1
H3P04 (75%
rotational
separation separation
i r M .•••iiJ 1
H?n } washing I soapy contents ^ H2SO4(30%)j
• ^ I
fatty acid
^ & steam I
l ' " ' . - „ „ y vacuum drying

' steam-V| iombar/90°C raffination
HCI active } bleaching I
H
H-RBntnnil
steaming
filtration
P( bleach
disposal
H
I steam J drying L ^ desodoration
2mbar/250°C PI refined oil
filter backlog
disposal 1
FIG. 22—Refining process of rapeseed oil.
CHj-OH
+ Ca(0H)2
H—C—H + CH3-C—H OH-CH2-C—C—H

9^3 O + NaOH 9^30
formaldehyde acetal
H—C—H + H—C—C—H HO-CH^C—C-
CH2-OH I
CH, CH,
formaldehyde i-butanal
CHj-OH
+ HCHO, H2O
O -HCOOH CH2-OH
OH-CH2-C—C—H OH-CH2-C—CH2-OH
9H3O CH,
+ H,
CHj-OH HO-CHj-C—C—H HO-CHj-C—CHj-OH
CH2-OH pentaerythrltol
CH, CH,
FIG. 23—Synthesis of alcohols by aldol condensation. FIG. 24—Synthesis of neopentylglycol.

Hydrolysis 1. Start
Hydroljîc cleavage of the pressure media based on natural

and sjTithetic esters represents a reaJ danger for the fluid, + RH -> XH + R
since the reaction to produce synthetic esters is an equilib-
rium reaction producing water. Since equilibrium reactions
may proceed in either the forward or reverse directions, es- 2. Chain building
ters exposed to water cleave again into their alcohol and acid
components. At room temperature and without mechanical R + O -> ROO
load, this reverse reaction proceeds very slowly with syn-
thetic esters so that no direct damage of the fluid contami-
nated with water is expected. However, u n d e r mechanical ROD + RH ->• ROOH + R
load and increased temperatures such as the t5rpical condi-
tions that occur in a hydraulic system, the hydrolysis process
RO + RH -> ROH + R
is accelerated. In general, hydrolosis may follow two differ-
ent paths: saponification or acid catalyzed hydrolysis [17].
Alkali saponification starts by adding a hydroxide ion to 3. Chain splitting
the carbonyl carbon atom of the ester. The hydroxide ion can
be added to the reaction, e.g., by mixing sodium or potassium
hydroxide to it. The reaction intermediate produces a very ROOH -> RO + OH
ROOH + ROOH • ROO + RO + H2O

cyclohexanol adipic acid
^CH, FIG. 27—Autooxidation process of ester based fluids.
CH-OH O H H H H O
HNO, or o.
II I I I I II
HO—C—C—C— C—C—C—OH
I I I I
CH, H H H H
4. Chain termination
cyclohexanone adipic acid
^CH,
CH,
HN03or o,
O
II
H
I
H
I
H
I
H
I
O
II R + R > R-R
—• HO—C—C—C — C—C—C—OH
I I I I
H H H H
R + ROO - • ROOR
FIG. 25—Synthesis of adipic acids. FIG. 28—Termination of oxidation process.
alcohol
alcohol synthesis
carbon acids
acid synthesis
bleaching
mineral acid
FIG. 26—Schematic ester synthesis.

1. step: hydroperoxide ion addition
R1-C—O—R2 + OH R1-C—O—R2
HO
2. step: allôxide ion formation
0~ O
R1-C—O—R2 ~*"
-h
R1-C—OH O—R2
I
HO
3. step: alkoxide deprotonation
O
-h _ II _ R2-0H
R1-C—OH ' O—R2 R1-C—O
FIG. 29—Alkalic saponification of esters.
1. step: ester protonation

0—R2 0 — R2
R1-C 1 -f- H
+
• R1 - c
II .
OH
0
2.step: water addition

0 — R2 H-- O — H OH H
R1-C -h HP ^ R1 - C — 0 — R2 R1-C—O*
il .
OH
1 I I
OH OH R2
3. step: alcohol split off

OH H OH
1
1
R1-C—O* —»• R1-C + R2-0H
1 1
OH R2
II .
OH
4. step: hydrogen split off

OH 0
R1-C -f R2-0H R1-C—OH + R2-0H + H

M +
OH
FIG. 30—Ester splitting under acid conditions.
basic cJcoxide ion during the subsequent elimination step. trary to saponification, acid catalyzed hydrolosis is reversible
This alcoxide ion reacts with the carboxyhc acid instantly to unless the water produced during hydrolosis is removed from
ydeld a non-reactive carboxylate ion. This reaction is called the systems.
saponification, and is shown in Fig. 29. Figure 30 shows the process steps of acid catalyzed hy-
During use, the precondition of the acid catalyzed hydrolo- drolosis. The proton of an acid is necessary to catalyze the
sis of ester-based fluids is met because the acidity of the fluid addition of water. Following a very fast and reversible pro-
increases during use due to fluid oxidation. However, con- ton displacement, splitting of the alcohol takes place. Acid
is produced after a H^-ion is removed. The H"^-ion is then sor connected to a computer for data storage measures the
available again for hydrolyzing another ester bond. The re- pressure in the steel container. For hydraulic fluids based on
action continues until the chemical equilibrium of the four esters, no water is added to the pressure vessel, since hydrol-
components is restored again. ysis could occur. Oxidation stability is defined by the time re-
In a pressure medium, free fatty acids represent the basic quired for maximum pressure to decrease 1.75 bar. This pres-
material for chemical reactions. They react with metallic sure drop depends on the amount of oxygen with which the
abrasive particles contained in the fluid. From this reaction, lubricant reacts as a result of the oxidation process. To dif-
so-called metallic saponification agents arise, leading to a ferentiate between the different fluids, tests are conducted at
possible functional i m p a i r m e n t of the hydraulic system. a temperature of 150°C.
Metallic saponification agents deposit on the surfaces of the Three different base oils were evaluated. They are distin-
hydraulic components leading to a premature blockage of the guished mainly by their degree of saturation and the alcohol
filters. used. Figure 32 depicts the test results for these three base
fluids.
Fluid G S l , an unsaturated trimethylolpropane ester, reacts
quickly with the oxygen in the test vessel, showing only an ex-
ALTERNATION OF TECHNICAL AND
tremely low resistance against oxidation. Continuous im-
CHEMICAL PROPERTIES BY AGING
provement of the oxidation stability is achieved by using
PROCESSES
partly a n d completely saturated esters. This can be read from
the test results for the fluids GS2 and GS3. Each of these base
Oxidation Stability
fluids represents the next developmental phase of synthetic
The aging stability of pressure media based on natural a n d esters. Although the first generation of esters contained un-
synthetic esters is influenced by its oxidation stability. Oxi- saturation, the next generation of fluids were saturated. The
dation stability is a fundamental quality used to differentiate current generation of hydraulic (GS4) fluids are saturated,
between the different performance classes of pressure media. but they are produced by more economical procedures. For
For a precise rating, different laboratory test procedures are comparison, a mineral oil without any additives was also
available. tested. Its oxidation stability is comparable to that of satu-
rated synthetic esters. However, the test times exhibited by
those fluids are not sufficient for use as pressure media.
Laboratory Aging Therefore, the use of additives is necessary to increase aging
The following describes different tests to evaluate oxidation coxidative stability. Corresponding improvements by using
stability which are performed with the modified Rotary Pres- additives can be observed in Fig. 33.
sure Vessel Test (RBOT) according to ASTM D 2272. The Results are shown for the oxidation of the base fluids with
RBOT test is conducted to determine the time necessary to additives according to their special requirements. The fluids
react with a certain a m o u n t of oxygen. This test is illustrated SI to S4 are each formulated from base fluids GSl to GS4,
in Fig. 31. respectively. The mineral oil HLP is a formulated fluid with
The test fluid and a copper coil are put into a breaker and the base of the fluid "H." The low oxidation stability of the
sealed in a steel container. The copper coil performs as a cat- fluid GSl is improved significantiy by using additives. How-
alytic agent to accelerate the oxidation reaction. Thus, in the ever, in comparison to HLP mineral oil and to the partly and
pressure vessel, metal catalytic oxidation takes place (see the fully saturated synthetic esters, the oxidation stability ob-
Alcohol Bonds section above). The pressure vessel is filled tained is too low for use in high performance hydraulic sys-
with a specified a m o u n t of oxygen and put into a heated bath. tems. Adequate oxidation stability is provided with a test
Temperature control equipment provides for an adjustment time above 200 min. Used oils should show a test time of at
between 40°and 150°C. least 180 min. to provide adequate oxidation stability.
The temperature is maintained at ± 1°C. An electronic sen- Further development of the base fluids and especially the
1——1
i.
2
Z3
W
'1,75 bar
CO
oxidation-
£
stability
a.
TQ time [min] T,
copper coii
FIG. 31—Rotary bomb test rig.
test parameter
40
35 temperature:
35
30
1 1 t
150 iC
1 1
II 1
25 atmosphere:
t
20 20 20
20
15
1 1 1 0 6,25 bar
oxygen
H 10 1 11 limit:
11 1 11 1,75 bar
o
5 3 1 0 pressure
0
1 11 1 catalyst:
drop
GS1 GS2 GS3 GS4 ^ g copper, 3m

base oil S 1,5 mm
FIG. 32—Oxidation stability of different base fluids (ASTM D 2272).
test parameter
300' 267 temperature:
1
!= 250- fr 150iC
220 213
!& 200-
1 150- 1
T 1
1 1
1
atmosphere:
/ * ^ 6,25 bar
\^Joxygen
• | 100"
W 1 70 limit:
^ T ^ 1,75 bar
tn
8 50- 24 ^ ^ pressure
x^P^drop
0- catalyst:
SI S2 S3 S4 ^ copper, 3m
HLP ^ 1,5 mm
nuid
FIG. 33—Oxidation stability of different ester formulations (ASTM D 2272).
use of fully saturated synthetic esters results in a significant bility compared to the remaining tested materials can easily
increase of oxidation stability. However, fully saturated base be recognized. For the pure metals that were tested, these re-
fluids are relatively expensive raw materials. sults coincide very well with the position of the different met-
Oxidation stability is also influenced by temperature. Oxi- als in the periodic systems. The position in the periodic sys-
dation stability decreases by one hcilf with every 10°C tem- tem gives preliminary information on the reactivity of the
perature rise. This rule of thumb is roughly confirmed for the metals. With decreasing periodic number, the catal5tic effect
examined fluids. Fluids with additives exhibit a slightly of the metals diminishes. Material coating and their base ma-
greater increase of reaction rate with increasing temperature terials exhibit a very positive influence on the oxidation sta-
than the base fluids (Fig. 34). bility in comparison to the standard construction materials.
Besides temperature, the catalyst being in contact with the For the use of rapidly biodegradable pressure media based on
fluid also influences oxidation stability. In hydraulic systems, synthetic esters, a significant improvement in oxidative sta-
many different materials are used for different tasks for a va- bility with increasing temperature is obtained by exchanging
riety of hydraulic components. To evaluate the usability of a traditional construction materials with newly developed ma-
fluid, the influence of those materials on the aging perfor- terial coatings.
mance of the fluid is important. In hydraulic systems, iron and
copper alloys and different coated materisils are used as con- Test Stand Aging
struction materials. Oxidation is significantly accelerated by Laboratory tests cire conducted to evaluate oxidation stability
the presence of certain metallic catalysts, as shown in Fig. 35. and the effects of aging pressure media. In a hydraulic sys-
The very strong influence of copper on the oxidation sta- tem, different parameters that affect oxidation stability usu-
ally occur in combination, thus accelerating the overall aging acids can attack non-ferrous metals, thus endangering the
process. Therefore, to evaluate the fluid performance, cus- hydraulic system during use.
tom aging test stands are required, which model a hydraulic In addition, viscosity is an excellent indicator of fluid qual-
system as precisely as possible. To obtain test results within ity. The molecular structure of the fluid influences its viscos-
a reasonable period, fluid loads in such test stands are greater ity and its viscosity temperature performance. Depending on
than those of practical applications. The primary task of the the reactions occurring in the fluid, viscosity increases or de-
test stand consists of examining fluid properties, thereby, the creases. As a lifetime criterion for rapidly biodegradable
test stand design should be very simple. Figure 36 shows a pressure media derived from esters, a viscosity increase of
test rig circuit fulfilling this requirement [8]. 20% is applicable [8,23].
The hydraulic test rig circuit is operated as an open circuit.
Test stands are constructed using mass-produced hydraulic Results of the Test Stand Aging Studies
components to model the loads activating the pressure media For the test stand aging studies, the same fluids were used
in a real system as accurately as possible. that were already tested with regard to their oxidation stabil-
Variations of the pressure media are determined by ana- ity. The influence of different loads on the fluid was realized
lyzing fluid samples taken periodically. Acid number (AN) by a variation of system pressures and temperatures. The in-
and viscosity are very important characteristic parameters to fluence of those system parameters on the aging behavior is
describe the aging condition. The load during operation is determined by the variation of acid number and viscosity at
primarily responsible for the production of free acids. Those 40°C, after an aging time of 1000 h as shown in Fig. 37 [8].
test Darameter
10000 •
• GS1 temperature:
QS1 t. variable
E 1 0 0 0 - ^^^^^^^=
i atmosphere:
Z * ^ 6,25 bar
9
\jjl oxygen
limit:
1 10" ^H ^ - 1 ^ 1 , 7 5 bar
^H ^ S f j pressure
1 -
90 j C
_• ^^^^^1
^^^1
120jC
1 •
1H H
15C>iC
>«_>'drop
catalyst:
^ p copper, 3m
temperature [\C] ^ ^ 1,5 mm
FIG. 34—Temperature influence on oxidation stability.
150 test parameter
• S1 temperature:
i
-.125 150 iC
110
E
>!ioo
84 atmosphere:
.a 77
RH
« 75 64 6,25 bar
oxygen
o 46
1 50 limit:
•a
"S 24 1,75 bar
o
25
®
catalyst:
pressure
drop
Cu Fe Cr CrN Ti TiN without ^S variable

materials and coatings
FIG. 35—Catalyst influence on oxidation stability.

FIG. 36—Oil aging test rig [8].
test parameter:
temperature:
I variable
pressure:
S y\ variable
volume flow:
® 20 l/min
water content:
^ < 0,03 %
4 HaO
300 bar 300 bar 150 bar 300 bar 300 bar 150 bar
test duration:
90°C 60°C eO-C 90°C 60°C 60°C
GS1 GS1 GS1 S1 SI S1 1000 hrs
FIG. 37—Change of TAN and viscosity after aging test runs.
The influence of high temperature and pressure indicates Test runs on the aging test bench confirmed the very good
a high specific load on the fluid. Comparing the aging in- oxidation stability of the more advanced fluids formulations
fluence of pressure and temperature shows that the temper- (Fig. 38). Fluid S3, in particular, exhibits an aging stability
ature exhibits the greatest influence on the aging. The in- comparable to mineral oils. The excellent stability is indi-
fluence of pressure is evidently less, at least as determined cated by the constant viscosity throughout testing time.
from tests performed at reservoir temperatures of 90°C and A comparison of results of the formulated fluids with their
60°C. base fluids shows that the additives used and the base fluid
Decreasing the reservoir temperature by 30°C reduces the correlate well with each other. Additives increase the aging
aging process four-fold in the fluid as indicated by viscosity resistance of the base fluid significantly.
change. On the other hand, a 50% reduction of pressure yields Table 3 illustrates the effect of additional fluid characteris-
only a very small reduction of the aging processes and rates. tics. Variations of these characteristics are only of minor im-
Absolute variation of fluid properties during tests are greater portance with respect to the aging performance. Therefore, a
than conventional mineral oil based fluids. graphical presentation is not shown.
Hydrolysis Stability The effect of hydrolytic stability was evaluated using the
same procedure described above for oxidation stability in a
Laboratory Aging laboratory test procedure. A procedure developed at IFAS
Rapidly biodegradable pressure media are primarily used in (Institute of Fluid Power Transmission and Control, Aachen,
mobile hydraulic equipment, since they are often used in eco- Germany) is used. A scheme of the test equipment is provided
logically sensitive environments. These machines are often in Fig. 39. In this case, a pressure-proof and lockable stain-
exposed to atmospheric influences so that there is always the less steel container is used. The container features a stirring
danger of water ingression into the hydraulic system. Due to device that mixes the oil turbulently with the water used to
their chemical structure, synthetic esters tend to be hydrolyt- contaminate the system. The container is heated by a heating
ically unstable in the presence of water (see the Hydrolysis bath so that the tests are run u n d e r actual operating condi-
section above). Thus, evaluation of hydrolytic stability is of tions.
central importance for the assessment of the usability of During the test, a defined amount of test oil is mixed over 72
rapidly biodegradable pressure media. h together with a specified amount of water. Metallic catalyst
28 test parameter:
1 1
• viscx3sity temperature:
g20
24
EBAN
IV.
CO
•5
X
I 90 °C
pressure:
o 300 bar
m
o_
•§12 0) volume flow:
>, ^°g. 1^- o>
®
V
c 20 l/min
1 8
1
(0
u O 00_
o
z water content:
I 4 lOCM
1^
o <
o" ^ < 0,03 %
W H,0
test duration:
GS1 GS2 GS3 S1 S2 S3 S4 HLP 1000 hrs
fluid generations
FIG. 38—AN and viscosity changes of different fluid generations after aging test runs.
TABLE 3—Important fluid properties.

Alternative Test
DIN Methods'"
Property Unit HEES 46 HLP 46 Standard" ASTM^ ISC^
Density kg/m3 ca. 920 ca. 880 51 757 D 1298
Viscosity nim2/s 46 51562T1 D445 3104
@40X 46
Viscosity mm2/5 7,1 51562T1 D445 3104
@ 100°C 9,3
Viscosity 100 ISO 2909 D 2270 2909
index 184
Pour-point ["C] -42 -27 ISO 3016 D92 3016
Flash-point [°C] 290 220 ISO 2592 D97 2592
FZG-test Load level 12 12 51 354 T2 D5182 14635
Vickers [mg] ring <120 <120 51389T1 D 2882 20763'*
pump test [mg] vane <30 <30 51 389 Tl
AN [mg KOH/g] 1.2 0,3 51 558 D 974 3371
D 664 D 664 6618
D 5770 7537
Corrosion
Steel 0-A 0-A D 665A
51 585 7120
D665B 7120
Copper 1-100A3 1-100 A24 51759 D130 2160
"The DIN test procedures shown here were used to obtain the values shown.
* Although DIN test procedures were used for this work, equivalent ASTM tests may
also be used.
'' In some cases, the ASTM tests are not truly equivalent but the ASTM procedures
cited may be used.
'' This ISO Standard is still under development and has not yet been published.
test fluid
(150 g)
+
catalyst fluid analysis
(iron or copper)
+
(variable)
FIG. 39—Hydroiytic stability test.
3,0 1 1 •— test parameter:

^^^^1,5% iron |^ temperature:
•32,5 Br 90°C
X
§2,0
fluid:
E
ft. "I-5 GS1
en
c
n
u1.0 test duration:
z
< 72hrs
0.5
0,0 catalyst:
0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 ^ iron,
water content [%] p 1,5%
FIG. 40—Hydroiytic stability of the GSI ester fluid vs. water content.
is added in the form of pulverized copper or iron to accelerate processes also occur since the reaction vessel was not purged
the hydrolosis reaction. Thereafter, the AN of the fluid is mea- with nitrogen. Contrary to the oxidation tests reported ear-
sured and the deposited hydrolysis products are investigated lier, the oxygen supply is very low since the container is only
by means of SEM and element determination. Viscosity mea- filled with atmospheric pressure air.
surement is not helpful because it doesn't provide repro- Besides the determination of AN, deposit formation during
ducible results due to the hydrolysis byproducts and deposits. the tests was determined. This was done by SEM microscopy
Figure 40 provides the test results obtained with varied wa- to determine structure as shown in RBOT tests reported ear-
ter content. It is evident that water contents below the satu- lier, Fig. 42. The structure of the deposited particles differs
ration point only causes hydrolysis. As free water appears in most with regard to particle size. The particle size of the de-
the fluid, an accelerated attack on the fluid occurs. At water posits was significantly smaller. The medium particle size of
contents above 1.5%, the effect no longer increases linearly the contaminants measures about 10 î,m vs. about 60 /xm for
with increasing water content. the iron test dust of the laboratory investigations.
Like the oxidation processes, hydrolysis is also strongly in- After ultrasonification, there was no significant difference
fluenced by the presence of metallic particles. In addition, in the particle size and amount between those generated in
with this reaction, the effectiveness of the individual ele- the test rig cind those generated in the RBOT laboratory tests.
ments is different. Figure 41 shows the influence of the In addition, the compositions of the deposits from the two
metallic catalysts on the hydrolysis of the GSI ester. Adding tests were essentially the same. In addition to iron and cop-
iron or copper chips considerably accelerates the reaction per, the deposits taken from the test rigs contained small
process. Iron exhibits the greatest effect relative to copper. amounts of tin and zinc, which are alloying elements of the
Increasing the temperature also accelerates the hydrolosis non-porous materials used for construction of the test rig sys-
reaction. The effect is exponential. Above 110°C, oxidation tem components. The presence of phosphorous or sulfur.
which would be attributable to the additives used for fluid studies were performed with significantly lower loads rela-
formulation, was not observed, which indicates that the data tive to those used for the studies discussed previously to pro-
obtained from the test rigs correlates well with results ob- long the use lifetime of the hydraulic components used for
tained from laboratory tests such as RBOT. the test stand. Initially, the first generation of ester-based flu-
The analyses techniques, however, were unable to detect ids (vegetable oils), were evaluated using varying water con-
hydrogen. Based on the chemical reactions occurring, the tent u p to a maximum of 0.1%, which is the maximum al-
presence of hydrogen would be expected, since metal lowable value r e c o m m e n d e d by VDMA (Association of
saponification occurs with the metal catalyzed hydrolysis. German Machine Manufacturers) [36,37]. (This is an empir-
Ester hydrolysis follows the reaction process described ear- ical recommendation, which was not derived experimen-
lier. The faster hydrolytic reaction of iron vs. copper is due tally.)
to the stronger acidity of iron relative to copper. For this work, the water contaminant was injected slowly
into the suction pipe of the p u m p on the test stand. Excellent
Hydrolytic Stability Test With Test Stands mixing of the fluid a n d water c o n t a m i n a n t was obtained
Further assessment of the hydrolytic stability of different es- from the "whirling" action of the oil flow in the p u m p and the
ter-based fluids was conducted using the test stand. These subsequent turbulent motion of the fluid on the pressure re-
1 1 test parameter:
- C ^ 1,5% iron temperature:
„5
X
04
-0— 1,5% cxDpper
I variable
fluid:
1
to O GSi
O) 0,8 % H2O
c
10 test duration
72lirs
^1
catalyst:
20 40 60 80 100 120 140 variable
temperature [°C]
FIG. 41—Hydrolytic stability influence of a catalyst on the hydrolysis of the GSI ester fluid.
ultra sonic
treatnmnt
latoratory
test
?m* '•:"|l
FIG. 42—Hydrolytic splitting products.

test parameter:
temperature:
I 60-0
pressure:
0; 150 bar
volume flow:
® 20 l/min
water content:
^ ^ variable
%0 see figure
test duration:
0,03% 0,1% 0,5% 0,03% 0,1% 0,5%
1000 lirs
GS1 GS1 GS1 SI SI SI
FIG. 43—AN and viscosity changes after aging tests in the test rig with water contamina-
tion.
test parameter:
temperature:
1
60 °C
pressure:
0- isobar
volume flow:
® 20 l/min
water content:
^ o.syoHjO
test duration:
GS1 GS2 GS3 S1 S2 S3 1000 hrs
FIG. 44—AN and viscosity changes after aging tests in the test rig with water contamina-
tion and using different generations of fluid development. The oldest was GSI and the most
recent fluid candidate is S3.
lief valve. Water content was determined at 24 h intervals and the most recently developed fluid candidate (SI). The results
corrected, if necessary, to maintain the water content in the showed that the susceptibility to hydrolysis decreases with
fluid for the duration of this test. increasing advances in ester-base stock fluid structure.
Figure 43 shows the results of the investigations conducted The observed improvement in hydrolytic stability is due to
with the fluids GSI and 81. The influence of the water content the greater stability offered by the saturated versus unsatu-
during the aging (hydrolysis) of the fluid is clearly evident rated structure and the improvement of the additives used.
from the variation of the AN of the fluid during the test. All the For example, fluids S2 and S3 exhibit significantly better
tests using these base fluids always showed a decrease of AN, demulsifying characteristics (ASTM D 2711) relative to the SI
whereas the tests in which water was added for the first time fluid, which causes the water to separate to the bottom of the
exhibited an increase of AN. This is an indication of increased fluid in a short time. This reduces the amount of water avail-
hydrolysis of the fluid into alcohol and acid components. able for hydrolytic degradation throughout the test, thus re-
Figure 44 illustrates the results obtained for different flu- ducing the overall hydrolysis rate.
ids, which were evaluated at 0.5% water. The fluids shown in Varying the viscosity and AN of water contaminated fluids
the figure vary in order from the earliest candidate (GSI) to is relatively unimportant compared to the impact of the effects
of increased system pressure and reservoir temperature. In ad- viscosity of synthetic esters is considerably lower than min-
dition, it is also important to consider system component eral oil, providing a safe operation of a hydraulic system af-
compatibility. For example, water is soluble in the ester-based ter changing over from a mineral oil to a synthetic ester of the
fluid u p to 0.1% b.w. and 60%. Under these conditions no dele- same viscosity class. At high temperatures, viscosity of the
terious system effects were observed. However, water contents same ISO viscosity class (ISO 3448, ASTM D 2422) is signifi-
of 0.5% b.w. are insoluble in the fluid and significant attack on cantly higher, so that oil of the next lower viscosity class
the system is observed. Although an oil-water emulsion is might be used. Consequently, synthetic esters perform like a
formed initially, phase separation does subsequently occur de- multi-grade oil. ASTM D 6080 provides a procedure for ester-
pending on the demulsification properties of the fluid. based hydraulic oil as a function of use temperature.
The extent of fluid hydrolysis was greatest with the GSI
fluid, which contained no additives. All of the fluid candi- Crystallizing P r o c e s s e s With Slowly Decreasing
dates contained emulsifies deposits at the b o t t o m of the Temperatures
reservoir and the filter elements during the test run.
With very slowly decreasing temperatures a first formation of
These deposits are formed due to the emulsification of the
crystals may occur at approximately - 2 0 ° C in synthetic es-
fatty acids, which react with the corrosion metals from the
ters. As experienced with vegetable oils, the degree of crystal-
system components. This process may result in filter plug-
lization is dependent on time [8,23,26,32]. For the fluid GSI,
ging even after only a few hours of operation during the test.
the completely crystallized condition is achieved after a four
This occurs because the filter elements are equipped with a
day storage time at a temperature of — 45°C.
by-pass valve that opens once a preset differential pressure is
exceeded at which time the fluid invades the system without Consequently, the temperatures necessary for crystalliza-
filtration. This results in an increase of solid abrasion partition are about—30°C lower than those for rapeseed oils and
cles (contamination) in the system. are below the temperatures where mineral oils are no longer
able to flow. Thus, a safe operation of hydraulic systems op-
The tests didn't show any impairment of the lubricating
erated with synthetic esters instead of mineral oil is guaran-
properties of the fluids caused by the water as contaminant.
teed at low temperatures.
However, indirect consequence of water contamination is
From Fig. 46 the start of crystallization can be taken for
that 3-body-abrasion causes increased wear on the hydraulic
the generations of fluids for the fluids SI, S2, and S3, which
components. The improved hydrolytic stability of more re-
are branched, saturated diester-based fluids. Moreover, dif-
cently developed fluids produces smaller amounts of deposits
ferent filterability tests were conducted to assess the low
on the bottom of the reservoir.
temperature performance. Good filtering properties of the
A comparison of the composition of these deposits relative
pressure media are a precondition for a safe operation of
to those found in laboratory tests was discussed earlier.
the hydraulic system because if the fluid is excessively vis-
cous, the p u m p will be starved for fluid and cavitation will
result. If the fluid viscosity is too low inadequate lubrication
LOW TEMPERATURE PROPERTIES OF will result. For the filterability tests the experimental system
ESTER BASED FLUIDS shown in Fig. 47 was used that was developed at IFAS. The
fluid volume enclosed in the cylinder is pressed through a
For the use of pressure media in mobile applications, the per- membrane filter by means of compressed air at different
formaiace at low temperatures is of great importance to pre- temperatures. Measures for filterability are either the time
vent failure on the hydraulic system during cold weather op- necessary for a certain volume to pass the filter or the vol-
eration (such as in the winter). u m e flow through the filter element in dependence of time.
The diagram shows the filterability properties of fluid GSI,
Viscosity Properties since no significant differences were found between the indi-
vidual fluids based on synthetic esters. Compared to mineral
To evaluate the viscosity properties of a pressure media at low oil HLP 46, those fluids show a considerably better filterabil-
temperatures, two characteristically different rates of cooling ity. In the case of mineral oil, the filter m e m b r a n e clogs at
can be distinguished. In a case of fast cooling, the change of temperatures of — 10°C after a test time of only 60 s. The vol-
viscosity with respect to temperature is important. This also u m e flow of fluid GSI through the filter element diminishes
determines the viscosity class that can be used to fill the hy- within the same time by only 25%. However, when the SJTI-
draulic system (ASTM D 6080). The low temperature behavior thetic ester is contaminated with 0.5% water, the good filter-
during slow cooling, exposure to low temperatures, a pro- ing properties are lost, causing the filter element to clog after
longed time is important, since esters often show a time-de- a very short time. Since the water is no longer dissolved, but
pendent solidification. This starts with a separation of paraf- finely dispersed in the Quid, ice crystals can form resulting in
fin crystals, such as that which occurs in diesel fuel. These clogged filter elements.
crystals may cause clogged filter elements.
Figure 45 shows the viscosity-temperature dependence as
ECOLOGICALLY TOXIC PROPERTIES
well as the viscosity index (VI) of different fluids. Viscosity in-
dex is measured at the variation of viscosity with tempera-
Test Methods
ture. The greater the VI, the less sensitive the fluid viscosity
is to variation in temperature. Comparison to a mineral oil is For the investigation and development of environmentally
provided. Synthetic esters show significantly better viscosity friendly, biologically fast degradable pressure media dis-
properties due to their higher VI. At low temperatures, the cussed above, various methods currently in use in Europe
test oarameter:
10^ ' ' • ' ' ' '—'—'—'— •^ GS1
• S2
•f- GS3
^^\*- ^«
+ P3
A.^
SN
VkV — HLP46
m
\ ',
KX \^
^
^3 fluid slope VI
^fe ? \ \
•1 • i •
S2 3.34 •
^M WM• i
• ^ in
1 80 . • •
^ 63,5-
% 50 •
§ 40 •
« 31,5.
>
25 .
20 •
15,8-
12,5- 1
in _
^
\ 1
u
-W
^\
6 5-
-60 -zto -2 0 (3 20 A0 60 80 100
temi:jera ture [iC]
FIG. 45—Viscosity vs. temperature of ester fluids.
aging parameter:
-10 i Hi ni 11 Mq HI I I temperature:
90 °C
a
MM nl I ! I 111 pressure:
/ * ^ 300 bar
volume flow:
® 20 l/min
water content:
new fluid
/ ^ < 0,03 %
1000 h aging W H,0
aging time:
GS1 GS2 GS3 S1 S2 S3
1000 h
fluid
FIG. 46—Crystallization of esters at low temperatures. (Crystallization properties are de-

termined by IFAS lab test procedure).
test parameter:
20 GS1 temperature.:
—A—
GS1 0,5% HP -10 °C
~~~~-J
— X - -HLP46
,,___^
I
compressed air
(6 bar) "^
"i
5 10.
o
5=
E
-~ <•
50 100 150 200 ZO

time [s]
filter [5|jm]
FIG. 47—Filtering properties of esters at low temperatures. (Flexibility was determined by

IFAS lab test procedure)
were employed. The examination of the toxicological proper- anaerobic media have been developed that are appropriate
ties of rapidly biodegradable fluids is a critically important for each compartment and aire reviewed here.
parameter in evaluation of the use-properties of these fluids.
This includes the self-classification of the test fluids into wa- D 5864—Test Method for Determining the Aerobic
ter hazard classes [40], since exclusively finished products Aquatic Biodegradation of Lubricants or Their
and no individual components were tested. These properties Components
were determined for this work using both new and used flu- This test method covers the determination of the degree of
ids. Aged fluids were evaluated to determine impact of aging aerobic biodegradation of fully formulated lubricants or
on biodegradability and toxicity. The VCI (Verband Chemis- their components on exposure to an inoculum under labora-
cher Ingenieure) classification system [6,29,32] comprises tory conditions. This test method is intended to specifically
the tests shown in Fig. 48 and Table 4. address the difficulties associated with testing water insolu-
ble materials and complex mixtures such as are found in
Test Results many lubricants.
Table 4 provides an insight into the test-substance specific in- D 6046—Classification of Hydraulic Fluids for
vestigations, results, and (preliminary) WGK-classifications Environmental Impact
(WOK = water hazard class) [40]. This classification covers all unused fully formulated hy-
ASTM International has developed various standards to draulic fluids in their original form. Classifications for cate-
provide guidance in determining the biodegradability and gories for the impact of hydraulic fluids in different environ-
ecotoxicity properties of hydraulic fluids. A brief summary of mental compartments is provided. Fresh water and soil
the slope of these tests will be provided here and more de- environmental compartments are addressed.
tailed discussion is provided in Chaper 34, Environmental
Characteristics of Fuels and Lubricants. Biodegadability is D 6384—Terminology Relating to Biodegradability and
one of three characteristics that are assessed when evaluating Ecotoxicity of Lubricants
the environmental impact of a hydraulic fluid. The other two Terminology relating to biodegradability and ecotoxicity of
characteristics are ecotoxicity and bioaccumulation. lubricants is provided in this standard.
D 6006—Guide for Assessing Biodegradability of
Hydraulic Fluids SUM]VIARY AND OUTLOOK ON FUTURE
This guide provides information to assist in planning a labo- DEVELOPMENTS IN THE FIELD OF
ratory test or series of tests that would provide information PRESSURE MEDIA
about the degradability of an unused fully formulated hy-
draulic fluid in its original form. Biodegradability may be The overall broad grouping of esters offers a variety of dif-
considered by type of environmental compartment: aerobic ferent fluids from which pressure media can be produced,
fresh water, aerobic marine, aerobic soil, and anaerobic me- making a uniform description impossible. However, due to
dia. Test methods for aerobic fresh water, aerobic soil, and their basic structure, ester-based fluids differ substantially
WGK
classification
r
pre test
.
J'"flS'Ctlr,nV-,l
compulsory H special case
i--.taxids-.i'J
daphni-
=•<•:••>-.'*'/
mm^ additional
toxicidy tests
bio-
test of degradability
components & mobility
FIG. 48—Ecological test for German water hazard classification [18,19,39,41-45].
TABLE 4—Ecological properties of a formulation and the base fluid.

Germ-toxic Fish-toxic Mammal-toxic Biodegradability Biodegradability Biodegradability WGK
Test method DIN 38412 T 8 OECD 203 OECD 401 CEC L-33-A-93 BODIS ISO/DIN VCI-strategy
Limittest 10708
Unit ECio [mg/L] LC50 [mg/L] LD50 [mg/L] Depletion [%] Depletion [%]
GS2 Unused > 10.000 > 10.000 >2.000 78 N/A 0
GS2 1000 h Aging > 10.000 > 10.000 >2.000 84 N/A 0
S2 Unused >10.000 > 10.000 >2.000 89 76 0
S2 1000 h Aging > 10.000 > 10.000 >2.000 89 64 0
transfer of triboligical properties from the

fluids to the materials
strategy
Oil less
OH - coatings addrtivs
complete - eccological acceptable fluids
addrtive - data bases & simulation tools
package
- examinations on trSbological modells
- examinations on machines
FIG. 49—Strategies for future fluid and material developments [21].

from mineral oil-based lubricants. The different basic struc- D 665 S t a n d a r d Test Method for Rust-Preventing
tures and their physical and chemicEil properties were ex- Characteristics of Inhibited Mineral Oil in the
plained in detail. Presence of Water
When examining their fluids, properties of the esters were D 974 Standard Test Method for Acid and Base Num-
found to be both similar and different to those of mineral ber by Color-Indicator Titration
oils. Esters offer considerable improvement relative to min- D 1298 Standard Practice for Density, Relative Den-
eral oils with respect to low temperature properties and lu- sity (Specific Gravity), or API Gravity of Crude
bricity. Oxidation stability, hydrolytic stability and, in gen- Petroleum and Liquid Petroleum Products by
eral, aging stability were deficiencies relative to mineral oil, Hydrometer Method
especially for unsaturated fluids. However, the use of com- D 15 3 3 Standard Test Methods for Water in Insulating
pletely saturated fluids eliminated those deficiencies. All tests Liquids by Coulometric Karl Fischer Titration
distinctly demonstrated the application-related advantage of D 2270 Standard Practice for Calculating Viscosity In-
completely saturated fluids in high-load hydraulic systems. dex from Kinematic Viscosity at 40 and 100°C
The direct assessment of the different developmental stages D 2422 Standard Classification of Industrial Fluid Lu-
of the fluids allowed an excellent coordination of the addi- bricants by Viscosity System
tives with the respective basic fluid. D 2619 Standard Test Method for Hydrolytic Stability
Future development in the field of lubricants will increas- of Hydraulic Fluids (Beverage Bottle Method)
ingly consider the entire tribological system with the aim of D 2882 Standard Test Method for Indicating the Wear
making it ecologically more compatible. This will require the Characteristics of Petroleum and Non-Petrol-
development of environmentally compatible lubricants as well e u m Hydraulic Fluids in Constant Volume
as the use of materials complementing those lubriccints with Vane P u m p
regard to their tribological properties, to provide increasingly D5182 S t a n d a r d Test Method for Evaluating the
more tribological functions of the lubricants. For example, a Scuffing Load Capacity of Oils (FZG Visual
further reduction in the toxicological properties of biodegrad- Method)
able hydraulic fluids is necessary. Additional improvements in D 5770 S t a n d a r d Test Method for Semiquantitative
ester-basestocks chemistry is also important to provide further Micro Determination of Acid Number of Lu-
improvement in film-forming and antiweeir properties. bricating Oils During Oxidation Testing
It's likely that the focus will remain on ester-basestock de- D 5864 Standard Test Method for Determining Aero-
velopment in view of their overall excellent biodegradable bic Aquatic Biodegradation of Lubricants or
and toxicological properties. However, further and substan- their Components
tial improvement is needed in their oxidation properties for D 6006 Standard Guide for Assessing Biodegradability
t h e m to rival those exhibited by mineral oil. These functions of Hydraulic Fluids
may potentially be provided by additive development. D 6046 Standard Classification of Hydraulic Fluids for
Calculation or simulation of friction and wear are still not Environmental Impact
possible. Therefore, work will continue to model tribological D 6080 Standard Practice for Defining the Viscosity
systems by analogy to those already known, using laboratory Characteristics of Hydraulic Fluids
tests. Of course, this process necessitates subsequent valida- D 6158 Standard Specification for Mineral Hydraulic
tion in actual hydraulic systems. Oils
D 6384 Standard Terminology Relating to Biodegrad-
ability and Ecotoxicity of Lubricants
ASTM STANDARDS E 203 Standard Test Method for Water Using Volu-
metric Karl Fischer Titration
No. Title
D 2272 Standard Test Method for Oxidation Stability
of Steam Turbine Oils by Rotating Pressure
Vessel OTHER STANDARDS
D 92 S t a n d a r d Test Method for Flash a n d Fire
Points by Cleveland Open Cup Tester International Organization for Standardization
D 95 Standard Test Method for Water in Petroleum (ISO)
Products and Bituminous Materials by Distil-
lation No. Title
D 97 S t a n d a r d Test Method for Pour Point of ISO 2592 Petroleum products; determina-
Petroleum Products tion of flash and fire points: Cleve-
D 130 Standard Test Method for Detection of Copper land open cup method
Corrosion from Petroleum Products by the ISO 3016 Petroleum products; determina-
Copper Strip Tarnish Test tion of pour point
D 445 Standard Test Method for BCinematic Viscosity ISO 3733 Petroleum p r o d u c t s and bitumi-
of Transparent and Opaque Liquids (the Cal- nous materials; determination of
culation of Dynamic Viscosity) water, distillation method
D 664 S t a n d a r d Test Method for Acid N u m b e r of ISO 6743/4 -1982 Part 4: Lubricants, industrial oils and re-
Petroleum Products by Potentiometric Titra- lated products (class L); classifica-
tion tion. Family H (hydraulic systems)
D e u t s c h e s Institut fur N o r m u n g (DIN) DIN 51 759 Testing of liquid hydrocarbons; deter-

mination of the effect of corrosion on
No. Title
copper; copper strip test
DIN 51 354 Part 2 Testing of lubricants: mechanical test-
DIN 51 848 Part 1 Testing of petroleum products; preci-
ing of lubricants by the FZG gear test
sion of test methods; general introduc-
rig method; gravimetric m e t h o d for
tion; concepts and their application to
A/8, 3/90 lubricating oils
petroleum s t a n d a r d s specifying re-
DIN 51 381 Testing of lubricants a n d hydraulic
fluids; d e t e r m i n a t i o n of air release quirements
properties; impinger method DIN 53 505 Testing of elastomers; Shore A and D
Testing of lubricants; mechanical test- hardness testing
DIN 51 389 Part 2
ing of hydraulic fluids by the vane- DIN 53521 Testing of rubber and elastomers: de-
p u m p method: m e t h o d A for anhy- termination of their resistance to liq-
drous hydraulic fluids uids, vapours and gases
Lubricants a n d related materials; DIN 53 538 Part 1 Standard reference elastomers; perox-
DIN 51 502
designation of lubricants and marking ide-cross-linked acrylonitrilelbutadi-
of lubricant containers, lubrication ene rubber (NBR) for characterizing
equipment and lubrication points service fluids with respect to their ac-
Lubricants; lubricating oils; C lubri- tion on NBR
DIN 51 517 Part 1
cating oils; m i n i m u m requirements
DIN 51 519 Lubricants; ISO viscosity classes for in-
dustrial liquid lubricants REFERENCES
DIN 51 524 P a r t i Pressure fluids; hydraulic oils; HL hy-
draulic oils: m i n i m u m requirements [1] Backe, W., The Present and Future of Fluid Power, Proceedings of
Viscometry; determination of viscos- the Institution of Mechanical Engineers, Institution of Mechan-
DIN 51 550 ical Engineers, Milwaulkee, WI, Dec. 1993.
ity; general principles
Testing of mineral oils; determination [2] Backe, W. and Busch, C, "Biologisch Schnell Abbaubare Hy-
DIN 51 558 P a r t i draulikflilssigkeiten," Tribologie + Schmierungstechnik, No. 1,
of neutralization number; color indi-
1995, pp. 30-35.
cator titration
[3] Becker, R. and Knorr, A., "Antioxidantien fiir Pflanzliche Ole,"
DIN 51 561 Testing of mineral oils, liquid fuels Tribologie + Schmierungstechnik, No. 5, 1995, pp. 232-240.
and related liquids; measurement of [4] Bongardt, F., Einfluji der Chemischen Struktur aufdas Luftab-
viscosity using the Vogel-Ossag vis- scheidevermogen und die Hydrolytische Stahilitdt von Estem, Teil
cometer: temperature range: approxi- 1, Fat Science Technology, No. 12, 1990, pp. 607-613.
[5] Bongardt, F., Einfluji der Chemischen Struktur aufdas Luftab-
mately 10 to 1 50°C
scheidevermogen und die Hydrolytische Stabilitat von Estem, Teil
DIN 51 562 Part 1 Viscometry; determination of kine-
2, Fat Sci. Technology, No. 12, 1990, pp. 614-619.
matic viscosity using the standeird de- [6] Bongardt, F., "Native Ester: Basisole fiir leistungsfahige und
sign Ubbelohde viscometer Umweltvertragliche Hydraulikfliissigkeiten," Tribologie 2000
DIN 51 566 (at present at the stage of draft) Test- Band 1, TAE, Esslingen, 1992.
ing of lubricating oils: determination [7] Busch, C, "Biologisch Schnell abbaubare Hydraulikfliis-
of foaming characteristics sigkeiten," Tribologie und Schmierungstechnik, Vol. 41, No. 1,
DIN 51 569 Testing of mineral oils, liquid fuels 1994, pp. 23-31.
and related liquids; measurement of [8] Busch, C, "Untersuchung und Analyse der Eigenschaften und
viscosity using the Vogel-Ossag vis- Eigenschaftsanderungen einer Rapsolbasischen Druckfliis-
cometer: t e m p e r a t u r e range: —55 to sigkeit in ihrer Funktion als Druckiibertragungsmittel," Disser-
tation RWTH Aachen, Aachen, Germany, 1995.
approximately + 10°C
[9] Busch, C, Rapsol auf dem Priifstand - Alterungsstabilitat und
DIN 51 585 Testing of lubricants; testing of corro- VerschleiySschutzvermogen, 10th AFK, Aachen, Germany, 1992.
sive effect of steam turbine oils and
[10] Dimming, T., Hartmann, J., Wunderwald, U., and Schafer, V.,
hydraulic oils containing additives "Additivkomponenten auf Basis nativer Ole," Tribologie +
DIN 51 587 Testing of lubricants: determination of Schmierungstechnik, No. 6, 1994, pp. 375-380.
aging behavior of steam turbine oils [11] Feldmann, D. G. and Remmelmann, A., Biologisch Schnell Ab-
and hydraulic oils containing addi- baubare Hydraulikfliissigkeiten—Ergebnisse von Priifstandstests
tives und Folgerungen fiir die Anwendung, 12th AFK, Aachen, Aachen,
Germany, 1996.
DIN 51 592 (at present at the stage of draft) Testing
[12] Feldmsinn, D. G. and Hinrichs, J., Biologisch Schnell Abbaubare
of lubricants; determination of the
Hydraulikfliissigkeiten—ein Neuartiges Konstruktionselement fiir
content of u n dissolved matter in lubri- Hydrostatische Getriebe, Konstruktion, VDI Verlag, Dusseldorf,
cating oils; membrane filter method Germany, 1995.
DIN 51 599 Testing of lubricating oils; determina- [13] Fessenbecker, A. and Korff, J., "Additive fiir Okologische Unbe-
tion of demulsification capacity by the denklichere Schmierstoffe," Tribologie + Schmierungstechnik,
stirring method No. 10, 1995, pp. 623-629.
DIN 51 757 Testing of petroleum products and re- [14] Mang, T., Umweltvertragliche Hydraulik, 12th AFK, Aachen,
lated materials; determination of den- Germany, 1996
sity [15] Fessenbecker, A., "New Additive for the Hydrolytic Stabilisation
of Ester Lubricants," Tribology Solving Friction and Wear Prob- [31] Spilker, M. and Bock, W., Die Umwelt als Ideologietrdger, Fluid-
lems, Technische Akademie Esslingen, Ostfildern, Germany, Technik,No. 4, 1995.
1996. [32] Vetter, J., "Synthetische u n d Nachwachsende Grundolkompo-
[16] Gold, P. W., "Tribologie 1," Umdrucke zur Vorlesung, RWTH, nenten—Produktsicherheit, Eigenschaften, Gesundheits- und
Aachen, Germany, 1996. Umweltaspekte," Biologisch Schnell Abbaubare Schmierstoffe
[17] Francke, W. and Walter, W., Lehrbuch der Organischen Chemie, und Arbeitsfliissigkeiten, Technische Akademie Esslingen, Ost-
23, S. Auflage, Ed., Hirzel Verlag Stuttgart, Leipzig, Germany, fildern, Germany, 1995.
1998. [33] Wendorf, J., "Daueruntersuchung von Hydraulikolen auf Rap-
[18] Hund, K. Fabig, W., and Btinemann, T. F., "Biologische Ab- solbasis in Mahdreschem und Selbstfahrenden Feldhackslem,"
baubarkeit von Synthetischen Schmierstoilkomponenten," Tri- Biologisch Schnell Abbaubare Schmierstoffe und Arbeitsfliis-
bologie + Schntierungstechnik, No. 1, 1993, pp. 48-56. sigkeiten, Technische Akademie Esslingen, Ostfildern, Ger-
[19] Freitag.R., "Gesetzliche VorschriftenfiirdieEntsorgungvonAl- many, 1995.
tol," Okologische und Okonomische Aspekte der Tribologie Band [34] Streitwieser, H. and Heathcock, J., Organische Chemie, 1. Au-
1, Technische Akademie Esslingen, Ostlildem, Germany, 1994. flage VCH-Verlag, Weinheim, Germany, 1990.
[20] Hart, H., Organische Chemie, ein Kurzes Lehrbuch, VCH Verlag, [35] DIN 51 524 T1-T4 Hydraulikole, Mindestanforderungen,
Weinheim, Germany, 1989. Deutsches Institut fur Normung e. V., Beuth Verlag, 06.1985,
[21] Holderich, W. F., "Umweltvertragliche Tribosysteme," Entwick- Berlin, Germany.
lung Neuartiger Schmierstoffe und Druckiibertragungsmedien mit [36] VDMA-Einheitsblatt 24 568: Biologisch Schnell Abbaubare Hy-
Hilfe Chemischer Methoden, Teilprojekt Al im SFB 442 RWTH, draulikfliissigkeiten—Technische Mindestanforderungen, 3,
Aachen, Germany, 1997. Beuth Verlag, Berlin, 1994.
[22] Ihrig, H., "Umweltvertragliche Schmierstoffe in den 90er [37] VDMA-Einheitsblatt 24 569: Biologisch Schnell Abbaubare Hy-
Jahren," Tribologie + Schmierungstechnik, No. 3, 1992, p p . draulikfliissigkeiten—Umstellungsrichtlinien, Beuth Verlag,
103-110. Berlin, 1994.
[23] Kempermann, C. and Remmelmann, A., Umweltschonende Hy- [38] Bundes Imimissionsschutz-Gesetz, Law of the Federal Republic
draulikflussigkeiten, o +p. No. 1, 1996, pp. 67-73. of Germany, 1998.
[24] Mang, T., "Schmierstoffe u n d Druckiibertragungsmedien im [39] AbschluySbericht zum Forschungsvorhaben, "Synthetische Es-
Maschinenbau," Umdruck zur Vorlesung, RWTH, Aachen, Ger- ter," VDMA, Frankfurt, Germany, 1997.
many, 1998. [40] KBwS: Bewertungsmuster zur Stoffeinstufung in Wasserge-
[25] Murrenhoff, H., "Grundlagen der Fluidtechnik, Teil 1 Hy- fahrdungsklassen im Sinne von § 19 Wasserhaushaltsgesetz;
draulik," Umdruck zur Vorlesung, RWTH, Aachen, Germany, Chemiereport VCI, 1989.
1998. [41] OECD: Guidelines for Testing of Chemicals; OECD 203, OECD
[26] Murrenhoff, H. and R e m m e l m a n n , A., "Environmentally 401, Organization for Economic and Co-operation and Devel-
Friendly Pressure Media Based on Synthetic Esters—New opment, Paris 1981 (adopted 1983, 1984, 1986, 1987, 1989 und
Changes for Mobile Hydraulics," SAE International Paper 1992).
98185, Presented at t h e Earthmoving Industry Conference, [42] DIN 38412 T 8: Testverfahren mit Wasserorganismen L8,
Peoria, IL, 1998, Society of Automotive Engineers, Warren- Beuth-Verlag, Berlin, 1993.
dale, PA. [43] ISO/DIS 10708: Water Quality—Evaluation in an Aqueous
[27] Paetzold, P., Einfiihrung in die Allgemeine Chemie, 2, Auflage Medium of the "Ultimate" Aerobic Biodegradability of Orgsinic
Friedrich Vieweg & Sohn, Braunschweig, Wiesbaden, Germany, Bonds—Method by Determining the Biochemical Oxygen De-
1988. mand (two-phase closed bottle test). International Organization
[28] Schmitt, H.-G., "Komplexester aus Pflanzlichen Olen," Tribolo- for Standardization, Geneva, 1995.
gie -h Schmierungstechnik, No. 1, 1994, pp. 38-43. [44] CEC L-33-A-93: Biodegradability of Two-Stroke Cycle Outboard
[29] Schiilert, G., Bernhard, U., Ude, G., a n d Geiger, G., "Al- Engine Oils in Water; Commission for Environmental Coopera-
terungsverhalten von Umweltschonenden Hydraulikfliis- tion, 1995.
sigkeiten," Okologische und Okonomische Aspekte der Tribologie [45] DIN 51828-2: B e s t i m m u n g der Schnellen Biologischen Ab-
Band 1, Technische Akademie Esslingen, Ostfildern, Germany, baubarkeit—Infrarotspektrometrisches Verfahren; Gelbdruck,
1994. Beuth-Verlag, Berlin, 1995.
[30] Schwetlick, K. U. A., Organikum, 20, Auflage, Johann Ambro- [46] UUmanns Enzyklopddie der Technischen Chemie, Vol. 11, Au-
sius Barth Verlag Heidelberg, Leipzig, Germany, 1996. flage Verlag Chemie, Weinheim, Germany, 1976.
MNL37-EB/Jun. 2003
Turbine Lubricating Oils and

Hydraulic Fluids
W. David Phillips^
T H E POWER GENERATION INDUSTRY IS CURRENTLY UNDERGOING back or outsourced. Operators are trying to extend the time
the most radical changes it has seen in its relatively short his- between overhauls and are therefore seeking longer compo-
tory. The very conservative, slow moving industry dominated nent lives. This review of turbine oils and fluids is therefore
by state utilities has, in the last ten years, seen a major tran- set against a background of significant technological change.
sition for both political and commercial reasons. Many areas Perhaps, not surprisingly, the same pressures that are chang-
of what used to be a highly regulated market have become ing the commercial landscape are also driving developments
very competitive with the privatization of large, government- in lubricant and hydraulic fluid technology.
owned power generators and a developing global energy mar-
ket [1,2].
With the break-up of the state monopolies, smaller, inde- TURBINE TYPES
pendent power producers have appeared seeking to install
plant at the lowest cost and to make a rapid return on their The source of the kinetic energy for conversion into power
investment [3]. At the same time, intense competition in the depends on the turbine type. In a steam turbine it is the
turbine industry has resulted in the development of equip- rapid expansion of high-pressure steam, and in a gas tur-
ment with substantially increased efficiency as the partici- bine, the expansion of fuel combustion products. With wind
pants seek to increase their meirket share. emd water turbines, the movement of a mass of air, or wa-
On the political front, apart from the decision to deregulate ter under pressure, is the energy source. To convert the ro-
the power industry, there has been environmental pressure to tational energy into a more useful form of power, turbines
halt the construction of, and even replace, nuclear power sta- are coupled to alternators for electricity generation or to a
tions and to reduce the effect of emissions on global warming pump, compressor, or fan when used as a mechanical drive
by switching from coal and oil to gas and 'green' energy such [8]. Depending on the speed of the turbine rotation it may
as wind power. In Europe, safety of machinery legislation [4] be necessary to introduce a reduction gear between the tur-
has been introduced which, although not specifically di- bine and driven equipment for steam, industrial gas, and
rected at the p o w e r industry, nevertheless imposes con- wind turbines.
straints upon it. Aero-engine gas turbines are not directly coupled to other
As might be expected, such changes, while determining the equipment, but instead the energy of the expanding gases is
commercial shape of the industry well into the next century, used to provide forward motion, as in aviation usage, or to
also have a major impact on its technical requirements. For drive a second turbine wheel, sometimes called a power tur-
example, increased competition has driven improvements in bine, which is independent of the power source and attached
equipment efficiency. This, in turn, has resulted in turbines to an alternator or compressor.
operating at ever higher temperatures [5]. According to one To summarize, turbines are manufactured in a wide vari-
report, for each increase of 100°F in firing temperatures of ety of sizes and for several different applications as follows:
gas turbines, the output is increased by 10-13% with a gain • For power generation, where they may drive a generator,
of 2-4% in simple cycle efficiency [6]. This has the effect of either directly or indirectly via a gearbox.
placing greater thermal stress on the system components— • As a direct mechanical drive for p u m p s and compressors.
including the lubricant—and an adverse impact on operating • As gas generators for propulsion (in the aircraft industry),
life. Such pressures have forced the steam turbine builders to or when used with an independent power turbine, for driv-
consider technology previously used only in aero-derivative
ing p u m p s and compressors.
gas turbines, w h i c h operate at the highest t e m p e r a t u r e s
found in the industry [7].
At the same time commercial pressures on the utilities to Steam Turbines
lower operating costs have resulted in a reduction of person- Steam turbines are currently manufactured in the following
nel (some units are now operating with a third of staff origi- approximate ranges:
nally employed). Where possible, maintenance has been cut
• Small (0.5-80 MW) units, which are used for mechanical
drive and industrial power applications. As these turbines
normally operate at high speed (2800-16000 rpm), they are
' Marketing and Technical Manager, Great Lakes Cliemical Cor-
poration, Performance Additives and Fluids, Tenax Road, Trafford used together with reduction gears and, for power genera-
Park, Manchester M17 IWT, England. tion, with air-cooled generators or alternators.
297

• Medium size units (100-300 MW) with rotor speeds of ibility of operation unless a clutch is used between the
1500-3600 rpm directly driving air/water-cooled genera- steam turbine and the generator. In this development a
tors. common lubrication system for all components may be
• Large sets of up to 1500 MW, also with direct drive and used which means that the oil has to withstand the ex-
normally used with hydrogen-cooled generators. These are tremes of operation required by the individual pieces of
favored by the large utilities for base-load power—particu- equipment, that is wet operation in the steam turbine and
larly for nuclear operations. high temperatures in the combustion turbine. A typical lu-
bricating oil system for a single shaft CCGT unit is shown
schematically in Fig. 1.
Gas Turbines
In the past gas turbines were so-called because of their sole Water Turbines
use of gas as a fuel, but developments in design now enable
"gas" turbines to operate on volatile liquid fuels such as Water or hydro-turbines are available in several different de-
kerosene or naphtha. They are perhaps more correctly, and signs, such as the Francis or Kaplan turbines, and selection
less confusingly, known as combustion turbines, but for the of the most appropriate design depends largely on the avail-
purposes of this chapter will be referred to as gas turbines. able head of water. A fixed blade propeller (Francis) or a vari-
Gas turbines can be also be subdivided into three cate- able pitch propeller (Kaplan) uses the hydrostatic head to
gories: drive a generator. For high heads (e.g., of 30-300 m) the
• Micro-turbines of 25-300 kW output, which are currently Francis turbine is preferred while for heads of 15-30 m the
of current interest to the automotive industry, in small Kaplan design is normally used.
power generation packs and as a mechanical drive [9]. The power output for water turbines is almost as wide as
• Industrial (heavy duty) units of 5-300 MW used for power for steam turbines with a current range of about 1-800 MW.
generation either in simple cycle or combined cycle opera- The function of the turbine oil system is to lubricate the bear-
tion (see below) and driving all designs of alternators either ings of the turbine and the generator, which normally sits
via a reduction gear, as is the case with small units up to above the turbine on the same shaft. A forced lubrication sys-
about 70 MW output, or directly for larger sets. Small in- tem can be used with the main oil pump driven from the ro-
dustrial sets up to 15 MW are also used for mechanical tor shaft. In such cases an auxiliary pump is necessary to pro-
drive applications, e.g., gas pumping. vide adequate oil pressure during start-up and shutdown. An
• Aero-gas turbines with outputs of 2000-6000 lb thrust alternative technique is self-lubrication by the suitable design
(turbo-propeller types) and 11000-110000 lb thrust (turbo- of the bearing pads and pad supports.^
fan and turbojet types) for aviation applications. In indus- Oil pressures vary between 2-10 bar and the lubrication
trial and marine applications a reduced range of engines is system capacities vary from 1-10 m^ for turbines of 10-300
used and their power output is slightly lower (13-51 MW) MW.
than when used in aviation applications. The non-aviation In addition to the lubrication system, there is a hydraulic
uses require, of course, an independent power turbine to circuit for operating the governor and inlet valve system. In
convert the energy generated by the combustion gases into the past the same oil was used for both the hydraulics and
power or for use as a mechanical drive. bearing lubrication with hydraulic pressures of 20-25 bar.
However, pressures in the hydraulic system have increased
When gas turbines are used alone for power generation or
over the years to their current levels of 100-160 bar with a
for the production of both heat and power (combined heat
consequent reduction in system volume from about 3-4 m^ to
and power—CHP—or co-generation applications [6,10]),
0.8-1.5 m^. Today, where hydraulic pressures are >60 bar,
they are said to be used in 'simple' cycle operations with op-
separate hydraulic and lubrication systems are used.
erating efficiencies of 35-50%. A demand for higher effi-
ciency has resulted in combining the operation of gas and Where the design involves separate systems, conventional
steam turbines in what are known variously as combined turbine oils of ISO viscosity grades (VG) 32-68 are used for
cycle units (CCGT) or "steam and gas" (STAG) or, in Ger- bearing lubrication and hydraulic oils of ISO VGs 32 and 46
many, as Gas und Dampf ("GuD"). In this application the for the hydraulic system-except for low temperature envi-
waste heat from the gas turbine is used to raise steam for ronments where oils of ISO VGs 10 and 22 may be used in
the steam turbine via a heat recovery steam generator the gate hydraulic control. (ISO Standard 3448 or ASTM D
thereby raising the overall efficiency of the process to 2422, Standard Classification of Industrial Fluid Lubricants
50-60% [11-13]. This is currently the most popular method by Viscosity System, classify industrial lubricants by viscos-
of installing new utility or independent power production ity grade. The grade number corresponds to the mid-point
(IPP) capacity—providing there is a source of gas available. of a viscosity range extending to ±10 % of the mid-point
As the investment required is lower than for a single steam value and is measured in centistokes at 40°C.) Bulk oil tem-
turbine of the same total output and installation more peratures are in the range of 40-55°C for the lubrication
rapid, the financial return is faster. system. Under these conditions the stress levels in the sys-
tem are low and the oil normally lasts the life of the turbine.
The latest developments in this field have been to design
the steam, gas turbine and generator (possibly also a pump
or compressor) on a single shaft [14]. This has the advan-
tage of lower capital costs, a simpler design, and a layout ^ Private communication with H. Moeller, Elsam, Nordjyl-
with a smaller footprint. This is, however, at the cost of flex- landsvaerket, Denmark.
CHAPTER 12: TURBINE LUBRICATING OILS AND HYDRAULIC FLUIDS 299
AC main AC auxiliary DC emergency Oil

iube oil lube oil pump lube oil pump purifier
pump
FIG. 1—Lubricating oil system for a single-shaft combined-cycle turbo generator.
Removal of excess water by centrifuge takes place every six Problems initially arose with the use of conventional tur-
months. bine oils in t e r m s of reduced oil life, deposit formation,
micro-pitting and bearing failure and led to the use of poly-
alphaolefin (PAO)-based oils owing to their better high tem-
Wind Turbines
perature stability. In spite of this the average life of the gear-
Wind turbines are a relatively recent development in which box oil in the small units was still only about 1-2 ycctrs. The
the rotation of a propeller is coupled to a generator either di- oil life has increased since temperatures were reduced to
rectly or via a gearbox. The power output currently varies ac- <70°C but the problems of micro-pitting smd bearing failures
cording to location. Typically, land turbines have an output have not yet been totally eliminated. However, all new gear
of 300-1000 kW while offshore turbines are larger with a ca- oils for this application are required to pass an FZG micro-
pacity of u p to 2-3 MW [15]. Units of 5 MW output are cur- pitting test (FVA test 54/I-IV, Test Procedure for the investi-
rently under development [16]. gation of the Micro-Pitting Capacity of Gear Lubricants).
Two basic types of propeller design are in use: those with a Higher viscosity products (ISO VG 320) are also used in an
horizontal axis (otherwise k n o w n as p i t c h turbines) a n d attempt to further minimize the problems. Even with these
those with a vertical axis (stall turbines). The former type changes, the current oil life expectations are, as yet, only 3-5
uses one (or even two) gearbox(es) [17] and a generator. The years. With additional research on the effects of oil cleanli-
gearbox is oil lubricated while the roller bearings of the gen- ness, moisture, and metal contamination, further improve-
erator are grease lubricated. A separate hydraulic system ments are thought possible.'^
containing a conventional ISO VG 46 hydraulic oil (40-60 L As well as the operating problems mentioned above, other
capacity with a pressure of about 60 bar) for altering the factors have to be taken into consideration during operation,
pitch of the propeller may also be included. Some designs for example the inaccessibility of the equipment in the event
have demonstrated it is possible to avoid the use of a gearbox, of a failure (especially if located offshore). Power generation
and with these the propeller directly drives a multi-pole gen- without producing carbon dioxide can also have a higher
erator. profit margin, so downtime losses/MW output are also higher
The early gearboxes on machines of < 5 00 kW had a capac- for this tjrpe of equipment.
ity of about 125 L and relied on splash lubrication with a n As well as the gearbox, almost all wind turbines have a
ISO VG 220 gear oil at temperatures of 80-90°C. For turbines small hydraulically operated braking system of 2-4 L capac-
with an output of >500 kW, forced lubrication systems are ity and working at about 100 bar pressure. Since conven-
used a n d system capacities for the larger machines have tional turbine oils are not used in wind turbines there will be
since risen to about 200 L. n o further discussion of this application.
THE FUNCTION OF THE LUBRICATING OIL oil systems is essentially the same across the range of turbine
AND HYDRAULIC FLUID types. With the exception of totcil loss systems in some mili-
tary aviation applications, the lubrication systems are closed
The primary function of the turbine oil is to lubricate the tur- circuits involving a reservoir, a pump train with main, auxil-
bine and generator bearings. However, it may also fulfill the iary, and emergency pumps, filters, a cooler and possibly a
following secondary functions: centrifuge or purifier (on a bypass to the oil tank) to remove
• Acting as a hydraulic fluid in steam/gas valve operation and excess water and dirt. The oil is supplied under a slight pres-
in the jacking systems for the rotor shaft and gear wheel sure to the bearings. Fig. 2 shows, in diagrammatic form, the
• Lubricating the reduction gear (if used) supply of lubricating oil to a steam turbine generator. In high
• Lubricating the exciter bearings pressure hydraulic systems there may additionally be accu-
• Acting as a shaft seal for hydrogen-cooled generators mulators to "store" the higher pressure until it is needed for
• Lubricating the coupling between the turbine and the al- valve displacement. When using fire-resistant hydraulic flu-
ids, the oil purifier's prime function is to remove acid that
ternator
would otherwise catalyze further degradation of the fluid.
In addition, the oil acts as a coolant for the lubricated sur-
faces, minimizes friction and wear; removes any wear parti- Where mineral oil is used, which is still the most common
cles to the filters, and protects the system from rust and cor- situation, lubricating and hydraulic oil systems are nor-
mally combined with lubricating oil system supply pres-
rosion.
sures at about 3-4 bar and a pressure at the bearing inlet of
The hydraulic control or governor oil system controls the
about 1-2 bar. Hydraulic pressures are somewhat higher at
rate at which steam is admitted to the turbine cylinders eind
7-20 bar and both the hydraulic system and lubricating oil
hence the turbine rotational speed. The hydraulic fluid is also
for the turbine, gearbox (if used), and generator are fed
used to operate emergency stop valves. from the same tank. Exceptionally, there are separate hy-
draulic systems containing mineral oil where the pressure is
THE OPERATING ENVIRONMENT FOR high at 160 bar.
LUBRICATING AND HYDRAULIC OILS In modern large turbines, with steam temperatures now
reaching 600°C, the presence of mineral oil in the hydraulic
Although the equipment varies considerably in its size and system presents a major fire hazard. The escape of mineral
complexity, the basic design of the hydraulic and lubricating oil and contact with steam pipes in the vicinity of the control
- EXCITER
ELECTHIC GENERATOR AND
B" LOW PRESSURE TURBINE
" A ' X O W PRESSURE TURBINE
HIGH PRESSURE AND

REHEAT TURBINE
MAIN SHAFT OIL PUMP
GRAVITY
DRAIN AND
GUARD PIPE
PRESSURIZED
OIL PIPES
OIL VAPOR EXTRACTOR
OIL RETURN
SCREENS
OIL
COOLERS
OIL RESERVOIR AND

OILE.IECTORS
FIG. 2—Shaft driven lubrication system of a steam turbine generator. Reproduced by permission of the Electric Power
Research Institute, Palo Alta, CA.
Fluid returns
> (Eh '^—-r 4x}
©-|J_yent
z
Fluid conditioning
^M-
t Cooling water> llling using

loling pump
C( Dllng water
-M- Emptying>
illing using
^ s n ianual pump
FIG. 3—Typical steam turbine control fluid system.
valves has caused many turbine fires [18,19]. As a result the creased safety and reduced downtime since 1958 and they are
industry, as long ago as the mid-1950s, introduced the con- now widely used in this application in North America [22]. In
cept of a separate hydraulic system containing a fire-resistant the 1970s they were introduced for use in the control and lu-
fluid [20]. Although there are alternative ways of reducing the brication systems of 70 MW sets for power generation [23]. A
fire hazard, e.g., by providing pipe-in pipe systems, fire-resis- t5rpical lubrication system for an industrial gas turbine is
tant hydraulic fluids are now widely used in electro-hydraulic shown diagrammatically in Fig. 4.
governor control and emergency stop-valve systems. In order Aero-derivative gas turbines were introduced during the
to reduce the volume of fluid used and the capital cost of a Second World Weir and, while mineral oils were initially used
separate system, the pressures in these circuits are normally for lubrication, it was soon realized that both the low tem-
m u c h higher than when oil is used. Currently 160 bar is the perature properties and the high temperature stability of the
m a x i m u m found, but an increase to 200 b a r is being consid- oils then available were inadequate for the more powerful en-
ered. A typiccJ hydraulic control circuit diagram is shown in gines that were being developed. Synthetic ester fluids were
Fig. 3. therefore introduced a n d have remained the most widely
Fire-resistant hydraulic fluids based on triaryl phosphates used type of fluid in this equipment for both aviation and in-
are now used in over 1000 large steam turbines worldwide. dustrial applications where they function as a combined hy-
More recently the same fluids have been developed for use as draulic fluid and lubricant for the turbine [24]. Mineral oils
a combined hydraulic fluid and main bearing lubricant for are still used in some of the older or smaller aero-engines for
both small and large steam turbines u p to 1000 MW and the military aviation, and in industrial applications where the
operating experience obtained since the early 1980s has thermal/oxidative stresses are lower.
shown them to be highly successful in this application [21]. Where aero-derivative units are used for mechanical drive
Although most industrial gas turbines use mineral oil or applications, the hot exhaust gases drive a power turbine that
synthetic hydrocarbons as the hydraulic fluid and lubricant is attached to a compressor or a gearbox/generator, etc. In
in a single system, there are applications where fire-resistant this application, a synthetic ester product lubricates the en-
hydraulic fluids are used in a separate system (in medium- gine, while the power turbine and the "driven" equipment are
large sized units) or as the operating media for both hy- normally lubricated with mineral oil in a separate system.
draulic and lubrication systems. As an example of the latter, When used for pumping natural gas, the power turbine cind
their use in gas pipeline turbo-compressors has provided in- compressor Eire often lubricated with a fire-resistant fluid.
IEGBO):
A Mr
A
A mm
• H MSuwIlF
DfMn
^ ->
Q ^ Q
)f>RESSUnE
'TRANSMITTEfl
TgwlflCSTiKfOMAt
FIG. 4—Typical lubrication system for an Industrial gas turbine. Reproduced with per-
misson of Solar Turbines, Inc., San Diego, CA.
There has also been some limited use of fire-resistant fluids The system design determines the degree of thermal and
in the hydraulic systems of aero-derivative gas turbines, but oxidative stress to which the fluid or oil is subjected. In most
as yet there is no significant experience with these fluids as turbines the thermal loading on the lubricant Eirises through
lubricants for this equipment. heat conducted along the rotor to the bearings (shaft tem-
The severity of lubricating oil service (and hence operating peratures in large steam turbines can reach 320°C at the
life) varies considerably and depends on a number of factors bearings), as a result of the heat generated through frictional
including: and viscous losses in the bearings, and during compression in
• System design the pumps.
• The duty cycle, for example continuous or intermittent op- Additionally, in gas turbines, Icirge quantities of sealing air
eration at temperatures of 200-350°C [26] are drawn into the bearing
• Oil stability and form an aerated mixture with the lubricating oil as it
• The quality of system maintenance drains back to the tank—an ideal environment for promoting
• The quality of oil or fluid maintenance oxidation and foaming. The inlet temperatures of industrial
• Top-up rates. gas turbines have risen over the years from around 700°C in
1950 to 1500°C in 1998 [27,28], as shown in Fig. 5 [28], while bine oil lives, particularly for gas turbines, are now giving
compressed air temperatures have also increased with the cause for concern.
trend toward higher compression ratios. Together this would Since the thermal/oxidative stress on the oil or fluid is a
suggest a significant increase in the heat being dissipated via factor of temperature, time and the extent of air contact, the
the engine structure. Certainly gas turbine bearings are now faster the oil temperature (and the air content) can be re-
operating at high stress levels. For example, temperatures of duced, the lower the amount of resulting fluid degradation. A
up to about 115°C are found for plain bearings and up to cooler in the return line is therefore preferred. The presence
about 300°C for roller beeirings. The various sources of heat of air depends to a large extent on tank design (including the
and its removal for a t5rpical gas turbine bearing are shown in location of return lines, baffles, and sieves to remove en-
Fig. 6. trained air), but it also depends on fluid circulation rates, the
Unfortunately, although the heat input at the bearings has level of fluid/oil in the tank, etc., Guidance on the basic sys-
steadily increased, the volume of fluid available for heat re- tem design parameters of turbine lubricating oil systems (in-
moval has not. If anything, oil volumes have been reduced as cluding the use of suitable materials of construction; design
a consequence of reducing the size and therefore the cost of features of the reservoir and pump train; the appropriate use
the system. This has been achieved by increasing circulation and location of coolers, valves and filters, etc.) is available for
rates (with an adverse effect on aeration) and, where possi- steam and industrial gas turbines when using conventional
ble, by more effective cooling. In most cases however, the re- turbine lubricating oil. This appears in such standards as
sult has been an increase in oil return line temperatures, in ASTM D 4241, Standard Practice for the Design of Gas Tur-
the case of recent estimates for steam turbines, by 10-15°C bine Generator Lubricating Oil Systems, ASTM D 4248, Stan-
[29]. As oxidation rates approximately double with every ten dard Practice for Design of Steam Turbine Generator Oil Sys-
tems, and the American Petroleum Institute (API) Standard
degrees rise in temperature, it is hardly surprising that tur-
1940 1950 1960 1970 1980 1990 2000

Year
FIG. 5—Development of gas turbine capacity, inlet/outlet temperature
and efficiency. Reproduced by permission of Verelnigung der
Grosskraftwerk Betreiber, Essen, Germany.
614, Lubrication, Shail-Sealing, and Control-Oil Systems for industrieJ gas turbines with some mineral oil types, top-up
Special-Purpose Applications, b u t is t h e n sometimes ig- rates can rise to as high as 3 3 % per year while aero-engines
nored. In fact, tank residence times have decreased in recent in aviation consume on average about 0.25 L per hour or a
years in the pursuit of lower costs, making it more difficult complete replacement charge in about 24-130 h of engine op-
for the air to be released and with an adverse effect on oxida- eration. In industrial operation the c o n s u m p t i o n may be
tive stability [29]. lower due to the fitting of more efficient oil demisters.
The duty cycle is important where the turbine experiences In the past, an oil change normally took place when equip-
frequent stops and starts or where the unit is used at maxi- ment builders' recommendations on used fluid performance
m u m power for only a short period, as in aviation applica- were exceeded. These would normally include limits on acid-
tions. If aircraft gas turbine oils were continually subjected to ity, water, viscosity increase, and dirt levels. When these val-
the same stress as found on take-off, the oil life would be sub- ues were reached or exceeded, the oil or fluid was considered
stantially reduced. By contrast, the long periods of continu- too degraded or contaminated for continued use. Today, fil-
ous operation in base-load thermal or nuclear power genera- tration techniques are available which can readily reduce the
tion are less demanding. The stability of the oil or fluid will levels of some contaminants, e.g., water and particulates.
obviously play an important peirt in determining its operating This improvement, together with the possibility of monitor-
life and may help identify the most appropriate type of prod- ing the depletion of additives and then re-inhibiting when
uct for the application. necessary, makes it possible to extend life substantially in
Depending on the quality of fluid maintenance (which is some applications.
discussed in more detail later) and also system maintenance, The volume of oil used in t u r b i n e lubrication systems
for example minimizing air and water leeiks into the oil, the varies considerably. While a figure of 270 L per MW used to
life of the lubricant can be extended considerably. The im- be quoted as typical, steam turbine lubrication systems today
portance of reguleir, planned, maintenance cannot be over- contain in the region of 1 0 0 ^ 0 0 L per Megawatt for turbines
emphasized in the pursuit of trouble-free operation. of <200 MW and from about 50-80 L per Megawatt for sets
Lastly, top-up rates will determine the rate at which new in the range 250-1500 MW. There is considerable variation as
fluids, and therefore additives, are replenished. Normally, the builders frequently use one size of tank for a range of tur-
top-up rates are fairly lo\? for steam turbines (about 3-10% bine outputs and the configuration of the unit, i.e., the type
per year), but much higher veJues have been reported in the of driven equipment, will also influence the volume required.
past (up to 27%) and the beneficial effects of such high top- Such large volumes of oil are used to provide adequate
u p rates in extending oil life have been investigated [30]. In time for the release of air from the bulk liquid in the tank.
Heat from shaft/bearing housing

(power output/duty cycle)
Lube oil inlet temperature

i Heat from seal air
(on external housing
and internally into bearing)
- compression ratio
- take-off point in compressor
Lube oil vapour/air to Lube oil outlet temperature

secondary breather
i
hot air to drain
- flow rate
- thermal conduction
- specific heat
- density
Heat transferred along
shaft or via housing
FIG. 6—Heat input and removal for a gas turbine bearing.

TABLE 1—Typical operating conditions for turbine lubricating oils.

Turbine Type
Medium-Large Aeroderivative-Gas
Medium-Large Steam Small Industrial Gas Industrial Gas Aviation Industrial Marine
System Property (250-1500 MW) (1-14 MW) (30-300 MW) (11 000-110 000 lb. thrust) (31 MW) (4MW)
Lube system capacity (m^.) 19-115 1-3 15-34 0.006-0.02 0.9 0.11
Circulation rate (changes/hour) 5.5-10 17-21 6-10 60-240 5 60
Bulk e u i d temp. (°C) 60-65 50-70" 45-80" 60-70 ISO"" 70
Bearing oil return temp. (°C). 70 60-115 55-85 120-130 150-180 150
''The bulk fluid temperature In the tank may be similar to bearing return oil temperature if the cooler is placed on the pressure side of the pump. In this case
the bearing oil supply temperature will be significantly lower than that in the tank.
Much smaller volumes and higher circulation rates are found replaced by fire-resistant fluids based on triaryl phosphates
in small industricd and aero-derivative gas turbines (Table 1) in order to avoid fires arising from oil escaping at high pres-
because of restrictions on space and weight. sure and coming into contact with steam pipes.
The volume of hydraulic fluid in steam turbines similarly The following is a brief summary of the basestock types
varies from about 1 m^ to 20 m^ depending on system design and additives currently in use and their advantages/disad-
and pressure and is substantially smaller in gas turbines. With vantages. A more detailed account of the different oil types
the emphasis on reducing costs, the size and volume of hy- used in hydraulic fluids and their properties, which is also
draulic systems have been steadily decreasing, but at the ex- largely applicable to turbine oils, is available from other ref-
pense of increasing pressure. Today, system pressures range erences [33].
from 40-160 bar, but are starting to increase to 200 bar.
Some of the operating conditions under which lubricating
oil is used in the different tjqjes of equipment are given in BASESTOCKS
Table 1. The data given is representative of the major appli-
cations and equipment but cannot possibly encompass all the Hydrocarbon Oils
equipment variations currently available. However, with re- Petroleum oils are complex mixtures of many different chem-
spect to the impact of these conditions on fluid life, the fol- icals and their relative amounts vary considerably from one
lowing generalizations can be made: crude source to another. The components do, however, fall
• For steam turbines, the life of mineral oil and synthetic hy- into a limited number of categories, principally straight- and
drocarbon ranges from 5-25 years (up to the life of the tur- branched-chain saturated hydrocarbons (also known as
bine) while currently averaging about 12 years. paraffins), cyclic saturated hydrocarbons (also known as cy-
• For industricd gas turbines, the lives vary between 1.5-6 cloparaffins or naphthenes), and unsaturated cyclic hydro-
years, but for new generation combined cycle gas turbine carbons (otherwise known as aromatics), examples of which
(CCGT) applications, operating lives to date are in the region are shown in Fig. 7. Additionally, small amounts of impuri-
of about 4-5 years. In aviation gas turbines, the synthetic es- ties, consisting mainly of cyclic derivatives of nitrogen, sulfur
ter oil is continually made up and therefore the whole charge and oxygen, and polar materials such as naphthenic acids,
is not normally replaced. In industrial applications it may be may be present. Fig. 8 shows typical examples of such hete-
changed annually or after 8000 operating hours. rocyclic compounds.
• For both fire-resistant hydraulic fluids and lubricants the Each hydrocarbon component influences the properties of
latest data suggests lives of 5 years to more than 20 years base oil to an extent dependent on its concentration (Table 2
depending on the type of in situ conditioning or purifica- [34]). The above impurities are present in solvent-refined oil
tion used. in small quantities, typically 0.1-0.5 %, but occasionally in
much larger amounts, and they can also impact the perfor-
mance of the fluid particularly in terms of stability and lu-
TURBINE OIL TYPES AND THEIR brication. Much lower amounts of impurities, if any, are pre-
FORMULATION sent in the hydro treated oils.
The need to quantify the different components in lubricat-
While the turbine oil market used to be almost exclusively the ing oils has resulted in the development of several analj^tical
domain of solvent-refined paraffinic mineral oils, the chang- test procedures. Currently these include ASTM D 2425, Stan-
ing technical requirements have resulted in a move to other dard Test Method for Hydrocarbon T5rpes in Middle Distil-
types of lubricants, both hydrocarbon-based and sjrnthetic. lates by Mass Spectrometry; ASTM D 3238, Standard Test
For example, in industrial gas turbines and combined cycle Method for Calculation of Carbon Distribution and Struc-
units, the high operating temperatures have resulted in a re- tural Group Analysis of Petroleum Oils by the n-d-M Method;
duced life for products based on solvent-refined oils. Lives of and ASTM D 5443, Standard Test Method for Paraffin, Naph-
a "few thousand" hours for such oils in high stress situations thene, and Aromatic Hydrocarbon Type Analysis in
have been reported [31,32] and replacement by special "GT" Petroleum Distillates Through 200°C by Multi-Dimensional
oils—in reedity hydrocracked oils—increases the operating Gas Chromatography. While the D 3238 method is easiest to
life up to 50000 h [31]. apply, being based on refractive index, density and molecular
In turbines operating with high temperature steam weight, it is more restrictive in its application with limits on
(>500°C), mineral hydraulic oil has been almost completely the total ring content and the ratio of aromatics to naph-
Type Structure Viscosity index
n-paraffin \ / \ / ^ / ^ high
CH,
CH, CH, CH,
iso-paraffin CHo CH ^Ho high
naphthene moderate
aromatic low
FIG. 7—Typical hydrocarbon structures.
(High T e m p e r a t u r e Method); ASTM D 2622, Standard

^ - - ^ Test Method for Sulfur in Petroleum Products by X-Ray
Spectrometry; or ASTM D 4927, Standard Test Method for
Elemental Analysis of Lubricant and Additive Components—
Barium, Calcium, Phosphorus, Sulfur a n d Zinc by Wave-
length-Dispersive X-Ray Fluorescence Spectroscopy.
Dibenzothiophene In order to provide general guidance on the identification
and selection of lubricants, ASTM has issued D 6074, Stan-
dard Guide for Characterizing Hydrocarbon Lubricant Base
^"^^ Oils. This document recommends methods for analyzing the
composition of base oils, describes their important chemical
properties, and discusses the toxicological requirements, in-
cluding regulations covering the presence of undesirable
I components such as polynuclear aromatics.
H
Conventional Solvent-Refined Types

Pyrrole 1,7- phenanthrone
In order to produce oils that meet industry requirements it is
FIG. 8—Impurities typically present in solvent refined min- necessary to remove or substantially reduce the level of those
eral oils. components that adversely affect performance, and this has
been achieved by various refining techniques. As indicated
thenics. The levels of impurities such as nitrogen and sulfur above, the oil produced by the solvent refining of a crude
are not available from these tests and this information has to paraffinic basestock (Fig. 9 [34]) is still in major use for both
obtained from other procedures, e.g., ASTM D 3228, Stan- steam and industrial gas turbine applications. In this bases-
dard Test Method for Total Nitrogen in Lubricating Oils a n d tock, about 45-60% of hydrocarbons are in the form of satu-
Fuel Oils by Modified Kjeldahl Method and ASTM D 1552, rated straight- or branched-chain paraffins and monocyclo-
S t a n d a r d Test Method for Sulfur in Petroleum Products paraffins, but there is still a significant a m o u n t of
TABLE 2—Effect of composition on base stock properties.

Volatility
Viscosity Pour Point Response to (High = Poor,
Chemical Component Index (High/Low) Oxidative Stability Antioxidants Low = Good)
n-Paraffin Very High High Good Good Good
Iso-Paraffin High Low Good Good Good/average
Naphthene Low Low Average Good Average
Aromatic Low Low Average/poor Some poor Poor
Polar compounds Low Low S is antioxidant; N and O Poor Poor
are pro-oxidants
ReprintedfromHandbook for Hydraulic Fluid Technology, 2000, p. 716, courtesy of Marcel Dekker Inc., NY.
Atmospheric/vacuum Solvent extraction Dewaxing

distillation
Crude oil
Conventional
base oil
Gas oil
T i
Wax
Extract
FIG. 9—Solvent refining process. Reproduced with permission of Petro-Canada

Lubricants, Mississauga, Canada.
TABLE 3—Chemical composition of lubricant base oils.

Oil Reference A B C D E F G
API Category I I II II II III III
Solvent Solvent Severely Severely
Description Refined Refined Hydro-Cracked Hydro-Cracked Hydro-Cracked Hydro-Cracked Hydro-Cracked
Dewaxing Solvent Solvent Solvent Solvent Iso- Solvent Iso-
Mass Spec. Analysis
Paraffins, n- & iso- 25.7 29 23.7 21.6 30.2 32.6 76.1
Monocycloparaffins 20.8 25 30.8 32.8 30.5 34.2 14.7
Polycycloparaffins 27.9 31.7 39.1 37.6 35.3 32.9 9.2
Aromatics 24.9 14.2 6.4 8 4 0.6
Thiophenes 0.7 0.1 0.0 0.0 0.0
Paraffins -1- 46.5 54 54.5 54.4 60.7 66.7 90.8
Monocycloparaffins
Reprinted with permission of Petro-Canada, Mississauga, Canada
unsaturated ring structures (Table 3 [35]). The refining pro- TABLE 4—American Petroleum Institute classification
cess removes wax (mainly high molecular weight paraffinic of base-stocks.
compounds), most of the aromatic hydrocarbons, as well as Base Stock Sulphur, Saturates, Viscosity
Group (wt%) (wt.%) Index
some of the polar compounds containing oxygen and nitro-
gen, products that would otherwise have significantly re- Group I >0.03 and/or <90 80-120
duced the stability of the oil. However, small amounts of sul- Group II <0.03 and >90 80-120
Group III <0.03 and a90 >120
fur-containing c o m p o u n d s , e.g., thiophenes, r e m a i n and Group IV All Poly-Alphaolefins (PAOs)
these can be beneficial in terms of increasing the stability of Group V All Basestocks not included in Groups I-IV
the base.
These basestocks are classified as Group 1 products by the of the aromatic content and the residual impurities. Since the
API Classification of Base Oils according to their viscosity in- mid-1980s, therefore, oils produced by hydrotreating, hydro-
dex, sulfur content and the content of saturated hydrocar- cracking or hydro-refining processes, involving the reaction
bons (Table 4 [36]). of hydrogen with the feedstock in varying degrees of severity,
have resulted in the availability of much purer basestocks
(Table 3 [35]). Using the API Classification [36] these fall into
Hydrocracked/Hydrotreated Basestocks Group II (mildly hydrocracked) or Group III (severely hydro-
In view of the demand from industry for oils with better oxi- cracked or hydrotreated) depending on the low sulfur levels
dation stability, as operating conditions become more severe, and increasing viscosity indices (Table 4).
attention has turned to processes that can remove yet more In addition to the hydrogenation of the lubricant feedstock.
the process m a y also include hydro-isomerization of the This is, however, more than compensated for by better re-
straight-chain paraffinic components of the wax removed sponse to antioxidants when carefully selected [32,37]. The
during solvent refining or hydrotreating (Fig. 10) [37]. This loss of aromatics also results in reduced additive solvency ne-
process involves a molecular rearrangement and converts the cessitating a careful choice of stabilizers emd the continued
straight chain hydrocarbons to branched-chain or iso-paraf- presence of small amounts of aromatics may be beneficial in
fins that are then blended into the hydrotreated basestock to such cases [39]. The loss of sulfur also reduces the anti-
give better low temperature properties. wear/extreme-pressure properties of these oils although these
As a result of the different processes, a range of improved can easily be improved by incorporating suitable additives.
basestocks is currently available with which to formulate tur- These base materials vary in price from a level which is
bine oils. These are sometimes referred to as High Viscosity comparable to that of solvent refined stocks to about three
Index (HVI) oils, which are classified as Group II products; times their price, depending on material type a n d local avail-
Very High Viscosity Index (VHVI) oils (Group III); or Ultra ability. As a result of the favorable price/performance char-
Pure Base Oils (also Group III products). Levels of aromatics, acteristics it is likely that their use in conventional turbine oil
sulfur, etc., decrease significantly on moving from Group I to formulations will spread.
Group III products but significant variability in composition
still exists within these groups [35]. Group II products appear
currently favored for formulation purposes but with a slight Polyalphaolefins (PAOs)
trend towards Group III.
These synthetic fluids are normally m a n u f a c t u r e d by the
The technical advantages of the new basestocks [32,38] in- oligomerization of Eilpha-olefins, particularly a-decene, but
clude: also by a-octene and a-dodecene and, until recently, were
• Excellent oxidation stability when formulated available in a range of viscosities u p to the ISO 100 grade. The
• High thermeJ stability latest development [40] reports the availability of very high
• Very low deposit-forming tendency viscosity products ranging from 150-3000 cSt at 100°C and
• Improved demulsibility intended mainly as blending components for other hydrocar-
• Reduced volatility bon oils. They are currently more expensive than other hy-
• Very low toxicity drocarbon types.
• Environmentally "friendly" PAOs are free of aromatic hydrocarbons, sulphur, oxygen,
There are few technical disadvantages of these new bases- and nitrogen compounds, and show excellent response to an-
tocks but, depending on the level of hydrotreating, they m a y tioxidants [41], although they are now being challenged by
be less oxidatively stable compared with solvent-refined prod- some of the severely hydro-cracked oils [42]. They also have
ucts in view of the removal of small amounts of sulfur and aro- high viscosity indices (as assessed by ASTM D 2270, Stan-
matic compounds that act as naturally occurring stabilizers. dard Practice for Calculating Viscosity Index from Kinematic
H, H2
I Atmospheric/vacuum I
• distillation n«.,,„i„„ »
- >
Ultra pure
base oils
Crude Atmospheric/vacuum
oil distillation HTU2
"Wax
HTU = hydrotreatment unit Hydro

Isomerization
FIG. 10—Hydrotreatment plus hydroisomerizatlon process. Reprinted with permission

of Petro-Canada Lubricants, Misslssauga, Canada.
TABLE 5—A comparison of some physical properties of 6.0 cSt PAOs with solvent-refined and hydrocracked oils of similar viscosity.
160 240 200 Very High Viscosity
Parameter Test Method PAO Hydro-Treated Neutral Solvent Neutral Index Oils
API Group IV II I I III III
Viscosity, cSt ASTM
at 100°C D445 5.98 5.77 6.98 6.31 5.14 5.9
at 40°C 30.9 33.1 47.4 40.8 24.1
at - 4 0 ° C 7830 SoUd SoUd Solid Solid NA
Viscosity Index 143 116 103 102 149 127
Pour Point (°C) ASTM D 97 -64 -15 -12 -6 -15 -12
Flash Point (°C) ASTM D 92 235 220 235 212 230 225
Evaporation Loss DIN 51581 6.1 16.6 10.3 18.8 8.8 6
(NOACK), %
NOTE—Reprintedfrom:Synthetic Lubricants and High Performance Functional Fluids, 1992, p. 13, courtesy of Marcel Dekker Inc., NY.
Viscosity at 40°C and 100°C) and flash points (by ASTM D 92, TABLE 6—Âviation lubricant types currently
Standard Test Method for Flash and Fire Points by Cleveland commercially available.
Open Cup); very good low temperature viscosities (ASTM D Engine Type Engine Lubricant Composition
445, Standard Test Method for Kinematic Viscosity of Trans- Turbo-propeller Diester -I- Thickener
parent and Opaque Liquids) and p o u r points (ASTM D 97, Turbofan 'High' Viscosity Polyol Ester
Standard Test Method for Pour Points of Petroleum Prod- Turbojet 'Low-Medium' Viscosity Polyol Ester
ucts), and a wide operating temperature range [42]. A com-
parison of the physical properties of PAOs with other hydro-
TABLE 7—A comparison of minersil oil and
carbon products of the same viscosity is given in Table 5 [43]. carboxylateester properties.
In view of the lack of aromaticity, additive solubility can be Mineral Mineral
a problem. PAOs also have limited dispersency and do not Lubricant Oil Ester Oil Ester
penetrate rubber seals to cause swelling (as assessed by FED- Kinematic viscosity
STD-791, methods 3604 and 3633, or by ISO 6072). As aresult, (cSt)at210°F 2.5 3.3 20.1 7.5
it is necessary to blend PAOs with small a m o u n t s of a seal- -40°F 3000 1700 Solid 12 000
swelling agent (usually a carboxylate ester) to avoid leakage. -65°F 25 000 11000 Solid Solid
PAO-based gas turbine oils have been available for many Viscosity Index 75 154 95 150
years [39] where the higher prices could be justified in terms Pour Point ("F) <-75 -80 0 -65
Vapor Pressure
of smaller volume and better stability. They have not, as yet, (psi) at
m a d e a n y significant penetration of the steam turbine oil 250°F 0.15
market [41]. 350°F 1.3 <0.01
400°F 3.5 0.016 <0.01 <0.01
550°F 0.52 0.065 0.28
Synthetic Ester Fluids Ryder gear machine 600 2000 -3000 3200
failure load lb/in.
Apart from the very early days of operation, carboxylate or tooth face width
synthetic esters (possibly in c o m b i n a t i o n with polyglyco- Flash point 295 430 485 465
lether thickeners) have been the only products used for the (COC, ''F)
lubrication of aero-derivative gas turbines in aviation appli- NOTE—Reproduced with permission of Elsevier Science, Oxford, UK.
cations. This market, like the others, is fragmented into dif-
ferent applications, this time in terms of the lubricant re-
quirements of the turbopropeller, turbofan (civil) or turbojet
(principally military) engines (Table 6) and into the different 2ROH -1^ HOOC(CH2)nCOOH ROOC(CH2)nCOOR
technical requirements of civil and military aircraft opera- alcohol diacid diester
tion. The turbopropeller engine, for example, employs a re- where, for aircraft turbine oils, n = 7-8 and R = Cs-g straight
duction gear to accommodate the propeller. This necessitates or branched chain
the use of a higher viscosity fluid to provide a thicker lubri- The resulting diesters have a viscosity of about 3 ^ . 5 cSt at
cating oil film with the ability to reduce wear at heavy loads. 100°C (ASTM D 445). In comparison with a well-refined min-
At the other end of the spectrum, the military requirement to eral oil these products have a similar thermal and oxidative
start an engine quickly at low temperatures requires the use stability, better load-carrying performance, lower volatility
of "lower" viscosity oils for turbojet engines. As a result, spec- (ASTM D 972, Standard Test Method for Evaporation Loss of
ifications for these oils currently cover four viscosity levels: 3, Lubricating Oils and Greases) and a m u c h wider operating
4, 5, and 7.5 cSt at 100°C. temperature range (see Table 7 [45]). They are also very re-
Diesters, the lowest viscosity oils used in this application, sponsive to the addition of antioxidants. They do, however,
were introduced after the World War II, initially for military slowly hydrolyze in the presence of water and, like most es-
applications. They were also used for the early commercial ters, are not compatible with n e o p r e n e seals, w h i c h are
turbo-jets and in blends with polyglycolethers, for turbopro- widely used with mineral oil.
peller aircraft [24,26]. Diesters are produced by the reaction The introduction of more highly-powered engines operat-
of an alcohol and an acid [44], viz ing at higher temperatures and the requirement in com-
mercial applications for extended drain intervals necessi- as fire-resistant fluids they contain a polymeric thickener
tated the development of more stable products, and the so- (also known as a viscosity-index improver), which increases
called "polyol" or "hindered" esters were introduced at the the droplet size in a spray. This reduces the surface area ac-
beginning of the 1960s [24]. These esters, based on the re- cessible to oxygen and renders the fluid more difficult to ig-
action products of neopentylglycol, trimethylolpropane, or nite under spray test conditions (combustion is an oxidation
pentaerythritol with monobasic acids as shown in the reac- process). However, as the polymer breaks down due to the
tion scheme below, have thermal degradation temperatures shearing action in p u m p s and gears, this advantage is lost
about 40°C higher than the diesters and are more oxida- and the viscosity (and hence fire-resistance) tends toward
tively stable [46]. They have since been the basis for all com- that of the basestock. This temporary improvement in fire-re-
mercial engine lubricants and an increasing proportion of sistance is limited to spray flammability and has no impact
military requirements where low temperature limitations on the ignitability of the fluid under other hazard conditions,
permitted. e.g., when it contacts a hot surface [49]. This is therefore an
artificial approach which, to date, has been rejected by the
C2H5 major turbine builders for new large steam turbines, al-
I C2H5 though small amounts are used in industrial units and in re-
3RCOOH + HOH2C—C—CH2OH -^ I furbished equipment. A comparison of the fire resistance
I RCOOH2C —C—CH2OOCR properties of mineral oil, polyol esters, and phosphate esters
CH2OH I is given in Table 8.
CH2OOCR
monoacid trimethylopropane ester
Tiiaryl Phosphates
CH2OH
I CH2OOCR In common with the other two groups of fluids there are vari-
4RCOOH + HOH2C—C—CH2OH + I ations in the chemistry of triaryl phosphates that have led to
I RCOOH2C—C—CH2OOCR the commercial availability of different products. In this
CH2OH I case, however, it has been the past limitations on suitable
monoacid pentaerythritol CH2OOCR raw materials that has resulted in the diversity of products
ester available. Traditionally, phosphate esters were manufactured
from the distillation products of coal tar, which were mix-
where R = C5_^9 tures of cresols and xylenols and known collectively as "cre-
The continual pressure on equipment builders to increase sylic acids." The phosphate esters produced from these feed-
engine power in both military and civil applications has re- stocks were referred to as "natural" products and were chiefly
sulted in a need to periodically review and, where necessary, tricresyl and trixylyl phosphate (TCP/TXP). When natural gas
improve the stability (oxidative and thermal) and deposition became widely available, the distillation of coal tar rapidly
performance of these oils. New versions of specifications, nor- declined and attention turned to the production of phosphate
mally calling for improvements in these areas, have appeared esters from synthetic feedstocks, specifically those based on
at intervals of a few years, particularly in the military arena. alkylated phenols [50]. The reaction scheme for the manu-
That continual improvements in oil performance have been facture of triaryl phosphates, is given below:
possible is due to the skills of the formulators and the avail-
ability of more effective additives [47]. The impact of changes ArOH + POCls^ (ArOsPO + 3HC1
in additive and basestock composition on oil stability is
shown in Fig. 11 [48]. In the oxidation test from which the a phenol phosphorus a triaryl
data has been taken, the B^^'^ temperature is the temperature oxychloride phosphate
at which the insoluble content of the oil exceeds 0.5mg/g over The reaction of propylene or butylene with phenol pro-
an 8-day test period when the oil is oxidized in the absence of duces mixtures of alkylated phenols and these became the
metals, and is used as a measure of bulk oil stability. The data feedstocks for a range of "synthetic" phosphates with viscosi-
shows the initial performance level of diesters in the 1950s fol- ties falling into ISO VGs 22-100. Since their introduction, the
lowed by improvements to the stabilizer package; the devel- raw material supply position for the production of the "natu-
opment of more stable fluids (the hindered or polyol esters) rcil" fluids has eased with the introduction of synthetic pro-
followed by yet more additive developments. More informa- cesses for the production of cresols and xylenols. As a result
tion on the various additive t3ês in use and their function is the distinction between "natural" and "synthetic" phosphates
given in the following section. has become blurred but the terms are still used today to dis-
Long chain polyol esters have also been promoted as "less tinguish between TCP/TXP and the synthetic products based
flammable" hydraulic fluids for steam turbine control sys- on isopropylphenols and tertiarybutylphenols.
tems on account of their relatively high flash and fire points. Although manufactured to the same viscosity level, com-
The esters used in this application are normally reaction monly ISO VG 32 or 46, commercially available fluids do
products of trimethylolpropane and oleic acid (a C18 unsatu- have somewhat different levels of performance relative to one
rated monobasic acid) and in some respects, are significantly another as indicated in Table 9. Therefore, depending on the
different to the short-chain products used in aviation gas tur- requirements of the application, one type of phosphate may
bines oils. For example, they are far less stable due to the unbe preferred. For example, in steam turbines where contact
saturation (or the presence of double bonds) in the molecule with water is most likely, the phosphate that is most hy-
and their low temperature properties are inferior. When sold drolytically stable, trixylyl phosphate, may be preferred. In
CHAPTER 12: TURBINE LUBRICATING OILS AND HYDRA ULIC FLUIDS 311
Ester limit?
Additional additive effect
Additive effect
1950 1960 1970 1980 1990 2000
year
FIG. 11—Developments In the stability of gas turbine lubricants. Reprinted with permis-
sion of B. Rayner, consultant.
TABLE 8—Â comparison of the fire-resistance properties of mineral turbine oil, polyol ester, and phosphate ester fluids.
Mineral Oil Polyol Ester Phosphate Ester
Property Test Method ISO VG 46 ISO VG 68 ISO VG 46
Flash point-COC (°C) ASTM D 92 220 258 270
Fire point ( X ) ASTM D 92 245 316 350
Autoignition temperature (°C) ASTM D 2155 340 425 580
Hot manifold ignition (°C) AMS 3150C 350 430 >800
Wick ignition ISO 14935 Fail Fail Pass
Compression ignition MIL-PERF-19457D
-Ignition ratio 10 >42
Spray ignition
-Persistence of burning F.M. Std 6930 Fail Pass Pass
- S p r a y Flammability Parameter F.M. Std 6930 Group 3 (worst) Group 1-2 Group 1
-Persistence of burning ISO 15029-1 Fail Pass Pass
-Ignitability Parameter ISO 15029-2 Class H (worst) Class H Class D/E
TABLE 9—Impact of chemical composition on phosphate ester compares the principal physical properties of an ISO VG 46
performance. mineral turbine oil and triaryl phosphate ester.
Fire Oxidation Hydrolytic
Phosphate Type Resistance Stability StabiUty Air Release
Trixylyl Good Good Good- Excellent ADDITIVES AND THEIR EVALUATION
phosphate Excellent
Tritertiarybutyl Good Excellent Poor Moderate
phenyl Additives play an important part in improving the performance
phosphate of all the above fluid types, but no more so than with the avia-
Triisopropyl Moderate Moderate Moderate Moderate tion esters. As the composition of the aviation lubricant bases-
phenyl tocks has remained stable for many years, the improvements in
phosphate
performance have arisen principally as a result of develop-
ments in additive technology—particularly in oil stabilization.
In comparison, major improvements in hydrocarbon oil stabil-
ity have been due to improvements in refining techniques and
TABLE 10—Â comparison of some typical properties of an additive response rather than to breakthroughs in additive
ISO VG 46 mineral turbine oil and phosphate ester
hydraulic fluid/lubricant. technology. The move from Group I to Group III has, for ex-
Mineral ample, resulted in a substantial increase in oxidation stability
Phosphate
Property Test Method Oil Ester for the same level of antioxidant (Table 11 [52]).
Kinematic viscosity ASTM D 445 While some additives, for example stabilizers, can be of
(cSt) at benefit in phosphates, these fluids are also used uninhibited.
100°C 6.7 5 As will be seen later, in situ conditioning techniques are used
40''C 46 43 with phosphates to remove degradation products as they are
0°C 450 1700
formed and this can remove the need for stabilizers. How-
Pour point (°C) ASTM D 97 -9 -20
0.15 ever, corrosion and rust inhibitors are normally highly polar
Acid number ASTM D 664 0.05
(mg KOH/g) products that would be removed by the conditioning medium
Specific gravity ASTM D 1298 0.87 1.135 (tjîcally an activated clay) and therefore cU"e not usually rec-
(20/20°C) ommended. Fortunately phosphates, as polar materials, have
Air release (min) ASTM D 3427 3 1 some inherent rust preventative performance as they tend to
Foaming tendency/ ASTM D 892 250/0 30/0 be adsorbed on to the metal surface and there form a "bar-
stability at
24°C (ml) rier" to water. Some of the acidic degradation products are
Water content (%) ASTM D 1744 0.001 0.06 also effective inhibitors. As a result rusting of the system is
Rust preventing ASTM D 665 Pass Fail not normally a problem except where wetting of the surface
characteristics does not occur.
(distilled water)
Thermal conductivity 0.134 0.134 Phosphate esters are good lubricants and are widely used
(W/mK) as antiwear additives in hydrocarbon oils. It is therefore not
Specific heat at 20°C usually necessary to improve this aspect of the performance
(J/gK) 1.76 1.69 of fire-resistant fluids.
Typical additive packages designed to meet turbine lubri-
cating and hydraulic oil specifications, whether for hydro-
gas turbines, high oxidative stability is needed and hence a carbon or synthetic ester-based fluids, are less complicated
tertiarybutylphenyl phosphate could be selected. These latter than, for example, automotive engine oils and would contain
fluids are at least as oxidatively stable as the best hydrocar- a balanced mixture of antioxidants, metal passivators, rust,
b o n oils available and do not normally require antioxidants and corrosion inhibitors, anti-wear and/or extreme pressure
[27]. additives, and possibly an antifoam. These types and the var-
The m a i n reason for selecting phosphates is, of course, ious methods used for their evaluation in turbine oils and flu-
t h e i r fire resistance. While they are n o t completely non- ids are now considered in more detail.
flammable (most organic materials will ignite in the presence
of sufficient energy) they do require a substanticilly greater
Antioxidants
energy input for ignition than hydrocarbons and most other
non-aqueous fluids in commercial use, and they are self-ex- The actual mode of oxidative decomposition of both hydro-
tinguishing once they have moved away from the ignition carbon a n d synthetic oils is a complex process involving
source. Additionally they are excellent lubricants as demon- many different mechanisms a n d a variety of intermediate
strated in p u m p tests, e.g., ASTM D 2882, Standard Test products depending largely on the temperature and the struc-
Method for Indicating the Wear Characteristics of Petroleum ture of the substrate. Fig. 12 [52] is a model of lubricant
and Non-petroleum Hydraulic Fluids in a Constant Volume breakdown at high temperatures, concisely illustrating the
Vane Pump, and have very low volatility in the ASTM D 972 different processes involved.
test procedure. Viscosity/temperature properties are, how- Antioxidants are chemicals that extend the life of the fluid
ever, poor [51]; they have a significantly higher density than by interrupting the oxidation process, e.g., by decomposing
oil and require more power for circulation. As with all esters hydroperoxide intermediates (ROOH, where R is an alkyl
they are sensitive to moisture and require different seals and chain) and scavenging free radicals [52]. In the past the dom-
paints to those used with conventional turbine oils. Table 10 inant stabilizer type for hydrocarbons in both automotive
TABLE 11—Comparison of oxidation stability of turbine oils formulated with two different antioxidants
in a hydrotreated and solvent neutral base stock.
Test fluids
H O — / ( ^ V - R-S-R1 0.25% 0.25%
mw = 492
0.25% 0.25%
HO—/QV-CH3
Corrosion inhibitor 0.05% 0.05% 0.05% 0.05%

Mineral oil balance balance balance balance
Oxidation stability
TOST (ASTM D 943)
(95°C; water, Fe and Cu catalysts; 3 L air/hour)
- t i m e to total acid n u m b e r of 2.0 mg KOH/g oil 4300 2400 2200 1100
-sludge (mg) (ASTM D 4310) 6 39 28 47
Basestock characteristics hydrotreated solvent neutral
ISOVG 32 32
CA (aromatic hydrocarbon) % 0 6.5
Sulfur % 0 0.54
NOTE—Reprinted from: Chemistry and Technology of Lubricants, courtesy of Kluwer Academic Publishers, Dordrecht, The Netherlands.
volatile low molecular

weight hydrocarbons
- volatile low molecular

volatile weight oxidation products
hydrocarbon - carbon dioxide
fragmentsi - carbon monoxide
air (with/without metal)
polycondensation
polymerisation
(with/without metal)
high molecular
products
polycondensation
polymerisation
sludge
FIG. 12—Model of lubricant degradation under high temperature conditions. Reprinted

with permission of Kluwer Academic Publishers, The Netherlands.
and industrial oils has been a zinc dihydrocarbyl diphio- bine builders are therefore placing strict limits on the zinc
phosphate (Fig. 13). This is a multi-functional additive in that content of approved oils, and so-called "ashless" antioxidants
it also possesses antiwear/extreme pressure properties and are being used in their place. These are either hindered phe-
under certain conditions can provide protection against "yel- nols or aromatic amines (Fig. 13) that are used separately or
low" metal corrosion. Different types of zinc dialkyldithio- in combination [53].
phosphates (or diaryl) are available depending on the alcohol The antioxidant most widely used in turbine oils in the past
or phenol used in their manufacture, and the hydrocarbyl was 2,6-ditertiarybutyl-p-cresol (also known as BHT). While
group present strongly influences their activity; the greater it is still featured in some turbine oil formulations on account
the thermal stability of the product, the lower the antioxidant of its relatively low cost and good efficiency, its high volatil-
activity [33]. There is, however, a move away from this tjê ity and solid form has lead to its replacement by higher
of antioxidant in turbine oils and hydraulic oils as the thio- molecular- weight products, preferably those that are liquids
phosphates are sensitive to moisture and the hydrolysis prod- for ease of blending. Although, in general, aromatic amines
ucts, (zinc oxide and hydroxide), can precipitate. Some tur- tend to be more active than hindered phenols across the tem-
RO S OR
\ . where R is typically C3 - Cg
Zn OR
zinc dialkyldithiophosphate
2, 6 - ditertiarybutyl - 4 - methylphenol (BHT)
CH2—CH2—C —OR where PL is Cg-Cig
long-chain esters of substituted hydroxybenzenepropionic acid
where R is C4-C9
dialkyldiphenylamine
FIG. 13—The structure of some common turbine oil antioxidants.
perature spectrum [52], there are exceptions. Some hindered to represent the materials of construction of the system, mea-
phenols are excellent high t e m p e r a t u r e antioxidants, but surements are also made of the weight changes of the metal
even these can be outperformed by certain amines or S3Tier- specimens. Oxidation is accelerated by holding the fluid at a
gistic mixtures of amines and phenols [52]. However, radical high temperature in the presence of air, which is usually bub-
scavenging efficiency is not the only criterion used in select- bled through the sample at a fixed rate. In some tests, partic-
ing an antioxidant. Cost is obviously important as are the ten- ularly for steam turbine oils, water is also present to repre-
dencies of amines to color the basestocks in which they are sent the effect of c o n t a m i n a t i o n t h a t is a fairly c o m m o n
used and also because they are more likely to form deposits occurrence in this application. The use of water can limit the
during oxidation. The type of mineral oil basestock, e.g.. temperature of the test in order to avoid loss due to volatility.
Group 1 or Group 2, etc., can also influence the choice of an- It can also preferentially solubilize acids that are generated in
tioxidant as hindered phenols are preferred in oils with a low the oil on oxidation and, if present as a separate layer, may
aromatic and low sulfur content. remove t h e m from the oil so reducing their impact o n oil ox-
Synergism is also displayed between radical scavengers idation and acidity measurements. On the other hand the wa-
and hydroperoxide decomposers, for example a r o m a t i c ter will promote rusting and the generation of sludge and
amines are used with phenothiazine derivatives (a sulphur- may also result in the partition of some additives into the wa-
containing antioxidant) in aviation turbine oils. Table 12 ter layer.
shows the synergism between an amine antioxidant and an The oxidation tests that are used to assess stability of tur-
organosulfur hydroperoxide decomposer [52]. bine oils fall into two categories; those which use water to ac-
The superior performance of aromatic amines, particular celerate the testing and/or make the test more representative
the alkylated derivatives [52], at high temperatures has re- of service, and those where the fluid is tested "dry." In spite
sulted in their exclusive use in aviation gas turbine oils. Here, of the fact that gas turbine oils are used at higher tempera-
in addition to their efficiency in reducing fluid viscosity in- tures than steam turbine oils and that service conditions are
crease and acidity development (which are the two most generally drier, "wet" tests are also used for evaluating the
c o m m o n parameters used in assessing oxidation stability), stability of these products—though sometimes in combina-
they have been able to control deposit formation on hot sur- tion with a dry test. The two principal tests used today for as-
faces. This is important because it is more likely that an en- sessing the stability of inhibited turbine oils are indicated be-
gine failure would take place as a result of deposits them as a low.
consequence of a rise in viscosity and acidity, especially as
the aero-engine oils are topped-up so frequently. 1. ASTM D 2272, Standard Test Method for Oxidation Sta-
bility of Steam Turbine Oils by Rotating Bomb—In this
Other stabilizers, for example phosphites, which are used
test (also known as the RBOT test), the fluid, water and a
in some oil applications as sjTiergists with hindered phenols,
copper catalyst are contained in a glass vessel. This is
are not used widely in general industrial turbine oils, possi-
placed in a pressure vessel equipped with a gauge or other
bly because these materials are usually very sensitive to the
means of monitoring the change in internal pressure. The
presence of moisture with the resulting development of acid.
"bomb" is charged with oxygen to a pressure of 6.2 bar (90
They have been used in aviation gas turbine oils where the
psi) and heated to 150°C. The time taken for the pressure
temperatures would limit the water level in the fluid, but as
to fall by 1.75 bar (25.4 psi) is monitored and recorded as
extreme pressure additives rather t h a n as antioxidants.
the life of the sample. Fig. 14 shows the b o m b and it's com-
The activity of antioxidants is normally assessed, as indi- ponent parts while Fig. 15 shows a typical pressure chart
cated above, by their effect in minimizing the physical after a test. This is a highly accelerated test that is normally
changes that occur in oil on oxidation, i.e., an increase in vis- completed well within 24 h. It does not represent what
cosity and the development of acidity and sludge. In tests happens in practice as the pressure prohibits the antioxi-
where metals are present, either to catalyze the oxidation or dant (and water) from volatilizing. However, it is main-
tained that it shows good correlation with service [54]. It is
also widely used in fluid development as a screening test
for quality control purposes and in monitoring the stabil-
TABLE 12—Oxidation stability of a lubricant stabilized with a
synergistic antioxidant combination. ity of used fluid. Typical limits on mineral turbine oil
would be >350 m i n for ISO 32 or 46 grade products
Test Fluid
Alkylated diphenylamine 0.25% 0.2% (ASTM D 4304). Higher values, e.g., > 4 5 0 min are required
S(CH2CH2COOR)2 0.25% 0.05% by some turbine builders.
Rust inhibitor 0.05% 0.05% 0.05%
Basestock balance balance balance
2. ASTM D 943, Standard Test for Oxidation Characteristics
of Inhibited Mineral Oils, also known as the TOST (turbine
Oxidation Stability
TOST (ASTM D 943) 2000 200 3300 oil stability) test, is the second principal test for steam tur-
(95°C; water; Fa and Cu bine oils. This involves heating the fluid together with wa-
catalyst 3 L air/h) time (h) ter at 95°C in the presence of iron and copper catalysts,
to total acid number of while air is passed through. At regular intervals the acid
2 mg KOH/g n u m b e r in the fluid is measured and the test terminated
sludge (mg) (ASTM D 4310) 172 >5000 89 when the level reaches 2.0 mg KOH/g. In contrast to the
Basestock characteristics ISO VG 32 RBOT procedure, and depending on the base stock and ac-
CA (aromatic carbon) = 6.5%
S = 0.54% tivity of the stabilizers, this test can take several thousand
hours to complete. Minimum requirements for ISO 32/46
NOTE—Reprinted from Chemistry and Technology of Lubricants, courtesy of
Kluwer Academic Publishers, Dordrecht, the Netherlands. viscosity grades are normally 2000-2500 h. Fig. 16 shows
FIG. 14—A view of the ASTM D 2272 pressure vessel, recorder, and sample container with cat-
alyst.
FIG. 15—Typical chart recording pressure changes in the RBOT test.

the arrangement of fluids and metal specimens in the oxi- in weight of the catalyst coil may be measured and, of course,
dation cell used for this test. the increase in acidity may be determined.
As the length of the D 943 method can make product de- Another goal of test method development in this Eirea has
velopment with this procedure a very time-consuming pro- been to find a method that could be used for both steam and
cess, some specifications (e.g., MIL-L-17331) have reduced gas turbine oils. Although the FED-STD-791 oxidation test
the duration to 1000 h but added limits on metal content and methods are quite widely used (see below), they are regarded
sludge. To meet the requirements for a procedure in which primarily as tests for aviation oils in view of the types of
sludge was determined, ASTM introduced D 4310, Standard metal catalysts used and the high temperatures normally
Test Method for Determination of the Sludging Tendencies of specified. When these conditions are used with mineral oils,
Inhibited Mineral Oils. This procedure utilizes the apparatus the results are regarded as "somewhat inconsistent" [54]. For
of the D 943 method but after 1000 h the test is concluded these reasons, it was eventually decided to specify a dry test
and the fluid filtered through a 5-fim filter in order to deter- procedure, which involved passing air through the oil or fluid
in the presence of copper and iron catalysts, but at the lower
mine the weight of sludge produced. Optionally, the change
temperature of 135°C. This formed the basis for ASTM D
5846, Universal Oxidation Test for Hydraulic and Turbine
.'S'îa Oils. In this case the acidity and sludge are monitored and the
test is terminated when the acid number reaches 0.5 mg
k^ KOH/g or the level of sludge (determined by rating the de-
posits left on a filter paper after placing a drop of used fluid
at its center), becomes unacceptable. Since its introduction,
the test has been of particular interest for gas turbine oil de-
velopment in view of the availability of more stable bases-
tocks.
The stability testing of gas turbine oils, particularly aero-
engine oils, has traditionally been at much higher tempera-
tures than for steam turbine oils in view of their more severe
operating environment. Most of the tests used in this area
have been variations on the FED-STD-791, Method 5308,
Corrosiveness and Oxidation Stability of Light Oils, which, in
its original version, involved oxidizing the fluid in the pres-
ence of six different metal specimens for 164 h at 120°C. A
modified version of this test still features in U.S. Navy speci-
fication MIL-PRF-23699F in which test conditions of three
days at 175°C, 204°C, or 218°C are required. Although ini-
tially used in the U.S. Air Force specification MIL-L-7808 it
was later replaced by FED-STD-791 method 5307, which has
a test duration of four days and possible temperatures of
248-680°F (120-360°C) in the presence of seven metal speci-
mens. The test (slightly modified) also features in the latest
USAF specification, MIL-L-27502, for a high temperature en-
gine oil in which conditions of two days at 220°C and 232°C
are specified. Unlike the 5308 test in which the fluid and cat-
alyst coupons are evaluated only at the end of the test, in the
5307 procedure, fluid samples are taken during the test and
monitored for viscosity and acidity increase. ASTM D 4636,
Standard Test Method for Corrosiveness and Oxidation Sta-
bility of Hydraulic Oils, Aircraft Turbine Engine Lubricants,
and Other Highly Refined Oils, was later issued as a com-
bined 5307/5308 method offering three alternative proce-
dures and the ASTM method is now also specified as an al-
ternative to the 5307 procedure in MIL-PRF-7808L.
The metal specimens used in the oxidation tests are nor-
mally (but not cJways) in electrical contact as this is how they
are found in the system and corrosion is frequently acceler-
ated by bringing together metals of different electrical poten-
tial. The arrangement of the metal specimens in the FED-
STD-791, method 5308 and Alternative Procedure 2 in ASTM
FIG. 16—Metal cata- D 4636 is shown in Fig. 17.
lyst, fluid, and water
arrangement in the Mineral gas turbine oils are also tested by a modification of
ASTM D 943 oxidation the 5308 procedure. General Electric, for example, specifies
test. this method for its high temperature gas turbine oil specifi-
bine oils meeting ISO VGs 32 and 46. To increase the test
severity the duration was extended from 3-9 days for most
oils. This resulted in the mineral oils starting to degrade sig-
nificantly.
Rust and Corrosion Inhibitors

Rust is a continuing problem in turbines when carbon steel
is present because water contamination of steam turbine oils
and fluids is very difficult to avoid. Acid is also invariably pre-
sent in degraded oils and this can attack certain metals. Al-
though the engine in aero-gas turbines is usually constructed
of stainless steel or exotic alloys, carbon steel can still be pre-
sent in the auxiliary equipment and the oil tank.
In order to avoid rusting and corrosion, certain chemicals
have been found to protect the metal surfaces. For steel, such
inhibitors are usually highly polar materials, e.g., organic
acids, esters or amides (Fig. 18), which form an adsorbed
film on the surface of the metal that physically hinders the
transfer of water to the metal surface. This necessitates care-
ful formulation to avoid interaction with other surface-active
materials, such as antiwear additives, and to minimize the
impact on foaming/air release properties. In view of the fact
that many turbines operate in saline environments, rust pro-
tection is frequently required against salt water. This is a
more severe requirement than distilled water protection.
Rust inhibitors may also be used in polyol and phosphate
esters. However, the polarity and film-forming tendency of
the latter when uninhibited already offer some protection
against rusting, which is enhanced by acidic degradation
products. If the phosphate is used in conjunction with adsor-
bent media for controlling the level of acidic degradation
products, careful selection of the inhibitor is required as the
adsorbent solids can remove both acidic and basic additives.
The most widely used procedure for evaluating rust in-
hibitors is ASTM D 665, Standard Test Method for Rust Pre-
venting Characteristics of Inhibited Mineral Oil in the Pres-
FIG. 17—Metal catalyst arrangement used in the FED- ence of Water. This involves stirring together 300 mL of the
STD-791 method 5308 oxidation test. fluid and 30 mL of either distilled or synthetic seawater for
24 h at 60°C. A cylindrical test specimen of carbon steel is im-
mersed in the mixture and, at the conclusion of the test, is as-
cations, GEK 32568 and GEK 101941, which call for a tem- sessed for the amount of rust produced. Ratings vary from a
perature of 175°C while reducing the duration to three days. "pass" where no rust is found, through light rust (<6 spots)
Because of the importance of deposit formation in aircraft to moderate rust ( < 5 % of the surface is covered by rust), and
lubricants, the accurate measurement of the amount of dirt to heavy rust ( > 5 % covered). If rusting is going to occur it is
or sludge produced during the high temperature oxidation thought that it will appear within the first 4 h of the test and
tests is as important a feature of these tests as the generation proposals are currently being considered by ASTM to reduce
of acidity and increase in viscosity. the test duration to this period.
Oxidation test conditions for phosphate esters tend to fall In addition to steel, there are other metals that can be at-
between those of mineral oil axid synthetic esters though, be- tacked by degraded oils and by some additives, such as sul-
cause of their tendency to hydrolyze, the tests specified are fur-containing extreme-pressure additives. Of these, copper
dry tests. Typical test conditions are 164 h at 120°C in the is by far the most important, not only because of its common
presence of copper and iron catalysts (ISO 15595) or three use in system construction but also because it may catalyze
days at 175°C (FED-STD-791, m e t h o d 5308 modified) as the breakdown of oils and fluids when present as soluble salts
found in b o t h ASTM D 4293, S t a n d a r d Specification for at concentrations of < 4 0 p p m [52]. The mechanism normally
Phosphate Ester Based Fluids for Turbine Lubrication and involves acid attack on the metal with the formation of metal
the General Electric specification GEK 28136 for phosphate salts, which then dissolve in the oil. However, copper is also
ester fire-resistant gas turbine lubricants. Table 13 [27] com- susceptible to attack from sulfur either present in the oil or,
pares the oxidation stability under stemdard and more severe more commonly, released from extreme-pressure additives
FED-STD-791 test conditions of uninhibited butylatedphenyl as they degrade. This can result in the formation of sulfide-
phosphate esters and commercially available mineral gas tur- containing deposits. Fortunately certain types of chemicals
TABLE 13--Comparison of the oxidation stability of mineral gas turbine oil with butylated phenyl phosphates
under extended FED-STD-791 test conditions.
Test Viscosity Acidity Metal Weight Change (mg/cm^)
Duration Increase Increase
Fluid (days) (%) (mg KOH/g) Fe Cu Cd/Fe Al Mg
ISO VG 32 phosphate 3 3 0.11 -0.11 -0.17 -0.03 -0.07 -0.03

(TBPP) 6 4.4 0.37 0.02 0.04 0.02 0.0 0.02
9 3.8 0.85 -0.01 0.1 0.03 0.0 -0.02
ISO VG 46 phosphate 3 6 0.27 -0.01 0.03 -0.01 -0.11 -0.02
(TBPP) 6 6.4 0.33 0.11 0.29 0.17 0.08 0.13
9 7.3 1 -0.04 -0.02 0.18 -0.11 0.07
Gas turbine oil A 3 3.6 0.44 0.0 0.02 -0.04 0.0 0.01
(ISO VG 32) 6 4.2 0.8 0.03 0.04 0.02 0.0 0.03
9 25 5.3 0.14 0.01 -0.15 0.09 0.06
Gas turbine oil B 3 18.3 2.2 0.03 0.08 -0.1 0.05 0.06
(ISO VG 46) 6 24.3 3.1 0.21 0.13 0.07 0.02 0.07
9 49.5 5 0.56 0.04 0.96 0.32 0.33
Gas turbine oil C 3 23.4 3 0.02 -0.03 0.05 0.03 0.02
(ISO VG 46) 6 28.6 4.5 0.04 -0.1 -0.05 0.03 0.01
9 80.6 7 0.18 -0.47 -11.7 0.05 0.04
Gas turbine oil D 3 13.4 2 0.06 0.02 -0.04 0.0 0.01
(ISO VG 46) 6 21.2 5.1 0.24 -0.13 0.02 0.52 0.35
Turbine industry limits 3 - 5 to +15 2.5 max
ASTM D 4293 limits 3 - 5 to +20 3.0 max
C12H22—CH — C O O H where R, is +-CH2CH2O-J-H

I
CH2—COOR1
C12H22—CH — C O O H where R2 is a polyamine residue
CH2—CONHR2
FIG. 18—Typical structures for turbine oils rust inhibitors.
can protect the metal from either type of attack by the for- Unfortunately, triazole derivatives titrate as acid and there-
mation of a protective layer of up to 5000A thick [55]. These fore contribute slightly to the acidity of the fresh fluid, a fac-
products, known as metal passivators are, for turbine oils tor that has to be considered when meeting specification lim-
and fluids, chiefly of the triazole family (Fig. 19), and the ef- its on fresh fluid.
fect of their activity is to substantially extend the life of fluids
in copper-catalyzed oxidation tests. Their effectiveness is
readily demonstrated in oxidation tests such as ASTM D 2272 Antiwear and Extreme-Pressure Additives
and ASTM D 943. Apart from their performance in these and Antiwear additives are compounds added to an oil to reduce
other metal-catalyzed oxidation tests, the corrosive tenden- the wear occurring between the surfaces in sliding contact.
cies of oils towards copper is most frequently assessed by They are normally effective at light to medium loads, for ex-
ASTM D 130, Standard Method of Test for Detection of Cop- ample in pump operation. These additives, of which neutral
per Corrosion from Petroleum Products by the Copper Strip triaryl phosphates are perhaps the most well known exam-
Tarnish Test. In this test, a copper strip is normally immersed ples, initially form strongly adsorbed layers on the surface.
in the oil for 3 h at lOO'C, but more severe conditions are also As the temperature increases due to the relative movement
used depending on the application. Following the immersion of the surfaces, a chemical reaction takes place with the sur-
period the strip is solvent cleaned cind visually rated for cor- face. The mechanism early suggested involved the formation
rosion by comparing the surface color or tarnish with the of a lower melting eutectic of iron and iron phosphide,
ASTM Copper Strip Corrosion Standards, which represent which flowed into the gaps between the asperities and there-
increasing levels of tarnish axid corrosion. Normally turbine fore helping to provide a greater surface area to cany the
oil specifications call for a maximum rating of lb, which is load. This idea was later rejected in favour of a metal phos-
slight tarnish. phate layer that assisted lubrication [56]. The latest work,
tolutriazole methylene-bis-benzotriazole
I
CH2NR2
N-alkylated benzotriazole N-alkylated 1,2,4, triazole

FIG. 19—Structures of some metal passivators used in turbine oils and fluids.
however, suggests the formation of a self-regenerating lubrication. These oils have traditionally required perfor-
polyphosphate layer possibly in the presence of amorphous mance on the Ryder Gear Tester (ASTM 1947—now discon-
carbon [57]. tinued—or FED-STD-791, method 6508). Increasingly, be-
As the temperature increases still further a point is reached cause of better precision, the test devised by the German
where the phosphate film breaks down and cannot prevent Forschungsinstitut fiir Zahnrad und Getriebe (FZG) is being
metcil to metal contact. In order to sustain even greater loads, used and this method has been standardized by ASTM as D
for example to provide adequate gear lubrication, it is neces- 5182, Standard Test Method for Evaluating the Scuffing
sary to generate higher melting films, which are normally Load Capacity of Oils. Both the FED-STD 791 method and
achieved by adding extreme pressure (EP) additives, particu- the FZG procedure involve "a recirculating power loop prin-
larly sulfur in the form of a sulphur carrier, e.g., ZDTP, sul- ciple, also known as a four square configuration, to provide a
furized fats or olefins. Combinations of phosphorus and sul- fixed torque (load) to a pair of precision test gears." A
fur are also widely used and cover a wider temperature range schematic is shown in Fig. 21. The drive gearbox and the test
than each element individually, providing both antiwear gearbox are connected through two torsional shafts. Shaft 1
properties and EP performance over a wide range of applied contains a load coupling used to apply the torque through the
loads. Figure 20 shows the structures of some typical anti- use of known weights hung on the loading arm. The proce-
wear and extreme pressure additives. dure involves operating the machine at a constant speed
Most specifications for hydrocarbon turbine oils do not re- (1450 rpm) and oil temperature (90°C) for a fixed period at
quire antiwear performance. There are also normally no successively increasing loads until the failure criteria are
load-carrying requirements for steam turbine oils except for reached. This is "when the summed total width of scuffing or
extreme pressure steam turbine oils, e.g., in marine applica- scoring damage from all 16 teeth is estimated to equal or ex-
tions, but they do exist for gas turbine oils, and where the oil ceed one gecir tooth width." The FVA micro-pitting test re-
is used for the lubrication of both a steam and gas turbine as ferred to above is in two parts. First, a load stage test is car-
in some combined cycle applications. These requirements ried out in which the test oil is run at each load stage between
are not particularly onerous, typically lying between FZG 5 and 10 for a period of 16 h. This is followed by endurance
failure load stage values of 5-8 while EP turbine oils require test involving 80 h at Load Stage 8 followed by 5 periods of 80
a failure load stage of 12 + . Micro-pitting resistance may aJso h at Load Stage 10. An assessment is made of the amount of
be required for this more severe application and is also ceir- pitting or profile deviation on each tooth at the end of each
ried out on the FZG gear rig using the Forschungsvereini- test period.
gung Antriebstechnik (FVA) method 54/I-IV. For aviation applications, the Ryder Gecir Test is still used
The other application to require gear testing is aero-engine with the MIL-PRF-23699F specification in accordance with
FED-STD-791 method 6508, in which the performance of the Antifoams

test oil is evaluated in comparison with reference oils giving
known failure loads. In this case the load-carrying ability is The inhibition of foaming is essential to ensure the correct lu-
defined as the "gear tooth load at which the average percent brication of pumps and bearings and, in hydraulic systems,
of tooth area scuffed is 22.5 %." The variability of the results the transmission of power. Foam can also result in a rapid
on this equipment requires eight determinations of the refer- loss in oxidation stability of the oil or fluid and, under the
ence oil and six determinations of the test oil. The perfor- worst conditions, can cause fluid loss from the tank. It is
mance is judged acceptable if the average of the six results is therefore important that air is lost quickly from the fluid and
not less than 102% of the reference oil. In the MIL-PRF- this can be assisted by the addition of very small quantities
7808L standard, however, it is now possible also to use the (usually a few parts per million) of specific chemicals known
ASTM D 5182 method where a minimum load stage failure of as antifoams that reduce the surface tension on the bubble
5 is required. Only an average of two tests is required on this envelope [58]. The most widely used of these are the silicone
equipment. fluids. Chemically, these are polydimethylsiloxanes, which
where R is typically CjjCj orC4
triaryl phosphate
dialkyl phosphite
where R is C4-C8
triphenylphosphorothionate
RO^ OH.HNR'2 R'zNH.HO' OH.HNR'2
amine phosphates
FIG. 20—Structures of typical antlwear/extreme pressure additives used in turbine oils

and fluids.
are available in a range of viscosities, b u t the most active diffusers produce bubbles of a known and consistent size. Af-
products are those that are not soluble but dispersible in the ter passing air through the fluid for 5 min at 24°C (TS^F), the
oil or fluid. Soluble siloxanes do not have the same activity at volume of foam (tendency) is noted immediately and then
the air/fluid interface. Other problems associated with these also after 10 min (stability). The test is repeated at 93.5°C
additives include the difficulty in obtaining a homogenous (200°F) and then again at 24°C to check if the foaming be-
dispersion—the polymers tend to accumulate at the surface havior has changed (possibly due to loss of cintifoam) as a re-
and then deposit on the walls of the tank so that over time the sult of the exposure to high temperature. The results are
efficiency of the additive is lost. At "high" concentrations they quoted in terms of the tendency/stability values obtained at
can also have an adverse effect on air release properties and, each of the three temperatures. Values are normally much
if the turbine oil escapes into the turbine, there have been re- lower at the higher temperature and hence limits under this
ports of the build u p of silicon on the turbine blades. As a re- condition are more severe.
sult, the trend in mineral turbine oils is away from the use of Because of the importance of foaming and its related topic,
silicones and towards other products such as polyglyco- air release, it is further discussed in the section on Perfor-
lethers and polyvinylethers, but larger quantities of these are mance Requirements, Their Significance and Evaluation.
normally needed. The performance of the oil is usually retained as long as the
The laboratory test procedure (ASTM D 892, Standard Test additives remain in solution a n d are not depleted owing to re-
Method for the Foaming Characteristics of Lubricating Oils, moval from the fluid as volatiles, by partitioning into any free
or the ISO equivalent method, 6247) involves passing air at a water, by precipitation, or by natural usage. If the additive is
fixed rate through either a spherical crystalline alumina dif- removed by any of these means, the rate of degradation, for
fuser or a cylindriccd sintered steel diffuser immersed in the example, can suddenly accelerate. If the oil monitoring is not
oil or fluid contained in a measuring cylinder (Fig. 22). These adequate it can result in the oil exceeding its operating limits
1 != pinion 5 = locking pin

2 = gear wheel 6 = lever arm iNWn weights
3 = drive gears 7 = torque measuring clutch
4 = load clutch 8 = temperature sensor
Schematic section of FZG Test Rig
torque measuring
shaft 2
clutch
test gears drive motor
drive gears
load clutch
shaft 1
FIG. 21—Diagram of the FZG Test Rig.

suggested a quantity of about 360000 tons of turbine oils, ex-

cluding aviation eind marine gas turbine requirements, were
sold worldwide. Obviously, with a global market of this size
there are a large n u m b e r of suppliers including both multi-
national companies and smaller, national oil companies.
One of the "problems" associated with the supply of min-
eral turbine oil is that the are produced in different parts of
the world from different crude sources. Although attempts
have been made by the oil industry to minimize these differ-
ences by introducing "formula numbers" or product identifi-
cation numbers that identify the product by certain physical
characteristics, e.g., viscosity, flash point and pour point,
etc., it is still possible for the base material to vary in its com-
position. As a result there may be variations in the perfor-
mance, particularly stability, of finished products sold under
the same trade name. This has caused some turbine builders
to abandon formal approval lists in order to avoid liability
claims and to rely on the local supplier to convince the end
user that a product is available that meets the specification
requirements.
In order to ensure that the quality of the turbine oil supplied
meets certain minimum standards, and to form the basis for
purchasing agreements, performance specifications have
been issued by international and national standards organi-
zations as well as by the turbine builders and some end users.
ASTM, for example, publishes D 4304, Specification for Min-
eral Lubricating Oil Used in Steam and Gas Turbines. As a re-
sult, the industry is now one of the most heavily specified. The
FIG. 22—The development of foam in the major specifications currently used by industry are listed in
ASTM D 892 test procedure. Tables 15 and 16 for the main turbine applications. While past
practice was for separate specifications on hydrocarbon-
unnoticed. It is n o w widely accepted that with m o d e m tur- based steam and gas turbine oils, the current trend is to issue
bine oils, condition monitoring is important; this aspect will a combined document as, for example, in D 4304. At present
be examined in more detail later. there are n o separate specifications for water turbine oils, but
requirements are sometimes included in standards for steam
and gas turbine lubricants, e.g., ISO 8068, Petroleum Prod-
THE CLASSIFICATION OF TURBINE ucts and Lubricants-Petroleum Lubricating Oils for Turbines
LUBRICANTS AND HYDRAULIC FLUIDS (categories ISO-L-TSA and ISO-L-TGA)-Specifications.
Although there has recently been significant consolidation
In order to clarify the different applications for turbine lu-
within the power generation industry, some of the specifica-
bricants and hydraulic fluids a n d hence ensure that the
tions listed are still published under the n a m e of the previous
correct type of oil or fluid is used, ISO Standard 6743-5, Lu-
builder. Some simplification of the list is therefore to be ex-
bricants, Industrial Oils And Related Products (Class L)—
pected.
Classification—Family T (Turbines), has been issued. This
When seeking approval, the oil or fluid supplier would first
classifies the type of turbine, e.g., steam or gas, and then sub-
approach the turbine builder or end user with a request for
divides the application according to whether the requirement
their product to be examined against the specification. Tests
is for normal service or for a special application as, for ex-
would be carried out by the specifier (in-house or at an inde-
ample, in high temperature service or high load carrying abil-
pendent laboratory) to ensure that the product was techni-
ity. A further subdivision is according to viscosify. Table 14
cally acceptable. If successful, approval for field trials or
shows the current classification and typical applications. At
commercial use would be given. In the former case it might
present the classification does not extend to lubricants for
be necessary to obtain several years of operating experience
water, wind, or aviation gas turbines although the standard is
before full approval was given. Where no formal approval
currently under revision.
process existed, the supplier would have to convince the user
that the product met the requirements, normally by provid-
TURBINE OIL AND FLUID STANDARDS ing the results of independent laboratory tests.
Although most specifications are primarily concerned with
The turbine oil market is one of the largest segments of the the quality of new fluid as delivered, some manufacturers
industrial oil market. An estimate of consumption in 1998^ also specify the quality of any flushing fluid to be used and
cilso the limits on fluid performance in use. The latter aspect
^ Private communication, D. J. Whitby, Pathmaster Marketing will be referted to in more detail in the discussion on moni-
Ltd., Woking Surrey, UK. toring used fluid quality.
TABLE 14—Classification of lubricants for turbines (ISO Standard 6743-5).

Application Specific Application Composition and Properties Symbol ISO-L- Typlcal Applications
Steam, direct coupled Normal service Highly refined petroleum oil TSA Power generation and industrial
or geared to the load with rust protection and drives and their associated
oxidation stability control systems. Marine drives
where improved load-carrying
ability is not required for the
gearing
Special properties Synthetic fluids with n o TSC Power generation and industrial
specific fire-resistant drives and their control systems
properties where special properties of the
fluid are advantageous, for
example oxidation stability, low
temperature properties.
Fire-resistant Phosphate ester lubricant TSD Power generation and industrial
drives and their associated
control systems with need for
fire- resistance
High load-carrying Highly refined petroleum oil TSE Power generation and industrial
ability with rust protection, drives; marine geared drives and
oxidation stability, and their associated control systems
enhanced load-carrying where the gearing requires
abilityoxidation stability, improved load-canying ability.
and enhanced load-carrying
ability
Gas, direct coupled or Normal service Highly refined petroleum oil TGA Power generation and industrial
geared to the load with rust protection and drives and their associated
oxidation stability control systems. Marine drives
where improved load-carrying
ability is not required for the
gearing
Higher temperature Highly refined petroleum oil TGB Power generation and industrial
service with rust protection and drives and their associated
improved oxidation stability control systems where high
temperature resistance is
required due to hot spot
temperatures
Special properties Synthetic fluids with no TGC Power generation and industrial
specific fire-resistance drives and their control systems
properties"'* where special properties are
advantageous, for example
oxidation stability, low
temperature properties.
Fire-resistant Phosphate ester lubricant TGD Power generation and industrial
drives and their associated
control systems with need for
fire-resistance
High load-carrying Highly refined petroleum oil TGE Power generation and industrial
ability with rust protection, drives; marine geared drives and
oxidation stability and their associated control systems
enhanced load-carrying where the gearing requires
ability improved load-carrying ability
Control system Fire-resistant Phosphate ester control fluid TCD Steam, gas, hydraulic turbine
control mechanisms where the
fluid supply is separate from the
lubricant and fire-resistance is
needed
Aircraft^ TA
Hydraulic" TH
"These products may not be compatible with petroleum-based products.
'This category Includes synthetic hydrocarbons as well as other chemical types.
"Classifications for these categories have not been established.
Reproduced with permission of the International Organization for Standardization, Geneva, Switzerland.
Specifications typically include r e q u i r e m e n t s o n b o t h the o x i d a t i o n t e s t s (for e x a m p l e t h e A S T M D 9 4 3 o x i d a t i o n t e s t

c h e m i c a l a n d p h y s i c a l c h a r a c t e r i s t i c s of t h e l u b r i c a t i n g oil o r referred to above) o r large-scale fire-resistance tests t h a t are
h y d r a u l i c fluid. T h e y a l s o i n c l u d e ( b u t o f t e n fail t o differen- clearly impossible and/or u n n e c e s s a r y to evaluate on a b a t c h
tiate b e t w e e n ) the so-called "type" tests t h a t identify a general p r o d u c t i o n b a s i s . A n e x c e p t i o n t o t h i s s i t u a t i o n is for m i l i t a r y
level of p e r f o r m a n c e a n d r o u t i n e t e s t s u s e d for r e g u l a r q u a l - a v i a t i o n s p e c i f i c a t i o n s , e.g., M I L - P R F - 2 3 6 9 9 F w h e r e t h e Ry-
ity c o n t r o l . T h e f o r m e r r e q u i r e m e n t c o u l d i n c l u d e l o n g t e r m d e r G e a r T e s t is p e r f o r m e d o n t h e first b a t c h of e a c h c o n t r a c t
awarded and the bearing test performed on the first three ISO/EN/national standards are also minimum requirements
full-scale production batches of any newly qualified oil. and, in some cases, may not be severe enough to meet the
The co-existence of both international and national stan- manufacturer's or user's requirements. In such cases the lat-
dards together with those of the individual turbine builders ter's specifications may still be used. National and interna-
and end users is, perhaps, surprising. Although the publica- tional standards also require considerable time for revision,
tion of a European (EN) Standard requires the withdrawal of a process that may be inadequate for manufacturers seeking
any competing national standcird, this is not the case for ISO to make rapid changes in technical requirements to respond
(International Organization for Standardization) standards. quickly to the concerns of industry.
TABLE 15—International and national specifications for turbine oils and hydraulic fluids.
International or Fire-Resistant
National Specifications Steam Turbines Industrial Gas Turbines Aero-Derivative Gas Hydraulic Fluid
International Standards ISO 8068 ISO 8068 CD 10050
Organisation
International Electrotechnical lEC 61221
Commission
European Standard EN61221
Canada 3-GP-357Mb
China DL-571 DL/T 571-95
France AIR 3514A AIR 3517
Germany DIN 51515 In preparation DIN 51518
Japan nS-K-2213 JISK-2213
India IS 1012 IS 1012
Russia Tp-22CTU 38.101821 COST 12245-66
Tp-22BTU 38.401-58 COST 13076-86
UK BS489
USA ASTM D 4304 ASTM D 4304
ASTM D 4293 ASTM D 4293
TABLE 16—Turbine builders and utility specifications for lubricating oils and hydraulic fluids.
Steam Turbine Industrial Gas Aviation Gas Fire-resistant Hydraulic
Turbine Builder/Utility Oil Specification Turbine Oil Specification Turbine Oil Specification Fluid Specifications
Alstom Power NBAP50001A SBVPRlOOl C
(France/UK)
Alstom Power Mannheim DIN 51515 HTGD 690149 VOOOIK
(Germany)
Alstom Power (Switzerland) H G T D 9 0 117V001Q HTGD 690 149 VOOOIK
Alstom Power (Sweden) 812101 812101 81 23 00
812102 812102
812106 812106
812107 812107
Alstom Energy Lincoln, (UK) 65/0027
Alstom Power (Germany) QM44-101/B QM44-100/B
Ansaldo 602W917
BHEL IS 1012 ST 22007
EDF HN 20-S-30 HN20-S-41
Fuji Electric JISK-2213 Siemens TLV 9013.04
General Electric- GEK 46506D GEK 32568C D50TF1-S4 GEK 46357E
Medium & Large Steam GEK 101941
Turbines GEK-28136A*
General Electric-Industrial 165A974CE
Steam Turbines
Hitachi JISK-2213 GEK 32568 (mod) GEK 46357E
GEK 4506D GEK 101941 (mod)
Kawasaki JISK2213 H T G D 9 0 117(ABB)
Mitsubishi Heavy Industries 769 45192 JISK2213 STM-1840
JISK2213
National Power (UK) Procurement Specification
207001, Part 9
Pratt and Whitney 521CTypell
Siemens TLV9013/04 TLV 9013/04 TLV:9012 01/05
TLV 9016 03/02
(hydraulic oil)
Solar ES 9-224
Toshiba JISK-2213 GEK 32568C GEK 46357E
Siemens Westinghouse 55125Z3 55125Z3 53740AL
TABLE 17—Military specifications for turbine oils and hydraulic fluids.

Industrial Gas Aviation Gas
Country Steam Turbine Oil Turbine Oil Turbine Oil
Belgium BN-PO-175A BA-PO-lOeA"
BA-PO-115A°
BA-PO-103B''
BA-PO-109C
Canada 3GP-357-Mb
France STM 7220B AIR3514/A
AIR3515/A-B''
AIR3516/A"
Italy MM-O-2001
UK Def Stan. 91-25/3 Def. Stan 91-93
Def.Stan 91-94
Def.Stan 91-97/1"
Def.Stan 91-98/1
Def.Stan 91-99/1"
Def.Stan 91-100
Def.Stan 91-101
USA MIL-L-17331H MIL-L-aOSlC
MIL-PRF-7808L
MIL-PRF-23699F
' Denotes a mineral oil-based product. The remainders are synthetic-based lubricants.
Table 17 lists some of the current military specifications In each case the data in the table is given on one viscosity
for turbine oils. Where no standard is listed for a specific grade only as all these specifications contain multiple re-
country it is probable that one of the standards developed by quirements. These would include, for example, a range of dif-
other countries (particularly the USA and the UK) is adopted ferent viscosities; applications with additional load-carrying
for use. As can be seen, there are no military standards avail- requirements; or, in the case of the aviation lubricant, grades
able for industrial gas turbines or fire-resistant turbine hy- with corrosion inhibiting or thermal stability requirements.
draulic fluids. The reason is that few industrial gas turbines For information on the grades not mentioned, reference
are used in this application because of limitations on size and should be made to the appropriate specification.
weight. There are military applications for fire-resistant flu- As will be seen, there is commonality in some physiccd and
ids but these are not in turbines. chemical tests but considerable differences exist as far as
One other complication in the chart is that there are sev- "performance" or "type" tests (for example, stability a n d
eral specifications available for aviation turbine lubricants. load-carrying requirements) are concerned. The following
These are divided between mineral oil (extreme pressure and comments explain the background to the incorporation of
non-extreme pressure grades) and synthetic-based products. the different performance requirements into the specifica-
The latter are further subdivided according to the different tions and outline the procedures available for their determi-
fluid viscosities. nation. Table 19 lists the common ASTM, Federal Standard
Method, or ISO standard tests used in turbine oil specifica-
tions; however, not all standards for the same property are
PERFORMANCE REQUIREMENTS, THEIR identical.
SIGNIFICANCE AND EVALUATION
As might be expected in an application that may be using Viscosity
the latest technological advances, the technical require- The viscosity of a liquid can be regarded as its resistance to
ments can be extensive and severe. This is also a result of flow, but is more precisely a measure of the interned friction
providing a resource on which industry and the consumer as the molecules move relative to one another. The property
totcdly depend and on which the safety of large numbers of is important as it enables us to rank oils and fluids in terms
the traveling public rely. Table 18 illustrates the technical of their relative "thickness" and to define the appropriate
requirements for: "level of thickness" necessary to ensure the presence of an ad-
1. A steam or industrial gas turbine oil without additional equate lubricating film in the p u m p , bearings, or gears
load carrying capacity (T5ê 1 oils listed in ASTM D 4304, throughout the operating temperature range of the equip-
Standard Specification for Mineral Lubricating Oil Used ment, including low temperature start-up capability. It was
in Steam or Gas Turbines). noted earlier, for example, that military requirements neces-
2. An aero-derivative gas t u r b i n e lubricant (MIL-PERF- sitate the use of a low viscosity lubricant for engine start-up
23699F, Lubricating Oil, Aircraft Turbine Engine Oil, in very cold climates. At the other extreme, when using min-
Synthetic Base, NATO Code N u m b e r 0-156, standard eral oils in turbines operating in high temperature environ-
grade). ments, it may be necessary to use higher viscosity products to
3. A fire-resistant turbine control fluid (lEC 61221, Petroleum achieve adequate lubrication. However, if a lubricant has too
Products and Lubricants-Triaryl Phosphate Ester Turbine high a viscosity, cavitation will occur while too low a viscos-
Control Fluids (Category ISO-L-TCD)—Specifications. ity can result in p u m p slippage and internal leakage (Fig. 23
[59]). Also related to viscosity are volatility and, to a limited tures for measuring viscosity, the most widely-used tempera-
extent, flash point properties. tures are now 40°C and 100°C, and these are cJso the basis for
The most c o m m o n procedure for measuring kinematic vis- the determination of viscosity index and viscosity classifica-
cosity (ASTM D 445, Standard Test Method for Kinematic tions (see below). The former temperatures, however, are still
Viscosity of Transparent and Opaque Liquids) involves mea- frequently quoted and care is needed to avoid confusing the
suring the time for a fixed volume of liquid to flow under different data. It is possible to measure viscosity over a wide
gravity through a calibrated glass capillary viscometer. Al- temperature retnge using this method and Fig. 24 illustrates
though in the past, 100°F and 210°F were standard tempera- the viscosity/temperature relationships for the major fluids
TABLE 18—A comparison of the technical requirements for turbine oils and fire-resistant hydraulic fluids.
Test Method
Steam/Industrial Aero-Derivative Fire-Resistant
Property Gas Turbine Oil Gas Turbine Oil Hydraulic Fluid ASTM FED-STD-791 etc. ISO etc.
Viscosity Grade 32 22 46 D2422 3448

Appearance (20°C) Clear and bright
Kinematic Viscosity (cSt) D445 3104
at 40X 28.8-35.2 >23 41.4-50.6
100°C 4.9-5.4
-40X max 13000
Vise. Change after 72 h at -40°C (%) mEix 6
Pour point (°C) max -6 -54 -18 D97 3016
Flash Point (X) min 180 246 D92
Density at 15°C max 1.2 3675
Total Acid No (mg KOH/g) max Report 1.0 0.1 D974 6619
SAE ARP 5088
Foaming Tendency/Stability D892 6247
Sequence 1 max 50/0 25/0 150/0
Sequence 11 max 25/0 25/0
Sequence 111 max 25/0 150/0
Air Release at 50°C m£ix 5 6 D3427 9120
Chlorine Content (mg/kg) max 50 15597
Water Content (%) max 0.1 760
Volume Resistivity at 20°C (Mfim) mm 40 lEC
60247
Emulsion Characteristics at 54°C 30 15 D 1401 6614
min. to 3 ml emulsion
Evaporation Loss (%) 10 D972
Rust Preventing Properties Pass D665
—Procedure A
Rubber Compatibility (% swell) 25-May D6546 3604/3433 6072
Corrosiveness to Copper Rating D 130
Fluid Compatibility-sediment (mg/L) max 20 3403
Trace Metal Content (ppm) max Various (1-11) Atomic Emission
Spectr.
Shear Stability-Viscosity Loss max 4 D2603
at 100°F (%)
Bearing Deposition-demerit rating max 80 3410
Thermal Stability & Corrosivity 3411
at 274°C
-Viscosity Change (%) max 5.0
-Acid Number Change (mg KOH/g) max 6.0
-Metal Weight Change (mg/cm^) max 4.0
Oxidation Stability h to acid min 2000 D943
number 2.0
Oxidation Stability-min. to min 350 D2272
175kPa drop
Oxidation Stability 5308
Viscosity change (%) max - 5 to + 25
Total Acid Number Change max 3.0
Sludge Content (mg/100 mL) max 25/50
Wt. change (mg/cm^)-Fe max ±0.2
Wt. change (mg/cm^)-Cu max ±0.4
Wt. change (mg/cm^)-Ag max ±0.2
Wt. change (mg/cm^)-Mg max ±0.2
Wt. change (mg/cm^)-Ti max ±0.2
Wt. change (mg/cm^)-Al max ±0.2
Oxidation Stability max 15595
Acid number increase (mg KOH/g) 1.5
Wt. loss-Fe (mg) max 1.0
Wt. loss-Cu (mg) max 2.0
TABLE 19—A summary of the principal test methods for evaluating turbine oil properties.
Others (FED-STD-791
Property ASTM Method ISO Procedure Unless Specified)
Color D 1500 102
Kinematic Viscosity D445 3104 305
Low Temperature Viscosity D2532 307
and Viscosity Stability
Viscosity Index D2270 2909 9111
Viscosity Classification D2422 3448
Density-hydrometer method D1298 3675
Density-digital density meter D4052 12185
Acid Number-Colorimetric D974 6618 5105
Potentiometric D664 6619 5106
SAE ARP 5088
Water Content D 1744 760 3253
12937
Pour Point D97 3016 201
Evaporation Loss D972 351
Flash/Fire Points-Open Cup D92 2592 1103
Autoignition Temperature D2155/E659 3988 1152
Spray Ignition 15029 Factory Mutual
Std. 6930
Hot Manifold Ignition 20823 6053
Wick Ignition D5306 14935
Foaming D892 6247 3213
Air Release D3427 9120
Demulsification D 1401 6614
D2711
Shear Stability-Oxidation Stability D943
D2272
D5846
5307/5308
15595
Hydrol5îc Stability D2619 15596
s h e a r Stability-diesel injector CETOPRP 112H
Shear Stability-sonic oscillator D2603/D5621
Shear Stability-tapered bearing CEC L-45-A-99
Thermal Stability D2070 2508/3411
Particle Contamination-optical F661 4402
Particle Contamination-microscopic F313 4407/8 3009
Particle Contamination-gravimetric D4898 4405
Sizing particles 4406
Trace Sediment D2273 3004/3010
Copper Corrosion D 130 2160 5325
Rust Preventing Characteristics D 665/D 3603
D 1748
Corrosion prevention 4404 4011
Seal Compatibility 6072 3604/3432
Fluid Compatibility 3403
Electrical Resistance D 1169 lEC 60247
4-Ball Wear Test D4172 CETOP RP 67H
Vane P u m p Test D2882 20763
Gear Test-Ryder D 1947 6508
Gear Test-FZG D5182 14635 DIN 51354
Bearing Test 3410
Deposition Test 5003
used in turbine fluids and lubricants. Very low temperature Other ASTM standards that involve the measurement of
viscosities (which are required for aviation gas turbine lubri- viscosity include the determination of viscosity index (ASTM
cants in view of their potential operation in very cold envi- D 2270, Standard Practice for Calculating Viscosity Index
ronments) are measured by a slightly different procedure. from Kinematic Viscosity at 40 and 100°C). Viscosity Index is
This involves not only a determination of viscosity at - 4 0 or a way of representing the change in viscosity of an oil or fluid
-65°F but also a cold "soak" to check whether the fluid with temperature relative to two reference mineral oils arbi-
changes viscosity on prolonged exposure to low temperatures trarily assigned viscosity indices of 0 and 100. The lower the
(ASTM D 2532, Standard Test Method for Viscosity and Vis- change of viscosity, the higher the Viscosity Index. Addition-
cosity Change After Standing at Low Temperatures of Air- ally, the classification scheme ASTM D 2422, Standard Clas-
craft Turbine Lubricants). This test is in addition to a re- sification of Industrial Fluid Lubricants by Viscosity System,
quirement for stability at -18°C for six weeks without (equiveJent to ISO 3448) enables fluids and lubricants to be
crystallization, separation, or gelling. classified according to their viscosity at 40°C (in centistokes)
in a series of eighteen grades. These range iirom 2-1500 cSt Products) involves cooling a fixed volume in a cylindrical
and the width of each band is ± 1 0 % of the mid-point. This container with a thermometer inserted just below the sur-
scheme is widely used to identify the level of viscosity re- face. As the t e m p e r a t u r e is lowered, the flow behavior is
quired for different applications. The ASTM D 4304 turbine noted by holding the container horizontal for 5 s and watch-
oil standard, for example, has limits on fluids u p to an ISO ing for movement in the meniscus. The pour point is that
150 viscosity grade while at least one major steam turbine temperature w h e n the fluid ceases to flow under these condi-
builder specifies an ISO VG 100 hydraulic oil. However, the tions and to which three degrees centigrade has been added.
common viscosity grades for both hydraulic cind lubricating Typical limits for Type 1 turbine oils (of all viscosities) given
oils in industrial steam and gas turbines Eire 32 and 46 while in ASTM D 4304 are - 6 ° C maximum.
products with ISO viscosity grades 10 and 22 are found in
aero-engine oil applications.
Acid N u m b e r
The acidity present in the new oil or fluid arises from two
Pour Point/Low Temperature Storage Stability
sources:
In addition to avoiding thickening at low temperatures, ei- 1. Residual acidity from manufacture (in the case of the es-
ther in use or in storage, it is also important to ensure that the ter-based products),
fluid in service does not solidify or precipitate. Such behav- 2. From the presence of additives—usually acidic rust in-
ior could lead to pumping problems or operational failure. hibitors and/or metal passivators, but also some antioxi-
Conventional solvent-refined mineral oils tend to precipitate dants.
wax at low temperatures; the hydrocracked products m u c h
A high level of acid in a n unused, inhibited, fluid is there-
less so and not at all with PAOs. In comparison, the synthetic
fore not necessarily indicative of a poorly processed product
esters may, if wet, become turbid at low temperatures and
or one that has aged significantly on storage. The latest ver-
also more viscous on storage. Phosphates normally solidify
sion of MIL-PRF-23699, for example, has a limit of 1.0 mg
without precipitation b u t may also become turbid in the
KOH/g. On the other haind the presence of a high level of
presence of water.
acidity cem be disadvantageous to surface active properties,
Additive incompatibility at low temperatures can also ad- for example foaming (ASTM D 892) and air release (ASTM D
versely influence the low temperature behavior of the oil or 3427). It may cause corrosion (ASTM D 665) and promote ox-
fluid and it is mainly for this reason that aviation gas turbine idation (ASTM D 2272). The level of acid in new, uninhibited,
lubricants are tested for extended storage stability. The qual- phosphate esters is tighfly controlled because this may con-
ification sample for approval against MIL-PRF-23699F, for tain strong acid, with a p H of < 4 , which can catalyze the hy-
instance, is stored at temperatures ranging from - 4 0 ° C to drolytic degradation process. A low initicd acidity in ester-
+60°C for a period of three yeeirs. If at any time during this based products therefore ensures good storage stability, a
period the fluid fails to meet any of the technical criteria, the satisfactory condition on filling into the system and a longer
approved is withdrawn. operating life. As will be shown later, the acidity level is a n
The normal procedure for determining p o u r point (ASTM important indicator of fluid "health." Monitoring this param-
D 97, Standard Test Method for Pour Point of Petroleum eter is therefore essential to ensure the trouble-free operation
of the system.
Two techniques are used for the measurement of acidity or
(mm2/sec) acid n u m b e r of turbine oils and fluids. Both involve neutral-
izing the acid by a base (potassium hydroxide) of known
10 000
strength in a measured quantity of fluid. One procedure uses
5000 Cavitation indicators that change color when the sample is neutralized
(ASTM D 974, Standard Test Method for Acid and Base Num-
2000 4Jpp6^viscosity limit ber by Color Indicator Titration). The other method mea-
1000 7) sures the acid n u m b e r by plotting the changes in the poten-
m <D
500 Slow respoRse- o O tial of a glass electrode as the alkali is added. The amount
8 X3 O
required to produce an inflexion point on the graph is taken
(0 a> 3 as the neutralization point. Where inflexion points are not
• > S 3 readily defined, a predetermined end point, for example a p H
,g 100 Low efficieaiey= 5' CD
'Jam of 11, is frequently used (ASTM D 664, Standard Test Method
ro Q.
50 3 CD
E O. for Acid N u m b e r of Petroleum Products by Potentiometric
(D
C 20 i3
Titration). While b o t h procedures give similar results on
CO fresh fluids, their accuracy, peirticularly reproducibility, is
10 (D
acceptable rather t h a n good. For example, in the colorimet-
5 Reduced volumetRelfticiency ric technique where the initial acidity lies below 0.1 m g
-4i^3lv3Q0S
KOH/g, the reproducibility is 0.04 m g KOH/g. More difficult
still is the accurate determination of used fluid acidity where
1 the fluid color has darkened or when the fluid has been dyed.
This makes indicator end points more difficult to detect and
FIG. 23—Significance of viscosity for tlie operation of a typi- precision may suffer with increasing acidity. The trend is
cal hydrostatic system. Reproduced from "Hydraulic Fluids,"
therefore towards the use of the potentiometric method for
with kind permission of Butterworth-Helnemann, Oxford, UK.
5.0
(0
o
.52
"c

o
E
(U
c
200
0 10 20 40 55 65 75 85 100
degrees farenheit
FIG. 24—Viscosity/temperature data for different turbine oil and fluid.
fluids in service. For aviation lubricants a potentiometric on initial acidity. ASTM D 4304 has no limits but values are
method has been developed by the Society of Automotive En- to be reported. Some turbine manufacturers also have no re-
gineers (SAE-ARP 5088) which is now included in MIL-PRF- quirement while others call for a limit of 0.2 mg KOH/g max-
23699F. imum for non-geared units and 0.3 mg KOH/g for geeired tur-
In the past, determination of acidity was traditionally car- bines. Higher limits are found for the ester-based aviation
ried at the close of an oxidation test. However, because the lubricants. MIL-PRF-7808L, for example, specifies 0.3 or 0.5
major criterion for failure in the D 943 method was the time mg KOH/g max. while at the other extreme, the specification
taken to reach a certain level of acidity, it was necessary to limit on fire-resistant control fluids is typically 0.1 mg KOH/g
follow the development of this parameter throughout the maximum.
test. This required regular sampling of up to 20 g of fluid per
determination. For long-term tests this could significantly re-
duce the fluid volume in the test and would therefore disturb Water Content
the relationship between catalyst surface area and the fluid Water is a problem contaminant for all tjrpes of fluid. It can
and also between water and the fluid, making it difficult to be present in either dissolved or dispersed form and, in the
compare test results. To reduce the effect of sampling on the case of major contamination, may form a completely sepa-
oxidation test conditions, methods of measuring acidity on rate layer. When the main reservoir contains mineral oil, free
much smaller samples were developed. Currently ASTM D water normally falls to the bottom of the tank owing to the
3339, Standard Test Method for Acid Number of Petroleum different density and requires removal by means of the vaJve
Products by Semi-Micro Indicator Titration, and D 5770, on the tank base or via a sediment drain to the tank side. If
Standctrd Test Method for Semi-quantitative Micro Determi- the fluid has a density greater than that of water, as in the
nation of Acid Number of Lubricating Oils During Oxidation case of phosphate ester, the free water layer will be on top of
Testing, are used. The former method uses up to 5 g of fluid the fluid in the tank and should be skimmed or siphoned off.
while the latter uses only "drops" of fluid. The D 5770 proce- Other methods used for free water removal include centrifu-
dure is regarded as less precise than D 974 or D 664 and is not gal separation and water absorbing filters. To remove dis-
recommended for monitoring oils in service. Its principal use solved water, vacuum dehydration is recommended. The lat-
is therefore likely to be product development and the method ter technique may take the form of an extractor on the tank
advises that "each laboratory shall develop its own criteria encouraging the flow of a stream of dry air across the surface
for determining when to switch from this method to a more of the oil or fluid. Alternatively, a vacuum dryer may be used
precise test method for acid number." on a by-pass to the main oil tank in which a thin film of the
Figure 25 shows typical automatic titration equipment oil or fluid is exposed to a counter-current of dry air. This
used for determining total acid number on a series of sam- technique reduces the water level more rapidly. Although wa-
ples. Specifications vary considerably in their requirements ter contamination is more likely on steam turbines, it can
FIG. 25—Equipment for the measurement of acid number by automatic titration.

also occur on gas turbines as these are occasionally washed peratures from knowledge of the values at these or two other
to remove deposits forming on blades, etc. temperatures.
The solubility of water in turbine oils is very low—about API Gravity is a special function of relative density, and is
30-100 mg/kg at ambient temperatures, and excess water in obtained by hydrometer measurement carried out at 60°F
new mineral oils can usually be detected visually as it causes (15.6°C). This test is not normally applied to non-hydrocar-
turbidity. With esters, the solubility is m u c h higher, in the bon oils and gives values that are numerically significantly
range of 2000-2500 mg/kg at ambient temperatures although higher than the other procedures mentioned. Density limits
levels in service are normally in the region of 500-1500 featuring in specifications depend on the type of fluid being
mg/kg. Small amounts of water can normally be tolerated, used. Mineral oils, for example, are typically quoted at 0.9
and are common in used steam turbine oils. While dissolved kg/1 maximum at 15°C while the API gravity for an ISO 32 gas
water can cause a reduction in viscosity, hydrolysis of addi- turbine oil is 29-33.5. Triaryl phosphates have a substantially
tives (or even of the ester fluids themselves) and hence a loss higher density and limits on this fluid would typically be 1.17
of stability, etc., it is dispersed or free water that is the usual kg/1 maximum for an ISO VG 46 product.
cause of emulsification, rusting, and possible extraction of
additives. With ester fluids, hydrolysis is the normal form of
degradation and the acid formed can promote further degra- F o a m i n g a n d Air R e l e a s e
dation. Monitoring the water content of oils or fluids is there- Air is a "contaminant" of every turbine oil and fluid. Whether
fore a n essential part of any fluid maintenance program. or not it causes problems it depends largely on whether it is
The procedure used for detecting water has to be capable soluble in the oil, or present as dispersed bubbles. System de-
of accurately measuring very small amounts and the tech- sign, circulation rates, fluid cleanliness, etc., are also factors
nique used is to titrate a measured a m o u n t of fluid or oil with to be considered. Dissolved air is not normally a concern but
standard Karl Fischer reagent to an electrometric end point. if it comes out of solution when pressure is reduced locally it
The most c o m m o n method is ASTM D 1744, Standard Test may cause p u m p cavitation. Dispersed air tends to be a prob-
Method for the Determination of Water in Liquid Petroleum lem if it is not readily released from the bulk of the fluid in
Products by Karl Fischer Reagent. Precision has been estab- the tank and compression of the bubbles by the p u m p does
lished for levels between 50 and 1000 mg/kg, but the method not cause their dissolution. Under such conditions dispersed
is frequently used for detecting m u c h higher values, peirticu- air can cause a loss of control due to a change in the com-
larly on used ester fluids. Limits are not frequently specified pressibility of the fluid, result in increased oxidation, and
for new mineral turbine oils in view of the low solubility of may have an adverse effect on lubrication. Foam is the accu-
w a t e r a n d the reliance on visual appearance (free w a t e r mulation of air bubbles surrounded by a thin film of oil and
causes turbidity). Occasionally limits of 0.01-0.02% w/w occurs at the surface of the liquid. Air release measurements,
(100-200 mg/kg) are quoted while, for fire-resistant control by contrast, are made in the bulk of the liquid where a rela-
fluids and aviation esters, the values are significantly greater tively thick film of oil separates the air bubbles.
(0.1 % w/w or 1000 mg/kg), reflecting the higher solubility There are a n u m b e r of factors relating to fluid properties,
and the hygroscopic (water absorbing) nature of these fluids. system design and use that can influence foam formation.
These include tank design and circulation rates [60], fluid vis-
cosity, surface tension, vapor pressure, contamination, bub-
Density
ble size [61], air leaks on suction lines, or simply too low an
Measurement of density or specific gravity is one way of iden- oil level in the tank. Some foam is inevitable as air is released
tifying the use of the correct fluid and ensuring that the cor- from the oil or fluid when the pressure returns to ambient. In
rect volume of fluid is purchased if the product is supplied by most systems the presence of a small a m o u n t of foam can be
weight. It is also a n important factor for designers in deter- tolerated without any significant adverse effect on fluid/sys-
mining the p o w e r required for p u m p i n g the oil or fluid tem performance. In extreme cases, excess foam may reduce
around the system and in arranging for removal of free wa- lubrication performance, induce bearing vibration, cause
ter. Phosphate esters, for example, have densities about 30% fluid oxidation or loss of fluid, and create m u c h inconve-
greater than mineral oils and require more power for circu- nience to maintenance staff.
lation. Also, ciny free water in the tank will accumulate on top In hydraulic systems operating at high pressures, the pres-
of the phosphate. This fluid t3rpe will hold more dirt in sus- ence of dispersed air will depend on the system pressure, the
pension than other fluids, which necessitates better filtration size of the air bubbles, fluid temperature, and the compres-
initiedly, but offers the possibility of a cleaner system in op- sion time in the p u m p . Where the bubble is small, the com-
eration. pression time relatively slow, Eind the pressure Eind tempera-
Density or relative density (specific gravity) values for both t u r e high, there is only a slight chance of bubbles being
transparent and opaque liquids Ccin be obtained either by the circulated that could affect the compressibility of the fluid
use of a hydrometer (ASTM D 1298, Standard Practice for euid hence the response time of the system. Conversely, if the
Density, Relative Density (Specific Gravity) or API Gravity of bubbles do not readily dissolve under pressure, not only is
Crude Petroleum and Petroleum Products by Hydrometer there a risk of a loss of control but there may also be a n as-
Method, or the ISO 3675 equivalent), or by a digital densito- sociated lubrication failure, fluid oxidation, and also the pos-
meter (ASTM D 5002, Standard Test Method for Density and sibility of "dieseling." This is a phenomenon where compres-
Relative Density of Crude Oils by Digital Analyzer, for which sion/ignition takes place inside the bubble with resulting
the ISO equivalent method is 12985). Values are normally fluid degradation [62]. In turbine lubrication systems, pres-
measured at 15 or 20°C, but can be calculated at other tem- sures are normally too low for this phenomenon to occur but
it is occasionally found in high pressure hydrauHc systems re- therefore, foaming tendency/stability values of 50/0 mL. for
suUing in a rapid darkening of the fluid, an increase in acid- all conditions (as defined in the ASTM D 892 test described
ity, and the development of a "humt" odor. above) are required in ASTM D 4304 while, for steam tur-
In addition to the D 892 foam test method discussed above, bines, the builder's requirements can be as high as 450/10,
military aviation lubricant specifications also call for the use 50/10, and 450/10 mL for the three test sequences. In gas tur-
of a dynamic foam test, FED-STD 791, method 3214 in which bines, some equipment memufacturer's limits are 10/0, 20/0,
the oil is heated and circulated around a loop consisting of a and 10/0 mL. For fire-resistant control fluids, limits are also
pump, oil heater, air injection orifice, foam test cell, and as- usually fairly severe at 50/0 ml. (all sequences) ranging up to
sociated instrumentation. As the oil is circulated at a temper- 150/0, 50/0, and 150/0 mL. For aviation gas turbine oils, lim-
ature of 80°C or 110°C, the sample is aerated for a period of its are also severe with the MIL-PERF-23699 requiring 25/0
30 min at a fixed rate with measurements being taken of the mL metximum at all temperatures.
foam, etc., every five minutes. At the end of the test, the foam Unfortunately, the laboratory test cannot simulate the con-
level, oil pressure and oil volume are noted together with the ditions that are found in the turbine; such is the influence of
time taken for the first patch of clear surface to appear or the system design. As a result, the test data should be treated as
foam remaining after 5 min. The test is then repeated with a indicative of a trend in fluid behavior and any significant
different air-flow rate or at a higher temperature. The equip- change, particularly the generation of stable foam, be initially
ment is able to operate at low pressures thereby simulating confirmed by investigating the behavior in the tank itself.
the effect of high altitude flight. Air release properties (ASTM D 3427, Standard Test
Typical foam limits for mineral turbine oils vary signifi- Method for the Air Release Properties of Petroleum Oils, or
cantly and can also depend on whether the application is in a ISO 9120) are similarly measured by saturating the fluid
steam or gas turbine. Limits in the latter application are usu- (normally at 50°C, but other temperatures are also possible)
ally stricter in view of the high aeration of the gas turbine oil with air bubbles and then measuring the time it takes for the
as it leaves the bearings. For both steam and gas turbines. fluid to return to an air content of 0.2%. Figure 26 shows the
c
(D
Group 1 Groups ISOVG32 ISOVG46 ISOVG46

mineral mineral polyol ester PAO phosphate ester
oil oil
FIG. 26—The effect of temperature on air release values for different turbine oils and
fluids.
air release properties over a range of operating temperatures sult of contact with a hot surface. An obvious example of this
for various turbine oils and fluids. would be a hot steam pipe, where temperatures are now
Typical specification requirements for mineral oils, e.g., as reaching 610°C. However, there are other potential sources of
required by ASTM D 4304, vary from 5 min (ISO VG 32), ignition such as bearing housings and gas turbine exhausts
through 7 min (ISO VG 46) to 17 min (ISO VG 150) for non- that may be hot enough to ignite oil vapor, if not the liquid it-
EP oils and up to 25 minutes for products with improved self [65].
load-carrying capacity. As would be expected, air release val- Unfortunately, there is no single test that can satisfactorily
ues increase with viscosity and this is reflected in these lim- predict fire behavior and several tests are necessary to obtain
its. Turbine manufacturers tend to have more severe require- a more complete assessment of performance. Much depends
ments with 3-5 min m a x i m u m frequently specified for both on the form in which the fuel (in this case the oil or fluid) is
steam and gas turbines. The air release properties of phos- present. For example, it is easier to ignite the fluid in the va-
phate esters vary significantly with chemical type. The "natu- por state as the access to oxygen is greater (combustion is an
ral" phosphates such as trixylyl phosphates tend to have very oxidation reaction with the release of heat in the form of a
low air release values of about 1 min while the synthetic types flame). The evaluation of fire resistance by tests that simulate
(ISO VG 46 grade) are in the region of 5-8 min, hence speci- the hazard is therefore of crucial importance. While many
fication limits for fire-resistant control fluids are frequently tests have been devised to assess this property, three types are
of the latter order. It is probable that m a n y fluid-related widely used: 1) Spray ignition behavior, 2) Hot surface igni-
problems could be avoided if there was a greater awareness tion, and 3) The flammability behavior when the fluid is ab-
of the impact of system design on air entrainment. sorbed onto a substrate [66].
Simple flash and fire points (ASTM D 92, Standard Test
Method for Flash and Fire Points by Cleveland Open Cup) are
Chlorine Content used to identify very flammable (and volatile) materials but,
Limits on chlorine content are required with phosphates in for products of low volatility such as are used as fire-resistant
order to avoid servo-valve erosion [63]. In fact it is the chlo- fluids, flash and fire points do not necessarily relate to the
ride ion (CI ) level that is critical and this can arise either performance of these fluids in other, more hazard-related,
as a trace contaminant from the manufacturing process tests. A high fire point, for example, does not automatically
(from the use of phosphorus oxychloride) or by air-bom mean good performance in spray or hot surface ignition tests
contamination. Another source is the incorrect use of chlo- (see Table 8 and [66]). Today, flash and fire point tests are
rinated solvents for cleaning system components. Although used more for quality control purposes rather than for mea-
the chlorine in solvents is not initially present in ionic form suring fire resistance [66].
it is thought that the solvents break down thermally in the As indicated above, in turbines, the main hazard is a hot
system to release chloride ion. While limits are placed on surface. Where the surface is lagged, the risk increases in
new fluid levels (normally 50 ppm), the content of chlorine view of exposure of thin films of oil or liquid to oxygen in the
in fresh fluid is usually significantly lower (typically 20-30 lagging. The wick test (below) does not properly simulate this
p p m ) . In spite of the importance of the level of chloride ion condition as the oil film in the lagging (unless saturation is
in the fluid, it is rarely specified for new fluid and the lim- reached) is thinner and the access to oxygen is greater. How-
its that have appeared in the past are at much lower levels, ever there is currently no standard method that accurately re-
e.g., 0.5-2 ppm. produces this condition.
The accurate measurement of very low levels of chlorine is The test methods that are most widely used to assess fire
not easy and the standard b o m b calorimeter tests are not suf- resistance include the following:
ficiently accurate, as the combustion of phosphates by macro
techniques is usually incomplete. ASTM D 808, Standard Spray Ignition Tests
Test Method for Chlorine in New and Used Petroleum Prod- These are of two types: 1) Those that attempt to ignite the
ucts (Bomb Method), a typical bomb calorimeter process, for fluid by spraying at elevated t e m p e r a t u r e and pressure
example, is only valid for chlorine levels of 0.1-50%. Instead, through a n open flame, noting whether ignition occurred
microcoulometry (e.g., IP proposed method AK99), a com- and, if so, whether burning continued once it had moved
bustion process which uses very small amounts of sample is away from the ignition source (ISO 15029, Parts 1 and 3,
preferred, or possibly X-ray fluorescence (ISO 15597). The Petroleum and Related Products—Determination of Spray
basis of all the calorimeter methods is the titration with sil- Ignition Characteristics of Fire-resistant Fluids). 2) Measur-
ver nitrate of the chloride ion produced by combustion. Due ing the heat emitted by the burning fluid (Factory Mutual
to the purity of phosphates in commercial production this Test Standard 6930 for the Flammability of Industrial Fluids
parameter is rarely a problem today and, as will be shown and ISO 15029-2). It might seem strange to assess the fire re-
later, is controlled in use by special filtration techniques. sistance of so-caJled fire-resistant fluids by deliberately ignit-
ing them, but "fire-resistant" in this context does not mean
non-flammable. Most, if not cdl, fire-resistant fluids will com-
Fire-resistance Tests bust if contacted by a high-energy source for a sufficient pe-
These properties are the most important requirements for the riod of time.
phosphate esters and for the small quantities of polyol esters Past spray tests tended to be pass/fail methods with poor
that are supplied as hydraulic fluids into this application. The precision but the latest methods, such as ISO 15029-2 and the
origins of fires in turbines are divided almost equally between new Factory Mutual procedure, are able to rank fluid behav-
the lubricant and hydraulic fluid [64] and are normally a re- ior with acceptable precision and generally in the same or-
exhaust channel
anemometer
exhaust gas nozzle
thermocouple (Tp/Tex) ambient air
\_ thermocouple
atomising air
hydraulic fluid
FIG. 27—Schematic representation of the test chamber used for the ISO 15029-2 Spray
Ignition Test. Reprinted with permission of the Health and Safety Laboratory, Sheffield,
UK.
der. Figures 27 and 28 are diagrammatic representations of S t a n d a r d Test Method for the Linear Flame Propagation
the equipment used to carry out the above tests. Rate of Lubricating Oils and Hydraulic Fluids, which, as the
title suggests, measures rate of flame travel along the wick.
Hot Surface Tests Alternatively, ISO 14935 records the time it takes for the
Although the latest spray ignition tests can indicate the rela- burning fluid to self-extinguish after removal of the ignition
tive fire resistance of fluids, the results tell us nothing about source. I n the case of the ISO standard, the ignition source is
the temperature at which the fluid would ignite on contact an oxy-propane flame while in the ASTM method, matches
with a hot surface. It is therefore important to obtain some are used to ignite the wick. Such a test might simulate the ig-
idea of this aspect from appropriate procedures. Currently nition of the fluid when soaked into cloth waste. In both tests,
only one test is specified for turbine fluids, the determination the unused fluid is usually evaluated whereas in reality the
of autoignition or s p o n t a n e o u s ignition t e m p e r a t u r e , by fluid may have been in contact with the absorbent over a pe-
ASTM D 286 or D 2155 (both now obsolete) or by E 659, Stan- riod of time allowing volatile components, such as water, to
dard Test Method for Autoignition Temperature of Liquid escape. This could significantly alter the behavior of the fluid.
Chemicals. In each of these procedures a small, measured Obviously where such tests are required it is expected that
a m o u n t of the test fluid is inserted into a heated glass con- the fluid would meet the criteria for a "pass" irrespective of
tainer (conical or round-bottomed flask). The temperature at its condition. Figures 29 and 30 show the equipment required
which the fluid ignites with the production of a visible flame for the two tests.
was the result recorded in the two earlier tests while the most
recent variant also observes the production of "cool flames,"
which occur at lower temperatures than conventional hot Water Separability/Demulsibility Tests
flames. As noted earlier, water is a common contaminant of steam
The recent procedures have resulted from attempts to ob- turbine oils. It may arise as a result of the penetration of seals
tain a more even temperature distribution throughout the by steam, from cooler leaks, condensation in the tank or from
container, while replacing the original molten lead bath, steam valves dripping onto hydraulic actuators, etc. Although
which was a health hazard. Major differences are found be- gas turbines are normally drier due to the absence of steam
tween the results of the three tests with the trend towards and the higher operating temperature, they also use water-
lower values with the later methods [66]. The reason for the filled coolers and may be periodically washed with water to
differences in results is mainly due to the increased size of reduce the build-up of deposits within the turbine. The oil
the container and therefore to the increased oxygen concen- tanks for some gas turbines are also located out-of doors and
tration present [67]. Unfortunately, the reduction in au- may not be protected from the elements. Consequently, un-
toignition temperature values with recent methods has occa- desirable levels of water in turbine oils and hydraulic fluids
sionally led the user to believe that an inferior product was can occasionally build u p . Free water is found more fre-
being supplied and as a result data is still quoted on the ear- quently with mineral oils because of its m u c h lower solubil-
lier methods, sometimes together with the figures from the ity in this medium.
latest test. A further hot surface ignition method (The Hot Water can affect turbine oil in m a n y ways: it promotes
Manifold Test), based on FED-STD-791 Method 6053, is cur- rusting and subsequent wear, causes a reduction in the oil
rently being developed by ISO as Standard 20823 and may be stability—^possibly by partition of the additives into the wa-
preferred to autoignition temperature in the future as the ter—and, in the event of the formation of an emulsion, has
conditions more obviously simulate a n industrial hazard. a n adverse effect on lubrication performance and may cause
filter blockage [68]. The effects of water can be enhanced by
Wick Tests the presence of other contaminants such as oxidation prod-
The flammability behavior of the fluid when it is absorbed ucts, dirt, rust and other additive-treated mineral oils [69].
into a substrate (or wick) can be assessed by ASTM D 5306, With both phosphate and polyol esters, the effect of water is
fire products
collector
1.25 m
nozzle 1.4 m
® ® flexible
T propane
^ y - / ^ ^/connectors burner
floor
MdNn
' sample
pressure propane
vessel
load cell
/7777Z
FIG. 28—Factory Mutual Research spray ignition test equipment. Reprinted with per-
mission of Factory IVIutual Research, Norwood, MA.
to cause hydrolysis and acidity generation with a potential by applying a vacuum to the fluid. Physical methods for dry-
adverse effect on stability, rusting and corrosion perfor- ing used oil and fluid are practiced widely but currently the
mance, and surface active properties like emulsification. A use of chemical adsorbents is only found with fire-resistant
high water content in the long chain polyol ester hydraulic fluids.
fluid has also been found to promote bacterial growth Although the behavior of the fluid in use is more critical
which, in severe cases, has resulted in fluid gelatification due to the likely presence of contaminants and fluid degra-
[70]. dation products, new fluid is tested to ensure that emulsifi-
Water must therefore be removed from the fluid or oil as cation does not initially occur as a result of the use of surface-
quickly as possible. In steam turbine systems free water can active products such as corrosion inhibitors.
be removed using a centrifuge and by filters coated with wa- The method most widely used to assess this aspect of per-
ter-adsorbing polymers. Dissolved water is removed using ei- formance is ASTM D 1401, Standard Test Method for Water
ther chemiccd adsorbents, for example a molecular sieve, or Separability of Petroleum Oils and Synthetic Fluids, (ISO
ceramic
fibre cord
chart recorder
50 g weight 1
50 g weight
FIG. 29—Diagram of apparatus for determining linear flame propagation.
reservoir wick
stop holes for
adjustment
< •
TF5^
burner position for
setting flame height
r
|l
|l
|l
burner may
be raised and
lowered in
clamp
stop bar
from propane
regulating valve
FIG. 30—Equipment used for the ISO 14395 wicl( flame persistence test.
6614) where the fluid at 40°C is stirred with an equal vol- ning Calorimetry (PDSC), [71]) and voltammetric techniques
ume of water and the time taken for separation of the re- [72,73]. The PDSC method involves heating a known (small)
sulting emulsion (if formed), is noted. Typical limits for sep- quantity of the oil or fluid under pressure in oxygen at a fixed
aration to a residue of 3 mL emulsion are 30 min maximum temperature until an exotherm or release of heat occurs. The
(mineral oils) and 15 min maximum for phosphate esters. time to the onset of the exotherm is reported as the induction
time at the specified temperature. Although it is an extremely
Stability Characteristics rapid test, "no correlation has yet been established with ser-
vice performance."
Oxidative Stability The Remaining Useful Life of a Lubricant Evaduation Tech-
All fluids are assessed for their oxidative stability as their ser- nique (RULLET) has recently been developed to assist the
vice lives depend to a large extent on this property, and the ef- maintenance of military aircraft engine oils. In order to de-
fects of fluid degradation in terms of acidity generation, vis- termine the remaining useful life, it is first necessary to ther-
cosity increase, and the production of deposits can have an mally and oxidatively stress a fresh oil in the laboratory at
important impact on the system performance. The principal 150-175°C and monitor the chemges in acidity and viscosity
methods used for evaluating oxidative stability were indi- as the test proceeds. When the changes in these values start
cated earlier in the discussion on the testing of antioxidants. to deviate from a steady increase, this point is taken as the
These methods are additionally used to assess the effects of end of the useful life in service and intermediate data on the
other additives, e.g., rust inhibitors on oxidation stability and oil are used to predict the percentage remaining life in service
assessing the performance of complete formulations. (Fig. 31 [73]). This method has good repeatability and appar-
In addition to the Universal Oxidation Test designed to ently correlates well with RBOT and PDSC tests.
overcome the long test duration associated with the ASTM D Cyclic voltammetric techniques can be used to quantify the
943 test, other approaches have been or are being evaluated. remaining antioxidant concentration in used oil or fluid [73].
These include a dry version of the TOST and, for research This technique involves the extraction of the antioxidants by
and development, quality control and residual life assess- a solvent containing a dissolved electrolj^te. The solvent/elec-
ments, high pressure differential scanning calorimetry trolyte system will vary depend on the type of fluid and an-
(ASTM D 6186, Standard Test Method for Oxidation Induc- tioxidant being analyzed. Using the solvent/electrolyte, a volt-
tion Time of Lubricating Oils by Pressure Differential Scan- age is applied across an electrode system consisting of a
Hours of stressing time

50 100 150 200 250
I l__ 1-22
21
--20
--19
(^
o
18 b
To
178
' ' in
--16
-Lis
200 150 100
IHours of remaining useful life
FIG. 31—Percent remaining useful life (RUL), viscosity (40°C) and total acid number
against h of stressing time and remaining useful life at 175°C for a typical aircraft engine
oil. Reproduced with permission of STLE, Park Ridge, IL.
"glassy" carbon electrode, a platinum reference electrode, Hydrolytic Stability

and a platinum auxiliary electrode. The voltage of the auxil- This property assesses the fluid stability in the presence of
iary platinum electrode is scanned from 0 to 1.5 V at 0.2 moisture. Normally the effect of water is to generate the acid
V/sec. Data is produced by measuring the current through the and alcohol (or phenol) from which the ester was originally
cell as a function of the applied potential and the different an- formed. All esters are sensitive in varying degrees to water
tioxidants produce a typical "signature" from which the com- and, since hydrolysis is the normal mode of breakdown, it is
position can be deduced. Comparison of the current pro- an important factor in determining the Hfe of both phosphates
duced for each antioxidant with reference data on solutions and the polyol ester fluids used in hydraulic and aero-engine
containing known amounts of the stabilizer will reveal the lubricant applications. In steam turbine systems particularly,
level of the antioxidant in the used oil. It was found possible water contamination of the hydraulic fluid and lubricant is of-
to correlate the remaining oil life with the residual antioxi- ten found and requires regular monitoring. As noted earlier
dant concentration, and both techniques can be of benefit in (Table 9) the structure of phosphates affects their hydrolytic
applying predictive maintenance. stability and may influence the selection of product for use in
The importance of avoiding deposits in aviation gas tur- steam (wet) or gas (dry) turbine applications.
bine lubricants is such that an additional full-scale bearing The test procedure most commonly used for assessing hy-
test that simulates engine behavior is specified for these oils. drolytic stability is ASTMD 2619, Standard Test Method for
Details of the test used to assess this aspect of performance Hydrolytic Stability of Hydraulic Fluids (Beverage Bottle
are given in FED-STD-791 method 3410 and involve lubricat- Method). In this test the fluid and water are mixed together
ing a heated 100 mm diameter roller bearing with the test in a rotating sealed container for 48 h at 93°C in the presence
fluid at an elevated temperature (between 300-400°F or of a solid copper catalyst, followed by measurement of the
149_204°C) for 100 h. At the end of the test the bearing is as- acidity level in both the fluid and the water layers and the
sessed for deposits against a "demerit rating scale" while the metal weight change. Procedures are available for fluids that
weight of filter deposits and changes in oil viscosity and acid- are more or less dense than water and Fig. 32 shows the bot-
ity are also measured. tle with oil, water, and catalyst coupon.
Thermal Stability
Tests for this parameter fall into two categories:
1. Those carried out in the absence of air, e.g., FED-STD-791
method 3411 (despite the fact that it is almost impossible
n
to find a condition where the oil or fluid is heated in the
complete absence of air).
2. Those where oxygen is present and may cause further
degradation over and above the physical and chemical
changes resulting from the thermal degradation of the oil.
An example of this type of test is ASTM D 2070, Standard
Test Method for Thermal Stability of Hydraulic Oils.
The Federal standard method is currently only used in avi-
ation turbine oil specifications, e.g., MIL-PRF-23699F, prob-
ably for historical reasons and to provide additional support
for the oxidation stabihty data in applications where the tem-
peratures are very high. This procedure involves sealing a
li
portion of the fluid together with a steel specimen in a glass
ampoule under vacuum, heating for 96 h at 274''C and then
determining the changes in viscosity, acidity, and the weight
of the metal catalyst. Limits of 5% on viscosity change and
6.0 mg KOH/g on acidity increase are called for in the above
specification.
The ASTM method involves heating the fluid (200 ml) in an
open beaker together with iron and copper catalyst rods for
168 h at 135°C. At the completion of the test the color of the
rods, which is the principal evaluation criterion, is assessed
and the amount of sludge produced, determined. This proce-
dure is used primarily to evaluate the stability of mineral hy-
draulic oils and is strongly influenced by the presence of ad-
ditives. However, the standard notes, "No correlation of the
test to field service has been made." By contrast the FED-
STD-791 method could be used to discriminate between ester
types that display different levels of stability depending on FIG. 32—The ASTM D 2619
their chemical structure. Diesters, for example, are able to beverage bottle container
find a decomposition path at lower temperatures due to their with oil sample (upper layer),
ability to more readily form a cyclic intermediate [74]. water, and copper catalyst.
For steam turbine control fluids, ISO 15596 is used. It is a injector nozzle set at a predetermined lifting pressure, for ex-
static procedure that is uncatalyzed and the acidity increase ample 17.5 MPa (175 bar) for 30 cycles, (ASTM D 3945, Stan-
of both fluid and water layers is measured. In this test, a limit dard Test Method for Shear Stability of Polymer-Containing
on total acidity increase of 0.5 mg KOH/g is specified. Oils Using a Diesel Injector Nozzle). More recently, ASTM D
5275, Standard Test Method for Fuel Injector Shear Stability
Shear Stability for Polymer-Containing Fluids has been published. The latter
Shear stability is an additional requirement that is part of method was originally Procedure B of the D 3945 method but
some specifications for non-hydrocarbon oils. This is the re- was separated after tests showed that the two procedures in
sistance of the fluid to shear stress as the fluid is forced the earlier method often gave different results. Although the
through a neirrow aperture and which can result in the break- principle of the two methods is the same, the equipment dif-
down of long-chain molecules into smaller units. It is of par- fers and the latest test uses conditions of 20.7 MPa (207 bcir)
ticular importance for hydraulic applications in view of the and 20 cycles. In both cases, reference fluids are required to
high pressures and very fine tolerances involved in pumps and calibrate the equipment prior to evaluating the test samples.
valves, particularly when the fluid contains a high-molecular- A concern over the lack of field correlation with the results
weight polymer, as is the case with polyol ester fire-resistant from the diesel injector rig has recently led to the proposal in
hydraulic fluids [66]. However, no specification requirements Europe to use a tapered roller bearing as the means for shear-
yet exist for the shear stability of these fluids in steam or in- ing the fluid. This is Co-ordinating European Council (CEC)
dustrial gas turbine applications. Limits do exist, however, for method L-45-A-99, "Viscosity Shear Stability of Transmis-
some aero-gas turbine oils, e.g., in the MIL-PRF-23699F spec- sion Lubricants" that promises improved precision and bet-
ification. This requirement is thought to date back to the sub- ter correlation with field data.
mission of thickened diester lubricants against early versions
of the specifications. The instability of these fluids resulted in
the addition of a limit on this parameter. Turbine oils (of all Rusting and Corrosion Behavior
t5rpes) are themselves quite shear stable. The requirement for an oil or fluid to prevent rusting (of fer-
Specifications for fire-resistant fluids based on phosphate rous metals) and corrosion (of non-ferrous metals) is an ex-
esters have, for many years, stipulated that polymeric thick- isting part of nearly all hydrocarbon turbine oil specifica-
eners are not to be used as additives. This was due to their re- tions. While most rust tests are carried out at typical bulk
moval by the conditioning media (usually fullers earth) with fluid temperatures of 35-60°C, high temperature corrosion
the resulting blocking of filter cartridges and a marked re- performance requires evaluation either by oxidation/corro-
duction in fluid viscosity. sion tests or by specific high temperature tests in non-oxidiz-
Shear stability has traditionally been measured by two ing conditions such as those specified by the aviation turbine
techniques viz resistance to high-frequency sound and circu- builders. Some tests, e.g., gas turbine "hot end corrosion"
lation under pressure through an orifice. cannot be satisfactorily simulated in the laboratory and re-
quire evaluation in an engine test.
Sonic Shear The most widely-used test for assessing rusting character-
The technique specified in MIL-PRF-23699F requires expo- istics was reported earlier as ASTM D 665, Standard Test
sure under prescribed conditions to vibrations from a sonic Method for Rust Preventing Characteristics of Inhibited Min-
oscillator followed by a measurement of the change in vis- eral Oil in the Presence of Water. In spite of the title, the
cosity (ASTM D 2603, Standard Test Method for Sonic Shear method is also used for non-hydrocarbon oils and there is pro-
Stability of Polymer-Containing Oils or ASTM D 5621, Stan- vision for the testing of products such as phosphate esters,
dard Test Method for the Sonic Shear Stability of Hydraulic which are heavier than water. Although it may be difficult to
Fluid). The scope of the early version of this method, which distinguish between the ratings for "moderate" and "heavy"
was last reviewed in 1998, indicated that while useful for rusting in this test, this is largely academic, as specifications
quality control purposes, it did not show good correlation normally call for a "Pass," that is, the absence of rust.
with the service behavior of polymer-containing oils and may One of the limitations of the D 665 method is that it evalu-
rate different types of thickener in a different order to the ates rusting on vertical surfaces only. In reality, horizontal
diesel injector test. The latest method however, states, "Evi- surfaces that can retain droplets of water are more prone to
dence has been presented that a good correlation exists be- rusting. A method has therefore been devised "to indicate the
tween the shear degradation that results from sonic oscilla- ability of oils to prevent rusting and corrosion of all ferrous
tion and that obtained in a vane pump test procedure." surfaces in steam turbines." This is ASTM D 3603, Standard
The principle of the test is first to degrade a reference fluid Test Method for Rust-Preventing Characteristics of Steam
with a sonic probe at 0°C using sufficient power for 12.5 min Turbine Oil in the Presence of Water (Horizontal Disk
to produce a viscosity decrease at 40°C of about 15%. Then, Method). The test involves immersing a horizontal steel disk
using the same power setting that gave the above level of vis- and a vertical steel cylinder in a stirred mixture comprising
cosity change, to irradiate the test fluid at 0°C for 40 min fol- 275 mL of the oil and 25 mL of distilled water for 6 h at 60°C.
lowed by a determination of viscosity. The initial and irradi- At the end of this period the specimens are washed and in-
ated viscosities at 40°C are reported. spected for rust. The test is carried out in duplicate and no
rust must be seen in either of the two tests for the oil to be
Resistance to Shear in a Diesel-Injector Nozzle considered a pass.
The second procedure involves measuring the viscosity loss The above procedures only consider rusting in fluid con-
at 100°C after the fluid has been circulated through a diesel tact with the metal surface whereas vapor-phase rusting is
also possible, for example above the liquid layer in the tank. passivators can minimize this problem, use of stainless steel
This condition is simulated in ASTM D 5534, Standard Test or titanium coolers—or even dry cooling—is now possible.
Method for Vapor-Phase Rust-Preventing Characteristics of Lead, silver, a n d magnesium, which are also prone to
Hydraulic Fluids. With the exception of cin additional steel acidic corrosion, may need special protection when used.
specimen, which is located in the vapor space above the liq- These metals have been used in aero-engine systems as
uid, the apparatus and test conditions are identical to those lightweight casings for components (magnesium) and in sol-
found in ASTM D 3603. The method is divided into two parts, der (lead a n d silver). To prevent magnesium corrosion the
the first relating to fluids where water is the continuous surface is painted and propyl gallate has been used as an in-
phase and the second to fluids where oil or other water-free hibitor for lead. A test for lead corrosion still features in MIL-
fluids (except phosphates) are in the continuous phase. In the PRF-7808L. This is FED-STD 791, method 5321, which in-
latter case the water necessary to cause corrosion is con- volves immersing lead and copper specimens in the fluid for
tained in a bcciker located below the specimen for assessing 1 h at 325°F (162°C) during which time air is passed through.
vapor-phase corrosion. Results are reported as a pass or fail. At the conclusion of the test the weight change of the lead
The introduction of a corrosion-inhibited grade of fluid in panel is measured. The same specification also requires a
the MIL-PRF-23699 specification has also resulted in the in- corrosion test to be carried out on silver and bronze using
corporation of a humidity cabinet test (ASTM D 1748, Stan- FED-STD-791, method 5305. This is a high temperature test
dard Test Method for Rust Protection by Metal Preservatives carried out at 450°F (232°C) in which strips of each metal cire
in the Humidity Cabinet.) This procedure involves immers- immersed in the oil for 50 h followed by an assessment of the
ing steel plates in the fluid, allowing them to drain and then weight change.
exposing t h e m to water vapor in the cabinet. The time tciken In systems using phosphate esters, a l u m i n i u m surfaces
for the production of rust is monitored. need to be hard anodized to prevent attack by acidic degra-
In use, metals of different t3rpes may be in contact with one dation products.
another and the potential difference of the metal couple in
these conditions can influence gcJvanic corrosion, particu-
Lubrication
larly with water-based fluids. An attempt to simulate this
condition for non-aqueous fluids is found in the CETOP The lubrication performance of a n oil or fluid can be re-
Method RP 48H, which is also being published as ISO 4404 garded as its ability to reduce weeir on metal surfaces sliding
Part 2. In this test, selected metal pairs in electrical contact, relative to one another under load. It is a combination of the
after cleaning and pre-weighing, are half immersed in the performance of the fluid base stock and the additive package.
fluid for 28 days at 35°C in a covered beaker. At the end of the All the finished fluids discussed so far are acknowledged to
test period the weight change is measured and examination have good lubrication performance and for most steam and
made of the specimens for signs of corrosion, including the gas turbine applications there are no additional lubrication
surface above the liquid layer, which will indicate whether performEince requirements. Occasionally there is a call for a
vapor-phase corrosion has tciken place. 4-ball wear test—ASTM D 4172, Standard Test Method for
Hydraulic or lubricating oil systems containing phosphate Wear Preventative Characteristics of Lubricating Fluid. This
esters can be made from either mild or stainless steel and, involves measuring the wear produced on three ball bearings
while rusting can occur with these fluids, it is not a common held stationary in a cup containing the test fluid. A fourth ball
occurrence and is normally limited to the area above the liq- is rotated in contact with the stationeiry bccirings while a load
uid layer in the tank where condensation occurs. If the tcink (normally 40 kg) is applied for a period of 1 h (see Fig. 33).
interior is coated with phosphate, this forms a protective For oils needing extreme pressure performance, a gear-test
layer and reduces the possibility of rusting. In cases where failure load may be specified. As indicated above, this is now
the mild steel surface does not come into contact with the carried out according to ASTM D 5182, S t a n d a r d Test
fluid, condensation may be prevented by maintaining w a r m Method for Evaluating the Scuffing Load Capacity of Oils
fluid in the tank and/or passing dry air over the surface of the (FZG VisucJ method), or in aviation oils by the Ryder Gear
liquid in the reservoir. As a result it is now standard practice Test.
to leave the interior surfaces of hydraulic systems unpainted
when using phosphate esters. In the past, epoxy coatings
were recommended, but unless the coating can be cured in Cleanliness
position, the long-term resistance of this type of paint cannot The importance of clean oil, to ensure that small orifices in
be guaranteed. However, due to the reduced risk of rusting valves remain clear, that bcciring surfaces cire undamaged,
with these fluids in turbine applications, the frequent use of and that p u m p s and motors r u n smoothly, is now well ac-
stainless steel systems and the possible removal of inhibitors cepted. Dirt can EJSO play a part in catalyzing oil and fluid
by the adsorbent solids used in fluid conditioning to main- degradation by stabilizing foam and increasing oxidation. It
tain low levels of acidity, there is normally no rusting re- may also promote emulsification in the presence of water
quirement in the specification for this type of fluid. and increase the conductivity of the fluid. Limits on cleanli-
With regard to non-ferrous metals, the corrosion of cop- ness have therefore become steadily tighter over the years. At
per/brass as is found, for example, in turbine oil coolers, can the same time the variety Eind efficiency of filters has im-
be a problem for all oil types, as the dissolution of this metal proved [53]. Today, turbine lubrication systems use 6 fim
will catalyze oil oxidation. The potential for oils to cause cor- (j8 = 200) filters while hydraulic systems generally have finer
rosion of copper and its alloys and the use of ASTM D 130 for filtration, typically 3 jam (jS = 200) filters to remove particles
assessing this condition was mentioned above. While metal as small as 3.0/im "absolute" in view of the use of fine toler-
Top ball turned

by drive motor
3 lower balls
clamped
Thermocouple
A/V\AAAA^ Heater
FIG. 33—Schematic of the four-ball wear test apparatus.
ance valves, such as servo-valves, where clearances can be of based on the assumption that the deposit is distributed
the order of 3-5 microns. evenly over the filter. Potentially the most accurate proce-
Several methods are available for the determination of par- dure, and sometimes used as a referee method in cases of dis-
ticulate levels. These fall into the categories of automatic pute, is the gravimetric method in which a known volume of
counting by light interruption techniques, manual counting fluid (usually 100 mL) is passed through a filter disk with a
of particles deposited on a filter paper, and gravimetric pro- pore diameter of 0.45^lm or 0.80/Am and the weight of the de-
cedures. posit accurately determined (ASTM D 4898, Standard Test
Light interruption methods are probably the most widely Method for Insoluble Contamination of Hydraulic Fluid by
used of the above and involve the passing of a fixed volume of Gravimetric Analysis). ISO 4405 is based on the same tech-
the fluid across a light beam. When a particle interrupts the nique. Again the method does not indicate the size of the par-
beam a record is made and the size is registered depending ticles, a factor that can be of use in determining the possibil-
on the extent to which the beam has been blocked. The parti- ity of damage to equipment and may also suggest the source
cle counters will automatically allocate the reading to one of of the contamination. For example, the presence of sub-mi-
several pre-programmed size ranges depending on the range cron sized particles can be indicative of "dieseling" in the hy-
required by the specification, for example, to a range of, draulic system.
>5)U,m, 5-15)am, 15-25jam, 25-50Atm, 50-100/j.m, etc. While The ability of the light interruption technique to size parti-
it is a relatively quick way of counting particles, it is not the cles in bands or ranges allows the development of a classifi-
most precise. It presupposes that the sample is homogenous, cation system based on the maximum number of particles in
i.e., the particles are evenly dispersed and that they are regu- each band. Original attempts to rank the contamination lev-
larly shaped—assumptions that are entirely theoretical. Light els of hydraulic fluids were published as ASTM, SAE, and
interruption techniques can also count products dispersed in NAS standards. However the distributions used were largely
the fluid, e.g., antifoams. The ASTM method using this tech- geometric progressions that were unrelated to the actual pat-
nique is F 661, Standard Practice for Particle Count and Size tern of particle distribution found in hydraulic fluids [76]. As
Distribution Measurement in Batch Samples Using an Opti- an alternative, ISO subsequently published a standard, 4406,
cal Particle Counter, while the equivalent ISO standard is Hydraulic Fluid Power-Fluids-Method For Coding Level of
4402. Contamination by Solid Particles, the latest version of which
The membrane filtration methods are more accurate. In (1999) classifies particles into ranges of >4 ^m, >6 ^m, and
the manual counting method, e.g., ASTM F 312, Standard > 14 ^tm, respectively and, depending on the numbers of par-
Test Method for Microscopical Sizing and Counting Particles ticles in each range, allocates a "scale number." This makes
from Aerospace Fluids on Membrane Filters, a known vol- possible a numerical description for the particulate levels in
ume of fluid is filtered through a membrane filter, the surface both new and used fluids. For example the scale number 15
of which is divided into squares of known and equal size. The corresponds to 160-320 particles/mL and scale number 12 to
number of particles in a representative selection (at least 10) between 20 and 40 particles/mL.
of these squares is then counted manually and sized and Most turbine oil and fluid specifications still have to be up-
scaled-up to produce an approximate total number on the fil- dated and are using the previous version of the ISO classifi-
ter pad. (ISO 4407/4408 are similar manual counting meth- cation based on the number of particles >5 /i,m and >15 yam
ods.) This procedure is very time-consuming and is also in size. They typically call for scale numbers of 17/14 or 18/15
for turbine lubricants and 15/12 for the control fluids. How- eter, which is the reciprocal of conductivity, has been found
ever, such is the pace of change that the SAE 749D classifica- to relate to the tendency of the fluid to produce servo-valve
tion procedure, which was disowned by SAE in 1971, is still erosion [63]. This is an electrochemical process caused by the
occasionally specified. development of a "streaming current" close to the valve sur-
In order to obtain meaningful data from any of these tests face arising from fluid flow across the valve. As well as being
it is essential that the correct sampling procedure, in terms of influenced by the chemical structure of the fluid, it also de-
where and how to take a sample from the system or container, pends on the presence of contaminants such as water, acid,
be used. ISO 4021, for example, indicates how samples should chloride ions, dirt, and metal soaps. Even polar additives can
be taken from the lines of an operating system. ISO 3170 de- reduce the resistivity.
tails suitable sampling procedures from containers while ISO The problem initially arose when polychlorinated biphenyls
3722 details how containers should be cleaned before use, a were used as fire-resistant fluids in turbine control systems
point that is frequently overlooked and can invalidate particle and investigators linked the phenomenon with chlorine con-
count data. It is also important to ensure that the sample bot- tent and low resistivity. A minimum limit on resistivity of 5 or
tle is compatible with the fluid being sampled. 10 by 10' ohm.cm. (50 or 100 Mi2m) was therefore introduced
and is now part of all fire-resistant control fluid specifications.
This property is measured by ASTM D 1169, Standard Test
Trace Metals Method for Specific Resistance (Resistivity) of Electrical In-
The introduction of trace metal analysis into turbine oil spec- sulating Liquids. Internationally, the method specified is lEC
ifications is now found quite widely, but for different rea- 60247, Measurement of Relative Permittivity, Dielectric Dis-
sons. sipation Factor, and d.c. Resistivity of Insulating Liquids.
In mineral turbine oils the trend to ashless products, and Both procedures involve measuring the resistance between
particularly away from the use of zinc dialkyldithiophos- the terminals of a test cell when a specified voltage is applied.
phate as an antioxidant/extreme pressure additive, has led to Accurate measurement of the test temperature is important as
the introduction of limits on zinc content. Current specifica- resistivity is very sensitive to this property. While the lEC
tion limits can be very low (about 2 ppm meix.) or somewhat method precisely specifies the voltage gradient, the ASTM
higher levels (100 ppm max.). procedure allows considerable latitude in this key aspect. In
In aviation gas turbine lubricants, limits of 2-10 ppm, de- order to improve the correlation between the methods, the
pending on the metal concerned, have long been in place. voltage gradient along with other test variables such as elec-
This is to minimize contamination, to avoid a possible cat- trode gap and test temperature should be the same. In view of
al5îc effect on oxidative breakdown, and because certain the effect of small amounts of impurities on the results, it is
organo-metallic additives, used in the past as extreme pres- important that no additional contamination of the sample
sure additives, precipitated on storage. Today, the data also takes place. Consequently, the sampling of the fluid and the
functions as baseline or reference information for the spec- cleanliness of the sample container are very important when
trographic oil analysis programs (SOAP), which are used to evaluating this parameter. Figure 34 shows a general view of
monitor the condition of used military aviation gas-turbine the test equipment used for determining volume resistivity,
lubricants. With phosphate esters, the final processing step in while Fig. 35 is a diagram of a typical test cell.
manufacture may involve contact with alkaline media to
lower the acid number and the resulting presence of soluble
metal salts can promote foaming and an increase in air re- Compatibility with System Materials
lease properties [77]. In use, phosphate esters are normally In selecting system components for use with both mineral
treated by an adsorbent medium to remove acidic degrada- and synthetic turbine oils, it is important to ensure that the
tion products. However, the most widely used adsorbents, fluid is compatible with the constructional materials, that is
fullers earth and activated alumina, contain compounds that contact with the fluid should not result in significant changes
react chemically with the acids to form soluble metal salts to the physical or chemical properties of the material. Small
[78]. These salts can adversely the surface-active properties changes are to be expected in some materials and, indeed,
of the fluid and therefore need occasional monitoring. One may be beneficial. For example, the controlled swelling of a
method used for measuring low levels of metal contaminants seal will help it fill the cavity and maintain its performance at
in hydrocarbon oils is ASTM D 4951, Standard Test Method high pressures.
for Determination of Additive Elements in Lubricating Oils
The main concerns in this area are the behavior of seals,
by Inductively-Coupled Plasma Atomic Emission Spectrom-
paints, and gasket materials in the presence of the operating
etry. With phosphate esters, this method can give incorrect
fluid. Inadequate compatibility with a seal, for example, may
results on certain metals (e.g., sodium) and for this medium
cause the swelling or softening of the rubber due to penetra-
at least, atomic absorption spectrometry (AAS) is preferred.
tion by the oil or fluid, with subsequent fluid leakage. The use
The ASTM procedure for AAS (D 4628) is currently targeted
of unsuitable paints could cause softening, flaking and sub-
towards the analysis of barium, calcium, magnesium, and
sequent filter blockage, perhaps leading to pumping prob-
zinc but can easily be adapted to detect other metals.
lems. Occasionally there are incompatibility problems with
metals. Phosphate esters do not "wet" the surface of alu-
minium and therefore this metal is unsuitable as a bearing
Volume Resistivity material for these fluids.
One requirement that is specific to phosphate ester control Hydrocarbons are generally less searching than synthetic
fluids is the measurement of volume resistivity. This param- fluids in this area although the PAOs are problematic owing
to their lack of seal swelling and necessitate the use of a co- tensile strength. Depending on the rubber type and applica-
component (usually a carboxylate ester) as a seal-swelling tion, the test temperature may vary significantly. Fluorocar-
agent. bon and perfluorocarbon rubbers are, for example, evaluated
The high operating t e m p e r a t u r e s experienced in a n in- at higher temperatures than nitrile and neoprene. However,
creasing n u m b e r of applications, for example aviation gas tests at high temperatures, e.g., 150°C as currently appear in
turbine lubricants, place severe stress on conventional elas- the latest draft ISO 6072 standard, may not be representative
tomers. Consequently, the use of fluorocarbon (and, to lesser of practice since, at this temperature, the basestocks and ad-
extent, perfluoroelastomer) seals is now widespread. Phos- ditive packages may not be stable and could give erroneous
phates eire also very selective with regard to seals and paints, results.
but fortunately a suitable range of materials is now available. Until recently, all methods specified relatively short peri-
Examples of suitable elastomers for turbine oils and fluids ods of immersion, usually u p to one week. It is now accepted
are given in Table 20. A general procedure for testing for the that this period may be too short for the degree of swell to
compatibility of seals in non-aerospace applications is de- have stabilized, and in the latest version of ISO 6072, tests of
tailed in ISO 6072, Hydraulic Fluid Power-Compatibility be- 1000 h in length are now proposed in addition to the shorter-
tween fluids cind standard elastomeric materials, while the term exposure.
aero-gas turbine oil specifications require performance No s t a n d a r d m e t h o d s in turbine oil specifications are
against FED-STD-791 methods 3604 and 3433 or procedures known for evaluating paint compatibility and this aspect is
listed by the equipment manufacturers. An ASTM standard generally left to the paint manufacturers w h o u n d e r t a k e
entitled "Standard Test Methods and Suggested Limits for long-term tests.
Determining the Compatibility of Elastomer Seals for Indus- The aspects of compatibility discussed above relate only to
trial Hydraulic Fluid Applications" is currently in develop- the fluid/constructional material interface. There is EJSO the
ment. Table 21 illustrates the conditions recommended for aspect of the compatibility of different oils and fluids with
testing different elastomers in the ISO 6072 standtird. The list each other. Should fluids from different manufacturers be
indicates the principal types of elastomers used with the dif- mixed? This aspect is viewed differently by different indus-
ferent fluids, but is not exhaustive. tries. On the one h a n d it is a condition of militciry aviation oil
All the procedures involve suspending a rubber specimen specifications that all approved products should be compati-
of known volume in the oil or fluid u n d e r fixed conditions of ble with one another. If this were not the case it could impair
temperature and test duration. This is followed at the end of the combat readiness of aircraft. In the industrial power gen-
the test by a second measurement of the volume to determine eration market some equipment builders specify that a new
the percentage swell that has occurred. Additional measure- fluid must be compatible with the residue of the previous
ments may be made of the chemges in elongation at break and charge without any adverse effect on the new oil. However,
FIG. 34—A general view of the test equipment for measuring d.c. resistivity.
090
1
1
1 = inner elecrode
2 = outer etecrode
3 = guard ring
4 = inner elecrode
5 = silica washer
6 = silica washer
7 = minimum level
of liquid
Volume of liquid is about 45 cm^

All surfaces in contact with liquid have a mirror finish
Dimensions in millimetres
FIG. 35—Example of a three-terminal resistivity cell. Reprinted with
permission of the International Electrotechnical Commission, Geneva,
Switzerland.
nothing is indicated regarding topping-up an existing fluid the builder had investigated the compatibility of the two flu-
with a product from a different supplier, probably because ids cmd/or the user had accepted the risk associated with mix-
such an occurrence is unusual. Obviously, mixing fluid tjrpes ing. In some cases oils can be mixed without problems but
that are not completely miscible should be avoided. Some laboratory tests are advisable to check the effects of physical
concern has also been expressed regarding the mixing of and chemical (in)compatibility, e.g., the impact on stability
products that have the same base material but different ad- and the surface active properties (e.g., foaming and air re-
ditive packages. This is because of possible interaction of the lease). The test used by the aviation turbine oil industry,
different additives resulting in a reduction in performance. FED-STD-791 method 3403, Compatibility of Turbine Lubri-
Very often, the attitude of the turbine builder is not to allow cating Oils, involves checking the miscibility with reference
the use of a second oil (for top-up) during the warranty pe- ester-based lubricants. Mixtures of the test oil and the refer-
riod of the turbine. Afterwards this would only be accepted if ence lubricants at three concentrations are heated in an oven
for 1 week at ZZl^F (105°C) followed by a determination of THE IMPORTANCE OF SYSTEM

the sediment produced. CLEANLINESS
One emphasis in this chapter has been on ensuring the clean-
Volatility liness of the oil or fluid. However, there is no advantage in
In military aviation applications where a low viscosity oil is having a clean fluid only to fill it into a dirty system. The per-
used in a high temperature environment, for example the 3 formance advantages of fresh fluid would soon disappear in
cSt oils specified in MIL-PRF-7808L, it is necessary to ensure these circumstances.
that the oil is not too volatile. This is determined in ASTM D There are two situations where attention to the system
972, Standard Test Method for Evaporation Loss of Lubri- cleanliness is most important. The first is during commis-
cating Greases and Oils. This procedure involves passing air sioning of the new equipment or after major overhauls when
at 400°F (205°C) over the surface of a weighed quantity of oil the system is flushed. This procedure will remove dirt,
heated to the same temperature and held in a test cell of spec- preservative oils and greases, cleaning solvents, and other
ified dimensions. After 6'/2 h the weight loss of the sample is residual matter from cleaning and assembly operations, e.g.,
determined. In order to ensure that the equipment is provid- welding slag and cleaning rags. Effective flushing may in-
ing the appropriate level of severity, a test is carried out with volve removing or blanking-off system components and sep-
a reference liquid and, if necessary, a correction factor ap- arately cleaning them while dividing the pipework into sec-
plied. The test limit is 10% maximum. tions and circulating a flushing fluid through each section,
Assuming that the new fluid meets all the requirements preferably under turbulent flow conditions to remove as
laid down in the specifications it may still be necessary to ar- much debris as possible.
range trials in the turbine builder's equipment. These can re- Some builders remove rust by "pickling" the pipework by
quire several years of satisfactory operation and be very circulating a dilute solution of acid followed by a water wash
costly to arrange and carry out. and then dry with a current of warm air.
In the past, chlorinated solvents have been used to remove
TABLE 20—Elastomer compatibilities of different
oil films on components during assembly and residual prod-
turbine oils and fluids. uct in the hydraulic system has subsequently caused servo-
Mineral Oil Phosphate Polyol
valve erosion [63]. As a result, use of this tjrpe of solvent is
Seal/Hose Material and PAOs Ester Ester now banned and has been replaced by hydrocarbons or, in
Neoprene Yes No No
some cases, by water-based products. Preservative oils con-
Nitrile Yes No Yes" taining inhibitors that prevent rust during the transportation
Chlor-sulphonated Yes Yes'' Yes and storage of the equipment can cause foaming of the oper-
polyethylene ating charge if they are not adequately removed.
Epichlorhydrin Yes No No
Styrene-butadiene No No No
The second important use of a flushing charge is when re-
Ethylene-propylene No Yes" No placing badly degraded fluid, which, in addition to contain-
Butyl No Yes No ing acid, may have resulted in deposit formation. In this case
Fluorocarbon Yes Yes* Yes it is important to remove all but traces of the previous fluid
Perfluoroether Yes Yes Yes and any associated deposits by a thorough flush and, if nec-
PTFE Yes Yes Yes
essary on examination, a manual cleaning of components in-
"Variations in the composition of these elastomers in particular can cause cluding the tarrk interior.
differences in fluid compatibility and the seal manufacturers should be
consulted before use. More detailed guidance on the cleaning and flushing of lu-
^Fluorocarbon rubbers are compatible with aryl phosphates, but not with brication systems is given in ASTM D 6439, Standard Guide
alkyl phosphates.
for the Cleaning, Flushing and Purification of Steam, Gas
TABLE 21—Conditions recommended for testing the compatibility of elastomers with different turbine fluids.
ISO Suitable Temperature Duration of
Fluid Classification Test Elastomer °C± 1 Test" h ± 2
Mineral oils HH, HL NBRl, 2 100
HM, HR HNBRl 130 168 1000
HV FKM2 150
Aryl phosphate esters HFDR FKM2 150 168 1000
EPDMl 130
Polyol esters HFDU NBRl, 2
HNBRl 100 168 1000
FKM2
Synthetic hydrocarbon HEPR HNBRl 130 168 1000
FKM2 150
"The test duration of 1000 h is recommended for evaluation of elastomer compatibility with highly critical fluids.
NBR = nitrile (acrylonitrile butadiene)
HNBR = hydrogenated nitrile
EPDM = ethylene propylene
FKM = fluorocarbon
Reprinted courtesy of the International Organization for Standardization, Geneva, Switzerland.
and Hydroelectric Turbine Lubrication Systems and, for hy- or not the system is being commissioned, and if opera-
draulic systems, in ASTM D 4174, Standard Practice for the tional problems are being experienced. Using the data pro-
Cleaning, Flushing and Purification of Petroleum Fluid Hy- duced to establish trends in performance can assist in iden-
draulic Systems. Both documents relate specifically to hy- tifying the source of problems and when action may be
drocarbon oils and discuss the types of contamination found needed [80].
in practice, how they can be controlled, guidance on suitable Unlike the extensive range of specifications available on
flushing procedures, oil sampling techniques, and condition fresh oil or fluid, the situation with regard to the used oil is
monitoring. For non-hydrocarbon fluids, information is to be less complicated. Many, but not all, of the turbine builders in-
obtained from the fluid manufacturers or other appropriate corporate used oil requirements into their new oil specifica-
standards, e.g., lEC 60978, Maintenance and Use Guide for tions. A few have separate standards and some of the oil or
Triaryl Phosphate Ester Turbine Control Fluids, which pro- fluid suppliers offer guidance in the absence of information
vides similar information except for recommendations on from the turbine manufacturers. Where no builder recom-
flushing. mendations exist, guidance is also available from national/in-
The fluid used for flushing is often the operating charge, ternational standards. For mineral turbine oils there are
but this is expensive if a second charge of fluid is used for ASTM D 4378, Standard Practice for In-service Monitoring of
normal operation. If only small amounts of the flush fluid are Mineral Turbine Oils for Steam and Gas Turbines; the lEC
left in the system after flushing and draining, the use of a Standard 60962, Maintenance and Use Guide for Petroleum
chemically similar material, usually the base stock for the op- Lubricating Oils for Steam Turbines; and the very detailed
erating charge may be considered. However, if significant EPRI report referred to earlier [79]. For fire-resistant hy-
quantities of the flush fluid remain in the system when the draulic fluids, lEC 60978 and ISO 7745, Hydraulic Fluid
operating charge is filled-in, the use of a cheaper fluid could Power-Fire-resistant Fluids-Guidelines for Use, are avail-
be counter-productive. The use of flush fluids that are a dif- able, while for aero-engine oils there are recommended lim-
ferent chemical type to the operating charge is to be avoided its on acidity and viscosity increase from the turbine
in view of concerns with regard to their compatibility with builders, but otherwise no published requirements. The
system components and the fact that it is very difficult to re- rapid rate of top-up of oil in this application—even in indus-
move residues from the system. trial applications—means it is unlikely that the physical
Depending on the level of contamination acquired during changes in fluid quality would normally reach values of con-
the flush, it may be possible to re-use the flushing fluid sev- cern.
eral times. The above industry guides are comprehensive documents
which typically examine the reasons for fluid degradation
and its impact on fluid performance, identify fluid sampling
techniques, give appropriate tests for monitoring both new
TURBINE OIL AND FLUID MAINTENANCE and used oil behavior, as well as a proposed schedule for
their use. Table 22, which is taken from ASTM D 4378, iden-
EPRI Report CS-4555 [79] comments that "failures of steam tifies the turbine properties of gas and steam turbine oils
turbine bearings and rotors cost the utility industry an esti- that are monitored in service, their warning limits and ap-
mated $150 million/year" and "one third of these failures in- propriate action to be taken in the event that these limits are
volve contaminated lubricants or malfunctioning lubricant exceeded. Quite a wide range of tests can be used to monitor
system supply." It is unfortunately the case that many of the fluid degradation, etc. These can be divided into primary
operating problems found with turbine oils and hydraulic tests that check for specific degradants or contaminants and
fluids are due to poor maintenance, occasionally com- secondary tests, the results of which are influenced by the
pounded by inadequate system design. As operating condi- degradant or contaminant. An example would be the mea-
tions become more severe, the importance of regular main- surement of water, which can be determined directly and in
tenance (both system and fluid) increases. This comes at a esters, its presence may be implied from a reduction in vis-
time when utilities are achieving cost reductions by shed- cosity or a rapid increase in acid number.
ding jobs and trying to increase equipment availability. As a Acidity is probably the most important property moni-
consequence, there is a distinct possibility that non-essential tored on a regular basis, but is the parameter most fre-
maintenance will suffer and the improvements in oil perfor- quently disputed. As indicated earlier, of the two techniques
mance available as a result of recent technical developments used for determining the acid number of both new and aged
will not be fully utilized. fluid or lubricant, only the potentiometric method is really
An essential part of all planned maintenance is the ability suitable for aged fluid [81]. This is because the fluid darkens
to carry out regular fluid monitoring. This involves taking on ageing and it becomes more difficult to estimate the end-
representative samples from the system under strictly de- point in the colorimetric method. Some fire-resistant fluids
fined conditions as indicated, for example, in the above are also dyed to ensure that they are not confused with min-
ASTM and ISO Standards and then evaluating critical pa- eral oils and for such fluids this technique is also unsuitable,
rameters to determine the current condition of the material. particularly when new.
Implicit in such a scheme is the availability of limits on these Other important properties that are routinely measured
parameters and recommendations on appropriate action for all Quids include viscosity, water content, and particulate
should they be reached. Also important is the frequency levels. In addition, rapid changes in color and appearance
of sampling. This will vary depending on the particular can be indicative of developing problems. A measure of the
parameter involved, the stress on the fluid in use, whether residual life or stability of the product may also be advanta-
TABLE 22—Interpretation of test data and recommended action for mineral turbine oils.
Steam (S) Oil Life
Test Warning Limit or Gas (G) (Running Hours) Interpretation Action Steps
Acid no. 0.1-0.2 m g K O H / g s up to 20 000 h This represents above normal Investigate cause.
Increase over G up to 3000 h deterioration Increase frequency of
new oil Possible causes are: testing—compare with
a) system very severe RBOT data.
b) antioxidant depleted Consult with oil supplier for
c) wrong oil used possible reinhibition.
d) oil contaminated
Acid no. 0.3-0.4 mg KOH/g S, G at any time Oil at or approaching end of Look for signs of increased
Increase over during life of service life, c) or d) above sediment on filters and
new oil oil charge may apply centrifuge. Check RBOT. If
less than 2 5 % of original,
review status with oil
supplier and consider oil
change. Increase test
frequency.
RBOT less than hcJf value S up to 20 000 h Above normal degradation Investigate cause.
on original oil Increase frequency of testing.
RBOT less than half value G up to 3000 h Above normal degradation Investigate cause.
on original oil Increase frequency of testing.
RBOT less than 2 5 % of S, G at any time Together with high acid no. Resample and retest. If same,
original oil indicates oil at or consider oil change.
approaching of service life.
Water content exceeds 0 . 1 % at any time Oil contaminated. Investigate and remedy cause.
Potential water leak. Clean system by suitable
method.'' If still
unsatisfactory, consider oil
change or consult oil
supplier.
Cleanliness exceeds accepted S, G at any time Source of particulates may Locate and eliminate source
limits" be: a) make-up oil; b) dust of particulates. Clean
or ash entering the system; system oil by filtration or
or c) wear condition in centrifuge or both.
system.
Rust test D 665, light fail up to 20 000 h a) the system is wet or dirty Investigate cause and make
procedure A* or both necessary maintenance
b) the system is not changes. Check for rust.
maintained properly (e.g., Consult oil supplier
water drainage neglected, regarding reinhibition if test
centrifuge not operating.) result unchanged.
Rust test D 665, light fail S, G after 20 000 h Normal additive depletion in Consult oil supplier regarding
procedure A* wet system. Maintenance reinhibition.
Appearance hazy S, G at any time Oil contains water, and Investigate cause or centrifuge
solids or both remedy. Filter. oil or both.
Color unusual and rapid S, G at any time This is indicative of: Determine cause and rectify.
darkening a) contamination
b) excessive degradation.
Viscosity 5% from original S, G at any time a) Oil is contaminated, Determine cause. If viscosity
oil viscosity b) oil is severely degraded, or is low, determine flash
c) higher or lower viscosity point. Change oil if
oil added. necessaiy.
Flash point drop 30°F or more S, G at any time Probably contamination. Determine cause. Check other
compared to new quality parameters.
oil Consider oil change.
Foam test D 892 exceeds following S, G at any time Possibly contamination or Rectify cause. Check with oil
limits antifoam depletion. In new supplier regarding
Sequence 1 tendency: 450 turbines residual rust reinhibition.
stability: 10 preventatives absorbed by NOTE: plant problems often
oil may cause problems mechanical in origin.
"Definition of suitable cleanliness levels depends on turbine and user requirements.
^Satisfactory for land turbines.
'Âppropriate methods may include centrifuging, coalescence, or vacuum dehydration.
geous. This can be obtained either by determining the RBOT reduce the operating margins for new business cind encour-
value, an indication from analytical methods of the level of age the suppliers to provide "cradle-to-the-grave" service
antioxidant concentration, or by the use of voltammetric agreements whereby they maintain the fluid throughout its
techniques. For phosphate esters, volume resistivity may ad- life, supply top-up material as needed, and eventually dispose
ditionally need to be monitored in order to avoid the possi- of the degraded product. The development of in situ condi-
bility of servo-valve erosion. tion-monitoring techniques will assist station staff in deter-
One basic difference between the use of fire-resistant flu- mining the level and timing of necessary fluid maintenance.
ids/lubricants ajid hydrocarbon oils and synthetic esters is The trend to environmentally friendly fluids, where re-
that, in order to remove the acid that is normally formed as quired, may also develop—^particularly for water turbine ap-
a result of fluid hydrolysis or oxidation, the fire-resistant flu- plications, where some experience has been obtained with
ids are purified or reconditioned in situ. This involves pass- biodegradable fluids [83].
ing the fluid on a by-pass loop from the m a i n reservoir One recent development not previously mentioned that
through an adsorbent solid that removes acid and chloride may have a future impact on the lubrication of gas turbines
from the fluid and also acts as a fine particle filter. For many has been the successful evaluation in a static engine test of a
years fullers earth has been used for this purpose but has of- vapor-phase lubricant based on a tertiarybutylphenyl phos-
ten resulted in the formation of soluble calcium and magne- phate [84,85]. Very small amounts of the lubricant are va-
sium soaps, which have h a d an adverse effect on fluid foam- porized and react with the metal surface of a ceramic bearing
ing a n d air release properties a n d w h i c h eventually to form a polymeric film that can sustain a load. The imme-
precipitate in the form of gels in filters and in parts of the diate interest appears to be for missiles and other unmanned
system where the fluid is cooled [80]. In an attempt to avoid aero-space vehicles because of the reduced weight penedty
this problem, other treatments have been used, notably acti- with the smaller volume of liquid required, b u t wider use in
vated alumina and blends of purified activated eJumina with the longer term may be possible.
alumino-silicates. The latter is a definite improvement but
can still eventually result in the dissolution of sodium and Acknowledgments
aluminium in the fluid unless the acidity is kept very low The author gratefully acknowledges the kind assistance (and
[80]. More recently, the use of ion-exchange media h a s patience) of R. Coombes and G. N. Kay of Alstom Power, M.
shown great promise a n d now enables the life of the fluid to Dennis of Rolls Royce, D. Irvine of Petro-Canada Lubricants,
be extended almost indefinitely [78] with a very positive ef-
G. Jones of G.E. Energy, E. Letterman of General Electric
fect on fluid maintenance costs and almost eliminating the
Power Systems, H. Moeller of Elsam, M. Morris, Consultant,
need for fluid disposal.
Dr. T. Okada of ExxonMobil, Dr. L. Quick of Siemens A. G.,
J. Pankowiecki of Siemens Westinghouse a n d B. Rayner,
Consultant. Lastly, thanks are cJso due to Alan Holt of Great
FUTURE TRENDS Lakes Chemical Corp. for the photographs and to Alan Wat-
son for editorial assistance.
Many of the developments discussed in the course of this
chapter will continue to influence the development and avail-
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MNL37-EB/Jun. 2003
Hydraulic Fluids
W. A. Givens^ and Paul W. Michael^
T H E PRIMARY PURPOSE OF A HYDRAULIC FLUID is to transfer Where:

power. The concept of fluid power is based on a principle ar- K = Bulk modulus
ticulated by Blaise Pascal, which is usually given as follows: Vo = Original volume
"Pressure applied to an enclosed fluid is transmitted undi- AP = Pressure change
minished to every portion of that fluid and the walls of the Ay = Change in volume
containing vessel" [1]. Within the context of fluid power,
pressure is related to the force acting on a confined fluid as
illustrated in Fig. 1 [2]. This principle has given rise to mod- Heat Transfer
e m hydraulics, which entails highly engineered systems for Heat is generated as a by-product of normal operation of a
efficiently controlling fluid flow to transfer energy and ac- hydraulic circuit. Friction between the moving parts of a
complish work. p u m p or hydraulic motor, as well as friction between the
The heart of any hydraulic system is the pump, which pulls fluid and surfaces of valves, pipes, and other circuit devices
in fluid from a reservoir by creating a vacuum at its inlet and generates heat. In addition, heat is generated in a hydraulic
then forces the fluid through its outlet, usually against pres- system as a result of the dissipation of the potential energy of
sure created by flow controllers and/or actuators down- pressurized fluid [8]. As a hydraulic fluid is circulated
stream of the p u m p . Pumps, actuators, and other system through a system, heat is transferred from high temperature
components have surfaces that move relative to each other, areas to coolers, reservoirs, and other regions of the circuit
often at high speeds, pressures, and temperatures. These where it is dissipated. As can be seen in Table 1, typical spe-
components require cooling and lubrication for efficient per- cific heat and thermal conductivity values for hydraulic oils
formance and durability. Consequently, hydraulic fluids not are a fraction of that of water [4]. These factors are an im-
only must transmit power, they serve critical functions as lu- portant consideration in sizing hydraulic system coolers be-
bricant and heat transfer medium. cause the inherent cooling efficiency of petroleum based hy-
draulic fluid is less than that of water. ASTM D 2717, Test
Method for Thermal Conductivity of Liquids and ASTM D
P o w e r Transfer 2766, Test Method for Specific Heat of Liquids and Solids are
used to determine these properties of fluids.
To transfer power efficiently, a hydraulic fluid must exhibit
minimal compressibility. Low compressibility allows all of
the pressure applied to the fluid to be available for direct Lubrication
and effective transmission to system components such as
motors, cylinders, or other actuators. The compressibility of The durability of hydraulic equipment depends to a large ex-
a fluid is generally discussed in terms of its "bulk modulus," tent upon the lubricating properties of the fluid. As a lubri-
which describes the change in fluid volume as a result of ap- cant, the key function of the hydraulic fluid is to reduce fric-
plied pressure [3]. The bulk modulus of a fluid, which is the tion between contact surfaces. A reduction in friction lowers
reciproccd of compressibility, is described by Eq 1. There contact t e m p e r a t u r e s a n d wear. This is accomplished
are a n u m b e r of m e t h o d s available for estimating the through a combination of hydrodjoiamic and boundary lu-
isothermal secant bulk modulus of a fluid based upon its brication mechanisms. The hydrodynamic lubricating prop-
viscosity and density characteristics [4,5]. As depicted in erties of a fluid are governed by its physical properties while
Fig. 2, the bulk modulus for oil also varies with temperature boundciry lubrication is a function of fluid chemistry. A dis-
cussion of hydraulic fluid wear testing is presented in the
[6]. For petroleum oils, compressibility is often assumed to
Wear Protection section of this chapter.
be 0.5% for each 1000 psi pressure increase u p to 4000 psi
[7].
Bulk modulus {K) = -Vo (\PI\V) (1) TRENDS

A brief outline of major trends in the motion control indus-
* Exxon Mobil Research & Engineering, Paulsboro Technical Cen- try, particularly with respect to hydraulic equipment design
ter, 600 Billingsport Rd., Paulsboro, NJ 08066. and fluid requirements, is presented as a backdrop for the
^ Benz Oil, 2724 West Hampton Avenue, Milwaukee, WI 53209. discussion of hydraulic fluids test methods. As motion con-
353
Force
Area
F = force in pounds
p = pressure in pounds / sq. incli (psi)
A = sq. in.
FIG. 1—Relationship of force, pressure, and area in fluid power. Any one of the param-
eters equals the other two in the relationship depicted by the triangle.
TABLE 1—Thermal conductivity and specific

heat values for oil and water.
40
Thermal Thermal Specific Specific
Conductivity Conductivity Heat Heat
Btu/h/ft^/F/Ft W/m-K BTU/lb°F J/kg • K
^ 30 @ 212°F @373K @68°F @293K
M
Q. Oil 0.08 0.14 0.47 1966
Water 0.39 0.67 1.0 4184
z
CO
20
I 10
Smaller c o m p o n e n t s will m e a n smaller p u m p displace-
ments [cubic inches or cc per p u m p revolution]. To main-
3
tain flow rates at present or higher levels, p u m p speeds will
m be increased [cubic inches/minute = displacement X speed
(rpm)]. Smaller reservoir sizes will mean shorter fluid res-
100 200 300 idence times and will therefore dictate use of hydraulic flu-
ids with improved air release characteristics.
FIG. 2- -Effect of temperature on the bulk modulus of petroleum Smaller dimensional clearances will be required. These
fluid. smaller clearances will dictate more stringent fluid cleanli-
ness requirements to prevent abrasive wear from particu-
late c o n t a m i n a n t s a n d failure of servo or proportional
trol technology advances, there is a trend towards higher per- valves.
formance and efficiency. For hydraulic equipment, this Fluid cleanliness will increasingly be emphasized as an ef-
translates into a concentration of horsepower in smaller fective way of increasing equipment durability and con-
components. There are a n u m b e r of reasons for such a trend. trolling warranty costs. As a result, users will move to finer
Equipment manufacturers are looking for ways to minimize filtration and specify pre-filtered hydraulic fluids [9]. Con-
raw material usage and cost. Users of the equipment demand sequently, the filterability of the hydraulic fluid will con-
smaller systems for better space utilization in industrial en- tinue to grow in significance. (Filterability is described in
vironments cind compact multifunctional capabilities in mo- section 4.6.)
bile equipment. These advancements in mechanical design Quieter hydraulic systems will be required in order to meet
along with e n c r o a c h m e n t of environmental, health, and workplace noise restrictions and compete with electric mo-
safety regulations fuel the following trends: tors. Reduction of noise levels in hydraulic equipment has
• Hydraulic equipment builders will continue to push com- been attained by the insulation that absorbs the noise. This
p o n e n t manufacturers to design parts to a c c o m m o d a t e insulation results in higher system temperatures, as heat is
high pressures a n d t e m p e r a t u r e s . F o r example, hoses, not as readily dissipated.
valves, and other fittings will continue to evolve in terms of Components and actuators, such as cylinders, will be de-
materials used as well as actual functional design. signed with tighter seals to increase efficiency and reduce
CHAPTER 13: HYDRAULIC FLUIDS 355
leakage. The effects of this trend include increased stress Solvent refining yields base oils that fall into Group I while
on seal materials and cylinder chatter resulting from re- hydroisomerization and deep hydrogenation processes yield
duced lubrication between seal and cylinder wall. In addi- low sulfur, high paraffin content Group II a n d Group III
tion, certain applications will require fill-for-life systems base stocks. Because of their lower aromatic and sulfur con-
that translate into lower maintenance and disposal costs. tent, hydraulic fluids formulated from Group II and Group
Consequently, fluids will remain in a system for longer pe- III base stocks typically have superior oxidation stability.
riods, since meike-up fluid is not required. However, more highly refined stocks tend to be less effective
• A growing awareness of the environmental impact of at dissolving additives. Not only is additive solubility a con-
chemicals will lead to further restrictions on performance cern, additive chemistries and their functional mechanisms
additives eind base stocks used in lubricants. As a result, may be b o t h synergistic a n d antagonistic. Thus, additive
lubricant p r o d u c e r s are required to address such is- chemistry must be ceirefully balanced to achieve optimum
sues through alternative (usually more costly) chemistry performance. In the following section, test methods for eval-
and the development of environmentally friendly (non- uating key fluid properties such as oxidation stability, wear
toxic/biodegradable) lubricants. prevention, and corrosion inhibition are discussed. These
• The hydraulic fluid industry has evolved from the use of methods have been developed to measure characteristics of
plain water in hydraulic systems to the use of advanced hydraulic fluids that are thought to correlate to performance
fluid technologies that continue to evolve as performance in "real-life" applications as well as gage additive response
requirements become more stringent and equipment defor the fluid formulator. In order to provide a link between
signs become more sophisticated [10]. Due to environmen- fluid tests and additive chemistry, a description of the gen-
tal health and safety issues, hydraulic systems are once erally accepted functional mechanisms of additives is also
again being designed to employ pure water as hydraulic included.
fluid [11].
PETROLEUM BASE STOCKS FLUID CHARACTERISTICS AND

PERFORMANCE
Most hydraulic fluids consist of a base fluid and additives
that are designed to i m p a r t chemical characteristics and Oxidation a n d Thermal Stability
functionality to the finished product. Operating conditions
An important characteristic of a hydraulic fluid is its ability
and equipment builder specifications generally dictate the
to withstand high temperatures. This is because horsepower
type of fluid that is needed and thus, the kind of base stocks
losses in hydraulic systems directly result in transfer of heat
and additives employed. In petroleum based hydraulic fluids
to the fluid. Resulting high temperatures can cause hydraulic
the typical concentration of additives is less than 3.0% by
fluids to react with oxygen. The rate of this reaction acceler-
weight. Paraffinic oils are the primary base stock utilized in
ates exponentially with increasing temperatures and is fur-
hydraulic fluids but other materials, from polyglycols to veg-
etable oil, serve as the basis for formulating hydraulic fluids. ther catalyzed by metals like copper and iron, especially at
From a historical standpoint, solvent reflned paraffinic oils temperatures above 200°F [14]. Rate constants for the oxida-
have been the most widely used base stock for hydraulic ap- tion of saturated hydrocarbons at 125°C are as much as 40
plications. In recent years alternative refining processes such times higher than rate constants at 60°C [15]. Thus, fluid ox-
as catalytic isomerization and deep hydrogenation have been idation is highly dependent upon hydraulic system operating
developed to yield higher purity base oils that are better temperatures. Lubricants expected to operate in high tem-
suited to withstand severe operating conditions [12]. These perature environments are tjrpically fortified with additives
base stocks are categorized by the American Petroleum Insti- known as antioxidants, which are discussed in the Antioxi-
tute (API) according to their composition and viscosity index dants section. Oxidative stabilization of the fluid translates
[13]. Groups I through III consist of crude derived base oils directly into extended oil service life. Failure to resist oxida-
while Group IV is reserved for synthetic polyalphaolefins. tion can result in thickening of the oil (viscosity increase),
Low viscosity index naphthenic oils and other base stocks formation of acidic byproducts, and subsequent deposit for-
that do not meet Group I through IV criteria are classified mation.
as Group V. The API Base Oil classification is described in Not only can heat cause oxidation, fluids may thermally de-
Table 2. grade upon exposure to high temperatures with litde or no
oxygen present. The thermal stability of a hydraulic fluid is
TABLE 2—API base oil classifications. dependent mainly on the intrinsic ability of the base fluid or
Viscosity its components to resist decomposition at high temperatures.
Category Composition Suliîr Index Unlike oxidation, controlled thermal degradation of certain
Group I < 9 0 % Saturates or >0.03% 80-120 types of additives [such as Zinc Dialkyldithiophosphate
> 1 0 % aromatics (ZDTP)] is desirable, because it is the very mechanism by
Group II £ 9 0 % Saturates or <0.03% 80-120 which they react with the metal surfaces they are designed to
< 1 0 % aromatics
protect [16]. Similar to oxidation however, the negative ef-
Group III > 9 0 % Saturates or <0.03% >120
< 1 0 % aromatics fects of thermal degradation may include increased acidity,
Group rV All polyalphaolefins (PAO) thickening of the oil, and deposit formation. Therefore, good
Group V All others not included in control of thermal degradation results in the retention of de-
Groups 1,11, m or IV sired fluid properties.
High Temperature/Oxidation Tests range. The hours to form 2.0 m g of KOH equivalents of acidic
One of the most commonly sited methods for measuring the oxidation products per gram of some typical fluids are shown
abihty of a fluid to resist oxidation is ASTM D 943, Standard in Table 3. In general, turbine oils provide longer TOST oxi-
Test Method for Oxidation Characteristics of Inhibited Min- dation life t h a n antiwear hydraulic fluids because turbine
eral Oils (also known as the Turbine Oil Oxidation Stability oils typically do not contain zinc dialkyldithiophosphate
Test - TOST). In this test, 300 ml of fluid a n d 60 ml of distilled (ZDTP). Zinc dialkyldithiophosphate r e d u c e s the t i m e it
water are placed in a large test tube together with coils of takes for a fluid to reach 2.0 mg KOH/g because it is acidic
copper and iron wire (Fig. 3). The fluid is heated to 95°C and its mere presence raises the acid n u m b e r of the fluid. In
(203 °F) and oxygen is bubbled through the fluid at a con- addition ZDTP is subject to hydrolysis and forms acidic com-
trolled rate. The test is complete when the Total Acid Num- pounds as it degrades. Ester based fluids such as rapeseed
ber (AN) of the fluid reaches 2.0 mg KOH/g. As can be seen oils are also subject to hydrolysis, which accounts for their
from the reaction scheme in Fig. 5, cJdehydes eire among the poor performance in the D 943 test. When the D 943 test is
chemical by-products of hydrocarbon oxidation. These alde- run without water (dry method), the oxidation life of a syn-
hyde compounds are readily converted to carboxylic acids in thetic ester can be extended by nearly a factor of 100.
the hydraulic system [17,18]. Since carboxylic acids are cor- The a m o u n t of sludge produced in the TOST test may be
rosive to yellow metals and agglomerate to form deposits, measured by ASTM D 4310, Test Method for Determination
they have a detrimental effect upon fluid performance when of the Sludging Tendencies of Inhibited Mineral Oils. In this
their concentration becomes excessive. The concentration of test, the fluid is subjected to D 943 test conditions for 1000 h.
acidic oxidation debris present in a fluid can be determined At the end of this time, the sludge produced is determined
by titration with potassium hydroxide. For the D 943 test, a gravimetrically by filtration of the oxidation tube contents
variation on ASTM D 664 Acid N u m b e r of Petroleum Prod- through 5-/u,m pore size cellulose acetate filter disks. To a cer-
ucts by Potentiometric Titration is used. This method, ASTM tain extent the D 943 and D 4310 tests evaluate different
D 3339, Test Method for Acid N u m b e r By Semi-Micro Color mechanisms of high temperature degradation. In the D 943
Indicator Titration is utilized because it permits a 0.2-1.0 g test, acidity is measured and this acidity is predominantly
sample size for total acid numbers in the 0.5-3.0 mg KOH/g due to formation of carboxylic acids by the conventional liq-
uid phase oxidation mechanism shown in Fig. 4. In essence
D 943 measures the stability of the base oils and the effec-
tiveness of oxidation inhibitors. Sludge formation in hy-
draulic oils is to a greater extent due to theimal degradation
of the ZDTP antiwear additive. Consequently, the result of a
D 4310 test is an indication of the thermal stability of ZDTP.
Figure 5 shows a model for the mechanism of sludge forma-
tion by zinc dialkyldithiophosphate [19].
Another method for measuring the sludging tendency of
hydraulic fluids is the Cincinnati Machine Heat Test [20].
This test has been adopted as an ASTM procedure and is des-
ignated ASTM D 2070, Standard Test Method for Thermal
Stability of Hydraulic Oils. In this test, polished pre-weighed
copper and steel rods are placed in a beaker containing 200
OXYGEN cc oil and heated to 135°C (275°F) for 168 h. At the end of the
DELIVERY test, the copper and steel rods are examined for discoloration
TUBE due to corrosion caused by carboxylic acids and sulfur com-
pounds formed by thermal degradation. Sludge content and
viscosity increase are also measured (Table 4).
Antioxidants
Oxidation inhibitors, commonly referred to as antioxidants,
are chemicals that reduce the rate at which oxidative degra-
dation of a lubricant occurs. Degradation begins with the re-
CATALYST action of hydrocarbon molecules at elevated temperatures to
COILS form unstable reactive species known as free radicals. These
TABLE 3—D 943 turbine oil oxidation test life of

typical hydraulic fluids.
Hours to TAN of
Fluid Type 2.0 by D 943 Method
Synthetic ester without antioxidant 65
Mineral oil without additives 300
Antiwear hydraulic oil. Group I base stock 2016
Antiwear hydraulic oil, Group 11 base stock 5040
FIG. 3—Oxidation cell and sampling tube for Synthetic ester with antioxidant, dry method 5500
R & O hydraulic oil >10,000
ASTM D 943 apparatus.
Temperature _
Initiation RH Alkyl radical
Light, catalyst
Propagation R • + O2 -• ROO* Peroxy radical
ROO• + RH -• ROOH + R* Hydroperoxide
Branching ROOH -*• RO • + • OH Alkoxy radical
RO» + RH -> ROH + R • Alcohol
• OH + RH -> H2O + R • Water
Termination R • + ROO • Alcohols
RO • + ROO • Aldehydes
ROO • + ROO • Ketones
RO • + R • Acids
Longer chain
R« + R«
hydrocarbons
FIG. 4—Reaction scheme for liquid hydrocarbon oxidation.
Hydraulic Oil
RO S S OR Base Oil
Machines
(Paraffinic)
and Outside
and
Environment
RO S—Zn—S OR Additives
Reaction withi Decomposition

Thermal P^°''^^ Oxidation
Deterioration Reaction with
Degradation witii Water l\êtai Ions
ZnSq Polyphosphates
RO 0 0 OR Oxidation Wear Particles,
Products Dust, Rust, Water
\ ^ and andOtliers
RO 0- -Zn—0 OR Metal Soaps
T
Sludge
FIG. 5—Mechanism of sludge formation by zinc dialkyldithiophosphate.

TABLE 4—Cincinnati machine thermal stabihty Detergents IDispersants

test performance requirements.
Detergents and dispersants are used to delay formation and
Property Requirement
subsequent deposit of insoluble oil degradation species. The
Condition of steel rod terms detergent and dispersant are often used interchange-
Visual No discoloration
Deposits 3.5 mg maximum ably, but are generally differentiated by their composition
Corrosion 1.0 mg maximum and primary functionality. Detergents are metallo-organic
Condition of copper rod compounds that neutralize acidic deposit precursors, while
Visual 5 rating maximum dispersants are predominantly organic chemicals that keep
Corrosion 10.0 mg maximum insoluble materials dispersed a n d suspended in the lubricant.
Condition of fluid
Viscosity The t e r m "ashless" dispersants, m e a n i n g non-metallic, is
5% change maximum
Sludge 25 mg/100 mL max used to further differentiate dispersants from detergents.
Total acid number ±50 % maximum Some detergents have the ability to disperse and suspend in-
solubles, while some dispersants are capable of neutralizing
precursors of deposits. Typical lubricant detergents include
barium, calcium, and magnesium phenates, phosphates, sal-
species react with oxygen and non-oxidized oil to form addi- icylates a n d sulfonates. Ashless dispersants are typically
tional free radicals, which propagate the oxidation process. alkyphenol-based or alkyl succinimides.
This generally accepted mechanism is described as free rad-
ical chain reaction and is illustrated by the steps shown in
Fig. 4.
Antioxidants interrupt this chain reaction and thus, reduce
the rate of oxidation and the resulting viscosity increase and
acid and deposit formation. There are two general mecha-
nisms by which these additives inhibit oxidation. The antiox-
idants are therefore categorized as primary or secondary, de- (R0)3P?-0—O3
pending u p o n the m e c h a n i s m of oxidation inhibition. (R0)3P + R'OOH
Primary antioxidants, commonly referred to as "free radical
scavengers," react with the peroxy radicals and hydroperox-
ides to form inactive compounds (Fig. 6) [21]. Examples of
H
primary antioxidants include hindered phenols and aromatic
amines. Secondary antioxidants, commonly referred to as
"peroxide decomposers," react with hydroperoxides or per- (R0)3P=0 + HOR'
oxy radicals to form less reactive compounds. Examples of
secondary antioxidants include sulfur a n d / o r p h o s p h o r u s FIG. 7—Secondary antioxidants such as the phosphite com-
c o m p o u n d s a n d metal dithiophosphates (Fig. 7). Antioxi- pound depicted above inhibit oxidation by decomposing hy-
droperoxides. This prevents the oxidation process from pro-
dants genereilly function in the bulk lubricant and are con-
gressing beyond the branching stage In the reaction
sumed as they do their job [22]. mechanism.
o»
+ R00»
ROO^^R
FIG. 6—Reaction scheme for primary antioxidants. Primary or free-
radical trapping antioxidants work by donating a hydrogen radical H* to
the peroxy radical formed during mineral oil oxidation. Due to steric hin-
drance, the antioxidant radical does not attack mineral oil molecules,
i.e., R-H bonds. Consequently, the radical chain is terminated.
Wear Protection the TOW for straight grade mineral oil based hydraulic flu-
ids. The viscosity grade indicated in the TOW corresponds to
Reduction of friction and prevention of wear is the funda- ASTM D 2422, Classification of Industrial Fluid Lubricants
mental purpose of a lubricant. Lubricants reduce friction in by Viscosity System. For example, ISO 32 hydraulic oil gen-
machine components by producing a physical or chemical erally will provide satisfactory performance in a temperature
barrier between surfaces that slide or roll past each other. De- window of - 8 to 64°C.
pending on equipment design and function, lubricants func- There are several methods for measuring the viscosity of
tion within three commonly recognized regimes: hydrody- hydraulic fluid. The most widely utilized method is the ASTM
namic, mixed-film, and boundary lubrication (Fig. 8) [23]. D 445, Standard Test Method for Kinematic Viscosity of
Hydrodynamic lubrication is often the dominant lubrica- Transparent and Opaque Liquids. In this test, the time is
tion regime under conditions of moderate temperatures and measured for a fixed volume of liquid to flow under gravity
loads. According to the ASM Handbook on Friction, Wear through the capillary of a calibrated viscometer at a closely
and Lubrication Technology, [24] hydrodynamic lubrication controlled temperature. The kinematic viscosity is the prod-
is "a system of lubrication in which the shape and relative uct of the measured flow time and the calibration constant of
motion of the sliding surfaces causes the formation of a fluid the viscometer. Based upon D 2442 and ISO 3448, the stan-
film that has sufficient pressure to separate the surfaces." In dard temperature for measuring hydraulic fluid viscosity is
this regime, viscosity is the most important fluid characteris- 40°C [26]. Typically, the viscosity of a hydraulic fluid is 15-68
tic because it, in combination with sliding speed, contact ge- mm^/s (centistokes) at 40°C. ASTM D 446, Standard Specifi-
ometry and load, determines the thickness of the lubricating cations and Operating Instructions for Glass Capillary Kine-
film, and determines whether or not the surfaces will contact matic Viscometers, describes more than 15 types of viscome-
each other. ters that may be employed in performing a D 445 viscosity
Fluid viscosity plays an important role in hydraulic appli- test. With the exception of invert-emulsion type fluids, hy-
cations. A hydraulic fluid that is too low in viscosity will draulic fluids are generally transparent. Consequently, a tube
cause low volumetric efficiency, fluid overheating, and in- suitable for transparent liquids such as the popular Cannon-
creased pump wear. A hydraulic fluid that is too high in vis- Fenske viscometer may be used. For opaque liquids, a re-
cosity will cause poor mechanical efficiency, difficulty in verse-flow tube is required because it is difficult to see the
starting, and wear due to insufficient fluid flow [25]. Since meniscus as the fluid flows by the timing marks on a stan-
dard viscometer. Cannon-Fenske tubes for viscosity mea-
viscosity is a function of fluid temperature, the temperature
surement of transparent and opaque liquids are depicted in
operating window (TOW) for a particular viscosity grade of
Fig. 10.
hydraulic fluid is a function of temperature. Figure 9 depicts
1
MIXFn FN M
LUBRICA-•|ON
B OUNDARY
LIJBRICATION
0.1
c
o
o
c 0.01
g>
o
»^
O
o
0.001
hULL-hlLM
LUBRICATION
1
0.001 0.01 0.1 1 10
Sommerfeld number, (rjA// P) x 10"^

FIG. 8—Stribeck Curve of coefficient of friction versus Sommerfeld Number (S), where
S = r}N/P. N shaft speed; P, average pressure between shaft and bearing due to applied
load; 7), lubricant viscosity.
100 212
90 94 — 194
80 84 176
70 73 158 LL.
o 60 64 140
<D CD
V—
5 50
-I—•
55 122
44 104 CO
CD
I" 30 32 86 O.
j5^20 CO E
.<!>
10 +10
+4 50
0 -2 32
-8
-10 -15 14
-20 -23 -4
-30 — 3 3 -22
-40 -40
10 15 22 32 46 68 100
ISO Viscosity Grade

FIG. 9—^Temperature Operating Window (TOW) for 100 VI mineral oil based hydraulic flu-
ids. Based upon survey of viscosity requirements for hydraulic pumps and motors, fluids
will generally provide satisfactory performance at the temperature range that corresponds
to 13 to 860 cSt.
FIG. 10—Cannon-Fenske standard and reverse flow kinematic viscosity tubes, respectively.
Frequently in high-pressure hydraulic applications, the termined by the properties of the surfaces and by properties
loading conditions are sufficient to rupture hydrodynamic of the surfaces and lubricants other than viscosity [27 ]. In hy-
lubricating films. Consequently, boundary and mixed-film draulic equipment, these surfaces are typically composed of
lubrication regimes play an important role in controlling ferrous or yellow metals. Under magnification, tribologicsJ
wear in hydraulic applications. In boundary lubrication, fric- surfaces in hydraulic components reveal the presence of sur-
tion cind wear between two surfaces in relative motion are de- face asperities. High load conditions cause these aperities to
make contact, resulting in friction and weeir. In most cases, pressures, and entry angles in a functioning hydraulic system
mixed-film lubrication takes place and some hydrodynamic [29,30].
lubrication occurs, even as "asperity contact" creates bound- One of the more c o m m o n bench tests used for screening
ary conditions. Depending upon the extent of asperity con- the antiwear performance of a hydraulic fluid is the Four-
tact, scuffing or adhesive wear may occur. A schematic de- Ball Method. There are two versions of the test for liquid lu-
scription of the various wear processes specific to hydraulic bricants: ASTM D 2783, Standard Test Method for Measure-
p u m p s is shown in Fig. 11. When cavitation, corrosion, or ment of Extreme-Pressure Properties of Lubricating Fluids
scuffing wear processes generate particles that are the same (4-Ball Method) and ASTM D 4172, Standard Test Method
approximate size as p u m p clearances, synergistic wear may for Wear Preventive Characteristics of Lubricating Fluids (4-
take place. Sjmergistic wear ultimately leads to failure that Ball Method). The former method is generally used for eval-
may appear to be abrasive in origin [28]. u a t i n g extreme pressure gear lubricants while the latter
Wear protection under conditions of boundary lubrication method is used for evEiluating antiwear hydraulic fluids. In
may be enhanced through the use of additives that interact the 4-Ball Wear Test (D 4172), three half-inch diameter steel
with surfaces to form protective chemical films. (See the An- balls are clamped together and covered with the lubricant to
tiwear Performance Testing section for description of the be evaluated. A fourth ball of equal diameter is pressed with
boundary lubrication additives utilized in hydraulic applica- a force of 1 5 ^ 0 kg into the cavity formed by the three sta-
tions.) These chemical films reduce friction by decreasing the tionary balls making a three-point contact (Fig. 12). Lubri-
shear strength of the surface relative to the underlying mate- cants are evaluated by rotating the top ball under load at 1200
rial. Thus, surface interaction under boundary lubrication r p m for 60 min and measuring the average scar diameters
conditions is primarily between the low-shear strength chem- worn in the three lower balls.
ical films rather than the metal substrate. Good wear protec- In cooperative testing of fluids performed by members of
tion and friction reduction result in enhanced equipment ASTM D02.L on Industrial Lubricants, the addition of zinc
durability, reduced heat generation, improved energy con- dithiophosphate to 46 cSt mineral oil decreased the scar di-
servation, and many other operational advemtages.
Antiwear Performance Testing

The majority of hydraulic fluids are formulated with anti-
wear additives because surface loads associated with high-
pressure p u m p operation necessitate the use of fluids with
enhanced wear protection. There are a variety of test meth-
ods available for assessing the antiwear performance of hy-
draulic fluids. These tests may either be bench-top or full-
scale tests employing high-pressure piston and vane pumps.
Bench tests are generally less expensive to perform t h a n
p u m p tests. However, translating bench test data into real- (a)
world performance can be problematic because of the com- FIG. 12—The four-ball test:
plexity involved in simulating all of the materials, velocities. (a) perspective view, (b) plan view.
EXTEERNAL
PAR"riCLE
INGREESSION
\Air:Ap
VVtArl
CAVITATION JElr FATIGUE DEBRIS
WEAR
ASPERITY TOTAL
CONTACT ADHESIVE WEAR ABRASIVE WEAR
WEAR DEBRIS1 > WEAR
— ^ •
ELECTROLYTE
(WATER) CORROSIVE WEAR DEBRI S
WEAR WEAR
DFRRI.q
FIG. 11—Synergistic view of pump wear process. Fatigue, adhesive, and corrosive wear
can be triggered Independently. Resulting wear debris generation leads to abrasive wear.
ameter in 4-ball wear tests from 0.72 m m to 0.42 m m at 40kg mL of oil that is heated to 90C (194°F). The test gear set is r u n
[31]. These results are tjpical of a mineral oil based antiwear in the test fluid for 15 min at successively increasing loads
hydraulic fluid where average scar diameters of less than 0.50 until the failure criteria is reached. According to the ASTM
m m are the norm (P. W. Michael, unpublished data). procedure, failure criteria are reached when the summed to-
While four-ball tests are effective in screening antiwear ad- tal width of scuffing wear damage from all 16 teeth is esti-
ditive response, they do not directly correlate with p u m p mated to equal or exceed one gear tooth width. In DIN 51524,
tests [32]. This is in part due to the fact that loads in the four- Part 2, a m a x i m u m weight loss of 0.27 mg/kW h for antiwear
ball tests are constant and do not pulsate in the same way hydraulic oil is specified as well as a m i n i m u m damage stage
that a hydraulic p u m p does as sliding surfaces transition of 10. While Reichel reported a correlation between FZG Test
from high pressure to low pressure regions of the pump. In results and hydraulic fluid performance in vane pumps, cor-
an effort to enhance the correlation between the four-ball test relation with piston p u m p performance has proven difficult
and full-scale p u m p eveJuations Penn State University has to establish [35].
performed investigations involving sequential four-ball wear The most widely referenced vane p u m p wear test for hy-
tests. In the sequential four-ball test, wear scars are evaluated draulic fluids is ASTM D2882, Standard Test Method for In-
at 10 and 40 kg and 600 r p m and the diameter of the scar is dicating the Wear Characteristics of Petroleum and Non-
measured after the fluid has been replaced by white oil in or- Petroleum Hydraulic Fluids in a Constant Volume Vane
der to measure the durability of the antiwear film [33,34]. Pump (Vickers 104C). In this test, a hydraulic fluid is circu-
This method yields better correlation with vane p u m p tests. lated through a rotary vane p u m p for 100 h at a p u m p speed
The FZG Test is another bench test used for screening hy- of 1200 r/min and a p u m p outlet pressure of 2000 psi. The
draulic fluids. FZG test equipment consists of two gear sets fluid temperature is controlled to 150°F at the p u m p inlet for
arranged in a foursquare configuration (Fig. 13). The FZG most fluids. Petroleum based fluids with a viscosity greater
p r o c e d u r e is described in ASTM D 5182 S t a n d a r d Test than 46 mm'^/s and some synthetic fluids must be evaluated
Method for Evaluating the Scuffing (Scoring) Load Capacity at 175°F. At the end of the test, the total cam ring and vane
of Oils. In this test, pre-examined gears are immersed in 1600 weight losses are measured and reported. Based upon ASTM
Drive gear case
Test gears with

long addenda
FIG. 13—The Neimann (FZG) Four-Square Gear Test Rig.

D 6158, Standard Specification for Mineral Hydraulic Oils, biodegradable vegetable oil based hydraulic fluids [39]. This
less than 50 mg of total wear is expected from properly for- test is based on a Komatsu HPV35+35 twin-piston p u m p us-
mulated petroleum based antiwear hydraulic oil. For invert- ing cycled pressure test conditions. In this test p u m p effi-
emulsion type fluids, higher wear rates in the 100-200 mg ciency change, wear and surface roughness, formation of lac-
range are c o m m o n while water glycol fluids routinely gener- quer and varnish, a n d hydraulic oil deterioration are
ate less than 50 mg wear in the D 2882 test. evaluated.
While the D2882 test is a popular benchmark for evaluat- Rexroth has proposed a three-stage piston p u m p test based
ing hydraulic fluids, this method is not without its problems. on the Brueninghaus A4VSO piston p u m p [40]. Stage one is
First of all, Vickers has discontinued production of the conducted at the m a x i m u m operating pressure and tempera-
V104C p u m p . This will ultimately necessitate the use of sub- ture and at the m i n i m u m viscosity specified for the fluid be-
stitute hardware or abandonment of the test procedure. Sec- ing tested. The test duration is 250 h at which time the p u m p
ond, rotor and bushing failures are common in the first few is dismantled and inspected. The second stage of the test is
hours of the test. This may be due to the fact that the p u m p pulsed pressure test at the m a x i m u m displacement of the
was originally designed for a m a x i m u m pressure of 1000 p u m p . This stage is operated for one million cycles. When
psig. Fluid performance in the V104C p u m p is evaluated at this stage is complete, the p u m p is dismantled and inspected.
1000 psi using the ASTM D 2271, Standard Test Method for The third stage is a variable displacement stage at maximum
Preliminary Examination of Hydraulic Fluids (Wear Test). In pressure, maximum temperature, and m i n i m u m fluid viscos-
this procedure, the p u m p stand is operated for 1000 h, which ity. The test duration is 280 h at which time the p u m p is dis-
provides an extended evaluation of p u m p wear behavior un- mantled and inspected again. The final pass/fail assessment
der normal operating conditions. Xie et al. provide a detailed is made with reference to a standard damage catalog.
discussion of the D 2882 Test Method in the Handbook of Hy- The Sundstrand Water Stability Test Procedure test origi-
draulic Fluid Technology [36]. nally employed a Sundstrand Series 22 piston p u m p at a con-
For higher pressure a n d mobile applications Vickers stant pressure [41]. Currently, this test procedure is con-
prefers their 35VQ25 vane p u m p for screening hydraulic ducted using a Sundstrand Series 90 piston p u m p with a 55-cc
fluid wear performance (Table 5). In the 35VQ25 test, three displacement. The objective of the test is to determine the ef-
50-hour tests are conducted on the same charge of test oil. fect of water contamination on mineral oil hydraulic perfor-
For each 50-hour test a new p u m p cartridge is used. The test mance and yellow metal corrosion. However, other fluids, in-
rig is operated at 3000 psi and 200°F with a p u m p speed of cluding water-containing fluids such as HFB and HFC fluids,
2400 rpm. Vickers limits the amount of wear on each test kit may also be evaluated using this test. The test duration is 225
to 90 mg: 75 mg ring, 15 mg vanes. In addition there must be h, at which time it is disassembled and inspected for wear,
no sign of scuffing on the cam ring. corrosion, and cavitation. If the flow degradation is equal to
or greater than 10%, the test is considered to be a "fail."
The Denison T6C vane p u m p test is a variable pressure
vane p u m p test. In this test, a Denison T6CSH 020 p u m p cy-
Antiwear and Extreme Pressure (EP) Additives
cles between 7 b a r (—100 psi) and 250 bar (—3600 psi) at one-
second intervals for 300 h [37]. The p u m p speed is nominally Antiwear and EP additives prevent wear of metal surfaces by
1700 r/min a n d fluid t e m p e r a t u r e is m a i n t a i n e d at 80°C forming a protective chemical film between moving parts.
(176°F) for mineral oil based fluids a n d 45°C (113°F) for These additives have traditionally been labeled as antiwear or
those based on water. The test is r u n in two 305-hour se- extreme pressure (EP), depending on the mechanism of pro-
quences. Each 305-hour test consists of a 5-hour break-in pe- tection. Antiwear additives are generally considered to form
riod followed by 300 h of high pressure cycling. After the first protective films that adsorb on the metal surface and func-
305-hour test, the p u m p cartridge is removed for inspection tion effectively under relatively mild conditions of load and
t e m p e r a t u r e . Extreme pressure additives form protective
and a new cartridge is installed for the second sequence. The
films by reacting with the metal surfaces at localized high
second 305-hour sequence is r u n with 1% distilled water
temperatures to form low shear strength films that are rela-
added to the fluid. The first stage of the T6C test serves as an
tively insoluble in the bulk oil. In either case, tribological
aging mechanism and increases the susceptibility of the fluid
contact is between the surface films rather than the metals.
to the deleterious effects of water contamination. After the
second 305-hour sequence the p u m p cartridge is again re- Various types of chemistry are employed in the prevention
moved for inspection. As with the 35VQ25 test, weight loss of of wear in hydraulic applications. Typical compounds in-
cam ring and vanes, vane tip profile, and visual appearance clude zinc dialkyldithiophosphates (ZDTP), tricresylphos-
of all components are all reported. In addition, a wet filter- phates (TCP), sulfur compounds, amine phosphates, dithio-
ability test is performed on the fluid to determine if water carbamates, and other chlorinated, phosphorus/sulfur, and
contamination will lead to filter blinding. (See the Filterabil- molybdenum compounds.
ity section for a discussion of filterability tests.)
Although the V104C and 35VQ25 vane p u m p tests have Water Content a n d Hydrolytic Stability
served the industry well for many years, these tests are not In many hydraulic systems, the lubricant is susceptible to
sufficient to screen hydraulic fluids that will be used in high- contamination with water. Contamination with water can
pressure piston p u m p s applications [38]. Thus, piston p u m p lead to a host of problems including loss of lubricity, corro-
tests have been to qualify the antiwear capabilities of hy- sion, additive degradation, and filter plugging. Consequently,
draulic fluids. Komatsu, Rexroth, and S u n d s t r a n d piston machine builders and equipment users often attempt to limit
p u m p tests are described below. the amount of water that enters their hydraulic systems. At
K o m a t s u developed a piston p u m p test to evaluate the same time, fluid formulators endeavor to manufacture
TABLE 5—Machine builder specifications for antiwear hydraulic oil.
Denison HF-0 Vickers Cincinnati iWachine 6 M LS-2
Properties Method(s) Requirements Requirements . P68 P70 P69 LH-02 LH-03 LH-04 LH-06
ISOVG 32 46 68 22 32 46 68
Kinematic Viscosity, cSt D445
0°C max., calc. D 5133 300 420 780 1400
40°Cmax. 35.2 50.6 74.8 24.2 35.2 50.6 74.8
40°C min. 28.8 41.4 61.2 19.8 28.8 41.4 61.2
100°Cmin. 4.1 5 6.1 7.8
Flash Point °C min. D92 188 196 196 175 190 190 195
Fire Point, C min. D 92 215 218 218
Pour Point, °C, max D97 -21 -18 -15 -12
Color, max D 1500 2 3 3
ISO Contam. Code, max ISO 4406 19/16/13
Density @15°C D1298 0.84 - 0.90
TAN, mg KOH/g, max D664/ D974 <1.S>
Rust Test A D665 A Pass Pses
Rust Test B (Salt Water) 0665 B Pass Pass
Cu Rating (3 hr, 100°C), max. D130 <1b>
TOST Oxidation, Hours to 2.0 ,^^,
<1500>
TAN "*^
Air Release @ SOX, minutes Q » J ~ ,
5 5 10 10
(max)
Foam tendency/statxiity D892
Seq 1 max -10 <:50/0>
Seq II max -/O <SO/0>
Seq III max -10 <50/0>
DemulsilJility @ 54°C D1401 Timeto40/40«)(O/W/E)
<30>
FZG Fail Stage D 5182 <10>
Change in Hardness
NBR1,168hrs@100°C Oto-8 Oto-7 Oto-7 Oto-6
Change in Volume (%)
NBR1,168hrs@100°C OtolS 0to12 0to12 OtolO
Viscosity Index, min D 2270 90 <90> <95>
Aniline Point C min. D 611 100
CM Thermal Stabtity D 2070 A
Viscosity Change, % max <5> <5>
TAN Variation, % max * <50> <50>
Comparative IR Scan Record
Sludge, mg/100 ml max 100 < 25 mg. /100ml > < 25 mg. /100ml >
Cu metal removed, mg/200 ml, max. 10 <10> <10>
Copper rod appearance, rating (max.) Report <5> <5>
Steel deposits, mg/200 ml, max <3.5>
Steel metal removed, mg/200 ml, max <1>
Steel rod appearance, rating (max) <1.5> <1.5>
Oxidation (1000 h) D4310
AN, mgKOH/g max 2
Total sludge, mg max. 200
Copper, mg max 50
Iron, mg max SO
Hydrolytic Stability D 2619 (1)
Copper wt loss, mg/cm^ max 0.2 <0.2>
Water layer TAN. mgKOH max 4.0 <4>
V104 C Pump I-2S6-S
mg wear, max D 2882 SO < 50 > (2)
Vickers 35 VQ 25 Pump Test M-2950^
Vane Wear, mg max 15 <10>
Rir^ Wear, mg max 75 <50>
Denison P-46 (100 h) Satisfactory no smear, scratch, etc
DenisonTBC, vane wear TP-30283 Satisfactoiy < 0.01 >
Cam ling wear No distress
Denison Fnterability Test, sec TP 02100
Dry, max 600 <600>
Wet, max 2xdry < 2 X dry >
(1) Rqmnt. Sut>ject to Denison discretion (based on other pump/fietd history)

(2) D 2882 mn at 79,4C (higher temp.) for ISO 68 and higher grade.
hydraulic fluids that resist chemical degradation or hydroly- may be registered either potentiometricly or by color indica-
sis in the presence of water and heat. Several ASTM methods tion. Although this method has the capability to be more ac-
are used to monitor water content of hydraulic fluids as well curate than distillation or centrifuge techniques, the Karl
as their ability to resist hydrolytic degradation. Fisher Test is susceptible to chemical interference. Calcium
sulfonate, magnesium sulfonate, ZDTP and other oil addi-
Distillation, Centrifuge and Karl Fisher Titration Tests tives react with iodine and have been known to interfere with
In ASTM D 95, Standard Test Method for Water in Petroleum the titration [43].
Products and Bituminous Materials by Distillation, the mate-
rial to be tested is diluted with a water-immiscible solvent Hydrolytic Stability Testing
such as toluene and heated under reflux conditions. The re- Hydrolytic stability refers to the lubricant's resistance to
sulting distillate is condensed and separated in a trap. The chemical interactions with water that result in undesirable
amount of water present in the sample is determined by ob- changes to fluid properties. Certain chemical components
serving the volume of water settled in the graduated section may react with water to decompose or form undesirable
of the trap. byproducts of hydrolysis. Heat and catalysts such as copper
Centrifuge tests such as ASTM D 96, Standard Test Method can accelerate the process of hydrolysis. Hydrolytically un-
for Water and Sediment in Crude Oil by Centrifuge Method, stable oils form insoluble contaminants and acidic com-
can also be used for un-emulsified or insoluble water con- pounds that create hydraulic system malfunctions similar to
tamination in fluids. While distillation and centrifuge meth- those produced by oxidation and thermal degradation of flu-
ods provide reasonably accurate results for samples that con- ids. Furthermore, antiwear additives and corrosion preventa-
tain free water contamination, these methods are generally tives that are susceptible to hydrolysis are likely to lose their
not sensitive enough for hydraulic applications. A more ac- ability to perform their critical functions in the presence of
curate method for quantifying water in hydraulic fluid is the heat and water.
Karl Fischer test (ASTM D 1744, Standard Test Method for ASTM D 2619, Standard Test Method for Hydrolytic Sta-
Determination of Water in Liquid Petroleum Products by bility of Hydraulic Fluids (Beverage Bottle Method) is used to
Karl Fischer Reagent) [42]. In this test, the fluid is dispersed measure this fluid property. In this test, 75 g of fluid and 25
in a solvent such as methanol and titrated with standard Karl g of water are sealed in a beverage bottle with a copper strip.
Fisher reagent to an electrometric endpoint (Fig. 14). The The test bottie is rotated in an oven for 48 h at 93°C (200°F).
endpoint of the titration, at which free iodine is liberated. At the end of the test, the oil and water layers are separated
FIG. 14—The Karl Fisher apparatus (a) titrant solution, (b) burette, (c) titration cell with
electrode, (d) solvent, (e) waste.
and insolubles are weighed. Viscosity a n d acid numbers are levels, entrained air is visible to the h u m a n eye as larger bub-
also determined. Based upon the Denison HF-0 specification bles and can cause the oil to become cloudy. Uncontrolled air
(see Table 5 for details of this specification), t h e weight contamination results in a n u m b e r of undesirable conse-
change of t h e copper specimen should b e less t h a n 0.20 quences. Entrained air increases the compressibility of the
mg/cm^ a n d the water layer acidity should be less than 4.0 mg fluid and can adversely affect its response to hydraulic con-
KOH. Since exposure to water can be expected throughout trol mechanisms or devices, especially in high-pressure sys-
the life of a fluid, hydrolytic stability is a n important design tems. Dissolved or entrained air expands into larger bubbles
characteristic of hydraulic fluids. as its solubility in the fluid decreases as a result of exposure
In genereJ, there are no additives specifically used to im- to vacuum conditions at the p u m p inlet. This leads to noise
prove hydrolytic stability. Instead, hydrolytic stability is and cavitation, which is the dynamic process of gas cavity
achieved by appropriate selection of stable components that growth a n d collapse in a liquid [47]. Several studies of this
maintain effectiveness even in t h e presence of water. Hy- p h e n o m e n o n have suggested theoretical m e c h a n i s m s a n d
drolytic stability is also a key factor in the wet filterability be- documented experimental evidence of wear a n d increased
havior of hydraulic oils (see the Filterability section) [44]. oxidation due to cavitation [48].
Foaming is very much rooted in the fundamentcJ problem
of air contamination and consequently, results in many of the
Demulsibility same negative effects of air entrainment. It is characterized
Demulsibilty is the term used to describe a fluid's ability to by the formation of a mass of relatively large bubbles on the
separate from water. As discussed above in the Water Content surface of the fluid and is usually brought about by turbulent
and Hydrolytic Stability section, water contamination of the return of oil to the reservoir or migration of entrained air to
hydraulic oil may lead to various problems that adversely af- the surface. It is desirable to have fluids with a low tendency
fect both fluid a n d equipment durability. Thus, it is desirable to form foam in the first place a n d have the foam collapse
for hydraulic oil and water to separate as quickly as possible. quickly once formed. For effective foam control, the rate of
In many industricJ applications, water is drained from the foam collapse must be faster t h a n the rate at which entrained
hydraulic oil reservoirs as it separates and settles on the bot- air migrates to the surface to form the foam. Otherwise, the
tom. For fluids with poor demulsibility, the separation is ei- foam layer will continue to increase and air may eventually
ther very slow or unlikely to occur to any significant degree. be re-dispersed in the bulk fluid [49]. In severe cases, oil that
produces a significant amount of foam may bubble out of hy-
Demulsibility Testing draulic reservoir breathers, creating a fluid spill.
The speed at which water is separated from oil and the ten- Air entrainment has increasingly become a concern due to
dency of an oil to form a cuff of emulsified oil at the interface a trend toward smaller reservoir sizes. Shorter fluid resi-
between the oil and water phases may be measured by ASTM dence times therefore dictate use of hydraulic fluids with im-
D 1401, S t a n d a r d Test Method for W a t e r Separability of proved air release characteristics for the reasons discussed
Petroleum Oils and Synthetic Fluids. In this test, a 40 ml sam- above. Several studies have shown that fluid viscosity is a
ple of oil a n d 40 ml of distilled water are stirred for 5 min at critical factor influencing air release properties. Within a
54°C (130°F) in a graduated cylinder. The time required for given class of fluids, higher viscosity and lower oil tempera-
the emulsion to separate into water a n d oil phases is tures translate into slower air release characteristics. While
recorded. An oil with good demulsibility will completely sep- different classes of base fluids have demonstrated unique air
arate in 30 m i n or less without a "cuff' of emulsified oil be- release advantages, there has been little success in identifying
tween the phases [45]. additives that improve air release properties of a base fluid.
Demulsifiers Foam and Aeration Tests

Demulsifiers are chemicals used to alter the surface tension Because of the importance of properly managing air contam-
at the oil/water interface to accelerate separation. T3rpical ination in hydraulic fluids, there are a n u m b e r of standard-
demulsifiers include alkylphenol ethers, low molecular ized test methods for evaluating this feature of fluid perfor-
weight synthetic sulfonates, and polyoxyalkylate resins. mance. The foaming tendency a n d stability of oil may be
measured by ASTM D 892, Standard Test Method for Foam-
ing Characteristics of Lubricating Oils. In this test, an oil
Aeration a n d Foam
sample is equilibrated at 24°C (75°F). Air is bubbled through
Under normal conditions there is always air present in a hy- oil for 5 min, and then the oil is allowed to settle for 10 min-
draulic fluid. By volume, it is present at about 7-9% at room utes. The volume of foam is measured at the end of both pe-
temperature a n d atmospheric pressure [46]. In this state, it is riods. The test is repeated at 93.5°C (200°F) and again at 24°C
not visible to the h u m a n eye and thus referred to as dissolved (75°F) after the foam breaks. Various levels of foaming ten-
air. Higher temperatures and/or lower pressures (such as vac- dency are permitted by industry standards, but stable foam is
u u m conditions) lead to lower dissolved air levels. (See chap- generally not tolerated [50,51].
ter on compressor lubricants for detailed discussion on gas Not only must a hydraulic fluid resist the tendency to form
solubility and methods of measuring gas solubility.) stable foam, it also must allow air to rapidly rise and separate
Fluid circulation through hydraulic systems and reservoirs from the fluid. The Waring blender test is one test method
may cause mecheinical introduction of air into hydraulic flu- that may be used to measure the air release properties of flu-
ids, particularly if reservoir size or design does not allow suf- ids [52]. In ASTM D 3519, Standard Test Method for Foam in
ficient residence time for air separation to occur. At elevated Aqueous Media (Blender Test), 200 ml of the fluid is stirred
at an agitation rate of 4000 to 13000 r p m for 30 s. The meixi- Filterability

m u m total height at zero time, at 5 m i n a n d 10 m i n is
recorded in order to assess the foaming and aeration ten- It is widely recognized that beyond proper fluid selection,
good fluid maintenance is the key to reliability and durability
dency of a fluid under high shear conditions.
of hydraulic equipment. Fluid maintenance is closely linked
Air release properties of a hydraulic fluid may also be
to fluid cleanliness and filtration. Filtration devices, there-
quantified by IP 313, DIN 51381 or ASTM D 3427, Standard
fore, are critical tools for maintaining hydraulic fluids and
Test Method for Air Release Properties of Petroleum Oils. In
system components. Hydraulic fluid "filterability" is con-
these tests, the time in minutes for finely dispersed air in oil
cerned mainly with the appropriate flow characteristics of
to decrease to 0.2% under standard test conditions is mea-
the fluid through filter media. For proper operation, the fluid
sured using a density balance. Air release times and specifi-
should readily flow with m i n i m u m pressure drop across the
cations typically vary with oil viscosity.
filter and with negligable depletion of additives. The viscosity
and chemistry of the lubricant will affect filterability. There-
Defoamants
fore, filter size and materials should be compatible with the
Antifoam additives, generally referred to as defoamers or de- circulating fluid. The drive to increase hydraulic system reli-
foamants, are materials that destabilize the liquid film that ability through the use of fine filtration magnifies the impor-
surrounds air bubbles. The most commonly used defoamants tance of this performance parameter.
are silicone polymers (particularly polydimethylsiloxanes),
which function as finely dispersed marginally soluble liquid
particles. Since silicon defoamants have very low surface ten- Filterability Tests
sions, they tend to accumulate at air/oil interfaces. When the Due to the likelihood of water contamination in many hy-
larger bubbles rise to the surface and join other bubbles to draulic systems and its potential impact on fluids, most of the
form foam with only very thin films separating them, silicone filterability tests are designed to r u n dry and wet (with water
defoamants cause these films to rupture, thus accelerating added). Hydraulic fluid filterability tests generally consist of
collapse of the foam. While silicone defoamants reduce the filtering a specified quantity of fluid t h r o u g h a standard
foaming tendency of a fluid, they may also tend to increase medium while monitoring changes in flow rate (Table 6). The
air entrainment (Fig. 15) [53]. results are tj^pically reported in terms of a ratio between flow
Besides affecting air entrainment in hydraulic fluids, sili- rates with and without water added to the fluid. This ap-
cone defoamants tend to have poor filterability and storage proach attempts to account for changes in filterability be-
stability due to their marginal solubility in oil. Non-silicone havior independent of viscosity. In Denison TP 02100 the
defoamants are increasingly used to address these disadvan- time required for complete flow of a standard volume of fluid
tages. Polyalkylacrylate additives are the most common class through a specified filter is evaluated. In the Pall Filterability
of non-silicone defoamants recognized in the industry. Al- Test the differential pressure across a specified filter assem-
though they do not possess the disadvantages of the silicone bly is monitored over the duration of the test and cin appro-
types, these polyalkylacrylates must be used at higher con- priate limit is established to discriminate between fluids with
centrations to deliver equivalent performance. good and poor filterability behavior. While key equipment
AIR RELEASED DURING

BLOWING PHASE
VOLUME OF AIR
BLOW IN
OIL WITH
O SILICONES
O
eg
<
h- BLOWING OR
TURBULENT PHASE"
SETTLING OR
"TRANQUIL PHASE" > »
TIME
FIG. 15—Impact of silicone defoamer on foaming tendency and air release. Silicone de-
foamer decreases the tendency of the oil to generate foam while increasing the tendency
of the fluid to retain air below its surface.
368 MANUAL 37: FUELS AND LUBRICANT HANDBOOK
TABLE 61—Filterability tests. of sodium chloride, magnesium chloride, calcium chloride,

Method AFNOR Pall" Denison and several other ionic compounds to distilled water. Part B
Medium pore size 0.8jU.M 3/LiM 1.2 ^M is particularly pertinent to maritime hydraulic fluid applica-
Percent water added 0.2 1.0 2.0 tions where seawater, rather t h a n fresh water or condensa-
Aging time 70 h 24 h None tion, is a likely source of contamination.
Temperature 70°C 70°C 25°C
The standard test method for measuring vapor phase cor-
"Parkhurst, H., Pall Filterability Index Test for Paper Machine Oils, SLS Re- rosion inhibition of hydraulic fluids is ASTM D 5534, Test
port No. 5669, April 1995.
Method for Vapor-Phase Rust-Preventing Characteristics of
Hydraulic Fluids. In this test, a steel specimen is attached to
the cover of an ASTM D 3603 test apparatus that contains hy-
draulic fluid maintained at a temperature of 60°C (140°F).
builders and industrial manufacturers may require fluids to
ASTM D 3603 is the Horizontal Disk Method for Rust-Pre-
meet certain filterability criteria as measured by these tests,
global hydraulic oil specifications (i.e. ASTM D 6158, ISO venting Characteristics of Steam Turbine Oils in the Presence
11158, DIN 51524) have not yet incorporated these proce- of Water. The specimen is then exposed to water and hy-
dures. draulic fluid vapors for a period of 6 h. At the end of this time,
the specimen is inspected for evidence of corrosion and re-
Filterablility Additives sults are reported on a pass-fail basis. The ASTM D 5534 test
is particularly relevant for water-glycol and invert-emulsion
From a formulation standpoint, identifying and replacing ad-
hydraulic fluids because corrosion of the underside of reser-
ditives with potential filterability problems (i.e., filter mate-
rial incompatibility, gel-forming tendency, hydrolytic insta- voir covers has been observed in systems that use these fluids.
bility, etc.) has been the primary method of improving fluid Accelerated corrosion can also occur when dissimilar met-
filterability. Recently, dispersants have been identified that als are in electrical contact in the presence of an electrolyte
enhance filterability by preventing agglomeration of insolu- (i.e., conductive solution). This corrosion mechanism,
ble species present in the fluid. These dispersants are typi- known as galvanic corrosion, has been found to be particu-
cally alkyphenol-based or alkyl succinimide polymers of larly relevant for certain biodegradable oils [54], The ability
varying molecular weights. of a fluid to prevent galvanic corrosion may be measured by
ASTM D 6547, Test Method for Corrosiveness of a Lubricat-
ing Fluid to a Bi-Metallic Couple. In this test, a brass clip is
Corrosion Protection fitted to the oil coated surface of a steel disk. The bi-metallic
Chemical contaminants and corrosive by-products of fluid (brass/steel) couple is then stored in 50% relative humidity
degradation can cause surface attack of metallic hydraulic for ten days. At the end of the ten-day period, the surfaces are
system components. Ferrous metal corrosion in a hydraulic inspected for evidence of staining like that depicted in
system is most often caused by water contamination, while Fig. 17. The steel disks are rated on a pass-fail basis.
copper and its alloys are susceptible to attack by the products Sulfur containing additives such as zinc dithiophosphate,
of high temperature fluid degradation. Rusting of ferrous sulfurized olefins, organic polysulfides, and carbamates may
metal is an electrochemical reaction that occurs between the be used as antiwear and extreme pressure additives in hy-
parent metal and the thin oxide layer on the metal surface draulic fluids [55]. Depending u p o n the chemical activity of
formed as a result of exposure to the atmosphere [20]. Rust, these sulfur compounds, hydraulic fluids exhibit varying de-
which is hydrated iron oxide, compromises the integrity of grees of corrosiveness to copper when activated by high tem-
the metaJ surface and adversely affects other important fluid peratures. ASTM D 2070, Standard Test Method for Thermal
properties w h e n it contaminates the bulk fluid. Ferrous Stability of Hydraulic Oils is one of the most effective meth-
metal corrosion protection in hydraulic systems is usually ac- ods for predicting the corrosiveness of a hydraulic fluid to
complished by incorporating surface-active additives such as copper and its alloys. The ASTM D-2070 test measures the
rust inhibitors. There are several ASTM methods for evaluat- aggressiveness of chemical constituents in the fluid toward
ing the corrosion inhibition properties of hydraulic fluids. yellow metals when aged under high temperature conditions.
(See the section on High Temperature Oxidation Tests)
Corrosion and Rust Testing In some cases, such as when a hydraulic fluid is contami-
The ability of fluids to prevent rusting of ferrous parts due to nated with sulfur containing metalworking fluid, the fluid
water c o n t a m i n a t i o n m a y be m e a s u r e d by ASTM D 665, may exhibit corrosivity to copper without requiring thermal
Rust-Preventing Characteristics of Inhibited Mineral Oil in degradation. The standard test method for measuring the cop-
the Presence of Water. In Part A of this test, 10% distilled wa- per corrosion properties of oil is ASTM D 130, Standard Test
ter is added to oil that has been heated to 60°C (140°F). Method for Detection of Copper Corrosion from Petroleum
Round steel rods are polished to remove their oxide coating Products by the Copper Strip Tarnish Test. In this test, a pol-
and immersed in the oil. The oil-water mixture is continu- ished copper strip is immersed in oil and heated for a prede-
ously stirred to avoid separation while the temperature is fined period of time. At the end of the test, the copper strip's
maintained at 60°C. At the end of 24 h the specimens are in- appearance is compared to a standard. The rating system used
spected for rust (Fig. 16). for the D 130 test appears in Table 7. The rating system is on
In Part B of the method, the same procedure is used, except a scale of one to four. The higher the copper strip rating, the
synthetic seawater is substituted for distilled water. As de- greater the degree of copper corrosion. Color standards are
scribed in Part B, synthetic seawater is made by the addition also available from ASTM for rating copper strips [56].
FIG. 16—ASTM D 665 passing vs. failing rod.
FIG. 17—Galvanic corrosion: staining on test specimen by vegetable oil.
Corrosion Inhibitors, Rust Inhibitors, and Metal mulated with water. Such fluids have entirely different cor-
Passivators rosion inhibition requirements. For instance, water glycol
Corrosion Inhibitors, Rust Inhibitors, and Metal Passivators hydraulic fluids must prevent corrosion in the vapor phase
are designed to prevent deterioration of metal surfaces that above the liquid due to evaporation. Thus they are formu-
are in contact with the lubricant. Corrosion inhibitors are po- lated with vapor phase corrosion inhibitors such as morpho-
lar molecules that are surface active. They adsorb on the line. Typical classes of rust inhibitors include metallic sul-
metal surface and inhibit the electrochemical reaction that fonates, amine phosphates, simple fatty acids, and succinic
produces rust. Some hydraulic fluids, particularly those used acid esters. Triazoles, or derivatives thereof, are commonly
in applications that require enhanced fire resistance, are for- used metal passivators.
TABLE 7—Copper strip classifications. TABLE 8—Recommended property change limits for
Rating Designation Description determining compatibility of elastomer seals for
industrial hydraulic fluid applications.
la Slight tarnish Light orange, almost the same as
Maximum Maximum Hardness Maximum
freshly polished strip
Volume Vol. Change, Tensile
lb Slight tarnish Dark orange Time in Swell, Shrinkage, Shore A Strength
2a Moderate tarnish Claret red Hours Points Change, %
2b Moderate tarnish Lavender
% %
2c Moderate tarnish Multicolored with lavender blue or 24 15 -3 ±7 -20
silver overlaid on claret red 70 15 -3 ±7 -20
2d Moderate tarnish Silvery 100 15 -3 ±8 -20
2e Moderate tarnish Brassy or gold 250 15 -4 ±8 -20
3a Dark tarnish Magenta overcast on brassy strip 500 20 -4 ±10 -25
3b Dark tarnish Multicolored with red and green 1000 20 -5 ±10 -30
showing (peacock), but no gray
4a Corrosion Transparent black, dark gray or
brown with a trace of peacock
4b Corrosion Graphite or lusterless black
4c Corrosion Glossy or jet black Seal Swell Agents
These chemicals react with the elastomeric materials to
cause slight swelling or softening to counteract the typical ef-
fects of temperature and mechanical stress. Seal swell agents
are typically used with base fluids having very low aromatic
content. Aromatic derivatives or phosphate esters are typi-
Seal Compatibility
cally used to enhance the seal swell characteristics of a fluid.
Very critical to the successful operation of a hydraulic system
is the ability to prevent leakage and accidents that are a result
Coolant Separability
of failed seals. Leaks can lead to contamination, loss of pres-
sure, loss of lubricating fluid, and environmental damage de- Hydraulic systems used in machine tool operations are sus-
pending on the severity of the spill. In extreme temperature ceptible to contamination by aqueous cutting fluids, which
and pressure operations, sudden failure of seeds may have life contain components with poor oxidation resistance, high de-
threatening consequences, considering the potential for ex- posit forming tendency, and/or high corrosivity. In metcd-
plosions, fires, etc. [57]. Hydraulic fluids and elastomeric working applications, the hydraulic fluid may be considered
seals are composed of complex chemical components that a contaminant of the cutting fluid that alters its effectiveness
can interact as they come into contact. Depending on the in metal removal operations. Regardless of the perspective, a
chemistries involved, time, t e m p e r a t u r e , a n d mechanical mix of these two categories of fluids is undesirable, especially
stresses cause fluid interactions with the seal material, re- if they have not been designed to be compatible. In this case,
sulting in swelling or shrinkage of the elastomer compound. compatibility is defined as the ability of either fluid to com-
It is desirable to select seal materials that exhibit minimal plement, enhsince, or at least have no impact on the perfor-
change in hardness, volume, tensile strength etc. in service. mance of the other w h e n mixed. The lubricant's ability to
Slight swelling of seals is preferable to shrinkage as indicated readily separate from coolants is highly desirable in most
in Table 8. This is because a reduction in seal volume may re- cases. However, the variety and complexity of coolant
sult in leakage of fluid due to failure of the seal to fill the chemistries makes it difficult to ensure good separability of
gland that retains it in place. the hydraulic oil from all metalworking fluids [59].
There are generally n o additives specifically designed to
Seal Compatibility Testing improve coolant separability, since coolant chemistries vary
In general, industry recognized seed compatibility tests entail so widely. The t3?pical approach is to formulate a lubricant to
exposure of the elastomer material to the test fluid for a spec- have good demulsibility (water separability) and then test its
ified duration and at a standard temperature u n d e r static compatibility with specific coolants with which it is expected
conditions. Familiar industry seal compatibility tests include to come into contact.
ISO 7619, ISO 6072, DIN 53 538, and ASTM D 6546-00, Stan-
dard Test Methods for and Suggested Limits for Determining Coolant Separability Testing
Compatibility of Elastomer Seals for Industrial Hydraulic A standard industry test method for assessing lubricant com-
Fluid Applications. Other major organizations such as ASTM patibility with coolants has not yet been established. How-
and SAE also have related specifications for sealing devices. ever, some Icirge industrial manufacturers and lubricant sup-
Due to variations in elastomer chemistry, it is necessary to pliers do have in-house test procedures designed to simulate
perform compatibility tests on the specific materials being oil contamination by a low percentage of coolant, as well as
used. While most standard tests measure changes in hard- coolant contamination by a low percentage of oil (typically
ness, stress/strain properties, and volume changes after ex- referred to as tramp oil). In general, these procedures consist
posure to the test fluid, translation of these results to a prac- of mixing the lubricant with the coolant at a specified ratio
tical application m a y be difficult, since geometry and a n d t e m p e r a t u r e for a s t a n d a r d duration. The fluid con-
mechanical conditions of the targeted application pro- tainer, t5îcally a graduated cylinder, is then allowed to sit
foundly impact the elastomer. It is therefore recommended while the degree of separation between the coolant and the
that seal materials be tested u n d e r conditions that closely lubricant is observed at specific time intervals. Properties
simulate the actual application [58]. such as additive leaching and foam stability may also be ob-
served. Rapid separation, implying absence of a stable emul- lOW-30 multigrade oil consists of a lOW base oil and suffi-
sion or cuff (the layer between way oil and coolant) at the in- cient polymer to thicken the oil at 100°C to a viscosity equal
terface, is very desirable (Fig. 18). to that of an SAE 30 weight oil (Fig. 19).
Viscosity Index Improvers are typically subjected to me-
Shear Stability chanical degradation due to shearing of the molecules in high
stress areas such as between gear teeth in gear pumps and
Mobile hydraulic equipment such as excavators, farm trac- vane-ring interface in vane p u m p s . High pressures generated
tors, cranes, and timber harvesters frequently are required to in hydraulic systems subject fluids to shear rates up to 10^ s~'
operate under extreme high and low temperature conditions. [60]. Not only does hydraulic shear cause fluid temperature
To accommodate wide-ranging environmental conditions, to rise in a hydraulic system, but shear may bring about per-
hydraulic fluids with enhanced viscosity - temperature prop- manent viscosity loss in hydraulic fluids [61]. Permanent vis-
erties are often employed. These fluids t3îcally contain viscosity loss results from mechanical scission of polymer
cosity index improving polymers that thicken oil at high tem- molecules in multigrade hydraulic fluids and often occurs af-
peratures, while having little impact u p o n their low ter a relatively short period of time (<24 hours of operation).
temperature fluidity. Viscosity index (VI) is a common means The polymer (as opposed to the base oil) is susceptible to me-
for expressing the variation of viscosity with temperature. chanical shear because it has a higher molecular weight and
The viscosity index of an oil is calculated from the measured therefore a larger molecular volume. As a result, with poly-
viscosity of the fluid at 40 and lOOX using ASTM Method D mer-containing multigrade hydraulic fluids, the functional
2270, Standard Practice for Calculating Viscosity Index from viscosity of an oil may differ from that predicted from kine-
Kinematic Viscosity at 40 and 100°C. A high VI indicates less matic viscosity measurements of new oil [62].
relative change in viscosity for a given change in tempera-
ture. Vl-improved oils are commonly referred to as multi- Shear Stability Tests
grade oils, because they meet both the low temperature re-
It is desirable to formulate hydraulic fluids with shear-stable
quirements of low viscosity oils and the high temperature
VI improvers so that the fluid retains its viscosity properties
requirements of higher viscosity oils. Conceptually, an SAE
throughout its service life. Several laboratory test methods are
Good Fair Poor
FIG. 18—Good vs. Bad coolant separability.

of resistance to mechanical shear, as well as their chemical

Multigrade Oils and thermal stability. For a given polymer type, shear stabil-
100,000 ity decreases with an increase in molecular weight. Shear is
10,000 indicated by a loss in fluid viscosity (Fig. 20). The "thickening
efficiency" of the viscosity modifiers generally increases with
1,000 an increase in molecular weight for a given polymer type. Se-
lection of the best VI Improver must entail consideration of
viscosity requirements, shear stability, and thermal and ox-
idative stability in actual equipment operation.
Low Temperature Pumpability

Paraffinic mineral oils, which comprise the bulk of hydraulic
fluids, contain some amount of wax that forms crystalline
2-i : . ^- structures at low temperatures. As these structures form, the
-40 -20 40 100 150 oil becomes more viscous. At very low temperatures the fluid
Temperature, ° C may become gel-like or even solid. For hydraulic systems,
FIG. 19—Impact of VI improver on lubricant viscosity. poor low temperature flow characteristics can result in catas-
trophic failures. During start-up at very low temperatures, sig-
nificant pump cavitation can occur due to inadequate oil flow.
designed to stress multigrade oils so that they produce a per- Low Temperature Pumpability Tests
manent viscosity loss such as would take place in service. The
two methods generally used are mechanical shearing with a A number of bench tests are commonly used to evaluate low
Bosch diesel fiiel injection pump and sonic shearing with a temperature flow characteristics of lubricants. One of the
high frequency sonic oscillator. In ASTM D 6278, Test Method most common tests specified for this purpose is ASTM D 97,
for Shear Stability of Polymer Containing Fluids Using a Eu- Standard Test Method for Pour Point of Petroleum Products,
ropean Diesel Injector Apparatus, the polymer-containing which measures the lowest temperature at which a lubricant
fluid is passed through a diesel injector nozzle at a shear rate will flow. ASTM D 6351, Test Method for Determination of
that causes polymer molecules to degrade. Under standard Low Temperature Fluidity and Appearance of Hydraulic Flu-
test conditions, the kinematic viscosity of the fluid is mea- ids is used for evaluating the pour characteristics of
sured after 30 to 250 cycles through the injector pump to de- biodegradable oils. While this test gives an indication of low
termine the extent of permanent viscosity loss that has taken temperature flow characteristics of the fluid, it does not nec-
place. In ASTM D 5621, Standard Test Method for Sonic essarily address fluid performance in many applications sub-
Shear Stability of Hydraulic Fluid, the polymer-containing oil jected to very low temperatures. Pumps, motors, engines, and
is irradiated with a sonic oscillator for 40 min and changes in many types of lubricated machinery require that the lubri-
kinematic viscosity are measured. Based upon data from cant be pumped or circulated effectively at start-up. As a re-
Kopko and Stambaugh, the Fuel Injector Shear Stability Test sult, several tests have been developed to determine fluid vis-
lacks the necessary severity to predict permanent viscosity cosity at low temperature. For hydraulic systems, tests such
loss produced by hydraulic equipment [62]. However, 40 min as Brookfield (ASTM D2 983), Scanning Brookfield SBV
of irradiation with a high frequency sonic oscillator produced (ASTM D 5133), and Mini Rotor Viscometer MRV (ASTM D
viscosity changes that closely correlate to that experienced in
the ASTM D 2882 Vane Pump Test. Consequently, this test
method has become the basis for ASTM D 6080, Practice for
Defining the Viscosity Characteristics of Hydraulic Fluids. Multigrade Oils and Shear Stability
Quiescent Polymer Coil in
Viscosity Index Improvers Oil Solution
Viscosity Index Improvers (also referred to as viscosity mod-
ifiers) are high molecular weight poljTuers that reduce the
magnitude of viscosity change as a function of temperature. Reversible/ sNonreversible
They function by enabling the oil to retain thickness at higher
temperatures while having minimal impact on viscosity at
lower temperatures. In general. Viscosity Index Improvers Rapture of Coil and
Orientation of Coil
are oil-soluble organic polymers with molecular weights Subsequent Orientation
Under Shear Forces
ranging from about 10000 to 1 million. The oil temperature Under Shear Forces
controls coiling of the polymer molecules, which in turn con-
trols the degree to which the polymer increases viscosity. The
higher the temperature, the less the coiling and the greater
the "thickening" effect of the polymer. Therefore, as temper-
ature increases, there is less thinning of the lubricant com- Temperature Permanent
pared to non-polymer-containing oils. Viscosity Loss Viscosity Loss
The performance of VI Improvers is also described in terms FIG. 20—Impact of shear stress on VI improver molecule.
TABLE 9—Low temperature viscosity that will crystallize at low temperatures and cause the fluid to
grades for hydraulic fluid classifications. solidify. These additives do not entirely prevent wax from
Viscosity crystallizing in the oil. Rather, they lower the temperature at
Grade Min. Max.
which large wax crystal structures are formed. By reducing
L5 -50 the size of the crystal matrix, pour point depressants permit
L7 -49 -42 lubricants to flow at lower temperatures.
LIO -41 -33
L15 -32 -23 Two widely used types of pour point depressants are alky-
L22 -22 -15 laromatic polymers, which adsorb on wax crystals to inhibit
L32 -14 -8 growth and adherence of crystals to each other, and poly-
L46 -7 -2 methacrylates (PMA), which co-crystallize with wax to mini-
L68 -1 4 mize growth of crystals. Depending mainly on the type of
base fluid, the pour point of oil can be lowered typically by
20-30°F (I1-17°C).
4684)—all of which include specified cooling cycle and low
shear rates simulating field conditions—can be used to assess
fluid pumpability. Performance specifications that include TYPES OF HYDRAULIC FLUIDS
low temperature pumpability requirements, such as ASTM D
6080, Standard Practice for Defining the Viscosity Charac- The major compositional categories of hydraulic Quids are
teristics of Hydraulic Fluids, typically specify a temperature Petroleum Based, Synthetic Based, Water Based, Vegetable
range for different viscosity grades. In Table 9 (from Stan- Oil Based, and Water (Fig. 21). As expected, these different
dard D 6080) the temperature range for a given L-grade is ap- categories have properties that make them especially desir-
proximately equivalent to that for an ISO grade of the same able in particular applications. In this section, the types of
numerical designation and having a viscosity index of 100. hydraulic fluids will be discussed in terms of their defining
For instance, the temperature range for the L32 oil is ap- functionality rather t h a n composition. For example, fire re-
proximately the same as an ISO VG 32 grade with a Viscosity sistant fluids, which are typically water-based or ester-based
Index of 100. fluids having high flash points, are used extensively in the ba-
sic metals industry where the risk of ignition is high, while
Pour Point Depressants "environmentally acceptable" fluids are used in environmen-
Pour point depressants are additives designed to reduce for- tally sensitive areas.
mation of rigid wax crystals in the lubricant at low tempera- Hydraulic system hardware is usually designed and for-
tures. Conventionally refined mineral oils typically require mally rated to work with mineral oils, since they are the
the use of pour point depressants because they contain wax predominant hydraulic fluid in use. Systems may have to
HVDRMjuc mxs
Pelrolaum 8a»«l SynlHtBc Ba»9Cl Witer Baaed V 9 a * f c b 0 1 Based
SynttieBc Hydiocarfcona (SHC)

R&OlfWbHed AnCweartAW) PoW/«'} Rapwwed
MuBgrade Polyalphaolat>i8(PAO) Sc»Bean

wsot 0 ^ SynHiellc SoluUon
Polyaloxarwa EMere EWare HatoaanalKl Cemiiounds
—Phosphale Eaan Polyetherg Water-h-QI (hvBrt) O U n - W W f ;So>i>le OB
SMeones Pol»olEg»re Aryieftera Ghlorinatad Hydrocarbons

Raflutor Mcra Emulalm
Silanas FluowEstere WiiBd Haloflan Coropounds
FIG. 21—Schematic of hydraulic fluid types.

be modified to accominodate alternative types of hydraulic precipitates that can cause hydraulic valve sticking and filter
fluids. plugging [65].
HM
Mineral Hydraulic Oils
Type HM fluids contain antiwear additives in addition to the
The majority of hydraulic fluids in service are mineral oil rust and oxidation inhibitors found in HL fluids. They are the
based because they generally provide excellent performance most widely used mineral oil based hydraulic fluids because
at a relatively low cost. Within the mineral hydraulic oil cat- antiwear additives provide enhanced performance in high-
egory there is a wide range of viscosity grades and fluid types. pressure hydraulic applications. The requirements for HM
The International Organization for Standardization (ISO) es- oils are listed in Table 11. While early versions of HM oils
tablished a classification system for hydraulic fluids that is lacked the thermal stability necessary for satisfactory piston
designated ISO 6743-4: 1999, Lubricants, Industrial Oils and p u m p performance, modern fluids are able to perform quite
Related Products (Class L)-Classification-Part 4: Family H well in piston p u m p applications.
(Hydraulic Systems). Using this classification system as a Zinc dialkyldithiophosphate is the most widely used anti-
foundation, ASTM created ASTM D 6158, Standard Specifi- wear additive for hydraulic applications. In recent years, con-
cation for Mineral Hydraulic Oils, which defines the physical cerns about the environmental effects of ZDTP have led to de-
properties and performance r e q u i r e m e n t s of mineral hy- velopment of zinc-free or ashless antiwear hydraulic fluids.
draulic fluids. Table 10 provides a list of mineral oil based These products utilize sulfur and phosphorus compounds to
fluids listed in ASTM D6158. achieve satisfactory antiwear performance. Thus, a type HM
fluid may contain zinc or some other type of antiwear addi-
HH tive chemistry.
Type H H fluids are straight base oils without any additives. HV
They may be used in air-over-oil hydraulic systems such as is
found in car lifts at automotive service centers. They are also Type HV fluids contain the same basic chemistry as HM flu-
used in manual hydraulic pumps, jacks, and other low-pres- ids plus a viscosity index (VI) improver. (See the Shear Sta-
sure hydraulic systems. While type H H fluids are able to per- bility section.) Viscosity index improvers impart multigrade
form the primary function of a hydraulic fluid, which is to functionality to type HV fluids. While a wide range of poly-
transmit power, they are unable to withstand high tempera- mers may be used for VI enhancement, these additives all
tures and have limited lubricating capabilities. Thus these function in the same basic manner. At low temperatures, VI
fluids find limited application in industry. improvers have a minimal effect upon fluid viscosity and at
high temperatures they have a thickening effect. This enables
HL the fluid to provide satisfactory performance at a wider oper-
ating temperature range [66].
Type HL fluids are also mineral oil based, but they contain
rust and oxidation inhibitors to protect equipment from the
detrimental effects of water contamination and chemical de- T r a c t o r F l u i d s , ATF, a n d E n g i n e O i l s
terioration due to heat. These fluids are also known as R & O
Tractor fluids are unique in that they are formulated to lu-
oils because they contain rust and oxidation inhibitors. Type
bricate transmissions, final drives, wet brakes, clutches, and
HL fluids are often recommended for use in machine tool ap-
hydraulic systems from a c o m m o n fluid reservoir on the trac-
plications where system pressures are limited to 2000 psi or
tor [67]. Consequently, tractor fluids are often used in agri-
less. They are also recommended for some piston p u m p ap-
cultural equipment, off-highway machinery, backhoes, and
plications. For example, type HL fluids are the preferred fluid
turf applications where a multifunctional hydraulic fluid is
for Denison piston p u m p s [63]. This is because some ZDTP
required. To lubricate gears, wet brakes, and hydraulic sys-
containing oils can be aggressive to yellow metal (brass and
tems, tractor fluids typically utilize phosphate ester based
bronze) and silver alloyed components in piston pumps.
friction modifiers and ZDTP.
R & O oils often are formulated using a rust inhibitor Automatic transmission fluids (ATFs) are similar to tractor
chemistry that contains succinic acid derivatives [64]. These fluids in that they are designed for multiple functionality,
additives may be incompatible with metallic sulfonate or however, they generally utilize ashless antiwear additives
phenate rust inhibitors or ZDTP antiwear additives used in r a t h e r t h a n ZDTP. ATFs tend to be used in applications
many antiwear hydraulic fluids, resulting in formation of where superior low temperature performance is desired be-
cause they are designed to remain fluid at temperatures as
low as —40°C. Years ago it was common to use lOW engine
TABLE 10—Mineral oil based hydraulic fluid classifications. oils in hydraulic applications. Until recently lOW diesel en-
Commercial gine oil was the primary hydraulic fluid recommendation for
Symbol Classification Designation
Caterpillar equipment because lOW diesel engine oil con-
HH Non-inhibited refined mineral oils Straight base oils tains ZDTP antiwear additives and is compatible with engine
HL Refined mineral oils with improved R&O oils oil [68]. The disadvantage of using ATFs and engine oils in
rust protection and oxidation
stability hydraulic applications is that they tend to have poor water
HM Oils of the HL type with improved Antiwear oils separation properties, which reduces wet filterability perfor-
anti-wear properties mance due to hydrolysis of the metallic sulfonates and phen-
HV Oils of the HM type with improved Multigrade oils ates. Consequentiy, fluids designed specifically for hydraulic
viscosity index properties performance are generally more desirable.
TABLE 11—International specifications for antiwear hydraulic oil.

ISO 11158 DIN 51524 Part 2 ASTM D6158
Properties ASTM HM (Antiwear) Requirements HM (Antiwear)
ISOVG 22 32 46 S8 22 32 46 68 22 32 46 68
Kinematic Viscosity, cSt D445
40'C max. 24.2 35.2 50.6 74.8 24.2 35.2 50.6 74.8 24.2 35.2 50.6 74.8
40°C min. 19.8 28.8 41.4 61.2 19.8 28.8 41.4 61.2 19.8 28.8 41.4 61.2
Flash Point, °C min. D92 140 160 180 180 165 175 185 195 165 175 185 195
Flash Point, °C min. 093 128 148 168 168
Brookfield Vis < 750 cP, Max D2983 -15 -8 -2 4
Pour Point, °C, max D97 -18 -15 -12 -12 -21 -18 -15 -12 -21 -18 -15 -12
Appearance Visual < Report > <C&B>
Water Content, wt% D1744 <-ao5-> < Report >
Density @1S°C 01298 < Report > < Report > < Report >
TAN, ma KOH/g, max 0664 or 0974 < Report > < Report > < Report >
Rust Test A D665A <Pass> <Pass> <Pass>
Rust Test B (Salt Water) 06658 - < Pass>
Cu Rating (3 hr, 100°C), max. 0130 2 2 2 2 2 2 2 2 2 2 2 2
TOST Oxidation, hours 0943 1000 1000 1000 1000
AN after 1000h, max. 2 2 2 2 2 2 2 2
Air Release @ 50°C, minutes
(max) D3427 5 5 10 13 5 5 10 10 5 5 10 13
Foam tendency/stability 0892
Seql max <i5ao> <15Qro> <15C/0>
SeqII max <75/Q> <7SI0> <7»0>
SeqIII max <150«)> <i5oro> <150«)>
Demulsibility @ 54°C 01401
Minutes to 37 mL water . 30 30 30 30 40 40 40 60 30 30 30 30
FZG Fail Stage 0 5182 10 10 10 10
Ctiange in Hardness 0 471
- 10 10 10
r288 hrs. f 000)
NBR1,168 hrs @ 100°C ISO 7619 < Report > Oto-8 Oto-7 Oto-7 Oto-6 Oto-8 Oto-7 Oto-7 Oto-6
Change in Volume (%)
NBR1,168hrs@100°C < Report > 0to15 0to12 0to12 OtolO Oto15 0to12 0to12 OtolO
Viscosity Index, min 0 2270 < Report > <-90->
CM Thermal Stab. 02070A
Sludge, mg/100 ml max < Report > 25 25 25
Copper rod appearwice, rating (max.) < Report > 5 5 5
Oxidation (1000 h) 0 4310
AN, mgKOH/g max 2 2 2 2
Total sludge, mg max. < Report > 200 200 200 200
Total Metals in oil/water/sludge < Report >
Vickers 104C mg. wear max. 0 2882 •: Report > < 150 in exterxled test> 50 50 50 50
Fire Resistant Fluids of the ISO designations for fire resistant hydraulic fluids [69].
While power transmission, heat transfer, and lubrication
Fire resistant hydraulic fluids are used in the basic metals in- are essential requirements for all types of hydraulic fluids, it
dustry, die casting, military, and foundry applications. They is sometimes necessary to compromise these properties to
may be found in any application where a ruptured hydraulic accommodate a critical fluid characteristic. This is especially
line presents a potential fire hazard. Fire resistant hydraulic true of fire resistant hydraulic fluids. Fire resistant fluids dif-
fluids are formulated with materials that have a lower BTU fer from mineral hydraulic fluids in density, compatibility,
content than mineral oils, such as polyol esters, phosphate es- and lubricating properties. As a result, hydraulic systems are
ters, and water-glycol solutions. As a result, they b u m with often modified when utilizing a fire resistant fluid. To opti-
less heat generation than mineral hydraulic oils. As with min- mize the performance of fire resistant fluids, the National
eral hydraulic fluids, the International Organization for Stan- Fluid Power Association and ISO have published guides for
dardization has established a classification system for fire re- their use [70,71]. These NFFA and ISO documents detail the
sistant fluids based upon composition. Table 12 provides a list operational characteristics of fire resistant fluids and provide
suggestions for storage, use, and handling of these fluids.
Table 13 provides a comparison of the properties of common
TABLE 12—ISO designations for fire resistant fire resistant hydraulic fluids.
hydraulic fluids.
Commercial HFA
Symbol Classification Descriptions
HFA fluids contain greater than 80% water. These products
HFAE Oil-in-water emulsions containing Soluble oils are sometimes referred to as 95:5 fluids, because 5% concen-
typically >80% water
HFAS Chemical solutions in water High water based trations are commonly employed. The ISO 6743-4 classifica-
containing typically >80% water fluids tion divides HFA into two sub-categories: HFAE and HFAS.
HFB Water-in-oil emulsions containing Invert emulsions HFAE fluids are oil-in-water emulsions. HFAS fluids are
approximately 45% water chemical solutions or blends of selected additives in water.
HFC Water-polymer solutions containing Water-glycols Typically these products are sold as concentrates and diluted
approximately 45% of water
HFDR Synthetic fluids containing no water Phosphate esters prior to use in service. Because of the high vapor pressure of
and consisting of phosphate esters water, the m a x i m u m recommended bulk fluid temperature
HFDU Synthetic fluids containing no water Polyol esters for HFA fluids is 50°C [72]. The antiwear properties of these
and of other compositions fluids are inferior to mineral hydraulic fluids because the vis-
TABLE 13—Comparison of c o m m o n fire resistant fluid properties.

Antiwear Hyd. Invert Water Phosphate Polyol
Property Oil Emulsion Glycol Ester Ester
ISO Designation HM HF-B HF-C HF-DR HF-DU
Heat of Combustion" 29.1 kJ/g 16.3 kJ/g 5.3 kJ/g 19.0 kJ/g 21.1 kJ/g
Autoignition Temp, "F* 650 830 830 1100-H 750"
Maximum" Temperature 150°F 120°F 120°F 150°F 150°F
Vapor Pressure, m b a r 0.001 @ 50°C NA 80 @ 50°C < 1 @ 150°C NA
Specific Gravity 0.85-0.88 0.91-0.93 1.05-1.10 1.02-1.16 0.91-0.96
Viscosity @ 40°C, cSt 32-68 80-100 40 22-100 46-68
Water 0.05% 43% 43% 0.05% 0.1%
Content
Vane p u m p rating" 100% 33% 67% 67% 100%
Compatible Seals Buna-N, Viton Nitroxyl, Buna-N Buna-N Butyl, EPR Viton, Buna-N
"Roberts and Brooks Flammability Data, NFPA T2.13.8-1997, a calculated estimate was used for HFDU.
cosity of HFA fluids is comparable to water, approximately 1 fluid (relative to water) while high molecular weight
cSt. Performance is satisfactory with HFA fluids when suit- polyalkylene glycol acts as a thickening agent, much like a
able components are used but is apt to be poor if used in con- viscosity index improver. This combination thickeners and
ventional hydraulic systems. Special precautions also are re- glycols enhance the lubricating properties of a water-glycol
quired in the selection of filter construction materials and and reduces the propensity of the fluid toward cavitation ero-
plumbing of p u m p inlets. Thus, it is necessary to work closely sion. Nonetheless, operating temperatures for water-glycols
with fluid a n d c o m p o n e n t suppliers w h e n utilizing HFA are limited to a maximum of 50°C because of the effect of
fluids. temperature on vapor pressure [74].
Water glycol fluids are highly alkaline due to the presence
HFB of amine based corrosion inhibitors. As a result, these fluids
HFB fluids are water-in-oil emulsions consisting of can attack zinc, cadmium, magnesium, and non-anodized
p e t r o l e u m oil, emulsifiers, selected additives, and water. aluminum, forming sticky or gummy residues. Consequently,
They are commonly referred to as invert emulsions. In an in- these metals should be avoided when selecting system com-
vert emulsion the oil phase, which provides lubricity and rust ponents. Special precautions also are required in the selec-
protection, encapsulates the water phase, which provides fire tion of filter construction materials and plumbing of p u m p
resistance. The water content of an HFB fluid is normally in inlets. Thus, it is necessary to work closely with fluid and
the 4 3 - 4 5 % range (w/w). When water content of these fluids component suppliers when utilizing HFC fluids.
drops below 38% due to evaporation, the fire resistance of the
invert-emulsion deteriorates. Maintenance of invert emul- HFD
sions is complicated by the fact that when these fluids lose HFD Fluids are non-water containing fire resistant fluids.
water through evaporation, a high-shear mixing device is The first edition of International Standard ISO 6743-4 clas-
normally necessary for proper addition of make-up. The vis- sification (1982) divided HFD into four sub-categories:
cosity properties of invert emulsions are u n u s u a l in that HFDR, HFDS, HFDT, and HFDU. In 1999 the standard was
evaporation of water results in a viscosity decrease. revised, deleting the HFDS and HFDT fluids from the clas-
Several ASTM methods have been developed specifically sification system. HFDS and HFDT fluids are no longer
for invert emulsion hydraulic fluids. ASTM D 3709, Standard commercially viable because they were based upon chlori-
Test Method for Stability of Water-in-Oil Emulsions Under nated materials such as polychlorinated biphenyls (PCBs)
Low to Ambient Temperature Cycling Conditions, is used to or other chlorinated aromatic compounds. Environmental
evaluate the freeze-thaw stability of invert emulsions. ASTM concerns associated with chlorinated hydrocarbons led
D 3707, Standard Test Method for Storage Stability of Water- to withdrawal of these products from the market. On the
in-Oil Emulsions by the Oven Test Method is used to deter- other hand, HFDR and HFDU fluids continue to be widely
mine if the emulsion has a propensity to separate after 48 h used in a variety of commercial and military hydraulic ap-
at 85°C. As with HFA fluids, special precautions also are re- plications.
quired in the selection of filter construction materials and HFDR fluids are composed of phosphate esters. The ma-
plumbing of p u m p inlets. Thus, it is necessary to work closely jority of phosphate ester type hydraulic fluids used in in-
with fluid and c o m p o n e n t suppliers w h e n utilizing HFB dustrial applications are based upon triaryl phosphate [75].
fluids. Trialkyl and mixed alkylaryl phosphate esters are used in
aviation because of their lower density [76]. Phosphate es-
HFC ters are difficult to ignite because they are non-volatile and
HFC Fluids are solutions of water, glycols, additives, and chemically stable. The stability of p h o s p h a t e esters is
thickening agents. They are commonly referred to as water- demonstrated by the fact that they do not propagate a flame
glycol hydraulic fluids. Typically, water-glycol fluids are for- in the Standard Test Method for Linear Flame Propagation
mulated with diethylene glycol or propylene glycol and a Rate of Lubricating Oils and Hydraulic Fluids (ASTM D
polyalkylene glycol based thickening agent [73]. The low 5306-92). The principal reason they do not propagate a
molecular weight glycol reduces the vapor pressure of tlje flame is that the chemical reactions that take place during
combustion of phosphate esters are endothermic. Thus, Environmentally Acceptable Hydraulic Fluids
phosphate esters generate less heat when burned relative to
Environmentally acceptable hydraulic fluids have found
other HFD fluids. In addition, because their Are resistance
their way into hydraulic applications where there is risk of
is not dependent upon the presence of water or mist sup-
fluid leaks and spills entering the environment (especially
pressing additives, the fire resistance of HFDR fluids does
waterways) affecting aquatic and terrestrial life. Some exam-
not degrade in service. ples of these niche markets include forestry, construction,
HFDR fluids have been used in hydraulic applications for locks a n d d a m s , heavy-duty lawn equipment, a m u s e m e n t
more than forty years and are known for excellent inherent parks/entertainment industry, offshore drilling, and mar-
lubricating properties [77]. In fact, aryl phosphate esters itime. Most environmentally acceptable hydraulic fluids
serve as antiwear additives in mineral oil based hydraulic flu- exhibit two key environmental characteristics: virtual non-
ids [78]. However, phosphate esters have a steep viscosity toxicity to aquatic life a n d aerobic biodegradability. Organi-
temperature curve, which makes their temperature operating zations such as the Organization for Economic Co-operation
window rather narrow [79]. Hydrolysis is the most c o m m o n and Development (OECD), the Co-ordinating E u r o p e a n
form of degradation in HFDR fluid, and can occur in the Council (CEC), and the U.S. Environmental Protection
presence of a small amount of water and heat. When hydrol- Agency (EPA) have developed standard test methods to de-
ysis takes place, phosphate esters break down into their con- termine the toxicity a n d biodegradability of substances.
stituent acids and alcohols. Due to the frequent presence of More recently ASTM has developed a Guide for Assessing
water in hydraulic applications, the sensitivity of phosphate Biodegradability of Hydraulic Fluids (ASTM D 6006) and a
esters to water has limited their use and significantly reduced Classification of Hydraulic Fluids for Environmental Impact
their service life. (ASTM D 6046) based on the above organizations' methods.
Phosphate esters are compatible with all common metals Utilizing the methodology from these organizations, stan-
except aluminum. Phosphate esters do not "wet" the surface dard classifications and performance requirements for envi-
ronmental fluids have also been established by the Interna-
of aluminum and thus aluminum should not be used in tri-
tional Organization for Standardization (ISO) and regional
bological contacts such as bearings [80]. Phosphate esters
environmental organizations t h a t a w a r d Eco Labels (i.e.,
should never be added to systems containing mineral oil or
German Blue Angel, Nordic Swan, Japanese EcoMark). ISO
water-based fire resistant fluids. Not only are these materials
environmental hydraulic fluid classifications are described in
chemically incompatible with each other, in all probability Table 14.
preexisting gaskets, seals, hoses, and coatings are also in-
compatible. Special precautions also are required in the se-
HETG
lection of filter construction materials and plumbing of
p u m p inlets. Thus, it is necessary to work closely with fluid Type HETG fluids are based on naturally occurring vegetable
and component suppliers when utilizing HFD fluids. oils or triglyceride esters. Without the addition of a thick-
HFDU fluids typically are composed of polyol esters al- ener, vegetable oils are limited to a narrow viscosity range be-
though other materials such as polyalkylene glycols are in- tween ISO 32 and 46. While HETG fluids biodegrade rapidly,
have excellent natureil lubricity and have a natural VI in ex-
cluded in the HFDU category. Trimethylol propane oleate,
cess of 200, they are unsuitable for use at high and low tem-
neopentyl glycol oleate, and pentaerythritol esters are the
perature extremes. This is because they tend to gel at low
most c o m m o n of the synthetic polyol esters. Triglycerides
temperatures and oxidize at high temperatures. The practical
derived from soybeans, sunflower, and rapeseed plants are
temperature limits for uses HETG fluids is —25°F to 165°F.
naturally occurring polyol esters that also are used in HFDU
fluids. Polyol esters derive their fire resistance from a com-
HEES
bination of factors. First, polyol esters have a relatively high
flash, fire, and autoignition point. Second, they b u m with Type H E E S fluids are based on unsaturated to fully saturated
less energy than oil because of the presence of oxygen in the synthetic esters. Common ester chemistries utilized for hy-
molecule. And finally, polyol ester fire resistant fluids em- draulic fluids consist of TMP oleates, neopentylglycols, pen-
taerythritol esters, adipate esters, and complex esters. The
ploy antimist additives that enhance their spray-flammabil-
synthetic esters provide better performance over HETG t5T3e
ity resistance [81]. Depending upon the shear stability of the
hydraulic fluids with wider operating temperature ranges,
polymer, the fire resistance of the fluid may deteriorate in
broad range of ISO viscosity grades, and better oxidation sta-
service.
bility while still maintaining biodegradability.
Like phosphate esters, polyol esters have excellent lubri-
cating properties but are prone to hydrolysis in the presence
of water [82]. In addition, they are vulnerable to oxidation be-
cause of unsaturation irl the fatty acid portion of the ester.
These factors tend to limit their service life relative to mineral TABLE 14—ISO environmental hydraulic fluid classifications.
oils. Most common metals used in hydraulic applications are Symbol Classification Commercial Designation
compatible with polyol ester hydraulic fluids, with the excep-
HETG Vegetable oil types Vegetable oils and natural esters
tion of lead, zinc, and cadmium. Unlike other fire resistant Polyol esters, neopentylglycols,
HEES Sjmthetic ester types
fluids, polyol esters performance is satisfactory with com- syntiietic adipate esters
m o n filter construction materials and system designs. Thus it HEPG Polyglycol types Polyglycols
is relatively easy to convert a hydraulic system that operates HEPR Polyalphaolefln types Polyalphaolefins (PAO) or
synthetic hydrocarbons (SHC)
on mineral oil based hydraulic fluids to HFDU fluids.
HEPG Another challenge that comes with the various hydraulic

Type HEPG fluids are polyethyleneglycols (PEG), which pos- applications is that of developing test methods that are truly
sess good oxidation stability and low temperature flow char- representative of performance in actual systems. Bench-top
acteristics. At molecular weights of up to 600-800, HEPG tests are to be used as logical indicators of a fluid's response
type fluids are ecotoxicologically harmless and readily to expected conditions of temperature, pressure, contamina-
biodegradable (>90% in 21 days) [83]. Some disadvantages tion, etc. A significantly higher number of variables concur-
of this class of fluids include miscibility with water, incom- rently influence the fluid more than any single bench test can
patibility with mineral oils, and aggressiveness toward some simulate. Therefore, standards and specifications consist of
common t5ês of elastomer seal materials. multiple bench tests as well as more realistic full-scale test
stands that use actual pumps in typical hydraulic circuits.
HEPR Test methods will continue to evolve as more sophisticated
techniques are developed to predict field performance of hy-
HEPR type fluids are polyalphaolefins (PAO) or synthesized draulic fluids.
hydrocarbon (SHC) base fluids, which have significantly bet-
ter viscometric properties over a wider range of temperatures
than mineral base fluids with the same standard viscosity ASTM STANDARDS
classification. Some low viscosity PAOs have shown accept-
able primary biodegradability, though not as rapid as veg- No. Title
etable or synthetic ester base fluids (Fig. 22). Additional ad- D 92 Test Method for Flash and Fire Points by Cleveland
vantages claimed for synthetic lubricants over comparable Open Cup
petroleum-based fluids include improved thermal and oxida- D 95 Test Method for Water in Petroleum Products and
tive stability, superior volatility characteristics, and preferred Bituminous Materials by Distillation
frictional properties. D 96 Test Method for Water and Sediment in Crude Oil
by Centrifuge Method
D 97 Test Method for Pour Point of Petroleum Products
CONCLUSIONS D 130 Test Method for Determination of Copper Corro-
sion from Petroleum Products by the Copper Strip
A well formulated hydraulic oil consists of a properly selected Tarnish Test
base fluid and the appropriate balance of additives, opti- D 287 Test Method for API Gravity of Crude Petroleum
mized to provide the best possible overall performance re- and Petroleum Products (Hydrometer Method)
quired for the targeted application. The versatility of hy- D 445 Test Method for Kinematic Viscosity of Transpar-
draulics makes fluid power advantageous in a wide variety of ent and Opaque Liquids (the Calculation of Dy-
industrial and mobile applications. With this versatility namic Viscosity)
comes the challenge of developing fluids that function ap- D 446 Specifications and Operating Instructions for Glass
propriately in a wide range of conditions, even as environ- Capillary Kinematic Viscometers
mental health and safety requirements become more and D 471 Test Method for Rubber Property-Effect of Liquids
more stringent. New fluid technologies continue to emerge to D 664 Test Method for Acid Number of Petroleum Prod-
meet these challenges. ucts by Potentiometric Titration
I I Mininnum
Polypropylene glycols
• Maximum
Mineral oils
Hydro-treated
mineral oils
Polyethylene glycols
—1 Vegetable oils
§
Synthetic esters
20 40 60 80 100%
FIG. 22—Chart comparing primary biodegradation of base fluids by CEC
method.
D 665 Test Method of Rust-Preventing Characteristics of pacity of Oils (FZG Visual Method)
Inhibited Mineral Oil in the Presence of Water D 5306 Standard Test Method for Linear Flame Propaga-
D 892 Test Method for Foaming Characteristics of Lubri- tion Rate of Lubricating Oils and Hydraulic Fluids
cating Oils D 5534 Test Method for Vapor-Phase Rust-Preventing
D 943 Test Method for Oxidation Characteristics of Inhib- Characterisitics of Hydraulic Fluids
ited Mineral Oils D 5621 Test method for Sonic Shear Stability of Hydraulic
D 974 Test Method for Acid and Base Number by Color- Fluid
Indicator Titration D 6006 Guide for Assessing Biodegradability of Hydraulic
D 1298 Test Method for Density, Relative Density (Specific Fluids
Gravity), or API Gravity of Crude Petroleum Prod- D 6046 Classification of Hydraulic Fluids for Environmen-
ucts by Hydrometer Method tal Impact
D 1401 Test Method for Water Separability of Petroleum D 6080 Practice for Defining the Viscosity Characteristics
Oils and Synthetic Fluids of Hydraulic Fluids
D 1744 Test Method for Determination of Water in Liquid D 6158 Specification for Mineral Hydraulic Oils
Petroleum Products by Karl Fischer Reagent D 6278 Test Methods for Shear Stability of Polymer Con-
D 2070 Test Method for Thermal Stability of Hydraulic Oils taining Fluids Using a European Diesel Injector Ap-
D 2270 Practice for Calculating Viscosity Index from Kine- paratus
matic Viscosity at 40°C and 100°C D 6351 Test Method for Determination of Low Tempera-
D 2271 Test Method for Preliminary Examination of Hy- ture Fluidity and Appearance of Hydraulic Fluids
draulic Fluids (Wear Test) D 6546 Test Methods for and Suggested Limits for Deter-
D 2272 Test Method for Oxidation Stability of Steam Tur- mining Compatibility of Elastomer Seals for Indus-
bine Oils by Rotating B o m b trial Hydraulic Fluid Applications
D 2422 Classification of Industrial Fluid Lubricants by Vis- D 6547 Test Method for Corrosiveness of a Lubricating
cosity System Fluid to a Bi-Metallic Couple
D 2619 Test Method for Hydrolytic Stability of Hydraulic
Fluids (Beverage Bottle Method)
D 2717 Test Method for Thermal Conductivity of Liquids OTHER STANDARDS
D 2766 Test Method for Specific Heat of Liquids and Solids
D 2783 Test Method for Measurement of Extreme-Pressure AFNOR NF E48-690: Hydraulic Fluid Power. Fluids. Mea-
Properties of Lubricating Fluids (Four-Ball Method) surement of Filtrability of Mineral Oils
D 2882 Test Method for Indicating the Wear Characteris- AFNOR NF E48-691: Hydraulic Fluid Power. Fluids. Mea-
tics of Petroleum a n d Non-Petroleum Hydraulic surement of Filtrability of Minerals Oils in the Presence of
Fluids in a Constant Volume Vane Pump Water
D 2983 Test Method for Low-Temperature Viscosity of Au- ANSI/(NFPA) S t a n d a r d T2.13.7R1-1996: Hydraulic Fluid
tomotive Fluid Lubricants Measured by Brookfield Power - Petroleum Fluids - Prediction of Bulk Moduli
Viscometer ISO 6743/4 Part 4: Family H (Hydraulic Systems), Lubri-
D 3339 Test Method for Acid N u m b e r of Petroleum Prod- cants, Industrial Oils and Related Products (Class L ) : Clas-
ucts by Semi-Micro Color Indicator Titration sification Part 4: Family H (Hydraulic Systems)
D 3427 Test Method for Air Release Properties of Petroleum ISO 12922: Lubricants, Industrial Oils, and Related Products
Oils (Class L)—Family H (Hydraulic systems)—Specifications
D 3519 Test Method for Foam in Aqueous Media (Blender for categories HFAE, HFAS, HFB, HFC, HFDR and HFDU
Test) ISO/DIS 15380: Lubricants, Industrial Fluids and Related
D 3603 Test Method for Rust-Preventing Characteristics of Procedures (Class L), Family H (Hydraulic Systems)-Spec-
Steam Turbine Oils in the Presence of Water (Hori- ifications for Catagories HETG, HEPG, HEES and HEPR
zontal Disk Method)
D 3707 Test Method for Storage StabiHty of Water-in-Oil
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P u m p Performance - A Basis for Fluid Viscosity Classification," 1994.
SAE International Off Highway Congress, Milwaukee, WI, Paper [79] Parker O-Ring H a n d b o o k Y2000 Edition, Parker Hannifin
901633, Society of Automotive Engineers, Warrendale, PA, 1990. Corp., Cleveland, OH, 1999, pp. 3-18.
[63] Hydraulic Fluids Information, Denison Corp., Marysville, OH, [80] Phillips, W. D., "Phosphate Ester Hydraulic Fluids," Handbook
1995, p. 2. of Hydraulic Fluid Technology, G. E. Totten, Ed., Marcel
[64] Rizvi, S. Q. A., "Lubricant Additives and Their Functions," ASM Dekker, NY, 2000, pp. 1025-1027.
Handbook Volume 18 Friction, Lubrication, and Wear Technol- [81] Gere, R. A. and Hazelton, R. A., "Polyol Ester Fluids," Handbook
ogy, ASM International, Materials Park, OH, 1992, p. 106. of Hydraulic Fluid Technology, G. E. Totten, Ed., Marcel
[65] Sharma, S. K., Snyder Jr., C. E., Gschwender, L. J., Lang J. C , Dekker, NY, 2000, pp. 983-1022.
and Schreiber, B. F., "Stuck Servovalves in Aircraft Hydraulic [82] Hohn, B. R., Michaelis, K., and Dobereiner, R., "Load Cjirrying
Systems," Lubrication Engineering, Vol. 55, No. 7, July 1999. Capacity of Fast Biodegradable Gear Lubricants," Lubrication
[66] Michael, P. W. and Webb, S., "Future Fluids - What's Coming Engineering, 1999, Vol. 55, p. 37.
Down the Hydraulic Line," OEM Off-Highway, January 1998, [83] Bartz, W. J., Environmentally Acceptable Hydraulic Fluids,
pp. 34-36. Technische Akademie Esslingen, Ostfildern, Germany.
MNL37-EB/Jun. 2003
Compressor Lubricants
Desh Garg, ^ George E. Totten, ^
and Glenn M. Webster^
COMPRESSORS ARE VITALLY IMPORTANT IN MANY INDUSTRIAL TECH- Charle's Law states that at a constant pressure, the volume
NOLOGIES. For example, compressors are used in nearly every of a gas increases in proportion to the temperature:
industry including steel, automotive, petroleum, mining,
food, gas production, and storage and energy conversion [1]. II
The purpose of the compressor lubricant is to reduce friction V2 T2
and wear of the working parts of a compressor such as bear- In addition, if the temperature of a gas increases as the pres-
ings, gears, and pistons; reduce internal leakage; and if the oil sure increases when the volume is held constant then Amon-
is compressed in the compression zone, to provide heat ton's Law states that:
transfer to reduce the temperature of the gas being com-
pressed [2]. In addition, a properly formulated compressor Pi_
lubricant should provide corrosion protection and be suffi- P2 T2
ciently stable to minimize the potential for deposit formation
on hot surfaces within the system [3]. For these calculations, all temperatures are in reference to
absolute zero. Therefore, if temperature in degrees Fahren-
The following topics will be discussed in this chapter: a ba-
heit (°F) is used, absolute temperature in degrees Rankine
sic tutorial on gas compression, the classification, operation
(°R) is calculated from:
and lubrication of typical gas compressors, lubricant types
and classifications, solubility of common gases, and a review "Rankine = °F 4- 460
of recommended compressor lubricant testing. The chapter
will not discuss refrigeration compressors applications. See Similarly, if the temperature is in degrees Celsius (°C), the ab-
Chapter 15. solute temperature in degrees Kelvin is calculated from:
"Kelvin = "C + 273
DISCUSSION Charle's Law and Boyle's Law are combined to form the well-
known Ideal Gas Law which states:
Gas Laws PxV, P2V2
The objective of this section is to provide a basic background Ty T2
of the behavior of gases with respect to pressure, tempera- Avogadro's Law states that the equal volumes of gases at the
ture, and volume. For example, Boyle's Law states that at a same temperature and pressure contain the same number of
constant temperature, the product of a pressure and volume molecules:
of a gas is constant: PV = nRT
PiFi = P2V2 Where n is the number of moles, R is the so-called gas con-
When performing these calculations, the reference value used stant that is selected to be consistent with the units of tem-
to determine the pressure must be indicated. If the reference perature, pressure, and volume used in the calculation (see
value is a vacuum, then the pressure is absolute {Pa) However, Table 1).
if the reference level is atmospheric pressure {Patm), then it is Dalton's Law states that the total pressure (Py) of a mixture
called gauge {Pg) pressure. They are related by: is the sum of the partial pressures of the constituent gases
(a,b,c, ) in the mixture:
PT = Pa + Pb + Pc+
Absolute pressures must be used for the gas law relationships
to be discussed here. Similarly, the total volume of a gas is equal to the sum of the
partial volumes of the constituent gases (Amagat's Law):
VT=Va + Vb+V,+
If the temperature of a gas decreases or if the pressure in-
' Desh Garg Consulting, 14 Carlson Terrace, Flshkill, NY 12524.
^G.E. Totten & Associates, LLC, P.O. Box 30108, Seattle, WA creases sufficiently, the gas will undergo a change of state to
98103. a liquid. Further decreases in temperature or increases in
3 63 Rockledge Rd., Hartsdale, NY 10530. pressure will convert the liquid into a solid. If the tempera-
383
ture is increased indefinitely, a point will be reached where PV curve as shown in Fig. 2 [4]. For isothermal compression,
the gas can no longer be liquified by increasing pressure. The temperature is held constant during compression by removal
highest temperature at which a gas can be liquified by in- of the heat of compression, and the work performed corre-
creasing pressure is called the critical temperature of the gas. sponds to:
The pressure required to liquefy a gas at the critical temper-
ature is called the critical pressure of the gas. A summary of PrVr = P2V2
physical constants for selected gases is provided in Table 2. Adiahatic (isoentropic) compression occurs when there is no
When pressure, temperature, and volume variation of a gas heat added or removed during compression:
follows the ideal gas law, it is referred to as an ideal gas. How-
ever, as the pressure increases, the behavior of a gas deviates PiVf P2V'2
from that predicted by the ideal gas law. This is due to the Where k is the ratio of specific heats.
compressibility of the gas and is accounted for in the ideal Comparison of the work required for an isothermal process
gas calculation by using the compressibility factor (Z); (ADEF) and an adiahatic process (ABEF) shows that less
work is required for an isothermal process. However, an
PiV, P2V2
isothermal process is impossible to achieve, although com-
TiZ, T2Z2 pressors are designed for as much heat removal as possible.
Values for the compressibility factor are obtained from refer- Similarly, adiahatic compression is also impossible since
ence charts called general compressibility charts such as
those available in Ref. 4.
t
The Gas Compression Cycle
PV Curves
The product of pressure (P) X volume (V) is work. Work is Pd
equal to force X distance where pressure corresponds to
force and volume corresponds to distance. The horizontal
line shown in the PV curve of Fig. 1 corresponds to the dis-
tance, for example, the distance a piston moves and the ver- I'".'"• .--' - V'. -'1-
tical line corresponds to force on the cylinder of a piston, for
example. The area under the curve is P X y and is equal to the 3
work performed during the cycle.
IJJ -J,-; WORK -h ;:v.
Isothermal versus Adiahatic Operation
Theoretically, there are two ways that a positive displace- '"•^"/t-i-'i-r'
ment compressor can be operated; either isothermally or adi-
abatically. These modes of operation are illustrated using a
Ps I
TABLE 1—Ideal gas law
constants (R).
8.3143 X l O V gs/deg mole VOLUME INCREASES
8.3143 joules/d eg mole
1.9872 cal/deg mole FIG. 1—Illustration of a PV diagram that d o e s not include
82.054 cc atm/deg mole clearance volume.
TABLE 2 --Physical constants of natural gas components.

Density @
60°F, 14.7 psia Specific Heat @
Critical Critical Molecular Specific 60°F, 14.7 psia
Chemical Temperature Pressure Weight Gravity Cp Cv
Gas Formula (°R) (psia) (g/mole) Air= 1.0 Lbs/ft^ BTU/lb/°F BTU/lb/°F Cp/Cv
Methane CH4 344 673 16 0.554 0.0424 0.527 0.403 1.308
Ethane C2H6 550 708 30 1.038 0.0799 0.410 0.344 1.192
Propane CjHg 666 617 44 1.523 0.1180 0.388 0.343 1.131
i-Butane C4H10 735 529 58 2.007 0.1578 0.387 0.353 1.097
n-Butane C4H10 766 531 58 2.007 0.1581 0.387 0.353 1.097
i-Pentane C5H12 830 483 72 2.491 0.190 0.383 0.355 1.078
n-Pentane C5H12 846 489 72 2.491 0.190 0.388 0.361 1.076
Hexane CeHn 915 440 86 2.975 0.227 0.386 0.363 1.063
Carbon Dioxide CO2 548 1073 44 1.519 0.1166 0.199 0.154 1.293
Hydrogen Sulfide H2S 673 1306 34 1.176 0.0897 0.238 0.180 1.325
Nitrogen N2 227 492 28 0.967 0.0738 0.248 0.177 1.400
Oxygen O2 278 732 32 1.105 0.0843 0.219 0.157 1.346
CHAPTER 14: COMPRESSOR LUBRICANTS 385
Ê D CB Leeikage past valves and piston rings,

AB - ADIABATIC
Slight increase of gas volume due to heat rise from the
AC - POLYTROPIC warm cylinder.
AD - ISOTHERMAL Theoretical volumetric efficiency (TJV) is calculated from
UJ
[4]:
. THEORETICAL
\ NO CLEARANCE Tjv = 100 - CiR^'") - 1)
0}
W where R is the compression ratio which is defined as the ab-
Ul
DC solute discharge pressure divided by the absolute inlet pres-
Q. sure of a compressor and C is the cylinder clearance (%). This
F is a theoretical value and equation must be modified to ac-
..A
count for inefficiencies such as internal leakage, gas friction,
pressure drops through valves, etc. This is done by introduc-
ing the factor "L."
—• 7)^ = 100 - C(i?^* - 1) - L
VOLUME
The value of L is variable depending on the compressor, lu-
FIG. 2—PV diagram illustrating theoretical compression cycles. bricant and the gas. For a moderate pressure air compressor
with a petroleum oil lubricant, the value of L may be approx-
imately 5%.
some heat is always added or emitted. Actual compression is Power Requirement
referred to a polytropic cycle:
To properly size a compressor and its components, it is nec-
essciry to determine the amount of power required to drive
the system. To do this, it is necessary to determine the
Where n is experimentally determined for each type of com-
amount of brake horsepower required to compress a given
pressor and usually not equal to k. Thermodynamically,
volume of gas from the incoming inlet pressure to the desired
isothermal and adiabatic processes are reversible but poly-
discharge pressure [5]. Brake horsepower is defined as the
tropic processes are irreversible, steady-state processes. ideal isoentropic (theoretical) horsepower plus any fluid
The value of n may also be calculated from: (valve, fluid flow, and other leakage) or mechanical friction
(n-l)/n losses [5]. Theoretical horsepower may be calculated from:
Ti Pi
Gas Compression Cycle

Consider the situation where a gas is compressed in a piston
cylinder from the inlet pressure, Ps, to the discharge pres-
sure, Pd, along the lone 1-2 in Fig. 3a. Since it is impossible to
discharge all of the gas due to the volume of space not cov-
ered by the piston stroke, there will be a residual value re-
ferred to as clearance volume. This is typically the area be-
tween the cylinder and the head of the piston illustrated in
Fig. 3a. Typically, clearance volumes range from 4-20%.
Figure 3fo illustrates the completion of the compression
stroke along the path 2-3. When the piston reaches point 3,
the discharge valve closes and the piston undergoes the ex- (B)
pansion stroke 3-4 (Fig. 3c) until the pressure drops below
the inlet pressure at point 4. At point 4, the inlet valve opens
and the gas fills the cylinder as shown in Fig. 3>d and the pro-
cess is repeated.
Volumetric Efficiency
Piston displacement represented by the line 5-1 on the PV
curve shown in Fig, 4. The actual capacity is less than that
represented by the piston displacement, line 4-1. The ratio of
the actual capacity to the total displacement is referred to as
the volumetric efficiency. The volumetric efficiency is always
less than that that derived theoretically because:
• The re-expansion of the gas trapped in the cylinder clear-
ances, FIG. 3—The compression cycle. A. Compression Strol<e, B.
• Entrance losses due to the pressure drop at the inlet. Discharge Stroke, C. Expansion Strolce, and D. Suction Stroke.
Gas Compressors
Compressors are used in many industrial operations to com-

press a variety of gases, such as natural gas, ethylene, air, and
ammonia. There are several major compressor designs that
may be selected to suit a variety of application needs. The se-
lection of a particular type of compressor depends on such ap-
plication requirements as the gas being compressed, flow rates,
pressures involved, and downstream considerations. In this
section, the classification of compressor types will be discussed.
This will be followed by an overview of the most commonly en-
countered compressor types and their lubrication demands.
Compressor types can be classified into two basic cate-
gories as illustrated in Fig. 6 [7 ] reciprocating and rotary. Re-
ciprocating compressors are used for compressing natural
gases and other process gases when desired pressures are
high and gas flow rates are relatively low. They are also used
for compressing air.
Reciprocating Compressors
Reciprocating compressors compress gas by physiccilly reduc-
ing the volume of gas contained in a cylinder using a piston. As
the gas volume is decreased, there is a corresponding increas-
ing in its pressure (as indicated by the gas laws discussed ear-
lier). Therefore, this type of compressor is also referred to as a
positive displacement type. An illustration of a reciprocating
Piston Displacement-
FIG. 4—Illustration of the determination of volumetric effi- TABLE 3—Effect of cylinder clearance and valve area on
compression ratio.
ciency from the PV diagram using piston displacement and ac-
tual capacity Compression Ratio More Important Factor
Very high 10-30 (vacuum pumps) Clearance
High 8-10 max. Clearance principally
Moderate 5 max. Balanced
Low 2 or less Valving
144 (k-l/k)
R - 1 (PsVs)
33000 \ k - 1
Where: 144 is in'^ per ft.^, 33000 foot-pounds per minute = 1
horse power, k = k-value of the gas, Ps = inlet pressure in
PSIA, Vs = inlet volume in ft^/min, and R is the compression
ratio. The relative effect of cylinder clearance and valving
(cylinder valve area) on the compression ratio is shown in 300
Table 3.
Compressors may also be characterized by specific power
consumption (Pspec) [6]: O
^spec = power consumption (kW)/volume flow (m^/min)
For example, Pspec for a compressor lubricated with a poly - 3
a - olefin or synthetic ester may exhibit a 1-3% advantage rel- 2 200
ative to a petroleum oil [6].
Temperature
E
<a
As indicated by the gas laws, gas compression occurs with a \-
rise in temperature. The greater the amount of gas compres-
sion, the higher the final temperature. If high discharge pres- 100
sures are required, this process is conducted with cooling in
two or more stages, which improves efficiency and reduces
power consumption [9]. The temperatures actually encoun- 1 1 1
tered in these compression processes must be considered in 50 100 150 200
lubricant selection since it affects fluid viscosity, oxidation, Air Delivery Pressure (psi)
and potential deposit formation. An illustration of the tem-
perature rise of air due to compression in a Broomwade FIG. 5—Air temperature rise versus delivery pressure for a
2050H reciprocating compressor is shown in Fig. 5 [8]. Broomwade2050H reciprocating compressor
compressor is provided in Fig. 7 [7 ]. Reciprocating compres- To consider the lubrication process, it is convenient to di-
sors are typically "once-through" processes. That is, gas com- vide the parts that need to be lubricated into two categories;
pression and lubricant separation occurs in a single pass. namely cylinder parts and running parts. Cylinder parts in-
Reciprocating compressors may be further classified as clude pistons, piston rings, cylinder liners, cylinder packing,
single acting or double acting. Single acting compressors, and valves. All parts associated with the driving end (i.e., the
also classified as automotive compressors or trunk piston crankcase end), cross-head guides, main bearing and wrist-
units [3], compress gas on one side of the piston, in one di- pin, crankpin, and cross-head pin bearings are running parts.
rection. Double acting compressors compress gas on both An equation recommended by Scales for estimating the
sides of the piston, bidirectional. amount of oil to inject into a cylinder for lubrication is [3]:
Figure 7 is an illustration of a typical double-acting recip-
rocating compressor, which consists of a crankshaft, con- BXSXNX 62.8
necting rods, cross-heads, piston rods, pistons, cylinders and Q
10 000 000
liners, and piston rings, which are all mounted onto a suit-
able frame. As the crankshaft turns, the connecting rod con- Where: B is the bore diameter size (in.), S is the stroke (in.),
verts the rotation to a reciprocating linear motion via the N is the rotational speed (rpm), and Q is the usage rate in
cross-head. The cross-head transfers this motion to the pis- quarts per 24-hour day. The constant 62.8 is used to convert
ton via the piston rod. The gas contained in the cylinder is the numerator into the amount of cylinder bore area swept
compressed and discharged through the discharge valve. The clean per day and is calculated from ITT X 10. The value TT
piston rod packing, also known as cylinder packing, seals the (3.14) is multiplied by 2 (6.28) since the pump cycle is in two
high-pressure gas from the low-pressure crankcase. directions. The 6.28 value is multiplied by 10 because it is as-
COMPRESSOR TYPES
RECIPROCATING ROTATING
i
FIG. 6—Classification of compressor types. Reprinted with permission from Universal Compression,
Inc.
Cylinder
Liner Crosshead Crosshead Piston Rod Water Jacketed
Guide pamnq Cylinder
\
Variable VOIURK
Clearance Pocket
FE 6501
Piston
Rod
Valve Frame Crankshaft Connecting Counter

W«ght
FIG. 7—Cross section of a reciprocating compressor. Reprinted with permission from Universal Compression, Inc.
sumed that ten cycles are required for the total cylinder area thin film on the rotors to prevent metal-to-metal contact, the
to be swept clean. The 10000000 value converts an average lubricant also provides a sealing function to prevent gas re-
assumed film thickness in microns to inches (in.) and also compression. It also serves as a coolant by removing heat that
converts in^/day to quarts/day. is generated during gas compression. For example, for rotary
The lubricant is then generally fed directly to the cylinders screw air compressors, the air discharge temperature may be
and packings using a mechanical p u m p and lubricator ar- 80-110°C (180-230°F), rapid oxidation is favored due to tur-
rangement. Single-acting machines, which are usually open bulent mixing of the air and lubricant [15].
to the crankcase, usually utilize splash lubrication for cylin- In addition to these functions, the bearings at the inlet and
der lubrication. Compressor valves are lubricated from the outlet of the compressor must be lubricated. With rotary
atomized gas-lubricant in the system. screw compressors, the lubricant is in contact with the gas
Compared with cylinder part lubrication, the lubrication of being compressed at high temperatures and experiences high
running parts is typically m u c h simpler because there is no shearing forces between the intermeshing rotors. This cre-
contact with the gas. The required viscosity grade is specified ates very demanding use-conditions for the lubricant with re-
by the equipment manufacturer. spect to both lubrication and stability.
Since gas temperature increases with increasing pressure,
if heat is not removed, the lubricant will be exposed to high
temperatures and undergo severe decomposition. Therefore,
compressor cylinders are equipped with cooling jackets. The TABLE 4—Comparison of the operational temperature
ranges for different compressor types.
coolant is usually water or a water-glycol refrigerant. One of
the most important roles of the compressor cylinder lubri- Operating
Compressor Temperature Range Lubrication Problems
cant is as a coolant. Although the same lubricant can be used
to cool both the cylinder and the running parts, there are Rotary screw 80-115°C(180-240°F) Deposits block filter,
separator elements
many cases where different lubricants are used because the Varnish on bearings
cylinder lubricant is exposed to compressed gas at high tem- Vane 80-150°C (180-300°F) Deposits block filters
peratures. Table 4 provides a comparison of illustrative com- Vane wear increases
pressor operation temperatures [15]. Therefore, the lubricant filter deposits and
should also exhibit thermal and oxidative stability. varnishing
Reciprocating Single stage to: Varnish and carbon
270°C (500°F) deposits on exhaust
Rotary Compressors (and inlet) valves
Rotary compressors are further classified as positive dis- Multi-stage to: Piston ring wear
placement or djTiamic type compressors. A positive displace- 160-210°C increases leakage
(325^25°F) and deposits
ment type of compressor utilizes gas volume reduction to in-
crease gas pressure. Examples of this type of compressor
include: rotary screw, lobe, and vane compressors that are il-
lustrated in Fig. 8 [10,12,14], Fig. 9 [9] and Fig. 10 [9].
The rotary screw compressor illustrated in Fig. 8 consists
of two intermeshing "screws" or rotors that trap gas between
the rotors and the compressor case [13]. One rotor is the male
rotor and is driven by the motor. The outer rotor is the female
rotor and is driven by the male rotor. Both rotors are encased
in a housing provided with gas inlet and outlet ports. Gas is
drawn through the inlet port into the voids between the ro-
tors. As the rotors rotate, the volume of trapped gas is suc-
cessively reduced and compressed by the rotors coming into
mesh.
These compressors are available as dry or wet (oil-
flooded) screw types. For the dry-screw type, the rotors run
inside of a stator without a lubricant (or coolant). The heat
of compression is removed outside of the compressor, lim-
iting it to a single-stage operation. For oil-flooded screw
type compressors, the lubricant is injected into the gas that
is trapped inside of the stator. The functions of the lubri-
cant include cooling, sealing, and lubrication. The gas is re-
moved from the compressed gas-lubricant mixture in a sep-
arator. As opposed to reciprocating compressors, which are
once through processes, rotary compressors, such as the
screw compressor, continuously recirculate (1-8 times a
min) the lubricant-gas mixture to facilitate gas cooling and
separation [13].
In a rotary screw compressor, the lubricant is injected into
the compressor housing. The rotors are therefore exposed to
a mixture of the gas and lubricant. In addition to providing a FIG. 8—Cross section of a rotary screw compressor.
Labyrinth Seal-, .y Impeller^

Impeller
Oil Pump •'Roller

Bearing
Timing
Gears
(a) (b)
FIG. 9—Cross section of a rotary straight lobe compressor.
i INLET lobes and then discharged. The bearings and timing gears are
lubricated using a pressurized lubricating system.
-THRUST PIN A rotary vane compressor schematically illustrated in Fig.
10 [9]. Rotary cane compressors consist of a rotor with mul-
SLOT
tiple sliding vanes that are mounted eccentrically in a casing.
DISCHARGE VANE As the rotor rotates, gas is drawn into areas of increasing vol-
u m e (A) and discharged as compressed gas from areas of
PACKING
small volume (B).
STRIP
As with reciprocating compressors, lubrication of rotary
vane compressors is also a once through operation. The lu-
bricant is injected into the compressor casing and it exits
with the compressed gas and is usually not recirculated. The
lubricant provides a thin film between the compressor casing
and the sliding vanes and also provides lubrication within the
ROTOR slots in the rotor for the vanes. The sliding motion of the
vanes along the surface of the compressor housing requires a
lubricant that can withstand the high pressures within the
compressor system.
A dynamic compressor, such as the centrifugal compressor
shown in Fig. 12 [9], operates on a totally different principle.
Energy from a set of blades rotating a high speed is trans-
FIG. 10—Cross section of a rotary sliding vane compressor. ferred to a gas that is then discharged to a diffuser where the
gas velocity is reduced and its kinetic energy converted to
static pressure. One of the advantages of this type of com-
pressor is the potential to handle large volumes of gases.
A simplified diagram for lubricant flow in a typical rotary In a centrifugal, the lubricant and gas do not come into
screw compressor is shown in Fig. 11 [12]. The lubricant and contact with each other which is a major distinction from re-
gas mixture from the compressor discharge line goes into a ciprocating, rotary screw and rotary vane compressors. The
gas/lubricant separator where the compressed gas is sepa- lubricant requirements are therefore simpler and usually a
rated from the lubricant. After separation, the lubricant is good rust and oxidation-inhibited oil will provide satisfactory
cooled and filtered, then p u m p e d back into the compressor lubrication of the bearings, gears and seals.
housing and bearings.
A schematic diagram for rotary lobe compressor is pro- Compressor Lubricants
vided in Fig. 9 [9]. The principle of operation is analogous to
the rotary screw compressor. As the lobe impellers rotate, gas Performance Demands
is trapped between the lobe impellers and the compressor The choice of a compressor lubricant is dependent on: type
case where the gas is pressurized through the rotation of a n d construction of the compressor, the gas being com-
LUBRICANT SCAVENCER LINE -AIR

DISCHARGE
FIG. 11—Oil-flooded rotary screw compressor lube system.
BACKPLATE
DIFFUSER
PACKING BOX-
LABRINTH
SEAL
SLEEVE
BEARING
FIG. 12—Illustration of a centrifugal compressor.
pressed, the degree of compression and the final outlet tem- of a reciprocating compressor. Therefore, the selection of the
perature. Piston compressors provide the highest gas pres- proper compressor and application-dependent lubricant
sures and are among the most difficult from the standpoint with the appropriate physical-chemical properties is vital to
of cylinder lubrication. Rotary compressors with final pres- a successful process [2]. A classification procedure (ISO
sures below 1 MPa are less difficult to lubricate. Because of 6743-Part 3A) for compressor lubricants based on the type of
the potential for vane-on-ring contact, rotary vane compres- equipment and operating conditions is provided in Table 5.
sors require the use of an antiwear oil [17], whereas an R & Some of the most commonly reported oil-related service
O oil is often sufficient for the crankcase splash lubrication problems with compressors include [22]:
TABLE 5—ISO 6743-Part 3A: Family D-Compressor lubricant classification oil-lubricated air compressors.
More Specific Typical Product Type and/or
Particular Application Application Symbol ISO-L Applications Performance Requirements Remarks
Positive Reciprocating DAA Light duty Intermittent operation Sufficient time to allow cooling
displacement (crosshead and between periods of operation
air compressors trunk pistons or Compressor stop and start
with oil-lubricated Rotary drip feed Variable discharge capacity
compression (vane) Continuous operation a. discharge pressure >10^kPa
chambers (lobar)
discharge temperature >160°C
stage pressure ratio >3:1 or
b. discharge pressure >10^ kPa
(lobar)
stage pressure ratio >3:1
DAB Medium duty Intermittent operation Sufficient time to allow cooling
between periods of operation
a. discharge pressure >10^kPa
(lobar)
or
c. discharge pressure > 10^ kPa
(lobar)
discharge temperature >140''C
or stage pressure ratio >3:1
DAC Heavy duty Intermittent or As for "medium," when
continuous operation conditions a, b, or c above are
fulfilled and where severe coke
formation in a discharge
system might be anticipated as
a result of previous experience
with a medium-duty oil.
Rotary oil-flooded DAG Light duty Air and air/oil discharge
(vane and screw temperature <90°C
compressors Discharge pressure
<800 k P a ' ( < 8 bar)
DAH Medium duty Air and air/oil discharge
temperature <100°C
Discharge pressure
800-1500 kPa (8-15 bar)
or
Air and air/oil discharge
temperature 100-110°C
Discharge pressure
<800 k P a ' ( < 8 bar)
DAJ Heavy duty Air and air/oil discharge
temperature > 100°C
Discharge pressure
<800 k P a ' ( < 8 bar)
or
Air and air/oil discharge
temperature f l O O X
Discharge pressure
800-1500 k P a ' ( 8 - 1 5 bar)
or
Discharge pressure
> 1500 b a r (>15 bar)
Positive displacement Liquid ring Lubricants suitable for gears,
air compressors with compressors bearings and transmissions
oil-free compression and w a t e r -
chambers flooded vane
and screw
compressors
Reciprocating oil-
free compressors
Rotary oil-free
compressors
Dynamic compressors Radial and axial Lubricants suitable for bearings
turbo and gears
compressors
'Under favorable conditions, light-duty oil may be used at discharge pressures higher than 800 kPa (8 bar).
• Increase in oil viscosity and total acidity TABLE 6—T3q5ical composition of mineral oil basestock used for a
32 centistoke compressor oil lubricant formulation.
• Copper corrosion (oil turns green)
Solvent Solvent
• Sludge deposits Refined Refined Two-Stage
• Substantial oil entrainment in discharge gas (air) due to Paraffinic Naphthenic Hydrotreated
decreased efficiency of the demister element ISO viscosity grade 32 32 32
• Oil strainer plugging Ave. molecular weight 395 330 405
• Bearing failure Total saturates (%) 84.14 58.22 99.97
Paraffins (iso+ normal) 17.74 12.22 32.60
For successful operation, a compressor oil must exhibit: ox- Cycloparaffins (total) 66.40 45.00 67.37
idation resistance, wide operating temperature range (high Monocyclo (24.46) (15.69) (30.81)
flash point, low pour point, high viscosity index), low volatility, Dicyclo (15.24) (12.82) (19.52)
superior jmti-wear performance, good demulsibility, adequate Tricyclo (9.10) (8.21) (8.87)
corrosion resistance, thermal/oxidative stability, rust and cor- Tetracyclo (10.58) (6.01) (4.75)
Pentacyclo (4.67) (2.45) (2.56)
rosion inhibition, hydrolytic stability, material compatibility,
Hexacyclo (2.35) (0.82) (0.86)
non-sludging performance, minimal oil loss to the system, Total aromatics (%) 14.37 31.06 0.03
non-foaming potential behavior, and m u s t be non-toxic Monoaromatics (10.49) (12.28) (0.03)
[8,10,24]. The successful development of a compressor lubri- Diaromatics (2.60) (12.58) Nil
cant will depend on how well the oil meets these technical re- Triaromatics (0.48) (2.72) Nil
Tetraaromatics (0.13) (2.28) Nil
quirements. Testing procedures that may be used to develop (0.67) (1.20)
Pentaaromatics Nil
and maintain compressor lubricants will be discussed here. Total thiophenes (%) 0.19 9.09 Nil
Total polar compounds (%) 1.30 1.64 Nil
Lubricant Basestocks S, ppm 500 13,400 2
N, ppm 30 160 1
Mineral Oils—Although it is more c o m m o n for naphthenic
mineral oils to be used as a basestock for compressor fluid
formulation, paraffinic oils may be used as well [15,23,26].
The composition of two illustrative examples is provided in
Table 6 [15]. In either case, the basestock is formulated with showed a significant improvement in oxidative stability when
additives to provide the desired stabilization to oxidation and evaluated in an air compressor test relative to normally re-
sludge formation, rust and corrosion control, foam control, fined basestocks [15].
demulsibility, and antiwear behavior [23,26]. The response of Synthetic Basestocks—In addition to exhibiting improved ox-
the base oil to these additives is dependent on the composi- idative stability relative to mineral oil, synthetic basestocks
tion of the oil [23]. also are used in compressing gases that may react with con-
Although the performance of these oils is generally good, ventional mineral oils. These reactive gases include: methyl
there is a temperature and pressure limit, beyond which a chloride, sulfur dioxide, hydrochloric acid, ammonia, and
mineral oil-based compressor lubricant should not be used. other process gases such as carbon dioxide (which may be
This is particularly critical for air compressors due to the rel- c o n t a m i n a t e d with acids, hydrogen sulfide, or other oxi-
atively poor oxidation resistance and sludge-forming charac- dants), chlorosiloxanes, chlorinated hydrocarbons, and gases
teristics of mineral oils in the presence of air at high temper- containing trace mineral acids. In many chemical plant pro-
atures. Figure 13 illustrates the guidelines recommended by cesses, mineral oil based lubricants are not allowed due to
Matthews, et al. for the use of mineral oil lubricants for air potential catalyst contamination [14].
compressors [23]. In these applications, an appropriate synthetic oil-based
The oxidative stability and sludge (coke) forming proper- lubricant must be selected. In this section, a brief overview of
ties exhibit a significant impact on both the operation and the more commonly encountered synthetic lubricant bases-
the explosion and fire h a z a r d of compressor oil in use tocks will be provided. The basestocks to be discussed here
[20,27,28]. As with other basestocks, mineral oil oxidation as include: polyalkylene glycol (PAG), ester, phosphate ester,
represented by the autoignition temperature is further exac- polyalphaolefin (PAO), silicones, fluorocarbons, and alkyl-
erbated by the presence of corrosion metals such as iron ox- benzenes. Compressor fluids formulated from these bases-
ide as illustrated in Fig. 14 [1]. tocks are the most commonly encountered in the industry
The poor fire-resistance, oxidative instability and other de- [16].
ficiencies of mineral oil compressor lubricants often limit Polyalkylene Glycol-PAG—Compressor lubricants formulated
their use. In these cases, a synthetic oil-based lubricant may with polyalkylene glycols are being used increasingly as com-
be selected. However, one approach to this limitation of the pressor lubricants, particularly in hydrocarbon gas compres-
use of mineral oil-based compressor lubricants is to further sion applications because of their resistance to hydrocarbon
refine the mineral basestock using a two-stage hydrotreating dilution [12,19]. The poor solubility of hydrocarbon gases in
process. In this process [15] and others that have been re- PAGs also assists in preventing the washing away of the lu-
ported [12,14], polycycloparaffins are broken u p and aro- bricant that would result in metal-to-metal contact (dry run-
matic compounds are converted into saturated cycloparaf- ning) [16]. However, at high operating pressures, hydrocar-
fins. In addition, sulfur, nitrogen, and oxygen-containing bon gases may continue to condense, leading to a build-up of
compounds are completely decomposed. Table 6 provides a a hydrocarbon-rich phase in the lubricant separation tank.
comparative illustration of the chemical composition of a This problem is easily remedied even though the lubricant-
two-stage hydrotreating process to a conventionally refined hydrocarbon phases do not readily separate by gravity. If
paraffinic and a naphthenic oil [15]. Data reported by Cohen such problems do occur, the hydrocarbon gas may be re-
350r
Aryl Ester Based Product
..Operating Envelope for Many

Reciprocating Air Compressors
100 200 300

PRESSURE (bar)
FIG. 13—Recommended guideline for the use of mineral oil lubricants for air compres-
sors.
Phosphate Ester
— - — — » _ ^ Phosphate Ester
_ w/ Iron Oxides
Polyol Ester
Diester, 100ISO
Polyalphaolefin
Mineral Oil #1
Mineral Oil #2
Mineral Oil #2
w/ Iron Oxides
90 120 150 180
PRESSURE (PSIG)
FIG. 14—Autoignition of various synthetic and mineral oils compared

to discharge pressures and temperatures. A. single stage, B. two stage,
and C. three stage.
moved using a flash still unit such as the one shown schemat- ample, it has been reported that a polypropylene glycol with
ically in Fig. 15 [19]. a pentaerythritol ester can be used for air compression in a
PAG polymers exhibit excellent viscosity-temperature be- rotary screw compressor (where the oil is recirculated) with
havior (high viscosity index) as shown in Fig. 16 [ 14] and they excellent long service life [11].
may usually be used up to compression temperatures of Polyalphaolefin (PAO)—Polyalphaolefins are also used exten-
200°C [16] However, they have been reported to degrade at sively as a synthetic basestock for compressor lubricant for-
compression temperatures of 230°C which would make them mulation. In addition to good viscosity properties relative to
unsuitable for high temperature air compressor applications mineral oil, as illustrated in Fig 16, PAOs exhibit excellent
[23]. Other reported advantages include low pour point, high thermal and oxidative stability, and are hydrolytically stable,
flash point, and low vapor pressure. PAG-based compressor as shown in Fig. 17 [19], and are not attacked by reactive gases
lubricants have been used with success in natural gas, nitro- such as ammonia [30]. These factors have led to their growth
gen, carbon dioxide, hydrogen, and helium compression [29]. in usage in rotary screw compressor applications [12].
Ethylene compression for low-density polyethylene (up to In some cases, compressor oils are used in the food indus-
50000 psig) has also been reported [29]. try and may come in contact with food. They may also be used
Blends of PAGs with other basestocks have been reported to compress gasses that are used in food applications, such as
to offer properties superior to either basestock itself. For ex- CO2 [2]. For these applications, a food-grade compressor lu-
COMPRESSED
Gas -GAS
Refrigerant DISCHARGE
r0cCOOLER n MOTOR
Condensibles
OMPRESSOR
Gas + Lube +
1 I LUBE
i r SEPARATOR
(fn
_F; H.C. Condensibles Z
fe 3
SUCTION Recycle Stream^<^ 1 Lube + H.C.
TANK H.C. Vapors Condensibles
IFILTER ^ ^ HEATER
LUBE PUMP
-Or FLASH
COOLER DISTILLER
FIG. 15—Flooded rotary screw gas compressor system equipped with a flash still unit.
bricant must be used, which may be a white mineral oil [2] or

100,000
20,000 a food-grade PAO [25]. Figure 18 illustrates the substanticJ
1,000
improvement in fluid lifetime for the food grade PAO com-
(0 300
pared to the white mineral oil used as a reference [25].
u Esters—Ester basestocks used in compressor oil formulations
75
include: diesters, polyols, phthalates, and trimellitates [21]
E 40
CO Esters are often used as low-cost basestocks for compressor
O 15 fluids used in air compressors because of their improved ox-
PAG
PAO idative resistance as shown in Fig. 14 [1]. Furthermore, esters
> Semi-Synfhetic have been used increasingly as cylinder lubricants for recip-
Mineral Oil rocating compressors due to their high-temperature stability
and solvency properties [12]. The use of ester basestocks, such
-30 0 50 100 150 200 250 300 350 as diesters and polyol esters, results in minimal deposit for-
TEMPERATURE (°F) mation on hot pistons and discharge valves [12].
-17.8 37.7 93.9 148.9 Silicones—Silicones, including dimethyl, alkylmethyl, and
TEMPERATURE (°C) fluorinated polymers are EIISO used to formulate compressor
fluids. These polymers are relatively inert to almost all chem-
FIG. 16—Comparative viscosity-temperature relationships icals except pure oxygen, and other strong oxidizing agents.
for different compressor lubricants. They are tj^Dically used to formulate compressor fluids used
100
90
80 Polyalphaolefin
70 "Fluid
9
60 /C DIester
3 Fluid
X 50
UJ 40-
>
30-
20
UJ
in 10-
0 •
500
' • •
1000
Jt-L
- 1 îOO
• • • • ' • • ' • _ ' ' • • • ' • • • ' '
2000 2500 3000 3500
WATER CONCENTRATION (PPM)
FIG. 17—Comparison of the hydrolytic stability of a compressor lubri-
cant formulated using a PAO and an ester basestock.
drocarbon gas and petroleum oils are very similar molecules

consisting of primarily C—H bonds. The solubility of hydro-
carbons is m u c h less in some synthetic lubricants, especially
PAGs. This is because, in a typical PAG molecule, each third
atom in the polymer backbone, is an oxygen atom, which
makes it quite polar. Therefore, hydrocarbons are less solu-
ble in PAGs.
In reciprocating and rotary screw compressors, the gas be-
ing compressed and the lubricant come into contact with
each other. Hydrocarbon gases are infinitely soluble in min-
eral oil-based compressor lubricants, and the solubility of hy-
drocarbon gases increases with increasing pressure at a con-
stant temperature in a less compatible fluid such as a ISO 220
"0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 polypropylene glycol, as illustrated in Fig. 19 [14]. Figure 20
WEEKS illustrates that increasing the temperature at a constant pres-
sure will result in lower gas solubility. [14]. At some point, if
FIG. 18—Comparison of the oxidative stability of a food
the viscosity reduction of the compressor lubricant is suffi-
grade Poly(Alphaolefin) (PAO) with a hydrocarbon white oil.
cient, lubrication failure may result because of loss of hydro-
dynamic lubrication [2].
The solubility of various gases in lubricants has been mea-
for HCl and chlorine compression [14]. Some silicones have
sured and reported [8,14,29]. The solubility was measured in
exhibited outstanding corrosion protection on metal surfaces
a fixed volume apparatus. A known a m o u n t of gas and lubri-
and have even been used as a corrosion inhibiting additive
cant was allowed to reach equilibrium at a given tempera-
for the formulation of PAO compressor fluids [14]. ture. Gas solubility was calculated using the gas laws. The lu-
Dimethylsilicones exhibit excellent viscosity-temperature bricant was stirred to facilitate equilibrium.
characteristics and are hydrolytically stable and, if used with Solubility of methane at pressures u p to 5000 psig is com-
an effective antiwear additive, exhibit acceptable lubricating pared at 50°C for three lubricants: PAG, PAO and a petroleum
characteristics and exhibit excellent oxidative stability [19]. oil in Fig. 21. The m e t h a n e gas solubility in PAG is roughly
Fluorinated Basestocks—There are three classes of fluori- one half of that for a PAO and petroleum oil and that the sol-
nated fluids that are used for lubricant formulation. These in- ubility was nearly as high in the PAO as in the petroleum oil.
clude: chlorofluorocarbons, perfluoroalkylpolyethers, and Gas solubility exhibits a significant effect on lubricant vis-
fluorosilicones. All are very expensive a n d are only used cosity. The greater the solubility of the gas in the oil, the
where their outstanding chemical inertness, even to liquid greater the viscosity loss (viscosity dilution). A lubricant vis-
oxygen and chlorine, is demanded [19]. cosity-dilution chart is shown in Fig. 22 for methane at 50°.
Phosphate Ssters—Phosphate esters are used primarily for Similar gas solubility comparisons for nitrogen, hydrogen,
their fire-resistance properties, particularly in the mining in- ethylene, propane, c a r b o n dioxide, are provided in Figs.
dustry [20], relative to mineral oil as illustrated in Fig. 14 [1]. 23-27, respectively. [29]
In addition, they exhibit high flash points, excellent resis-
tance to aging, and minimal coke formation. They eire used in
high-pressure multistage compressors and other applica- 300
tions. However, if the lubricant degrades, by-products with • j f
poor material compatibility may be formed. In some cases, it
has been reported that there may be problems with boundary
lubrication between aluminum and cast iron cylinders. <
Alkylbenzenes—As illustrated in Fig. 13, the thermal-oxidative
stability of mineral oils, particularly solvent refined naph- Q^ 200
thenic oils, is somewhat limited, particularly in air compres-
LU
sion operations. In such applications, it has been shown that
DC
selected, well-refined alkylbenzenes do not exhibit carbona-
ceous sludge formation in reciprocating compressors with fi- i/>
nal compression temperatures of 220°C and 0.8-1.0 MPa [20] crfSs-
Uj 100
Alkylbenzenes m a y also be used to formulate a m m o n i a ^5^=^
compressor fluids although they do exhibit slightly greater
a:
ammonia solubility than paraffinic oils and PAOs [30]. How- Q.
ever, vapor pressure is lower than solvent refined naphthenic
oils, but greater than PAOs or hydrotrated oils. Alkylbenzenes
0
also exhibit relatively poor viscosity-temperature properties. 0 10 20 30
Gas Solubility in the Lubricant % GAS
The solubility of natural gas and other hydrocarbons is m u c h FIG. 19—Hydrocarbon gas solubility in an ISO 220 poly-
higher in petroleum oils. That is expected because both hy- propylene oxide at constant temperature.
o
o
> 2000 3000 4000 5000
PRESSURE (PSIA)
500
FIG. 23—Nitrogen gas solubility comparison in a PAG versus
1000 a PAO at 50°C.
500i
0 20 40 60 80 100
TEMPERATURE (°C)
FIG. 20—Effect of hydrocarbon gas dilution on viscosity with
increasing temperature of a hydrocarbon gas in an ISO 220
polypropylene oxide fluid.
"0 1000 2000 3000 4000

Pressure (PSIA)
FIG. 24—Hydrogen solubility comparison in a PAG.
2000 3000
PRESSURE (PSIA) Lubricant Solubility in the Gas
FIG. 21—Methane gas solubility comparisons for a polyalky- The lubricant solubility in the gas should be minimized to re-
lene glycol, Poly(Alphaolefin) and petroleum oil at 50°C. duce carryover by absorption of the lubricant in the gas. The
absorption of the lubricant in natural gas was evaluated by
Matthews using a constant pressure flow through a load
(gravimetric) cell [8]. The results of this work, shown in Fig.
28 indicated that there was an appreciable absorption of the
mineral oil in the gas. The PAG lubricant showed no appre-
ciable loss.
Test Procedures
Kinematic Viscosity (ASTM D 445)
Compressor fluid viscosity is important with respect to lubri-
cation of bearings, gears, and other moving surfaces within
the pump and for providing adequate sealing within the com-
2000 3000
pressor. Typically, fluid viscosity at 40°C and 100°C is deter-
PRESSURE (PSI)
mined [8,25,32,34] and, if low-temperature use is expected,
FIG. 22—Viscosity dilution comparison for methane in a the viscosity at 0°C is determined [11,34]. Higher fluid vis-
Poly(Alkyleneglycol) (PAG) and a petroleum oil at 50°C. cosities result when the fluid is oxidized. Therefore, viscosity
^ 0.5
( I I I
lU 0.4-
>• t t * (
• t i l
CD 0.3
: J i i S J PAG
t i l l
^ 0.2 ^ ^ s * ^ ^ 1 1 ( 1
m
0.1 —-{—"4—f
— i""-i
1 1 1 1 •
o i 1 i i 1
(O i i i i i
1000 2000 3000 4000 5000 6000 7000 0 10 20 30 40 50 60 70 80 90 100 110 120
(a) PRESSURE (PSIA)
TEMPERATURE C O
FIG. 27—Solubility of carbon dioxide in a PAG at SOX.
Specific Gravity (Test Methods D 287 and D 729SJ—Specific

gravity depends on the chemical composition of the base
stock used to formulate a compressor, such as the naph-
thenic/paraffinic ratio of a mineral oil. Test Methods D 287
and D 1298 for specific gravity require the use of both a hy-
drometer and an accurate thermometer or a thermohydrom-
eter. Because specific gravity is temperature dependent, the
temperature of the oil at the time of measurement, typically
25°C or 77°F, must be determined precisely [11,31,34].
1000 2000 3000 4000 5000 6000 7000 Pour Point (Test Method ASTM D 97)
(b) PRESSURE (PSIA)
Pour point is used to characterize the suitability of a lubri-
FIG. 25—Ethylene solubility comparison at 50°C of: A. a PAG cant for use at low temperatures. Pour point is defined as the
versus a petroleum white oil and B. a PAG versus a polybutene. lowest temperature at which the movement of the fluid is ob-
served.
Water Content (Test Methods D 95, D 1744, D 4007)
-^ 0.5 1 1 1 I r
The presence of moisture in a compressor fluid, particularly
X with hydrocarbon gas compression, is important because hy-
o drocarbon gases may form a "cold sludge" in the presence of
moisture [6]. (If the compressor fluid contains trace amounts
of water, it must be operated above the dew point of the fluid
E 0.4 [10].) Also, water may condense in the system under condi-
tions of low temperature and high humidity [11]. The pres-
•.^.PJAG i j ence of large slugs of water may lead to fatigue failure of
^ 0.3 bearings. Fluids that are susceptible to hydrolysis may then
5 0.2 react with the residual water upon heating, thus reducing
their lifetime and possibly leading to corrosive system dam-
O i ! i age.
0.1
48 60 72 84 96 108 The presence of water in a compressor fluid may be deter-
TEMPERATURE (°C) mined by titration of the oil with Karl Fisher chemical
reagent to an electrometric endpoint (Test Method D 1744).
FIG. 28—Solubility of propane in a PAG at SOX. This test is recommended for water levels of 50-1000 ppm
(less than 0.1%). Higher levels of water contamination may
be quantified by distillation (Test Method D 95) or centrifu-
is also an important fluid maintenance procedure and is use- gation of the sample and measurement of the volume of sep-
ful for comparison with the viscosity of a fresh fluid. Viscos- arated water according to Test Method D 4007.
ity measurement by various tests, including Test Method D
445, is discussed in detail in Chapter 32—Flow Properties Demulsibility (Test Method D 1401 or D 2711)
and Shear Stability, and will not be discussed further here. The ability of a fluid to separate from water is called "Demul-
The viscosity-temperature relationship (viscosity index) of sibility." Demulsibility properties of a compressor fluid
a compressor fluid is another important physical property may be determined using Test Method D 1401 where a 40
that may be determined according to ASTM D 2270. mL sample of the fluid and 40 mL of distilled water are
PRESSURE 340 bar

TEMPERATURE 100 "C
I I MINERAL OIL (ISO 680)
^ ^ 2 0 0 est PAG
a.
O 40
OT 30
o
o
W 20
hOGAS 340 bar N, SATURATED WITH

ATMOSPHER C PRE URE METHANE
FIG. 28—Effect of pressure and gas dilution on the viscosity of a min-

eral oil and a PAG cylinder lubricant.
stirred for 5 min at 54.4°C (130°F) in a graduated cylinder Air Release (Test Method D 3427)
[10,26,31,32,34,35]. The time for separation of the emulsion
In addition to foaming, it is important to monitor the ability
that is formed is determined. Test Method D 2711 is recom-
of a fluid to release entrained air because excessive air en-
m e n d e d for evaluating the demulsibility properties of
trainment may reduce fluid delivery rates to the compressor
medium to high-viscosity lubricating oils.
rotors. This has the same effect as operating the compressor
below recommended fluid levels [25,32].
Hydrolytic Stability (Test Method D 2619)
Air entrainment may be determined using Test Method D
Some compressor lubricants hydrolyze in the presence of wa- 3427 where compressed air is blown through the test fluid
ter at elevated temperature such as those based on ester base- which has been heated to 25, 50, or 75°C. After the air flow is
stocks [8]. Therefore, it may be important to determine the stopped, the time required for the air entrained in the fluid to
hydrolytic sensitivity of a compressor fluid to water. Con- reduce in volume by 0.2% under the conditions of the test
ducting Test Method D 2619, the Beverage Bottle Method, and at the test temperature is measured.
can do this.
Test Method D 2619 covers the determination of the hy- Corrosion (Test Method D 4310)
drolytic stability of synthetic or petroleum-base hydraulic A well-formulated compressor fluid will contain additives to
fluids b u t is as applicable to compressor fluids. In this provide adequate copper and iron corrosion protection
method, 75 g of the compressor fluid and 25 g of water and a [10,11,15,22,32]. A build-up of corrosion metals in the sepa-
copper test specimen are sealed in a pressure-type bottle. The rator could block the lubricating lines and impede fluid flow
bottle is rotated, end for end, for 48 h in an oven at 93°C through the filter. Furthermore, if not properly inhibited,
(200°F). Layers are separated, and insolubles are weighed. corrosion metals such as copper and iron will catalyze the ox-
The weight change of copper is measured. Viscosity and acid idation of many fluids [11].
numbers and the acidity of the water layer are determined.
Copper Corrosion (Test Method D 130)~ASTM Test Method D
This method differentiates the relative stability of com- 130 (Copper Strip Corrosion Test) will evaluate the corro-
pressor lubricants in the presence of water under the condi- siveness of a compressor lubricant toward copper. In this
tions of the test. Hydrolytically unstable fluids form acidic test, a polished copper strip is immersed into the test fluid
and insoluble contaminants, which may cause compressor and heated at a temperature a n d for a length of time that is
system malfunctions such as corrosion, valve sticking, or characteristic of the fluid being tested. At the conclusion of
change of viscosity of the fluid. the test, the copper strip is removed, washed, and compared
with ASTM Copper Strip Corrosion Standards.
Foaming Tendency (Test Method D 892) Iron Corrosion (Test Method D 665)—Iron corrosion, or "rust"
The assessment of a wet or dry fluid to foam is important for potential of a compressor fluid is evaluated by Test Method D
various reasons. One is that foaming fluid may fill the sepa- 665, which is also known as the Turbine Oil Rust Test. This
rator and saturate the filter element, leading to severe fluid test evaluates the ability of a compressor fluid to inhibit rust-
loss with the compressed gas. A "bubbly fluid" may cause lu- ing of ferrous parts should water become mixed with the
brication failure, poor sealing properties and reduced effi- compressor fluid. The test is conducted by mixing 300 mL of
ciency [11]. As described in Test Method D 892, the foaming distilled water (or synthetic sea water) at 60°C (140°F) with a
tendency of a fluid should be determined at 24°C and 93.5°C cylindrical steel test rod completely immersed into the
[26]. This test is conducted by equilibrating the test fluid at fluid/water mixture. The test is usually run for 24 h at which
24°C (75°F) at which point air is blown through the fluid at a time the steel test rod is inspected for rusting.
constant rate for 5 min, then allowed to settle for 10 min. The
foam volume is measured at the end of both periods. The test Flash and Fire Points (Test Methods D 92)
is repeated on a second sample at 93.5°C (200°F), and then af- The fire resistance and safety properties of a compressor
ter collapsing the foam at 24°C (75°F). fluid are t5rpically determined from its flash and fire point
[10,11,25,26,31,32,34,35]. The flash point is the lowest tem- due to evaporation. The NOACK evaporation loss is subse-
perature, corrected to a barometric pressure of 101.3 kPa quently determined from the specimen weight percent loss
(760 m m Hg), at which the application of an ignition source versus time curve (TG Curve) as the mass percent lost by the
causes the vapors of a fluid being tested to ignite under the specimen at the NOACK reference time determined under
specified conditions of the test. The test usually cited for the same TGA conditions. This procedure requires m u c h
compressor fluids is the so-called Cleveland Open-Cup flash smaller test specimens and is m u c h faster when multiple
point. This test procedure is described in detail in Chapter samples are sequentially analyzed; it is also safer than the
25—Volatility. NOACK Test Method D 5800.
The fire point is the lowest temperature, corrected to a
barometric pressure of 101.3 kPa (760 m m Hg), at which the Carbon Residue
application of an ignition source causes the vapors of a fluid One of the greatest problems encountered when using a com-
being tested to ignite and continue to b u m for 5 s under the pressor fluid is the formation and accumulation of sludge,
specified conditions of the test. which can lead to a safety problem, possibly even an explo-
sive situation if coupled with overheating. This will occur if
Autoignition (Test Method E 659) sufficient quantities of c a r b o n a n d sludge are formed to
Compressor fluids should not be used above their autoigni- cause the valves to stick open (Reference ISO 5388 part
tion temperature. Autoignition temperature is the tempera- 6.6.1). Therefore, it is desirable to determine the sludge-
ture at which the fluid will ignite spontaneously in contact forming potential of a compressor fluid.
with air and may be determined by Test Method E 659. No Conradson Carbon Residue (Test Method D189)—One method
sparks or open flame need be present. Hydrocarbon fluids of quantifying the sludge-forming potential of a compressor
absorbed on porous surfaces can ignite at temperatures more fluid involves determination of the Conradson carbon residue
t h a n 50°C (approximately 100°F) lower t h a n indicated by (Test Method D189) [31 ], which measures the amount of poly-
Test Methods E 659. meric material remaining in the oil after heating to elevated
temperatures in the absence of sufficient oxygen to burn off
Evaporation all of the organic compounds present. The Conradson carbon
Increasing volatility of the compressor fluid will result in in- residue is determined by placing a weighed sample in an iron
creasing carbon build-up in the discharge system of a com- crucible. The crucible is heated with a Meeker-type gas burner
pressor [27]. This will occur if the oil fractions are suffi- to a sufficiently high temperature to evaporate and b u m the
ciently volatile to r e m a i n in the vapor state of the hot oil. The sample is further heated until the bottom and sides of
discharge zone where the oil can break down into carbon. the crucible are cherry red and is held at this temperature for
Evaporation Loss (Test Method D 972)—Oil volatility can be 30 min. The crucible is then cooled and weighed. The amount
measured by Test Method D 972. In this test, a weighed sam- of tar remaining in the crucible relative to the original amount
ple of the compressor oil is placed in a bath maintained at the of the oil define the Conradson carbon residue value. Test
desired test temperature, typically 100-150°C (210-300°F). Method D 189 may be affected by some additives used to for-
Heated air is passed over its surface for 22 h. The evaporation mulate the compressor fluid.
loss is calculated from the loss of mass of the sample. Ramsbottom Carbon Residue (Test Method D 524)—Another
NOACK Evaporation Loss (Test Methods D 5800 and D test that is used to determine the tendency for a compressor
6375)—The NOACK test method is a method of measuring lubricant to form carbonaceous residues is Test Method D
evaporative loss of an engine oil during use, but can be re- 524, the Ramsbottom Carbon Residue test [15]. In this test,
lated to any set of conditions. It was recently applied to mea- the sample, after being weighed into a special glass bulb, is
suring the evaporative loss of compressor fluids [35]. This placed in a metal furnace and heated to 550°C. In this way,
test is conducted using the NOACK Evaporative Tester illus- the sample is quickly heated to the point where all volatile
trated in Fig. 29. In this test, a measured quantity of the com- material is evaporated out of the bulb, with or without de-
pressor fluid is placed in an evaporation crucible, which is composition, while the remaining residue undergoes crack-
then heated to the desired temperature with a constant flow ing and coking reactions. After the test, the bulb is cooled and
of air drawn through it for 60 min. The loss in mass of the oil weighed. The residue remaining is reported as % of original
is determined. In this test, Wood's metal, which contains sample and is called the Ramsbottom Carbon Residue.
lead, bismuth, antimony, a n d cadmium, is used. These com- "Micro Method" for Carbon Residue (Test Method D 4530)—In
ponents have been found to be health hazards. Therefore, if the "micro method," a weighed sample of the fluid is heated
it is possible. Test Method D 6375 should be used (see fol- in a 2 mL glass vial at 500°C under an inert atmosphere (ni-
lowing discussion). trogen) in a controlled manner for a specific time. The sam-
An automated, smaller scale variant of Test Method D 5800 ple undergoes coking reactions a n d the volatiles that are
is Test Method D 6375, the "TGA NOACK Method." This formed are swept away by the nitrogen. The carbonaceous
method is applicable to lubrication oils that exhibit NOACK residue formed is reported as % of original sample as "carbon
evaporative losses of 0-30%. In this test, a sample of the de- residue (micro)." This test method is reported to be equiva-
sired compressor fluid to be tested is placed in an appropri- lent to the Conradson Carbon Residue.
ate Thermogravimetric Analyzer (TGA) specimen pan. The
pan is placed on the TGA p a n holder and quickly heated to Precipitation Number (Test Method D 91)
between 247-249°C under a stream of air and then held for Sludge formation in a compressor oil is caused by oxidation of
an appropriate time. Throughout the process, the TGA mon- various components, leading to polymerization and cross-
itors and records the mass loss experienced by the specimen linking reactions. These cross-linked and polymerized byprod-
~N Manometer
Thermometer
j ~ To Pump
FIG. 29—Schematic illustration of the NOACK Evaporative Tester (ASTM Test Method D 5800).
ucts are sufficiently fiigfi in molecular weight to cause them to stretching vibrations ofC = O a t l 7 1 0 cm ', for carboxylic
be Insoluble in the oil. As indicated above, sludge can lead to acids contained in oxidized oil. IR analysis has been used to
valve sticking, creating an unsafe condition (ISO 5388). In- detect and quantify other carbonyl-containing compounds
creasing sludge formation often indicates increasing oil oxi- [37]:
dation. The amount of sludge can be quantified by adding Metal carboxylate salts-1600 and 1400 cm"'
naphtha solvent to the compressor fluid sample and deter- Carboxylic Acids-1710 cm"'
mining the volume of precipitate (sludge) after centrifuging. Metal sulfates-1100 and 1600 cm"'
Esters-1270 and 1735 cm "'
Acid Number (ASTM D 664 and D 974)
The acid number (AN) measures the acidity of the fluid, acid- Fluid Oxidation
ity produced when the fluid is oxidized. Fresh, oxidation in- The severity thermal and oxidative stresses that a compressor
hibited, compressor fluids tjrpically exhibit AN values of ap- fluid is subjected to are compressor dependent. For example,
proximately 0.15 or less [22,26]. The AN value may be thermal and oxidative stresses on a fluid in a rotary vane and
determined by Test Method D 664, which covers lubricants rotary screw compressor are considerably more moderate
soluble or nearly soluble in mixtures of toluene and iso- thcin a fluid would encounter in a reciprocating compressor.
propanol. It is applicable for determination of acids whose However, although the thermal and oxidative stress is
dissociation constants in water are larger than 10"'. Ex- greater/cycle in a reciprocating compressor, it is only a "once
tremely weak acids whose dissociation constants are smaller through process," whereas the expected lifetime of a fluid for
than 10~' do not interfere. Salts react if their hydrolysis con- a rotary vane or rotary screw compressor would be expected
stants are larger than 10~'. For Test Method D 664, the com- to last for several thousands of hours [23].
pressor fluid is dissolved in a mixture of toluene and iso- Various tests have been proposed to determine relative life-
propanol containing a small amount of water and titrated times of a compressor fluid under rigorous thermal and ox-
potentiometrically with alcoholic potassium hydroxide, us- idative conditions. The tests that have gained greater accep-
ing a glass electrode and a calomel reference electrode. Test tance as reasonably predicting actual production experience
Method D 974 is similar except the sample is titrated colori- in a compressor will be reviewed here.
metrically using a p-naphtholbenzein as the indicator. Turbine Oil Stability Test - TOST (Test Method D 943)—Sug-
iura, et al. [23] has reported some success with the Test
Infra-Red Spectroscopy Method D 943 to determine the long term oxidative stability
An alternative method that is being used increasingly to iden- of a compressor oil. Test Method D 943 evaluates the oxida-
tify and quantify oil oxidation, even in the presence of additive stability of a lubricant with a specific gravity less than
tives, is infra-red (IR) spectroscopy [22]. Figure 30 provides water, which contains rust and oxidation inhibitors in the
an illustration of the use of IR spectral analysis to identify oil presence of oxygen, water, copper, and iron at an elevated
oxidation [36]. Mang and Jiinemann monitored the IR temperature. In this test, the sample is contacted with oxygen
in the presence of an iron-copper catalyst at 95°C. The test is the ISOT test reported by Sugiura [22] involves blowing dry
continued until the measured acid n u m b e r is 2.0 mg KOH/g air at 10 L/h through 300 mL of the test fluid held at 165.5°C
or above. The n u m b e r of hours required for the test fluid to (329.9°F) in the presence of a copper and iron catalyst. The
reach 2.0 mg KOH/g is the "oxidation lifetime." Sugiura, n u m b e r of hours to reach a AN of 0.4 mg KOH/g is deter-
however, utilized a m u c h lower critical AN value of 0.4 mg mined.
KOH/g since his work indicated that the oxidation rate of the Wolf Strip Oxidation Test [8]—Matthews has reported excel-
compressor oils he examined increased dramatically above lent correlations with carbon and sludge forming tendencies
0.4 mg KOH/g [22]. of a compressor fluid in an air compressor using the Wolf
Rotating Bomb Oxidation Test-RBOT (Test Method D 2272)— Strip Test [8,23]. This is a 12 h test that is conducted by
Various workers have reported the use of RBOT as an accel- pumping a fluid sample over an inclined steel plate test strip,
erated test to evaluate compressor fluid lifetime [11,23,26]. which is heated to 250°C. The oil is removed from the plate
This test m e t h o d utilizes an oxygen-pressurized vessel to by solvent washing at the conclusion of the test and the steel
evaluate oxidation stability of new and used compressor flu- test strip is air dried. The weight of the residue adhering to
ids in the presence of water and a copper catalyst at 150°C. the test strip is measured and the evaporative loss of the total
For this test, the compressor fluid, water, and copper catalyst volume of the oil after the test completion is recorded. This is
coil, contained in a covered glass container, are placed in a very similar to the hot panel coking test which utilizes an alu-
vessel equipped with a pressure gauge. The vessel is charged m i n u m test plate [38] and has been used in the automotive
with oxygen to a gauge pressure of 620 kPa (90 psig, 6.2 bar), lubricants industry for many years [23].
placed in a constant-temperature oil bath set at 150°C, and
rotated axially at 100 r p m at an angle of 30° from horizontal. Liquid Heptane Washing Test for Oil Film Wash-Off
The n u m b e r of minutes required to reach a specific drop in Resistance f8]
gauge pressure is the oxidation stability of the fluid. Matthews has devised a test to indicate the resistance of an oil
Indiana Stirring Oxidation Test-ISOT (Test Method JIS K film to be removed by heavier hydrocarbons (C7 or higher),
2514)~The ISOT, although developed in the U.S., has only which may be present in natural gas [8]. This test is conducted
been standardized in Japan as JIS K 2514 and has been re- by pre-weighing dry steel plates that are dipped into the test
ported to provide superior correlation with actual results for lubricant and then suspended for 1 h to allow the excess oil to
actual industrial compressor use [22,26]. This test cell for drain off from the surface of the steel. The steel plates are
this method is illustrated in Fig. 3 1 . This modified version of reweighed to determine the weight gain due to the oil film and
Wave Number (cm'^)

FIG. 30—Infra-red spectral identification of oxidation of a used compressor oil (mineral
oil-derived fluid).
[15] or 1 h at 40 kgf, 1500 rpm [8]. In both cases, the wear

Dry Air
10 ±1 Mir. scar at the completion of the test is measured. Matthews also
reported the weld load, which is a determination of the load
carrying (extreme pressure-EP) properties of the fluid using
Test Method IP 239. The weld-load is the lowest applied load,
fr in kilograms, under the conditions of the test at which the ro-

tating ball welds to the three stationary balls, indicating that
the extreme - pressure level of the lubricant-force has been
exceeded. ASTM Test Method D 2783 can be used to deter-
mine the EP properties of a lubricant and it is conducted, af-
ter properly preparing the test machine, at the desired start-
ing temperature: 18.33-35°C (65-95°F), 1760 ± 40 rpm, and
a series of tests of 10 s duration are made at increasing loads
Oil Bath until welding occurs. This is called the "weld point."
Temperature = 170 "C
FZG Visual Method (Test Method D 5182)—This test method,
the Forschungstelle fiir Z a h n r a d e r u n d Getriebebau (Re-
4-5-
search Site for Gears and Transmissions) is commonly re-
ferred to as the FZG Visual Method. This method is intended
Sample • to measure the scuffing load capacity of oils used to lubricate
hardened steel gears. Scoring, is included as a failure criteria
4J.44
in this test method. The FZG Gear Test Machine is operated
at a constant speed (1450 rpm) for a fixed period (21700 rev-
olutions—approximately 15 min) at successively increasing
loads until the failure criteria is reached. The initial oil tem-
^ ^
Dimensions in miilimeters (mm) T
FIG. 31—Illustration of the test cell for 100
the Indiana Stirring Oxidation Test
Liquid Heptane
(ISOT). Wasiiing Test
then the plates are dipped into a bath of heptane for 5 s. After
ten dipping cycles, the steel plates are suspended in air to al-
low the h e p t a n e to evaporate and then the plates are
reweighed to determine the a m o u n t of oil film removed. An il-
lustration of the relative weight loss of two different com-
pressor oils subjected to this test is provided in Fig. 32 [8].
Antiwear Properties
If possible, it is desirable to determine the lubrication prop-
erties of every compressor oil in every compressor. However,
in addition to being prohibitively expensive and requiring
enormous amounts of time, industrial equipment is not de-
signed with the precision required for ideal laboratory test in-
struments. Therefore smaller scale lubrication testing is per-
formed as a laboratory fluid development tool and while very
useful, these data must, at some point, be confirmed by in-
field testing in actual compressor units and processes where
the use of the fluid is contemplated. Although any test could
conceivably be used if properly correlated with compressor
operation, there are two bench tests that are encountered
most often in the published literature: FZG [23,32,35] and 4-
ball [8,15,25]. These tests will be discussed here.
4-BaU EP and Wear Test (Test Methods D 2783, D 4172 and IP
239)—Test Method D 4172 is used to measure the relative
wear preventive properties of lubricating fluids under sliding
contact conditions using a Four-Ball EP and Wear Test Ma-
chine. Although Test Method D 4172 calls for test loads of 15 Cycles
or 40 kgf at 1200 r p m and 75°C, any load condition can be FIG. 32—Comparison of the liquid heptane
used, if more appropriate. Some test conditions that have wash-off results for a 200 cSt PAG and a mineral
been reported include: 1 h at 40 kgf, 1800 rpm and 54.4°C oil compressor lubricant.
perature is 90°C beginning at load stage 4. The test gears are compressor is mounted on the crankcase at 90°. Multi-stage
examined initially and after the prescribed duration at each water inter-coolers are filtered after each compression stage.
load stage for cumulative damage (scuffing) to the gear tooth Each compression valve combines both suction and delivery.
flanks. Generally, it is expected that compressor fluids will The conventional trunk-type first and second stage pistons
pass at least ten load stages in this test [32]. utilize splash lubrication generated by the rotating (1450
Compressor Tests—Âs with any machinery lubricant, the best rpm) crankshaft in the sump. The crossheads and guides for
test is to evaluate it in the machine of interest. However, just the third and fourth stage pistons are lubricated separately
as bench tests do not necessarily correlate with machinery re- using a mechanical lubricator. The operating conditions are
sults, it is also true that performance in one machine does not summarized in Table 8 and Table 9.
necessarily predict performance in a different m a c h i n e . The test stand was fitted with transducers to monitor the
Matthews has reported the development of two compressor inlet and outlet temperatures and pressures at each stage. A
tests where tests with different compressor fluids do seem to water-flow control valve operated by a thermocouple located
correlate well with other compressors in the field. These two in the air delivery stream at Stage 4 was used to control the
tests will be outlined here, although they are not national or air delivery temperature. Over-pressure relief valves were
used on each stage to prevent overheating.
international standard tests at this time.
Broomwade 2050H Compressor Rig Test [8]—The Sebe (Com- New valves were used for each test and seals replaced as
pare) Broomwade 2050H is a single-stage, air-cooled, belt- necessary. The compressor was run continuously with peri-
odic inspection of the valves and cones. Valve removal should
driven, twin-piston air compressor that is mounted on an air
not be performed since this process would disturb the accu-
receiver tank as shown in Fig. 33. A gear p u m p is used to
mulated carbon deposits that would falsely indicate an ap-
splash-lubricate the bearings a n d cylinder walls using a
parent increase in the lifetime of the lubricant. Therefore, the
rapid, 825 rpm, crankcase movement in the sump. The oper-
valves should be left in position and the pressures and tem-
ating conditions are summarized in Table 7. peratures, which are continuously monitored, would be used
The compressor rig was modified as follows: to indicate compressor malfunction that would typically be:
1. The air discharge t e m p e r a t u r e is controlled by a mini-
1. Lifting of the inter-stage relief valves that would be indica-
ether operating a magnetic on/off valve which regulates
tive of a leaking inlet valve.
the delivery pressure in response to a thermocouple lo-
2. Unacceptably low inter-stage delivery pressures that
cated in the air outlet stream.
would indicate a delivery valve failure.
2. The discharged air is passed through an air-cooled heat ex-
3. Rapid rise in air delivery temperature indicating possible
changer to reduce the temperature to an acceptable level
internal combustion.
during continuous operation.
4. Very high oil consumption indicating worn piston rings.
Before each test is performed, the compressor is fitted with
new inlet and delivery valves, seals, gaskets, and filters and
the cylinder head is ultrasonically cleaned and solvent
TABLE 7—Operating conditions for the Broomwade
washed between tests. The compressor is run continuously 2050H compressor.
with visual inspections at 100 h intervals. At the conclusion
Electric Motor Output 7.5 k W
of the test, the piston ring gap is measured in addition to the
visual inspection. Speed 825 rpm
Maximum oil deliveiy pressure 10bar(150psig)
Reavell VHP 15 Compressor Rig Test [8]—The Reavell VHP 15 Oil capacity 4.5 L
is a 4-stage, single acting, air compressor that is driven by an Free air delivered 15.2L/sat lOOpsig
electric motor, illustrated in Fig. 34. The cylinder, V-form Air discharge temperature 300-325°C
H.P. AIR DELIVERY (t')
MANUAL REGULATING
VALVE
— CONDENSATE DRAIN
FIG. 33—Schematic of the Broomwade 2050H compressor rig test.

404 MANUAL 37; FUELS AND LUBRICANTS HANDBOOK

LP AIR T O
ATMOSPHERE
 C/W RETURN "mERMOCOUPLE

(STAGE 4)
Sr^ ^-© © @
RECIRCULAtORY H.P.AIR ^-^ •—'
COOLING WATER - FLOW
REAVELL VHP15 &
4 STAGE AIR 10
COMPRESSOR
LPAIR-
1. Non-retum valve
2. Pressure reHef
3. Manual blow-down
4. Over-pressure switch
5. Pressure-maintaining valve DRIVE
6. Manual cooling water valve MOTOR
7. Motorized cooling water valve 22 Kw
8. Temerature controller CONDENSATE
9. Pressure storage vessel DRAINS
10. Pressure storage vessel
FIG. 34—Schematic of the Reavell VHP 15 compressor rig test.
TABLE 8—Operating conditions for the reavell VHP 15

Coalescer Blocking Tendency (CBT) Test [32]—As discussed air compressor.
earlier, compressor fluids are recycled through a rotary com- Electric Motor Output 22 kW
pressor, such as a rotary screw compressor. To this, the resid- Speed 1450 r p m
ual gas that is being compressed must be removed from the Maximum delivery pressure 350 b a r (5000 psig)
Free air delivery rate 13.3 L/s
compressor fluid before it can be sent back to the reservoir. Sump oil capacity 23.1 L
This is done using a coalescer for gas removal. During use,
compressor fluids will contain degradation by-products that
will adhere to or block the coalescer filter. This will create an
increase in differential pressure across the filter that may TABLE 9—Stage temperatures and pressures.
lead to machine stoppage. Therefore, coalescer blocking ten- Stage
dency is an important parameter since it defines the useful 1 2 3 4
life of a compressor fluid in a compressor.
Delivery pressure (bar) 3.1 19.6 84.5 310
As indicated in Table 10 [32], although there are various Delivery temperature (°C) 140 179 146 180
bench tests to evaluate fluid oxidation, carbon and sludging
tendencies, and filterability, no single test correlates well
with actual compressor usage. The best test still is a com- 4. A high-resolution Bourdon gauge was used to monitor the
pressor test. One test developed by Mills, et al. will be out- pressure differential across the coalescer.
lined here [8,32]. 5. The working discharge pressure of the compressor was es-
The CBT test is conducted using an oil-flooded 22 kW (30 tablished using a gate valve in the discharge main area.
Hp) rotary screw compressor with a free air delivery rate of 6. The inlet oil temperature, air/oil outlet temperature, and
42 L/s (93 ft^/min) was used. The specifications for the com- air delivery temperature of the compressor was continu-
pressor are summarized in Table 11 [32]. ously monitored on a chart recorder.
The following modifications were made to the compressor Before each test, the compressor was flushed using a flush-
to construct the test stand illustrated in Fig. 35 ing fluid of the same type being tested. (Mill called for using
1. Oil temperature was controlled by using a control system a mineral oil compressor fluid but this would not be appro-
that maintained the inlet oil temperature at 40-170°C ± priate if it we not compatible with the fluid type being tested.)
2°C. The flushing conditions are; oil charge 22.5 L (6 gal), outlet
2. The compressor's 5-10 micron air filter was proceeded by air pressure 690 ± 1 5 kPa, inlet oil temperature 70 ± 2°C for
two in-series foam air filters, each rated as 99.5 % efficient 24 h. When the flushing is complete, the flushing fluid is
at 5 microns. The purpose of this modification was to min- drained hot from the reclaimer, compressor unit, and oil
imize the day-to-day variation in air dust on the severity of cooler for 15 min.
the test. A new 85% masked coalescer and new oil filter are in-
3. An oil flow rate meter was placed in the oil feed circuit to stalled, the unit is charged with 22.5 L (6 gal) of the test fluid
monitor oil flow rate and an oil removal filter was fitted to and the soluble catalyst system. The catalyst system is 20 g
the discharge air to give a maximum oil content of 0.01 each of copper and iron as a naphthenate in a hydrocarbon
ppm. The purpose of this modification was to minimize oil solvent. This will provide approximately 60 ppm of copper
carryover. and iron in the test fluid.
TABLE 10-—Performance of commercial mineral oil-based compressor fluids in various bench tests.
Test 1° Test l*" Test 3' Test 4''
% % % Viscosity Filtration Filtration Field
Compressor Carbon Evaporation Increase TAN Increase % Time Time Rating
Fluid Residue Loss at 40°C (mg KOH/g) Sludge (min) (min) (1 = Best)
A 3.0 0.44 7.4 0.48 0.11 17.6 Blocked 3
B 0.5 0.83 2.0 0.40 0.25 Blocked Blocked 4
C 1.5 0.98 1.6 0.06 0.06 Blocked 16 1
D 4.3 0.49 1.0 0.37 0.21 10.0 Blocked 2
"Test 1: DIN 51352 Fart 1 (PNEUROF Oxidation Test-Conradson carbon residue.
^Test 2: Modified DIN 51352-Same as Test 1 but 120°C, 100 h with 50 ppm Fe catalyst as iron naphthenate.
''Test 3: Beaker Filtration test-300 mL oil, 120°C, 168 h, filtered at ambient temperature through 47 mm diameter, 1.2 /xm Millipore filter under 88 kPa
(26 in. Hg) pressure.
''Beaker Filtration test-100 mL oil, 120°C, 28 days,filteredas described for Test 3.
TABLE 11—Specifications for compressor used for the The compressor is then started under the test conditions:
coalescer blocking tendency test. outlet air pressure 830 ± 1 5 kPa, inlet oil temperature 100 ±
Air Delivery Pressure Minimum 70 psi (5 bar) 2°C until a pressure differential across the coalescer of 207 kPa
Normal 100 psi (7 bar) is obtained. At this point, the coalescer is defined as "blocked."
Maximum 150 psi (10 bar)
Every hour the coalescer pressure differential is measured
Free Air Delivery 42 L/s (93 hVmin)
Oil Capacity (nominal) Unit 40 L (10.6 gal) and recorded. Every 24 h, the compressor is shut down for
Reclaimer 32 L (8.5 gal) 2-5 m i n for a 60 m L sample to be removed from the re-
Compressor Single stage, oil injected, asymmetric claimer. (A 100 m L presample is taken to flush the sampling
screw system.) The oil carryover filter bowl contents are measured
Motor 22 kW (30 Hp)
Compressor-Air/oil cooled and discarded during the shut down period.
Cooling
Air Cooler-Thermostatically controlled No attempt is made to top-off the compressor fluid since
updraft fan losses should be very small. If the fluid level drops sufficiently
Filters Inlet air 5-10 micron paper cartridge for air entrainment to occur (as indicated by the oscillating
Oil 15 micron paper cartridge outlet air pressure), or any other malfunction occurs in the
Coalescer 1-2 micron
Air Flow Differential

ON Flow Pressure
Alr/OII Flow Gauge
Water Flow
5M 5-10 M
Air • Air
Filter Filter
Motor
Oil Cooler
Drain Valve
FIG. 35—Schematic illustration of compressor test circuit used for coalescer blocking tendency test.
system, then the test is invalidated.

Gas Solubility into the Lubricant L = 0.300 exp o.639m;^ /H3.333LO
Knowledge of gas solubility is of vital importance when con-
sidering compressor lubrication. It is particularly important Where T = temperature in K, L = Ostwald coefficient at T
in b o u n d a r y lubrication, where sudden release of the dis- for a liquid of density 0.85 and LQ = Ostwald coefficient at
solved gas may cause lubricating film collapse or even cavi- 273 K for a liquid of density 0.85. For liquids with a differ-
tation. There are various tests that can be conducted for gas ent density (d), calculate Lc from:
solubility determination. These test procedures will be dis- L, = 7.70L (0.980 - d)
cussed here.
Gas Solubility in Petroleum Oils at Atmospheric Pressure (Test Where Lc = the Otswald coefficient at T for a liquid of the
Method D 2779)—Tesi Method D 2779 may be used to esti- specified density.
mate the solubility of several common gases in hydrocarbon • Step 4—Calculate the Bunsen Coefficient (B) from:
liquids. These include petroleum fractions with densities that
range from 0.63-0.90 at 288 K (59°F). The solubihties can be (P-Pv)L
B = 2697
estimated over the temperature range of 228 K(— 50°F) to 423
K(302°F). The test method is based on Henry's Gas Law and
Where: P = pressure of the gas in Mpa, Py = vapor pressure
the Perfect Gas Law. This test is conducted as follows:
of the liquid at the specified temperature (T).
• Step 1—Determine the density of the compressor fluid by • Step 5—Calculate the solubility of the gas, which is some-
Test Method D 1298 if it is not already available. times expressed as part per million by weight, using the fol-
• Step 2—Determine a value of "L" for the gas of interest at lowing equation:
the desired temperature from Fig. 36 if it is shown. If it is
not shown, then it may be calculated from the following r - 288 - 2
1 - 0.000595
equation and the value of Lo taken from Table 12. 0.224
TEMPERATURE,-F
100 200 30O
-SO 90 100 tSO 200 eso

T E M P E R ATURE.'C
FIG. 36—Solubility of gases in petroleum liquids witii a density

(d) = 0.85.
TABLE 12—Ostwald coefficients at 0°C for Si = 8.63 2 + 0.96

petroleum liquids with d = 0.85. ^ IlD
Ostwald Step 2—Obtain the value of the equivalent solubility pa-

Gas Coefficient (LQ) rameter of the gas, S2, (MPa)''^ from Table 14.
Helium 0.012 Step 3—Calculate the Ostwald coefficient (L) for a lubri-
Neon 0.018 cant from:
Hydrogen 0.040 L = exp[(0.0395 (Si - 82)^ - 2.66) - 3.03Si
Nitrogen 0.069 - 0.0241 (17.60 - 82^ + 5.731]
Air 0.098
Carbon monoxide 0.12 To calculate the Ostwald coefficient for a distillate fuel or
Oxygen 0.16 a halogenated liquid, multiply by the fuel factor from Table
Argon 0.18 14.
Methane Use Fig. 36" Step 4—Calculate the Bunsen coefficient (B) as follows:
Krypton 0.60
Carbon dioxide 1.45"
Ammonia 1.7" B = 2697
T
Xenon 3.3
Ethylene Use Fig. 36" Step 5—For hydrocarbon oils, calculate the density of the
Hydrogen sulfide 5.0"
liquid at a specified temperature px as follows:
''Do not use this method for these gases in highly
aromatic liquids r-288.2
PT- 1 - 0.000595
Where: 0.0224 is the molar volume at 273 K and 101.3 kPa Alternatively, the density may be determined experimen-
in liters/mole, and 0.000595 and 1.21 are the empirical con- tally by Test Method D 1298 or it may be obtained from the
stants for correcting d to a specified temperature, T. fluid supplier. Another method of density temperature cor-
Step 6—Calculate the gas solubility as mole fraction from: rection is to use the value dp/dT from Table 13 and calcu-
late as follows:
X= 10"
MG
p^ = p-(T- 288.2) - ^
Where ML = the moles of liquid and Mo = the moles of gas.
Henry's Law constant (H) is calculated from: • Step 6—Calculate the gas solubility G in mg/kg using the
value of M2, the molecular weight of the gas (g/mole), from
// = Table 14 and the following equation:
X
Estimation of Gas Solubility in Petroleum and Other Organic G = 44.6G^

Pi
Liquids (Test Method D 3827)—This test method provides a
procedure for estimating the equilibrium solubility of sev- • Step 7—Determine the value of the molecular weight of the
eral c o m m o n gases in petroleum oil and synthetic lubri- liquid. Ml, by:
cants at temperatures between 0 and 488 K. This method is a. For synthetic non-hydrocarbons, use the value of Mi
limited to systems in which polarity and hydrogen bonding from Table 13, or calculate it directly.
are not strong enough to cause serious deviations from ideal b. The value of Mi for refined hydrocarbons or sjrnthetic
behavior. Specifically excluded are gases such as HCL, NH3 hydrocarbons may be determined experimentally using
and SO2 and hydroxy liquids such as alcohols, glycols, and Test Method D 2502.
water. Also the estimation of CO2 in non-hydrocarbons is
excluded.
The calculation procedure is as follows:
TABLE 13—Constants for synthetic hydrocarbons.
• Step 1—Determine the value of Si (solubility parameter of Compound dp/dT
S, M,
the liquid in (Mpa)''^ by one of the following procedures:
Di-2-ethylhexyl adipate 18.05 370 0.928 0.00075
a. Procedure 1—If the liquid is a non-hydrocarbon, deter- Di-2-ethylhexyl sebacate 17.94 427 0.916 0.00073
mine 5i from Table 13. If the fluid is not listed in Table Trimethylolpropane 18.48 459 0.962 0.00070
13 and the structure is known, use the method of Fedors pelargonate
provided in Ref. 39. Pentaerythritol caprate 18.95 540 1.002 0.00065
b. Procedure 2—If the liquid is a refined petroleum or a Di-2-ethylhexyl phthalate 18.97 390 0.986 0.00075
Diphenoxy diphenylene 23.24 440 1.178 0.00079
synthetic hydrocarbon, then determine the density of ether
the fluid p by Test Method D 1218. If the fluid density p Diphenoxy triphenylene 23.67 520 1.205 0.00076
is 0.885 g/mL or less, calculate 5i as follows: ether
Polychlorotrifluroethylene 15.47 600 1.925 0.00166
Si = 12.03p + 7.36 Polychlorotrifluroethylene 15.55 700 1.942 0.00154
Polychlorotrifluroethylene 15.71 1000 1.998 0.00152
c. Procedure 3—If the liquid is a refined hydrocarbon or a Dimethyl silicone 15.14 10000 0.969 0.00093
synthetic hydrocarbon with p = 0.886 or greater, or a Methyl phenyl silicone 18.41 5000 1.063 0.00080
nonhydrocarbon of unknown structure, determine the Perfluoro polyglycol 14.30 1000 1.914 0.00180
refractive index, nn, by Test Method D 1218 and calcu- Tri-2-ethylhexyl phosphate 18.27 467 0.923 0.00090
Tricresyl phosphate 18.82 368 1.158 0.00090
late as follows:
TABLE 14—Solubility parameters of gaseous solutes. and gas at the desired temperature. Gas is typically trans-
Gas M, 52 at 298 K Fuel Factor ferred to the Parr reactor from a gas-charging vessel. The lu-
He 4 3.35 1.27 bricant is stirred to obtain equilibrium as indicated by reach-
Ne 20 3.87 1.37 ing a constant pressure. Viscosity of saturated lubricant at
H2 2 5.52 1.27 final pressure is measured with a viscosity probe and it's as-
N2 28 6.04 1.70 sociated electronics. Gas solubility can be calculated from
Air 29 6.67 1.44
initial and final pressures using gas laws and compressibility
CO 28 7.47 1.37
32 7.75 1.28 factors. It can also be obtained by weighing the gas-charging
O2
Ar 40 7.71 1.37 vessel before and after equilibrium.
CH4 16 9.10 1.42 Absorption of the Lubricant into the Gas Phase—This is the
Kr 84 10.34 1.37
test procedure published previously by Matthews, which was
CO2 44 14.81 1.14
performed to determine the amount of lubricant lost into the
gas being compressed [8]. The test is conducted by weighing
the test oil into a small aluminum container of about 25 m m
c. The value of Mi for non-hydrocarbons of u n k n o w n diameter which was then placed into a 50 mL stainless steel,
structure may be determined experimentally using Test high pressure reactor which was then heated to 100°C. The
Method D 2503. test gas is then pressurized to 400 bar and fed through stain-
7. Step 8—Calculate the gas solubility as a mole fraction less steel tubing into the stainless steel reactor containing the
from: test oil. The pressure is maintained by releasing the gas
through a needle valve and the total volume of the gas being
X= 10" discharged is metered. At the end of the test, the aluminum
M2 container is re-weighed and the weight loss is recorded.
8. Step 9—Calculate Henry's Law constant (H) as:
Heat Transfer Efficiency
(P - Pv)
H = Thermal Conductivity (Test Method D 2717) and Specific Heat
X
(Test Method D 2766)—These thermal conductivity and spe-
Experimental Determination of Gas Solubility in Liquids (Test cific heat tests are difficult to carry out, facilities for per-
Method 2780)—This procedure covers the experimental de- forming them are few, and the precision data is yet to be es-
termination of the solubility of gases in liquids and is suitable
for gas/liquid mixtures that do not react with each other. This
method also permits the determination of the concentration
of gases in solutions that are not saturated with the gas. Gos Inlet g. >v Gas Outlet
In this test, the liquid is saturated with the gas of interest
under specified temperature and pressure conditions. (The
apparatus for ambient pressure is illustrated in Fig. 37 and
for gas solubility experiments conducted at elevated pres-
sures, the apparatus illustrated in Fig. 38 is used.) If the ob-
jective is to determine gas concentration, the saturation step
is eliminated. A portion of the solution is then transferred to 1000-ml Seporotory
a gas extraction apparatus shown in Fig. 39 where the gas is Funnel (peor-shopedl
quantitatively removed from the liquid. The separated gas is

Control
transferred to a gas burette in which its volume is deter- ThecTnocouple
mined.
Viscosity of Gas/Liquid Mixtures Under Pressure—It is not
only important to determine the solubility of a gas a com- Test Liquid
pressor fluid, but it is also important to determine the impact
of dissolved gases on fluid viscosity. This is of particular im-
portance in determining the lubricating ability of the com-
pressor fluid during gas compression.
Healing Mantle Ts" \ ,
Measurement of viscosity of lubricants saturated with gas
at elevated pressures is done in a fixed volume apparatus. Cos Dispersion
Typically a Parr reactor (or other high-pressure autoclave) Element
equipped with a stirrer, pressure transducer, thermocouples,
and heating and cooling devices is used to conduct these ex-
periments at desired temperatures. The vessel is fitted with a
viscosity measurement probe suitable for measurements at PTFE Stopcock A
high pressure. Viscosity probes that can operate u p to 5000
psia (—340 Bars) are readily available. Viscosity and gas sol- Boll Joint B
ubility data at a given temperature and pressure can be ob- i 12/2
tained from the same experiment. FIG. 37—Schematic illustration of an ainblent pressure satu-
The Parr reactor is charged with a known mass of lubricant rator.
tablished. Values can be estimated for design use from the

Pressure Goge
general chemical composition. The VEilues for thermal con-
ductivity and specific heat may be available from the fluid
Tube Connection supplier.
A"
Elastomeric Seals Compatibility (Test Method D 471)
Seals may degrade in use. As an oil deteriorates in service, ad-
Thermocouple
ditional tests may be required to assure that seals remain
compatible with the degraded oil. Mills et. al, have reported
the determination of seal compatibility by a short term test
by immersion of 50 m m X 25 m m X 2 m m test specimens of
the elastomer (most often a nitrile rubber) into the compres-
sor fluid of interest at 120''C for 168 h [32]. Volume swell was
2500-ml
d e t e r m i n e d according to the procedures outlined in Test
Stainless Method D 471 and the hardness was determined according to
Steel \fe$sel
Test Method D 1415. The authors recommended setting the
volume swell limits at —5 to -1-15% and the change in hard-
ness to -t-20%. Although an accelerated test may be per-
formed, it is preferable that the temperature ranges of the
Thermostotic tests should correspond to temperatures to which seals will
Control
Jacket be exposed in service and the tests should be conducted for at
least 1000 h.
Paint Compatibility Test [32]

Paints are used to protect metal surfaces of the compressor
components and machinery. However, they may be attacked
readily by the compressor fluid being used. The paint may
; 12/2 Stoinless Steel then be removed and become a contaminant in the fluid,
BaH Joint B
causing great damage. Therefore, it is important that the
FIG. 38—Schematic illustration of an elevated pressure satu- paints that are used be compatible with the compressor fluid.
rator. A simple test used to determine paint compatibility is to
To Condenser K
14/35
Solid Broce
stopcocks
L,M,N, ore 'Ê-0.5 mm Cleoronce
2-woy
—60mn(i 0.0.
•—SOmmO.D.
Lewting
Bulb
(Mercury)
To Leveling
Co pillory
BulbH-
Monometer
J 12/2
(Opin-Endl
(a) Boiler-1 to Boiler I (b)

FIG. 39—Gas extraction system: A. schematic illustration of the entire apparatus and B: Illustration of the gas extrac-
tion chamber.
paint a small steel test specimen with the paint of interest and D 445 Test Method for Kinematic Viscosity of Transpar-
let it dry [32]. The painted surface is then scratched in the ent and Opaque Liquids (the Calculation of Dy-
form of a cross and then immersed into the compressor fluid namic Viscosity)
at 120°C for 168 h. If the paint is lifted or removed by the D 471 Test Method for Rubber Property-Effect of Liq-
fluid, it fails the test. uids
D 524 Test Method for Ramsbottom Carbon Residue of
Filter Bowl Compatibility Test [32] Petroleum Products
A filter bowl is used to retain the compressor fluid after it is D 664 Test Method for Acid N u m b e r of Petroleum Prod-
removed from the compressed gas by an absorbent filter. A ucts by Potentiometric Titration
commonly reported field problem is that compressor fluid at- D 665 Test Method of Rust-Preventing Characteristics
tacks the filter bowl, whcih is often constructed from a plas- of Inhibited Mineral Oil in the Presence of Water
tic such as polycarbonate. A simple test that is used by many D 892 Test Method for Foaming Characteristics of Lu-
compressor manufacturers is to pressurize a filter bowl con- bricating Oils
taining the compressor fluid being tested to 6900 kPa (100 D 943 Test Method for Oxidation Characteristics of In-
psig). The test is considered to be a pass if the filter bowl does hibited Mineral Oils
not fail within 100 h. D 972 Test Method for Evaporation Loss of Lubricating
Greases and Oils
D 974 Test Method for Acid and Base Number by Color-
SUMMARY Indicator Titration
D 1298 Test Method for Density, Relative Density (Spe-
In this chapter, an overview of basic compressor fluid tech- cific Gravity), or API Gravity of Crude Petroleum
nology has been provided. This discussion included a de- Products by Hydrometer Method
scription of the gas laws and how they applied to gas com- D 1401 Test Method for Water Separability of Petroleum
pression. Also provided was a short tutorial on how c o m m o n Oils and Synthetic Fuels
types of compressors operate. This was followed by a sum- A 1415 Test Method for Rubber Property-International
mary of the properties of the most common classes of com- Hardness
pressor fluids in current use in the market place. Finally, D 1744 Test Method for Determination of Water in Liq-
there includes an extensive listing of various test procedures uid Petroleum Products by Karl Fischer Reagent
that have been applied to the analysis of the expected perfor- D 2270 Practice for Calculating Viscosity Index from
mance of compressor fluids such as water content, oxidative Kinematic Viscosity at 40°C and 100°C
stability, carbon and sludge formation, gas solubility and lu- D 2272 Test Method for Oxidation Stability of Steam Tur-
brication properties. bine Oils by Rotating Pressure Vessel
However, it is must be realized that there is no one single D 2502 Test Method for Estimation of Molecular Weight
bench test that will best predict the performance of a partic- (Relative Molecular Mass) of Petroleum Oils from
ular compressor fluid, in a given compressor, in a given in- Viscosity Measurements
dustrial process. This is illustrated in Table 10, which shows D 2503 Test Method for Relative Molecular Mass (Molec-
that no one single test predicts the actual relative perfor- ular Weight) of Hydrocarbons by Thermoelectric
mance of a compressor fluid in an industrial process. It is Measurement of Vapor Pressure
therefore recommended that groups of tests be performed D 2619 Test Method for Hydrolytic Stability of Hydraulic
and overall ranking be used. Of course, whatever the bench Fluids (Beverage Bottle Method)
tests indicate, whether individually or collectively, final com- D 2711 Test Method for Demulsibity Characteristics of
pressor machine performance validation is necessary. Lubricating Oils
D 2717 Test Method for Thermal Conductivity of Liquids
D 2766 Test Method for Specific Heat of Liquids and
ASTM STANDARDS Solids
D 2779 Test Method for Estimation of Solubility of Gases
No. Title in Petroleum Liquids
D 91 Test Method for Precipitation Number of Lubri- D 2780 Test Method for Solubility of Fixed Gases in Liq-
cating Oils uids
D 92 Test Method for Flash and Fire Points by Cleve- D 2783 Test Method for Measurement of Extreme-Pres-
land Open Cup sure Properties of Lubricating Fluids (Four-Ball
D 95 Test Method for Water in Petroleum Products and Method)
Bituminous Materials by Distillation D 3427 Test Method for Air Release of Petroleum Oils
D 97 Test Method for Pour Point of Petroleum Prod- D 3827 Test Method for Estimation of Solubility of Gases
ucts in Petroleum and Other Organic Liquids
D 130 Test Method for Determination of Copper Corro- D 4007 Test Method for Water and Sediment in Crude Oil
sion from Petroleum Products by the Copper by the Centrifuge Method (Laboratory Proce-
Strip Tarnish Test dure)
D 189 Test Method for Conradson Carbon Residue of D 4172 Test Method for Wear Preventive Cheiracteristics
Petroleum Products of Lubricating Fluid (Four-Ball Method)
D 287 Test Method for API Gravity of Crude Petroleum D 4530 Test Method for Determination of Carbon
and Petroleum Products (Hydrometer Method) Residue (Micro Method)
D 5182 T e s t M e t h o d for E v a l u a t i n g t h e Scuffing L o a d Ca- [10] Short, G. D., "Development of Synthetic Lubricants for Ex-
p a c i t y of Oils ( F Z G V i s u a l M e t h o d ) tended Life in Rotary-Screw Compressors," Lubrication Engi-
D 5800 T e s t M e t h o d for E v a p o r a t i o n L o s s of L u b r i c a t i n g neering, Vol. 40, No. 8, 1983, pp. 463-470.
Oils b y t h e N o a c k M e t h o d [11] Carswell, R., McGraw, P. W., and Ward, E. L., "A Blend of a
Polyglycol and a Trtra Ester as a Lubricant for Rotary Screw Air
D 6375 T e s t M e t h o d f o r E v a p o r a t i o n L o s s of L u b r i c a t i n g
Compressors," Lubrication Engineering, Vol. 39, No. 11, 1982,
O i l s b y T h e r m o g r a v i m e t r i c A n a l y z e r (TGA) pp. 684-689.
Noack Method [12] Miller, J. W., "Synthetic and HVI Compressor Lubricants," Jour-
E 659 T e s t M e t h o d f o r A u t o i g n i t i o n T e m p e r a t u r e of nal of Synthetic Lubricants, Vol. 6, No. 2, 1989, pp. 107-122.
Liquid Chemicals [13] Kist, K. R. and Doperalski, E . J . "Brief Introduction to the Screw
Compressor," Paper 68E, AIChE 8 6 * National Meeting, 1979.
[14] Tolfa, J. C , "Synthetic Lubricants Suitable for Use in Process
and Hydrocarbon Gas Compressors," Lubrication Engineering,
Vol. 47, No. 4, 1990, pp. 289-295.
OTHER STANDARDS
[15] Cohen, S. C , "Development of a "Synthetic" Compressor Oil
Based on Two-Stage Hydrotreated Petroleum Basestocks," Lu-
No. Title brication Engineering, Vol. 44, No. 3, 1987, pp. 230-238.
DIN 51352 P a r t 1 D e t e r m i n a t i o n of A g i n g C h a r a c t e r i s t i c s [16] Kajdas, C , "Industrial Lubricants," Ch. 8, Chemistry and Tech-
of L u b r i c a t i n g O i l s . I n c r e a s e i n C o n r a d s o n nology of Lubricants, 1992, pp. 196-222.
[17] Arbocus, G., "Synthetic Compressor Lubricants-State of the
c a r b o n residue after aging by passing air
Art," Lubrication Engineering, Vol. 34, No. 7, 1977, pp. 372-374.
t h r o u g h t h e l u b r i c a t i n g oil.
[18] Chen, C.-I., "Typical Lubricating Oil Properties," Tribology Data
DIN 51352 P a r t 2 D e t e r m i n a t i o n of A g i n g C h a r a c t e r i s t i c s
Book, E. R. Booser, Ed. CRC Press, Boca Raton, FL, 1997, pp. 3-
of L u b r i c a t i n g O i l s . I n c r e a s e i n C o n r a d s o n 33.
c a r b o n residue after aging by passing air [19] Miller, J. W., "Synthetic Lubricants and their Industrial Appli-
t h r o u g h t h e l u b r i c a t i n g oil i n t h e p r e s e n c e of cations," Journal of Synthetic Lubricants, Vol. 1, No. 2, 1984, pp.
iron(III) oxide. 136-152.
IP 239 D e t e r m i n a t i o n of E x t r e m e P r e s s u r e a n d Anti- [20] Klamann, D., Ullmann's Encyclopedia of Industrial Chemistry,
w e a r P r o p e r t i e s of L u b r i c a n t s - F o u r Ball M a - 5"" ed.. Vol. A15, VCH Verlagsges mbH, 1990, pp. 423-518.
chine Method [21] Randies, S. J., "Esters," Ch. 3, Synthetic Lubricants and High-
ISO 5388 Stationary air compressors-Safety rules a n d Performance Functional Fluids, 2"^ ed., L. R. Rudnick and R. L.
c o d e of p r a c t i c e Shubkin, Eds., Marcel Dekker Inc., NY, 1999, pp. 63-102
[22] Sugiura, K., Miyagawa, T. and Nakano, H., "Laboratory Evalu-
I S O 6743-3A L u b r i c a n t s , i n d u s t r i a l oils, a n d r e l a t e d p r o d -
ation and Field Performance of Oil-Flooded Rotary Compressor
u c t s (Class L ) - C l a s s i f i c a t i o n - P a r t 3A: F a m i l y
Oils," Lubrication Engineering, Vol. 38, No. 8, 1982, pp. 510-
D (Compressors) 518.
JIS K 2514 T e s t i n g M e t h o d of O x i d a t i o n C h a r a c t e r i s t i c s [23] Matthews, P. H. D., Walkden, R. H., and Williams, G. C , "Cur-
of E n g i n e Oils rent and Future Developments of Lubricants for Industrial Air
Compressors," Paper N u m b e r C477/023/94, ImechE Confer-
ence, Proceedings of the Institute of Mechanical Engineers, 1994,
REFERENCES pp. 175-183.
[24] Van Ormer, H. P., "Trim Compressed Air Cost with Synthetic
[1] Lilje, K. C , Short G. D., and Miller, J. W., "Compressors and Lubricants," Power, 1987, pp. 43-45.
Pumps," Ch. 4, Synthetic Lubricants and High-Performance [25] Miller, J. W., "New Synthetic Food-Grade Rotary-Screw Com-
Functional Fluids, 2"'' ed., L. R. Rudnick and R. L. Shubkin, pressor Lubricant," Lubrication Engineering, Vol. 40, No. 7,
Eds., Marcel Dekker Inc., NY, 1999, pp. 539-558. 1983, pp. 433-436.
[2] Patzau S. and Szchawnicka, E., "Oils for Air and Technical Gas [26] Takashima, H., "Gas Compressor Oils," Toraiborojisuto, Vol. 38,
Compressors," Trybologia, Vol. 20, No. 4, 1989, pp. 18-21. 1993, pp. 135-139.
[3] Scales, W., "Air Compressor Lubrication," Ch. 19, Tribology [27] Hampson, D. F. G., "Reducing the Risk of Fires in Large Recip-
Data Handbook, E. R. Booser, Ed., CRC Press, Boca Raton, FL, rocating Air Compressor Systems," Wear, Vol. 34, 1975, pp. 399-
1997, pp. 242-247. 407.
[4] Bloch, H. P., A Practical Guide to Compressor Technology, Mc- [28] McCoy, C. S. and Hanly, F. J. "Fire-Resistant Lubes Reduce
Graw-Hill Inc., NY, 1996. Danger of Refinery Explosions," The Oil and Gas Journal,
[5] "Unit Course 2-For Natural Gas Compressors-Considerations November 10, 1975, pp. 191-197.
for Sizing a Reciprocating Gas Compressor Package," Weather- [29] Garg, D. R., "Polyalkylene Glycol-Based Compressor Lubri-
ford Compression, Corpus Christi, TX. cants," presented at the Sixth Annual Reciprocating Compressor
[6] Istvan, V., "Interplant Tests of Chemical Plant Lubricants: - Part Conference, Salt Lake City, UT, 23-26 Sept. 1991.
2-Compressor Oils and Heating System Oils and Their Applica- [30] Oberle J. and Rajewski, T., "The Development of Lubricants for
tion: Grease Lubrication," Magyar Kemikasok Lapja, Vol. 53, Ammonia Refrigeration Systems," presented at the 11AR 19'*'
No. 3, 1998, pp. 139-144. Annual Meeting, 23-26 March 1997, New Orleans, LA.
[7] "Unit Course 1-For Natural Gas Compressors-An Introduction [31] Whiting, R., "Monitoring Energy Savings of Diester Compressor
to the Basic Function and Components of a Gas Compressor Oils," 6 * International Colloquium, Technische Akademie Essli-
Package," Weatherford Compression, Corpus Christi, TX. gen, 1998, pp. 14.41-14.43.
[8] Matthews, P. H. D., "Lubrication of Reciprocating Compres- [32] Mills, A. J., Tempest, M. A., and Thomas, A. S., "Performance
sors," Journal of Synthetic Lubricants, Vol. 6, No. 4, 1990, pp. Testing of Rotary Screw Air Compressor Fluids in Europe," Lu-
292-317. brication Engineering, Vol. 42, No. 5, 1986, pp. 278-286.
[9] Wills, J. G., "Compressors," Ch. 14, Lubrication Fundamentals, [33] Blackwell, J. W., BuUen, J. V., and Shubkin, R. L., "Current and
Marcel Dekker, Inc., NY, 1980, pp. 365-394. , Future Polyalphaolefins," Proceedings of the Conference on Syn-
thetic Lubricants, A. Zakar, Ed., Hungarian Hydrocarbon Insti- Technology, ASM International, Materials Park, OH, 1993, pp.
tute, Szazhalombatta, Hungary, 1989, p p . 36-68. 191-238.
[34] Witts, J. J., "Diester Compressor Lubricants in Petroleum and [37] Mang T. and Jiinemann, H., "Erdol kohle-Erdgas-Petrochem,"
Chemical Plant Service," Journal of Synthetic Lubricants, Vol. 5, vemeigt Brennstoff-Cheniie, Vol. 25, No. 8, 1972, pp. 459-464.
No. 4, 1989, pp. 319-326. [38] Rounds, F. G., "Coking Tendencies of Lubricating Oils," Paper
[35] Legeron J-P. and Beslin, L., "Rotary-Vane Compressors: Some 570097, Presented at the SAE National Fuels and Lubricants
Technical Aspects for Long-Life Lubricants," Journal of Syn- Meeting, Cleveland, OH, 1957.
thetic Lubrication, Vol. 6, No. 4, 1990, pp. 299-309. [39] Fedors, R. F. "A Method for Estimating Both the Solubility Pa-
[36] Totten, G. E., Bates, C. E., and Clinton, N. A., "Quench Bath rameter and Molar Volume of Liquids," Polymer Engineering
Maintenance," Ch. 6, Handbook of Quenchants and Quenching and Science, Vol. 14, 1974, p. 147.
MNL37-EB/Jun. 2003
Refrigeration Lubricants-
Properties and Applications
H. Harvey Michels^'^ and Tobias H. Sienel^
T H E PRIMARY FUNCTION OF A LUBRICANT IS TO REDUCE FRICTIONAL additives have been developed to improve the properties of a
LOSSES. This is achieved by interposing a film between the lubricant [7]. These include acid neutralizers, extreme pres-
moving sohd surfaces that reduces or ehminates direct sohd sure (EP) agents (for startup and compressor break-in oper-
to sohd contact [1]. In h y d r o d y n a m i c lubrication (HD), ation), and anti-oxidants. The diminishing use of chlorinated
where contact surfaces conform geometrically, only the lu- refrigerants such as CCI3F, CCI2F2, and CHCIF2, mandated by
bricant viscosity governs friction and lubricant film thickness the Montreal Protocol of 1987 to help reduce ozone depletion
[2]. In this region, which is typical of many bearing and pis- in the atmosphere, has put new requirements on refrigerant
ton surfaces, the contact surfaces are completely separated lubricants. The intrinsic lubricity characteristics of chlori-
by the lubricant film and nominal contact pressures are low nated refrigerant molecules are not found in the newer re-
(<50 MPa). The lubricant film thickness varies with the same placement refrigerants, such as the hydrofluorocarbons
dependence on operating parameters, such as speed, shear (HFCs). Further, many of the newer lubricants that have
rate, and applied force, as the viscosity for this region. This been formulated to be compatible with HFCs exhibit lubrica-
makes the correct choice of lubricant viscosity become an tion cheiracteristics that differ from the older mineral oils, es-
important issue in the HD region. Low viscosity may lead to pecially in mixtures with HFC refrigerants. Such lubricants
solid contact, while too high viscosity leads to an increase in often depend heavily on additive properties to improve lu-
frictional losses resulting in increased motor loading a n d bricity and anti-wear characteristics.
higher p o w e r c o n s u m p t i o n . In regions of elastohydrody- The proper choice of refrigerant lubricant also depends on
n a m i c lubrication (EHD), such as bearings or gears with the design of the A/C or refrigeration system and the choice
high-pressure loadings, additional lubricant properties such of compressor. Since the compressor and evaporator are usu-
as the pressure-viscosity coefficient and limiting shear stress ally at the coldest region of the refrigeration system, migra-
come into play [3,4]. Temperature plays a critical role in both tion of the refrigerant to these parts of the system during
the HD and EHD regions because of its strong effect on the shutdown can cause dilution of the lubricant, resulting in a
viscosity of a lubricant. In typical air conditioning (A/C) or re- large decrease in solution viscosity. Several compressor de-
frigeration systems, both of these regions of lubrication may signs have significant storage of lubricant in the sump region,
be encountered. The m a x i m u m pressure attained in a refrig- thereby making the dilution of the lubricant from the con-
eration system can be as high as 2.5 GPa, indicating opera- densed refrigerant a major start-up issue. This is often ad-
tion well into fully developed elastohydrodynamic or bound- dressed by adding a strip heater and associated controls to
ary lubrication regions. Here, the thermophysical properties boil off the more volatile refrigerant before starting the com-
of the lubricant that become important are molecular con- pressor cycle. Alternatively, additives are added to the lubri-
formability and resistance to physical degradation [5]. cant to prevent direct metal to metal contact during start-up
Secondary functions of a lubricant include: the transfer of with a reduced viscosity lubricant/refrigerant mixture.
heat from one region to another; to act as sealants, especially A further consideration for proper choice of lubricant de-
in pressurized systems; to protect surfaces from corrosion; pends on whether the system is of the hermetically sealed
and to capture and suspend system debris. Refrigerant lubri- type, such as that found in window rack or other portable A/C
cants often require compatibility with the system refrigerant installations, or is designed to be serviced periodically, such
in terms of solubility, miscibility, and chemical stability [6]. as outdoor residential and commercial units. In hermetically
The solubility issue of lubricants with refrigerants is espe- sealed systems, the motor windings are exposed to the refrig-
cially critical since dilution of the lubricant results is a erant/lubricant mixture. This mixture must have both good
dramatic reduction in the solution viscosity and a parallel re- electric insulating properties a n d chemical compatibility
duction in the lubricant film thickness and lubrication prop- with seals, materials of construction, and residual contami-
erties. These characteristics have brought about a complex nants. A hermetically sealed system is charged with refriger-
array of lubricants designed for specific system require- ant and lubricant and sealed only once, with an expected
ments, including the operating ranges of temperature and maintenance-free life of fifteen years or more. The older lu-
pressure, and the duty cycle. In addition, many chemical bricants, such as mineral oil or synthetic alkylbenzene for-
mulations, were mainly non-polar and did not dissolve and
hold significant amounts of residual materials of construc-
^ United Teciinologies Research Center, East Hartford, CT 06108. tion, assembly cleaning solvents, and the like in suspension.
^ Present address: Physics Department, University of Connecticut,
Storrs, CT 06269. The solubility of such compounds is much higher in many of
413
the newer polar lubricants, such as the polyolesters. Further, Very recently, the use of immiscible lubricants, such as min-
the polar nature of several of the newer lubricants results in eral oils, in systems using hydrofluorocarbon refrigerants, has
a hygroscopic characteristic whereby any residual water in been the subject of renewed discussion in the Heating, Venti-
the system is dissolved in the lubricant as well as carried lation, and Air Conditioning, (HVAC) and refrigeration in-
about the system in the circulating vapor. This can permit industry. The initial decision of the HVAC industry to use
soluble residues to form, especially in additized lubricants, polyalkylene glycol (FAG) and polyolester (POE) lubricants in
which then deposit in capillary tubes or other expansion de- conjunction with the new hydrofluorocarbon refrigerants was
vices, causing plugging and loss of performance [8]. In sys- based on the assumption that high mutual solubility and mis-
tems with service ports, a change of lubricant is possible af- cibility between a lubricant and refrigerant were required for
ter compressor break-in, which allows removal of insoluble proper lubricant circulation and compressor operation. Thus,
system debris. In hermetically sealed systems, this residue lubricants such as POEs were chosen because their polar
problem must be addressed in the original system design. characteristics are similar to hydrofluorocarbons, resulting in
Complex lubricant additive packages and the use of filter dri- good mutual solubility and an assumed system behavior sim-
ers to remove excess water and trap insoluble deposits are ilar to the older hydrochlorocarbon and mineral oil mixtures.
among current solutions being tested. Recent lubricant circulation studies have shown, however,
A separate characteristic of refrigerant/lubricant mixtures that except for low temperature refrigeration applications,
that m u s t be considered is their foaming tendency. With immiscible lubricant (alkyl based)/refrigerant mixtures can
most of the older chlorofluorocarbon/mineral oil mixtures, a be used in systems where return lines have been properly
dense, slowly collapsing foam is generated in the compressor, sized [12,13]. The potential for significant cost reductions due
leading to good noise suppression and little carry-over to the to the use of lower cost lubricants, such as mineral oils, rather
condenser. The newer more polar refrigerant/lubricant mix- than the more expensive synthetic lubricants, has generated
tures exhibit rapidly collapsing foam characterized by initial renewed interest from HVAC system manufacturers. How-
large bubble formation. Such mixtures are less effective in lu- ever, there are many issues associated with proper lubricant
brication of inlet ports in compressors and can result in ex- circulation, mixture chemical stability, and compressor lu-
cessive lubricant carry-over out of the compressor during brication that must be addressed before there will likely be a
start-up. Lubricant manufacturers often add small amounts significant industry movement toward the use of immiscible
of compounds, such as the polysiloxanes, that modify the lubricant/refrigerant mixtures.
mixture surface tension. The chemical stability and long- In the sections below, the properties of mineral oil based
term behavior of these compounds are not well known. and synthetic refrigerant lubricants will be described. These
In addition to the chemical stability characteristics of re- lubricants differ in their chemical stability, solubility charac-
frigerant lubricants, there are equipment design and opera- teristics in different hydrohalocarbons, and viscosity and lu-
tional issues associated with the choice of lubricants for use bricity properties. There is extensive literature on the natural
with the newer hydrofluorocarbon refrigerant blends, such mineral oil based lubricants [14,15]. This review will focus
as R-410A, R-407C, and R-404A. The standard notation for more on the properties of the newer synthetic lubricant struc-
single component refrigerants and refrigerant blends is given tures. The critical system issues such as oil holdup and com-
in ANSI/ASHRAE 34-2001. The designations are a function of pressor compatibility are also reviewed.
the refrigerant atomic composition and, for blends, are cho-
sen as ASHRAE industry standards. Miscible lubricants dis-
solve in the refrigerant and are circulated to a small extent CHEMICAL STRUCTURE OF
throughout the system, returning to the compressor by either REFRIGERANT LUBRICANTS
gravity or the drag force of the circulating refrigerant. Sev-
eral of the new refrigerant blends, such as R-407C, exhibit Mineral oil based lubricants used in refrigeration are gener-
fractionation owing to the different volatilities of the compo- ally of three types: paraffinic, which consist of both straight
nents of the blend [9,10]. The solubility characteristics of a and branch chain saturated hydrocarbons; napthenic, which
lubricant may therefore be different in a compressor sump are saturated hydrocarbons that mainly consist of cyclic or
than in the evaporator or condenser. Regions of limited lu- ring structures; and aromatics, which are comprised mainly
bricant miscibility may therefore be encountered in the evap- of unsaturated cyclic hydrocarbons. Typically, the crude oil
orator, for example, resulting in lubricant holdup and insuf- sources from which these lubricants are distilled and refined
ficient oil r e t u r n to the compressor. The required vapor contain a mixture of these mineral oil types. For this reason,
velocity to insure good lubricant return can usually be ob- it is c o m m o n to identify mineral oils in terms of the number
tained by proper sizing of the return lines [11]. For cooling of carbon atoms associated with each of the structures, paraf-
mode operation, typical of an air conditioner (A/C), the worst finic (Cp), napthenic (CN), and aromatic (NA): the carbon-type
lubricant return conditions are likely to be at the evaporator composition is usually expressed in terms of weight percent.
exit, where the vapor refrigerant line feeds into the accumu- Since this type of identification requires a time consuming
lator. For heat p u m p operation, the worst lubricant circula- laboratory analysis, more qualitative methods of analysis
tion condition is usually found in the vapor line leaving the based on refractive index and photoabsorption have been in-
compressor, where the evaporator now serves as the system troduced and standardized as ASTM D 2140, ASTM D 2549,
condenser. These equipment design issues associated with and ASTM D 2008. In general, paraffinic oils have a higher
proper lubricant circulation and the elimination of excess percentage of paraffin wax (saturated straight chain
holdup have been the subjects of several recent experimental molecules) than napthenic oils, which results in high pour
studies. points (ASTM D 97), the temperature at which the oil will flow
CHAPTER 15: REFRIGERATION LUBRICANTS—PROPERTIES AND APPLICATIONS 415
TABLE 1—Typical properties of refrigerant lubricants.

Mineral Oil
Polyalkylene
Property Naphthenic Parafflnic Alkylbenzene Glycol Polyolester Polyvinylether
Density @ 15°C (g/cc) 0.92 0.86 0.87 0.99 0.97 0.92
Viscosity @ 40°C (cSt) 33 34 32 30 30 30
Viscosity Index 12 95 27 210 90 69
Pressure Viscosity
Coefficient @ 6 0 X (GPa"') 25 30 25 14 15-18 20
Average Molecular Weight 300 378 320 750 500-600 500-600
Pour Point (°C) -43 -18 -46 -46 -48 -45
Flash Point (°C) 170 200 178 200 234 212
Lower Critical
Solution Temperature 0* 52* -70* — <34 S50
withR-134aorR-22'"(X)
" Solutions witli mineral oil or alkylbezene.
CH3 CH3
I I
CH3 — CH — CH2 - C - [CH—CH2]„—CH —CH3 CH3 - CH - CH2 • CH - CH2 - CH2
I I ' I I I
CH3 / ^ CH3 [CHd^ [CHz]^ [CHj],
I I I
n = 2-5 branched alkyl groups CH3 CH3 CH3
FIG. 1—Structure of a commercial branched FIG. 2—Structure of an oligomer of 1-

chain alkylbenzene. decene.
under gravity at prescribed conditions. Parafflnic oils, how- group can be either a straight chain or branched chain paraf-
ever, exhibit a m u c h higher viscosity index (ASTM D 2270) a fin, usually containing 10-20 carbon atoms. A typical struc-
measure of the viscosity change with temperature, t h a n ture of a commonly used branched chain alkylbenzene is
napthenic oils. Owing to concerns about expansion valve and shown in Fig. 1.
capillary line plugging, and oil trapping in evaporators, typi- Alkylbenzenes have excellent low temperature fluidity and
cal mineral oil formulations that have been in use in refriger- low pour points. Their viscosity indexes are somewhat lower
ation have low wax content. Mineral oils are formulated in a than those of typical mineral oils. They are stable against
fixed range of viscosity by adjusting the refining process. Spe- oxidation, high temperature decomposition, and hydrolysis,
cific system requirements, such as high resistance to oxida- and are completely compatible with mineral oils [19]. Alkyl-
tion, are mainly addressed by the use of additives. benzenes have found widespread use with refrigerant sys-
Synthetic lubricants are produced by chemically combining tems using R-22 and R-502, but have had limited use to date
base stock hydrocarbon components in fixed proportions to with hydrofluorocarbon refrigerants owing to their immisci-
form a mixture with the desired lubrication characteristics. bility with these more polar molecules. However, since alkyl-
Unlike mineral oils, which may consist of hundreds of differ- benzenes are man-made compounds, there have been several
ent hydrocarbon molecules and whose composition varies recent studies directed toward changing the typical balance
with the source of the crude oil, synthetic lubricants are tai- of low, intermediate, and high molecular weight compounds
lored from a small number of different molecular weight start- that are formed in the synthesis process [12,13]. If the per-
ing components that are reacted to yield a final mixture of centage of high molecular weight components could be kept
compounds with the desired viscosity properties. These man- low, the resulting alkylbenzene blend may have sufficient
made lubricants can be classified by the type of base stock used fluidity to be carried by the vapor stream back to the com-
in their manufacture. The following synthetic types are compressor with m i n i m u m holdup in the evaporator, for exam-
monly used in A/C and refrigeration systems: alkylbenzenes, ple. These newer alkylbenzene formulations are sometimes
olefin oligomers (poly-a olefins), dibasic acid esters, poly- referred to as hard alkylbenzene lubricants (HAB). They are
olesters, and polyalkylene glycols [16,18]. Other synthetic lu- currently under evaluation for use in hydrofluorocarbon sys-
bricants such as the phosphate esters, silicones, monocarbon- tems using rotary compressors, where vane wear is a serious
ates, and fludrocarbon lubricants have not met with wide issue with several of the synthetic lubricants.
usage due either to their poor thermal stability, their viscosity
and/or solubility characteristics with refrigerants, or their high
cost of manufacture. Typical properties for several of the com- Poly-a Olefins (PAO)
m o n refrigerant lubricants are given in Table 1. These compounds are formed by combining a low molecular
weight unsaturated material, such as ethylene, into a specific
olefin. The olefin structure is then polymerized to form a
Alkylbenzene (AB)
branched hydrocarbon structure, usually consisting of three
These synthesized hydrocarbon molecules are formed by the or more repeating units. An example of this type of com-
alkylation of an aromatic compound, usually benzene, in the p o u n d is shown in Fig. 2; it is formed by the polymerization
presence of a catalyst such as aluminum chloride. The alkyl of the olefin 1-decene.
Poly-a olefins are similar to paraffinic mineral oils but thesized that exhibit similar physical properties [23]. These
since they are m a n - m a d e , their c o m p o n e n t structure and polybasic esters have tetrahedral character about a central
composition are reproducible. By varying the pendant chain carbon atom, similar to several of the polyolesters. They can
lengths and degree of branching, different viscosity formula- be formed by the reaction of acrylate esters with malonate es-
tions can be achieved. These compounds exhibit very high ters to form, for example, estrs of 1,3,3,5-pentanetetracar-
viscosity indexes and low pour points resulting in good low boxylic acid. Dibasic esters are used in the formulation of
temperature fluidity [20]. They are often used in the formu- sjTithetic automotive lubricants and in jet engine oils. They
lation of synthetic automotive lubricants. Poly-a olefins have are not highly miscible with the new hydrofluorocarbon re-
excellent thermal and oxidative stability and are compatible frigerants but their use in some refrigeration systems has
with mineral oils. They have found use in severe service re- been reported. However, this class of synthetic lubricants has
frigeration systems that employ screw compressors, using R- not yet found widespread usage in new A/C and refrigeration
22 as the refrigerant, and in ammonia systems. Like mineral systems.
oils, they exhibit good miscibility with several chlorofluoro-
carbons, such as R-12, but the use of this class of refrigerants
is phasing out u n d e r the Montreal protocol. Poly-a olefins Polyolesters (POE)
have limited miscibility in both R-22 and ammonia and typi- Polyolesters are the condensation product of an alcohol with
cally are not used in light service A/C or refrigeration appli- two or more hydroxyl groups (polyhydric alcohol or polyol),
cations [21]. They are immiscible in hydrofluorocarbons due and a monobasic (carboxylic) acid. In these structures, the
to their non-polar nature. carboxylic acid links to all available hydroxyls in the polyol,
splitting off water molecules at each linkage. A typical poly-
olester is shown in Fig. 4.
Dibasic Acid Esters (Diesters)
Similar to the dibasic esters, the polyolester structure can
This class of molecules is formed by combining a dibasic be varied by changing the carboxylic acid and by the use of
acid, such as adipic acid, with an alcohol that contains only one or more polyols [22]. Typically, neopentyl glycol, pen-
one reactive hydroxyl group. The esterfication process joins taerythritol, and dipentaerythritol are chosen as the polyols.
the alcohols at the end of the dibasic acid, splitting off two Dipentaerythritol is used mainly to form polyolesters of
water molecules to form the final ester compound [16,22]. An higher viscosity but is typically found as a significant (—12%)
example of this type of ester molecule is shown in Fig. 3. by-product in commercial grades of pentaerythritol. Upon es-
Dibasic acid esters typically have very low pour points and terfication with a carboxylic acid, the result is a compound of
excellent low temperature fluidity. Their viscosity indexes are high molecular weight and high viscosity. Such compounds
tjTjically lower than poly-a olefins and they exhibit good ther- are desired for high viscosity lubricant formulations but can
mal and oxidative stability. As with most ester structures, lead to plugging and waxing in certain low temperature sys-
they exhibit a lower hydrolytic stability t h a n mineral oils tems. Generally, pentaerythritol is reacted with two or more
since the double bonded oxygens have an affinity to hydrogen carboxylic acids to form an ester mixture with desired prop-
bond with water molecules. The viscosity of dibasic ester lu- erties. Owing to the tetra-hydroxy structure of pentaerythri-
bricants is determined by both the dibasic acid chain length tol, the use of two carboxylic acids results in the formation of
and the type of alcohol employed in the esterfication process. five different esters. The number of possible esters increases
A wide range of viscosities is possible by changes in the acid rapidly if more carboxylic acids (or alcohols) are used result-
and alcohol structures. Polybasic esters have also been syn- ing in complex chemical mixtures of the possible esters.
O O
CH3 — [CH2]3 — CH — CH2 O - C - [CH2]4 - C - 0 - CH2 - C H - [CHzls - C H 3

I
CH2 CH2
I I
CH3 CH3
FIG. 3—dibasic acid ester of adipic acid and 2-ethyihexanoi.
O O
CH3 - (CH2)4 - C - O - CH2 ^ ^ CH2 - O - C - (CH2)4 - CH3

c
CH3 - (CH2)4 - C - O - CH2 / CH2 - O - C - (CH2)4 - CH3
II 11
o o
FIG. 4—Polyolester of pentaerythritol and n-hexanoic acid.
Ri — O — [CH2 — CH — 0 ] n — R2
I
CH3
n = # of branched — [CH2 — CH — O] —groups

I
CH3
Rl ,R2 = alkyl end groups
FIG. 5—Polyalkylene glycol derived from propylene oxide.
The viscosity a n d solubility properties of polyolesters (HSPOE), but their stability against hydrolysis is a function
can be modified by the use of different polyols and, more fre- of all other acids used in their formulation [27]. This hydroly-
quently, by the use of carboxylic acids t h a t are either sis problem is of major concern since the resulting organic
branched or straight chain in character. Straight chain acids acids may initiate a chain of reactions with additives, metals,
lead to esters with good lubricity, but these structures often process fluids that are present in a system as contaminants,
suffer from limited miscibility and solubility characteristics and even react with polyolester components in a process
with hydrofluorocarbon refrigerants. Similarly, b r a n c h e d known as transesterfication that can result in ester modifica-
chain acids lead to esters with good miscibility and solubility tion. To minimize hydrolysis effects in hydrofluorocarbon
characteristics but poorer viscosity characteristics. Typically, systems, it is c o m m o n practice to incorporate a filter drier in
a balance of acids (mixed acid POE) is used to formulate a the system to keep the water content to very low values (< 100
polyolester blend with the specific properties required by the p p m ) . Despite the hydrolytic stability concern of poly-
refrigeration equipment [1,24]. Ceu-boxylic acids that are in olesters, they have emerged as the major lubricants in hy-
c o m m o n use in forming polyolester blends are n- and i- drofluorocarbon A/C and refrigeration systems. It is clear
pentanoic, n- and i-hexanoic, and 3,5,5-trimethylhexanoic. that their optimum formulation is dependent on the system
Blends using both straight and (n) branched (i) chain acids application and compressor type.
up to nonanoic (C9) structures have been foimulated [25].
Polyolesters have good high temperature stability and with
Polyalkylene Glycols (PAG)
proper acid (or polyol) choice, can be formulated with good
low temperature fluidity and low pour point. They are chem- Polyalkylene glycols are sometimes referenced as polygly-
ically compatible with the hydrofluorocarbons that have cols, polyethers, or polyglycol ethers. They are synthesized
been identified as replacement refrigerants for the chloroflu- typically from ethylene or propylene oxides that are sub-
orocarbons. However, they exhibit several negative features jected to a polymerization process initiated using an alcohol
in comparison with tjîcal mineral oils. Polyolesters have or water [28]. The polymerization process can result in either
lower pressure-viscosity coefficients than mineral oils and monoether or diether types of structures, usually as a mixture
alkylbenzenes. The pressure viscosity coefficient is defined as with a range of molecular weight c o m p o u n d s . A typical
(3 In Tj/a p)x. This is a measure of how the viscosity of a lu- polyalkylene glycol is represented in Fig. 5.
bricant increases with pressure at a constant temperature. Owing to their polar nature, polyalkylene glycols are com-
See Table 1 for typical values for different lubricants. A lower pletely miscible with most hydrofluorocarbon refrigerants.
pressure viscosity coefficient translates into reduced lubri- They have very good lubricity properties and exhibit large
cant film thickness u n d e r high pressure loading such as viscosity indexes. Polyalkylene glycols have good low tem-
would be encountered, for example, in rotary compressors. perature fluidity and low pour points, typical of naphthenic
Polyolesters formulated with long, straight chain acids ex- mineral oils [29]. They are not miscible with mineral oils and
hibit somewhat better pressure viscosity coefficients than are somewhat less stable chemically than other synthetic lu-
those formulated with b r a n c h e d chain acids. Perhaps the bricants, especially at high temperatures [30]. For many ap-
most serious problem with polyolesters is their low hy- plications, thermal stability is not a major problem since the
drolytic stability. Hydrolysis of all polyolesters is thermody- decomposition products are typically volatile, resulting in lit-
namically similar with a small positive Gibbs energy change tle sludge buildup. Thermal and chemical decomposition sta-
(—10 kJ/mol). Although this suggests that these compounds bihty can be analyzed using the ANSI/ASHRAE 97-1989 test
may hydrolyze at higher temperatures, the presence of a high procedure. The major disadvantage is that these compounds,
energy activation barrier normally prevents their reaction like all ethers, are very hygroscopic, due to hydrogen bonding
back to form an organic acid. This activation barrier is larger of water at the ether linkages. This reduces the electrical re-
(=» 40 kjol/mol) for polyolesters formed from a-branched car- sistivity of these lubricants to the point where they usually
boxylic acids, where the branching nature of the alkyl chain cannot be safely used in hermetically sealed or closed sys-
hinders hydrogen bonding of water at the unsaturated 0 = C tems in which the motor windings are directly exposed to the
linkage in the ester. The carboxlyic acid, 2-ethyl (AG^ a 50 refrigerant. Typical PAG formulations exhibit a volume resis-
kv/mol) hexanoic, has been used extensively in Japan in poly- tivity of ~ 1 0 ' ^ fl cm in contrast to mineral oil and alkyben-
olester formulations since it results in a very effective steric zene lubricants that typically exhibit values > lO^"* Cl cm. Vol-
h i n d r a n c e against hydrolysis [26]. These polyolesters are u m e resistivity can be measured using the ASTM D 1169 test
generally referred to as hydrolytically stabilized polyolesters procedure. This problem could be circumvented by care-
ful water control in the system, but their use in these appli- REFRIGERANT LUBRICANT ADDITIVES
cations has been replaced by polyolesters that are m u c h less
hygroscopic. Polyalkylene glycols can be effectively used in
Additives are chemical compounds added to lubricants to de-
systems using external motor drives for the compressor and
liver specific properties such as moisture control, lubricity
have found significant acceptance in the automobile A/C
improvement, antioxidant character, etc. [7,33]. Standard in-
market that has adopted R-134a as the replacement refriger-
dustry test procedures are ASTM E 203 and D 6304 (moisture)
ant for R-12.
and ASTM D 664 (total acid). Oxidation test include ASTM D
943 and ASTM D 5846. They can act chemically with system
Polyvinylethers (PVE) components or react with water and system debris to modify
the break-in characteristics of an A/C or refrigeration system.
Recently, a polyvinylether (PVE) structure has been syn- Additives can also act to modify the physical properties of a
thesized at Idemitsu Kosan in Japan. This new ether-type lubricant such as its pour point or viscosity index. Most addi-
structure is chemically similar to typical polyalkylene glycol tives contain large hydrocarbon groups that often have a het-
structures with the exception that the ether linkages are in eroatom, such as P, N, O, or S for functionality or to impart
the branched hydrocarbon segments instead of being located polar character. The solubility properties of additives in lu-
in the backbone chain of the molecule [31]. A typical molec- bricants can be modified by changes in the hydrocarbon chain
ular structure for a poljrvinylether lubricant is given in Fig. 6. length or, in the case of additives used in synthetic lubricant
The groups indexed by n and m are adjusted to control lu- formulations, by changes in the polarity of the molecule. Ad-
bricity and refrigerant solubility characteristics. Lubricity ditives that are chemically active, in the sense that they can re-
characteristics Eire discussed in ASTM F2161. A standard test act with metals in the system or with contaminants in the lu-
procedure is available as ASTM D2670. bricant, include dispersants, oxidation inhibitors, extreme
Similar to polyalkylene glycol structures, and in contrast to pressure agents, corrosion inhibitors, and detergents. Addi-
polyolesters, polyvinylethers do not hydrolyze to form or- tives that change physical property characteristics include
ganic acids. However, because of the ether groups, they are pour point modifiers, anti-foam agents, viscosity improvers,
hygroscopic. Tests indicate somewhat better stability against and emulsifiers. Test procedures include ASTM D 97 (pour
water pickup than is exhibited by many polyalkylene glycols. point), ASTM D 892 (foam tests), and ASTM D 445 (viscosity).
Polyvinylethers exhibit high pressure-viscosity coefficients The functionality of additives can be time dependent, such as
that are nearly comparable to those measured for mineral those used for system break-in, or they can be expected to pro-
oils. They are somewhat less thermally stable than the poly- vide protection for the life of a system. In general, additives
olesters. Poljrvinylethers are very miscibile in most hydroflu- are more chemically reactive than the base stock lubricant or
orocarbon refrigerants and exhibit a viscosity reduction in the refrigerant, and their formulation and dosage must be
refrigerant/polyvinylether mixtures that is comparable to carefully examined. Excessive use of additives can lead to re-
refrigerant/polyolester mixtures. Miscibility is usually de- actions that produce unwanted products that are insoluble or
scribed as the temperature at which a second liquid phase is corrosive. Unfortunately, many lubricant manufacturers are
formed, measured as a function of the refrigerant/lubricant reluctant to disclose additive formulations and it is often a hit
composition. A lower temperature for phase separation indi- or miss situation in formulating an additive package that pro-
cates better miscibility. Their oxidation characteristics are vides the necessary protection for a system. It is often the case
somewhat poorer than mineral oils and alkybenzenes, and that an additive, such as an extreme pressure agent, can func-
they are not as stable as polyolesters with regard to this prop- tion properly in its role as added bearing protection during
erty. The potential oxidation and hygroscopic characteristics compressor break-in. However, it can also react with water
exhibited by polyvinyl ethers have been addressed by the use and organic acids that may be present in the system to form
of additives. This is a new class of refrigerant lubricants and insoluble compounds that can cause blockage in capillary
will likely undergo extensive industry tests before decisions tubes or expansion devices. The chemical formulation and re-
are made for its potential application in residential or com- quired quantity of additives that are optimum for a given sys-
mercial equipment [32]. tem design are difficult choices for both the lubricant supplier
In refrigerant system applications of these lubricants, and the compressor or system manufacturer.
some of the undesired properties can be modified by the ad-
The formulation of additives for use in synthetic lubricants
dition of a small a m o u n t of an additive. The modification of
is especially challenging since the possible chemistry with the
the oxidation properties of a lubricant by the addition of an
more polar refrigerant and lubricant molecules is complex.
oxidation inhibitor is one of the oldest examples of this ap-
Additive formulations that have been successfully used in
proach.
chlorofluorocarbon/mineral oil systems have often proved to
exhibit detrimental reactions in hydrofluorocarbon/synthetic
lubricant systems (see [7] and references thereir). This has
[Ri —CH2 — CHJn — CH2 — CH— R3 caused some HVAC equipment manufacturers to avoid the
use of additive packages altogether, relying on system design
0 0-[R4-0]m-R5 changes for reliability. In general, less is better in the rule
adopted for the use of additives in m o d e m equipment design.
R,
The functionality of lubricant additives include pour point de-
Rx (x = 1-5) = alkyl groups pressants, viscosity index improvers, anti-foaming agents, de-
FIG. 6—General molecular structure for tergents and dispersants, oxidation and corrosion inhibitors,
polyvinylethers. rust inhibitors, and antiwear agents. There is a large literature
on the chemistry and properties of these additives (see [7] and uncovered several severe problems. Since most of these
references therein). This review will focus on problems that agents are designed to chemically react with metals, insolu-
have been addressed by the use of additives in hydrofluoro- ble reaction products have been encountered that cause cap-
carbon/s5mthetic lubricant systems. illary and expansion device restrictions. Reaction of these
agents with several types of synthetic lubricants has also been
observed. Tricresyl phosphate, a particularly effective ex-
Anti-Oxidants treme pressure agent, is known to produce undesired reac-
All lubricants, since they are hydrocarbon in character, have tion p r o d u c t s when used with some synthetic lubricants.
some thermal limit against reaction with oxygen. Mineral Polyolester lubricants can absorb sufficient water to cause,
oils have some natural anti-oxidant properties due to sulfur under high temperature conditions, a series of reactions lead-
or nitrogen based components that are found in petroleum ing successively to diaryl phosphate, monoarylphosphate
feedstocks. Synthetic lubricants that are used in high tem- and phosphoric acid, which then reacts with iron bearing
perature applications, such as heat pumps, generally require surfaces to form a protective iron phosphate surface coating.
the use of an anti-oxidant to modify their chemical reaction The problem is that these intermediate reaction products
rate with oxygen [34]. Their chemical role is to modify the have limited solubility in hydrofluorocarbon/polyolester sys-
radical chain mechanism of the oxidation process, slowing tems and typically deposit as metallic soaps rather than con-
it to a rate that is consistent with long term stability against tinuing in the reaction chain to form the desired ferrous
significant decomposition [35]. Alkyl phenols, such as phosphate coating. The use of oversized filter driers and care-
dibutylhydroxytoluene, are often used to protect polyolester ful control of moisture in a system are typical measures taken
lubricants against oxidation. Nitrogen containing inhibitors, to circumvent this problem. Typically, 1.0 weight percent of
such as the arylamines and phenols, that are often found in extreme pressure agents are used in synthetic lubricant based
petroleum feedstocks and are effective anti-oxidants in min- systems, but values as high as 3.0 percent have been used in
eral oil formulations, have been found to exhibit unwanted some polyolester based systems.
reactions in some synthetic lubricants. The typical amount
of anti-oxidant that is used is 0.1-0.5 weight percent, de-
pending on the potential exposure of the system to air in Acid Catchers
servicing operations. The use of compounds to control acid levels is especially im-
portant in synthetic lubricant systems. In contrast to mineral
oil lubricants, polyolester and polyalkylene glycols can ad-
Anti-Wear Additives sorb (by hydrogen bonding), significant amounts of water. In
Lubricants that are used in A/C and refrigeration systems some cases, the lubricant or system processing fluids can re-
suffer from dilution effects of the refrigerant with a corre- act with water, forming organic acids that can result in wear
sponding decrease in viscosity. In systems that employ chlo- and corrosion. Tjrpical compounds that are used to control
rofluorocarbon refrigerants, the refrigerant can react with acid level are the alkanolamines, long chain amides and
the bearing metal under pressure, and the resulting frictional imines, carbomates, and epoxides. This latter class of com-
heat generated by sliding metal surfaces forms a metal chlo- pounds has found extensive use in polyolester based systems.
ride coating that protects against direct metal to metal con- T5rpical concentrations of 0.1-0.5 weight percent are used for
tact. Hydrofluorocarbon refrigerants do not offer this protec- water and acid control in hydrofluorocarbon systems. A po-
tive feature and anti-wear additives are tjîcally added to the tential disadvantage in the use of acid catchers is their reac-
synthetic lubricants that are used in these newer systems. tivity with other additives such as anti-weeir agents. Control
These additives can be classified into two categories: those of water and acid by proper system design, cleanliness in sys-
that are formulated to provide protection under normal op- tem assembly, and proper maintenance are preferred strate-
erating conditions (anti-wear agents) and those that are for- gies.
mulated for use during system break-in and extreme operat-
ing conditions (extreme pressure agents) [36]. Extreme
pressure (EP) agents can be evaluated using the ASTM D Anti-Foaming Agents
3233 test procedure. Both anti-wear and extreme pressure Foaming in a refrigeration system is caused by mechanical
agents function by thermally activated chemical reactions, mixing of the lubricant and the refrigerant, by the sudden re-
forming compounds that react with the metal surface to form lease of refrigerant gas from the lubricant when pressures are
a protective layer. Thiophosphates have t3TDically been used reduced, and by outgassing that can occur at system start-up.
as anti-wear agents. Extreme pressure agents include aryl The type of foam that is formed in chlorofluorocarbon/min-
disulfides, thiocarbamates, and several classes of organic eral oil systems is persistent and undergoes a slow collapse.
phosphorous compounds [37,38]. Extreme pressure agents In hydrofluorocarbon/synthetic lubricant systems, foam typ-
react at higher temperatures than anti-wear agents. At higher ically forms and collapses rapidly with the potential of lubri-
temperatures (>200 C) and under heavy loads, these agents cant transport out of the compressor sump zind ineffective-
modify the structure of sliding surfaces by lowering the ness in its action to modify compressor noise. Compounds
height of aspertites and forming a protective film. In effect, that have been used to control foaming characteristics in-
they act as polishing agents that reduce the high level of fric- clude the poly dimethyl siloxanes, polyalkoxyamines, a n d
tion that may be encountered during system break-in. polyacrylates. These compounds act to modify the surface
Experience with the use of anti-wear and extreme pressure tension of the lubricant/refrigerant mixture. They are typi-
agents in hydrofluorocarbon/synthetic lubricant systems has cally employed at the 100-1000 p p m level. Their disadvan-
tage is that other chemical compounds in the system can of- where T is absolute temperature, p in g/cc and X = (1 —
ten react with foaming agents rendering them ineffective. T/Tc)^'^, where Tc is the refrigerant critical temperature, the
Their chemical stabihty under severe system operating con- temperature above which a substance cannot exist in the liq-
ditions is also uncertain. uid state regardless of the pressure [40]. For lubricant den-
Other additives that have been considered for use in A/C sity, the simpler polynomial form is often used:
and refrigeration systems are copper deactivators to protect
connecting lines and components, viscosity improvers, seal- /»L(T) a -F bT -(- cT^ (5)
swell agents, detergents, and emulsifiers/demulsifiers. Such where T is absolute temperature, p in g/cc.
additives have the potential of creating more problems than For refrigeration and other low temperature applications,
are solved by their usage. Proper system design and choice of a property known as the pour point is often important. The
lubricant are more fundamental to long life system operation pour point of a lubricant is defined as the lowest temperature
than the use of additives with their potential for adverse at which a lubricant will flow under gravity when tested by a
chemical reactions. prescribed method such as ASTM D97. The pour point is a
complex function of viscosity, lubricant type, wax content
(high molecular weight components) and additives [33]. It is
PURE LUBRICANT AND REFRIGERANT of less value in A/C and refrigeration systems where the lu-
PROPERTIES bricant is diluted to some extent by the presence of the re-
frigerant but is of some value in the choice of lubricants that
The most important lubricant property from an A/C or refrig- are immiscible with the refrigerant, such as carbon dioxide
eration system application viewpoint is its viscosity. Viscosity and ammonia systems. Other lubricant and refrigerant prop-
is defined as the ratio of shear stress/shear rate and is a mea- erties that are often measured are the flash and flame points.
sure of the resistance of a fluid to flow. This property is often These are used to evaluate if a lubricant could decompose
expressed in units such as Saybolt Seconds Universal viscos- (coking) under extreme operating conditions. Vapor ignition
ity (SSU), which are derived from a calibrated instrument points (lower flammability limits) have become of greater
used to measure flow resistance. The common metric unit for concern with the increased use of hydrofluorocarbon refrig-
measuring absolute (djTiamic) viscosity is the poise or cen- erants. These data have been used to screen refrigerants and
tipoise (cP). An alternate measure is called kinematic viscos- refrigerant mixtures to assure that they will not support
ity, which is measured in centistokes (cSt). These different vis- combustion when exposed to air under normal system oper-
cosity measures are related by the density of the lubricant: ating conditions. Flammability limits of refrigerants can be
determined using ANSI/ASHRAE 34-1992 and ASTM G 125
McP) = p(g/cc) X T7(cSt) (1) test procedures.
The viscosity of a lubricant decreases as its temperature is
The models chosen to represent thermophysical proper-
increased. This viscosity decrease results in a thinning of the
ties of pure lubricants and refrigerants must be extended or
protective film that a lubricant forms on moving surfaces and
modified to include the composition dependence of lubri-
is of critical concern in the choice of the viscosity grade of a
cant/refrigerant mixtures. The density of a lubricant/refrig-
lubricant. High viscosity lubricants can result in increased
erant mixture can be expressed from a rigorous thermody-
compressor requirements owing to fractional drag, while too
namic analysis but requires mixture experimental data that
low a viscosity can result in equipment failure. The tempera-
are generally not available. The viscosity of lubricant/refrig-
ture impact on the viscosity of a lubricant is often referred to
erant mixtures is less well defined but several recent studies
as the viscosity index (see ASTM D 2270). An empirical rela-
have resulted in useful (and accurate) models for A/C and
tionship between kinematic viscosity and temperature is
refrigeration temperature and composition conditions
given by:
[49,51]. The most difficult property of mixtures to model is
ln[ln(T7 + 0.7] = a -I- b InT (2) the solubility of a refrigerant in a lubricant. Solubility ef-
fects are very important since the addition of a refrigerant
where 77 is the kinematic viscosity given in cSt, T is the abso- to a lubricant lowers its viscosity [41,42]. This does not
lute temperature in Kelvin degrees and a and b are constants stand on its own but is described in detail in the following
derived from experimental data. A more rigorous model for section.
describing the temperature dependence of viscosity is the ex-
tended Andrade equation [39]:
lnfi = A + YB + CT + DT^ (3) SOLUBILITY AND VISCOSITY MODELING

OF LUBRICANT/REFRIGERANT MIXTURES
where fji. is the absolute viscosity and A, B, C, and D are con-
stants fitted to experimental data. This form is often more The role of refrigerant lubricants in A/C and refrigeration
useful for modeling viscosity at the lower temperatures en- systems is complex. Their primary function is for compres-
countered in refrigeration. Eq 3 has been applied to model sor lubrication, but they also must function as coolants to
the temperature dependence for both refrigerant and lubri- remove heat from bearings and to transfer heat from the
cant viscosity. compressor shell to the exterior. Lubricants also minimize
Pure refrigerant density is often represented by the gas leakage at gaskets and fittings in the system and can act
equation: to reduce noise generated by the compressor. The principal
differences between refrigerant lubricants and those used,
ft.(T) = a -I- bX -I- cX^ -t- dX^ + eX'' (4) for example, in automotive applications are the solubility ef-
fects arising from a dilution of the lubricant with refriger- Assuming ideal behavior, Eq 7 becomes:
ant. Under normal system operating conditions, the lubri-
cant in the compressor crankcase may be diluted by a few 1
— Vmixture — X L V L + XRVR (8)
percent of the refrigerant. Upon start-up, however, if the Pmixture
ambient temperature at the compressor location is cold, the or recasting as mass fractions:
lubricant in the compressor sump can be highly diluted
(—30%) with refrigerant that has migrated to this cold point 1 xf
(9)
in the system. In most A/C and refrigeration applications, Pideal mixture PR
some lubricant is carried out of the compressor and circu- where x*" now represents mass fraction and p"" represents
lates with the refrigerant. Typically, the percentage of circu- mass density in g/cc. Empirical corrections to Eq 8 have been
lating lubricant is small, especially for systems with scroll suggested in the form: Pmixture = pideai mixture/A, where A is a
design compressors, but can be as high as 3% for systems density correction factor that can be as large as 6% for high
with reciprocating compressors that have seen extensive temperatures and high lubricant dilution. If the molecular
service. This circulating lubricant-rich mixture can impact weights of the refrigerant and lubricant are known (typical),
system performance in several ways. Refrigerant/lubricant Eq 6 can be used to extract partial molar volume data directly
miscibility limitations may result in a two-phase liquid re- from measured mixture densities. This approach permits a
gion under certain conditions of temperature and pressure. cortelation of the deviations from ideal behavior with the in-
The most serious effect is the possible development of a dividual component properties. The measurement of liquid
highly viscous phase in the evaporator section that may re- densities to high accuracy is difficult (see ASTM D 891 for
sult in decreased heat transfer rates. general methods).
In the case of refrigerant blends, such as R-407C, a new
problem arises since the individual system components may
exhibit different solubilities in the lubricant [9,10]. These dif- Viscosity
ferent component solubilities can give rise to fractionation
Viscosity models based on empirical polynomial expansions
(distillation) effects in the evaporator, condenser, or com-
in temperature and composition have often been used to de-
pressor sump that result in different vapor-liquid equilibrium
scribe mixture behavior. Almost all models assume or require
conditions and corresponding composition shifts. The effects
that values for the viscosity of the p u r e components be
of these refrigerant/lubricant interactions may impact both
known. Thus, the primary feature for judging the validity of
cycle analysis and system performance. If these chemical in-
viscosity models for mixtures is their utility in interpolating
teractions are significant (non-ideal solution behavior), they
data from the extreme composition limits of pure refrigerant
may result in detrimental performance and lower system op-
and pure lubricant. It is known that the viscosity of liquid
erating efficiency. Several models have been developed to an-
mixtures is not a simple function of composition. The viscos-
alyze the solubility effects of lubricant/refrigerant mixtures.
ity of mixtures may exhibit a maximum, a minimum, or both
The thermophysical properties, density, viscosity and vapor
over a specified composition range. For the pure compo-
pressure, must be modeled to include the effects of mixture
nents, the extended Andrade [39] equation, a polynomial in
composition.
temperature, is often used to represent the temperature de-
pendence of viscosity. Studies show that a four or five term
Density expansion can accurately represent viscosity for pure com-
p o n e n t s over the n o r m a l operating range of interest,
The molar volume of a lubricant/refrigerant mixture can be —20°C-80°C, for both refrigerant and lubricant.
written as: Difficulties can arise in developing reliable models to cover
V„ mixtures ranging from pure lubricant to high refrigerant dilu-
U L V L + nRVR (6)
tion levels. Owing to the large size differences between refrig-
where UL and n^ refer to the n u m b e r of moles of lubricant erant and lubricant molecules, a reliable model must account
and refrigerant in the mixture, and VL = (3V/3nL)T,p,nR; VR = for both the difference in molar volumes of refrigerants and lu-
(c)V/c)nR)T,p,nL are the partial molar specific volumes of lubri- bricants a n d for differences in molecular interaction
cant and refrigerant in the mixture, respectively [43]. Equa- strengths. Most studies of the viscosity of liquid mixtures have
tion 6 can be cast into density form as: focused mainly on systems of molecules of nearly equal size
and have been restricted mainly to near-ideal mixtures. An
1 ideal mixture is one that undergoes zero volume change and
Vmixture — ^ L V L + X R V R (7)
Pmixture zero heat exchange upon mixing. For such mixtures, Arrhe-
where vmixture is the volume of one mole of the mixture and XL nius [44] proposed that mixture viscosity should be an additive
and XR represent the mole fractions of lubricant and refriger- property, linearly connected to the viscosity of the pure com-
ant, respectively. It is often assumed that the specific volumes ponents. Mixtures that exhibit this type of behavior are typi-
of the lubricant and refrigerant in the mixture are equal to CcJly non-polar. Examples are hydrocarbons and halogenated
their values as pure components: VL = VL and VR - VR. This hydrocarbons, such as CFCs. The introduction of HFCs as re-
simplification is useful if the lubricant and refrigerant frigerants, which are m u c h more polar, has led to the use of po-
components are chemically alike and are similar in size. Un- lar polyolester lubricants to improve solution solubility and
fortunately, this is often not the case for synthetic refriger- miscibility. However, these new refrigerant/lubricant mix-
ant/lubricant mixtures, such as R-32/POE combinations, tures exhibit significant non-ideal character with very Icirge
where the mixture exhibits significant non-ideal behavior. molecular size differences between refrigerant and lubricant.
If 4>i is taken as the volume fraction of component i, we can Data

represent the viscosity of a binary lubricant/refrigerant mix- Arrhenius:
Kendall:
ture as:
Frenkel:
In rj„ = (f>i In 171 + 4)2 In 172 (10) Grunberg-Nissan:
Yokozeki:
Equation 10 is commonly referred to as the Arrhenius [44] McAllister 3-Body Model:
equation for ideal binary mixtures. It is useful for mixtures McAllister 4-Body Model:
—Q— Michels-Sienel:
where there are no strong intermolecular forces (non-polar)
and where there is n o volume change upon mixing. A varia-
tion of Eq 10 was proposed by Kendall [45], where composi-
tion is measured using mole fraction instead of volume frac-
tion. Mixture equations of this additive type have b e e n
0.3 0.4 0.5 0.6 0.7 0.8
extended by adding terms with one or more disposable con- Mass Fraction Refrigerant
stants. An example is the Grunberg-Nissan [46] equation,
which for binary mixtures can be written as:
lm7„ 01 In TJi -I- <^2 In T?2 + 24>i(l>2Gi2 (11) FIG. 8—Viscosity fits for R134a/POE-68. (POE-68: polyolester
of viscosit y 68 cP at 40°C.)
For binary polar mixtures, Irving [47] finds that the Grun-
berg-Nissan equation has the smallest average error when
tested with nearly 1000 data points, taking 4>i as the mole temperature. Yokozeki finds that k ~ 0.58 for many refrig-
fraction of component i and optimizing the value of the ad- erant mixtures but finds that k must be treated as an ad-
justable parameter, G12, using mixture data. A variation of Eq justable parameter for refrigerant/lubricant mixtures. For k
11, based on a kinetic model involving binary pair activation = 0, the Yokozeki model reduces to the model proposed by
energies, is due to Frenkel [48]: Kendall. For k = 1, the concentration measure becomes
In T7„ix,ure = xf In Tji + xl In 172 + 2x1X2 In 1712 (12) weight fraction rather t h a n mole fraction. A genereilized
definition of the concentration measure, î, can be shown to
In Eq 12, Xi refers to the mole fraction of component i, and In be related to the familiar q-ratio (the ratio of the van der
TJ12 is a n interaction parameter between unlike molecules, Waals surface area for lubricant and refrigerant) in UNI-
usually determined experimentally from mixture data. Irving FAC and other solution theory models [50,51]. In Figs. 7
finds that Eqs 11 and 12 have comparable accuracy, compar- and 8, the viscosities of R-22/AB150 and R-134a/FOE-68
ing both polar and non-polar mixtures. mixtures are compared against several models that have
Recently, Yokozeki [49] has proposed a mixture viscosity been proposed [51]. In general, one- or two-parameter mod-
model in the form: els are required to quantitatively represent experimental
mixture data.
mfxi
In rjn 5^ î In Tji; 6 (13)
Solubility
In Eq 13, Xj and m^ refer to the mole fraction and molecu- The solubility of a refrigerant in a lubricant has been mod-
lar weight of component I, respectively, and k is an empiri- eled using several different approaches. The older literature
cal parameter, often modeled as a simple polynomial in the solubility data on mineral oil/CFC mixtures have mainly been
analyzed using empirical correlations in temperature and
composition [52]. Models that are thermodynamically more
rigorous have been developed that are applicable to the
Data
more polar hydrofluorocarbon/synthetic lubricant mixtures
-Airheimis: [44]
[9,43,49,53]. These models have been based either on a n
-Kendall: [45]
-Frenkel [48]
equation of state approach or on non-ideal solution theory. A
-Grunberg-Nissan: [46]
comparison of the features of these different approaches is
-Yoko2Eld: [49] given in Table 2.
- McAllister 3-Body Model: [47] Empirical correlations are usually polynomial fits of the
- McAllister 4-Body Model: [47] mixture vapor pressure as a function of temperature (T) and
-Michels-Sienel: [51] composition (x).
I P = X aioT' + x X a i i P + x^ £ a i 2 r + .
(14)
P = £ bio/P + X X b„/T> + X2 X b i 2 / r +.
D(x)
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 InP = C(x) (Antoine form) [54]
Mass Fraction Reffigerant T + constant
FIG. 7—Viscosity fits for R22/AB 150. (AB 150: allcylbenzene C(x) = Yi CiXi; D(x) = 5^ diXi
of viscosity of 150 cP at 40°C.)
TABLE 2—Approaches to modeling solubility of be formally described in terms of the component fugacities in
refrigerant/lubricant mixtures. the liquid and vapor phases. At equilibrium, we have
Empirical correlations:
• mathematically simple models (+) fr = yiPT<î' = f i = Xi7iPr</.*F} (15)
• often thermodynamically inconsistent (—)
• applicable to limited composition ranges (—) where
• not useful for evaluating blend fractionation effects (—) yi = vapor phase molar composition of component i,
• limited to bubble point predictions (-) PT = total system pressure at temperature T,
• limited to two component (refrigerant/lubricant) composition 4>i = vapor phase fugacity coefficient which, for moderate
analysis (-) pressure, can be estimated from second virial coeffi-
Equation-of-state (EOS) approach: cient data,
• mathematiccJly more complicated (—)
Xi = liquid phase molar composition of component i,
• thermodynamically rigorous for pure components (+)
• requires vapor phase properties of lubricant ( - ) •Yi = liquid phase activity coefficient,
• all thermodynamic properties derived from single EOS (+) P,^ = vapor pressure of pure component / at temperature T,
• EOS mixture rules are often arbitrary and thermodynamically 4)* = fugacity coefficient for pure i at the system T and P,
inconsistent (—) Fi = pointing factor for compressibility of the liquid
Non-ideal solution theory: phase.
• mathematically more complicated (—)
• models are often thermodynamically inconsistent (—)
• applicable to multi-component mixtures over entire compo-sition F o r 4>}' ^ J , * ^= T7?
(f)* F | = 1.0, this analysis reduces to an idea
range {+) solution description and is representative of Raoult's Law.
• obviates need for vapor properties of the lubricant (-I-) Combining the fugacity coefficients and Poynting factor into
• applicable to both bubble and dew point predictions {+)
• not useful in the vicinity of the critical point (—) a correction term, F„ the vapor-liquid equilibria for compo-
• difficult to model temperature dependence (—) nent i in solution can be written as:
• most accurate modeling approach for mixtures, except in the
iVc!
yiPr = Xi7iPrFS (16)
vicinity of the critical point (-I-)
The correction term, Fu can be evaluated from liquid density
and second virial coefficient data for pure refrigerants. One
convenient source is the tabulation given in the NIST REF-
These forms are convenient for fitting to experimental data PROP [57] database. The difficult part of this modeling ap-
for mixtures. They often yield very inaccurate predictions if proach is the representation of the liquid phase activity coef-
used outside of the fitting range and typically do not accu- ficients, 7,, w h i c h are formally connected to the excess
rately represent the vapor pressure of the pure refrigerant. (non-ideal) Gibbs energy. These liquid activity coefficients
The non-ideal behavior of the liquid and vapor phase is may be extracted from experimental data or estimated using
lumped together in the expansion coefficients of these mod- group additivity models such as UNIFAC [50]. The latter ap-
els. In general, there is n o thermodynamic basis for these proach is difficult at present due to limited knowledge of the
functional forms. The Antoine form, for example, is devel- chemical formulations of the synthetic lubricants and the
oped from the Clausius-Clapeyron equation only for a pure lack of reliable functional group interaction parameters.
fluid.
Preliminary evaluation of the non-ideal behavior of HFC-
In the equation-of-state (EOS) approach—models for mix- 32/POE, HFC-125/POE, and HFC-134a/POE binary mixtures
tures are based on extension of the theory of corresponding has indicated b o t h positive and negative deviations from
states for pure substances using empirical mixing rules. Gen- ideal solution behavior [9,58]. Many of the proposed forms
erally, cubic EOS are required for any quantitative treatment for liquid phase activity coefficients cannot mathematically
of mixtures: represent such behavior. The Wilson [59] model for the ex-
a) van der Waals model cess Gibbs energy, for example, is not applicable over the
b) Soave modification of Redlich-Kwong equation (SRK) entire refrigerant/lubricant composition range. Various mod-
c) Peng-Robinson equation (PR) ifications of the Wilson model have been proposed [60] in-
These EOS are described in detail by Prausnitz, et al. [43]. cluding those described in the literature as the Heil [61],
Yokozeki [49] and Morrison et al. [56] have independently NRTL [62], and T-K [63] equations. All of these equations
developed EOS models that have been used to describe the represent local composition models in an attempt to incor-
solubility behavior of hydrofluorocarbon/polyolester lubri- porate effects of molecular size as well as mixture concentra-
cant mixtures. These models involve the difficult task of de- tion. Their derivations, however, are mainly empirically
scribing the pressure-volume-temperature (PVT) behavior based, and can lead to computed solution parameters that
for mixtures of two substances with vastly different vapor lack physical meaning. Recent studies have shown that the
pressures. The usual mixture rules for combining the EOS fit- Wohl [3]-suffix expansion [64] for representing the excess
ting parameters for pure components are not applicable for Gibbs energy, written in terms of an effective volume mea-
refrigerant/lubricant mixtures without complicated modifi- sure of composition, yields reliable results for many lubri-
cations and inherent difficulties in fitting experimental data. cant/refrigerant mixtures. A comparison of experimental va-
The primary advantage of EOS models is their usefulness p o r pressure data and calculations based on the Wohl
near the critical region of these mixtures. [3]-suffix model is shown in Figs. 9 and 10 for R-134a/POE-
The most reliable solubility models are generally those that 68 and R-410A/POE-68 refrigerant/lubricant mixtures [9].
are developed from the thermodynamics of non-ideal solu- The theory is somewhat better for modeling single compo-
tion theory [43]. The vapor-liquid equilibria of a mixture can nent refrigerants, such as R-134a. Solution theory models, in
surements but can be formally located through an analysis of

T=60C.--
— • T-OfC the Gibbs excess energy for the mixture [43].
-T=20fC
— - T=40° C
- T=60° C
LUBRICANT CIRCULATION
c A T=0°Cdata The purpose of the lubricant in the HVAC system is to lubri-
o
•a
• T= 20° C data cate, cool, seal, and otherwise protect the compressor in the
• T= 40° C data system from failure. In the course of executing these func-
• T=60°Cdata tions, some lubricant is captured in the compression process
and carried by the refrigerant out of the compressor. Within
0 0.2 0.4 0.6 0.8 1 the remainder of the system, the lubricant serves little to n o
R-134a liquid mass fraction
useful function, and acts as a detriment to system perfor-
mance u n d e r most conditions. The challenge to the system
FIG. 9—Vapor pressure of R-134a/POE-68 mixture. designer is to ensure that the lubricant returns to the com-
pressor satisfactorily u n d e r all operating conditions, as a pro-
longed migration of the lubricant from the compressor into
the system will result in performance degradation and even-
tually compressor failure due to lack of lubricant. The design
_ . - T-OPC considerations influencing adequate lubricant return consist
-T=2ff'C of line sizing, lubricant and refrigerant selection, system op-
erational envelope, and transient effects, each of which will
— - T=40° C
be described in further detail. Measurement of the circula-
- T=60° C
tion in these systems is also a challenge, particularly when
A T=0°Cdata
transient phenomena occur, and this will be considered in
• T= 20° C data further detail as well.
• T- 40° C data
• T- 60° C data
0.2 0.4 0.6 0.8 HVAC Cycle
R-410A liquid mass fraction Vapor compression systems, in basic form, consist of a com-
pressor, a heat rejecting heat exchanger (typically referred to
FIG. 10—Vapor pressure of R-410A/POE-68 mixture. as a condenser), an expansion device, and a heat absorbing
heat exchanger (t5îcally referred to as an evaporator). The
cycle begins with the refrigerant as a high pressure vapor at
the exit of the compressor. It next flows through the con-
general, do not universally apply to liquid-liquid equilibria denser, rejecting heat, cooling, and condensing to become a
such as is required for studies of immiscibility. An advantage liquid at the discharge of the condenser. Next, the pressure of
of a solution theory approach is that there is no need for va- the refrigerant is dropped as it flows through the expansion
por phase lubricant properties since it is a good assumption device, which can be as simple as a kink in the refrigerant line
that the concentration of lubricant in the vapor phase is neg- or as sophisticated as a microprocessor-controlled, electroni-
ligible. A disadvantage of this approach is that solution the- cally-actuated stepper motor connected to a needle valve. At
ory models are most useful for T < Tc. the exit of the expansion device, the refrigerant has typically
A very useful method to determine the kinematic viscosity entered into the two phase region again and enters the evapo-
of lubricant/refrigerant mixtures is based on combining vis- rator. The evaporator absorbs heat from the environment and
cosity and solubility data as shown by Daniel [20]. In this rep- uses it to evaporate the refrigerant back to vapor form. Finally,
resentation, the kinematic viscosity of refrigerant/lubricant the vapor refrigerant enters the compressor, where it is com-
mixtures is plotted against temperature with mixture isobars pressed and heated to begin the cycle again. This process is
as parameters. These plots are now universally adopted by lu- shown schematically in Figs. 1 2 a n d l 3 , which depict the pres-
briccmt manufacturers to display the solubility characteris- sure-enthalpy and temperature-entropy diagrams of the cycle.
tics of their lubricants. A typical Daniel plot for R-41OA and a This cycle is important to understand as it influences all of the
22 cSt mixed acid polyolester is shown in Fig. 11. The rapid design considerations impacting lubricant transport.
decrease in mixture viscosity that results from refrigerant di- In addition to the basic components, many systems are
lution of a lubricant is apparent for the lower temperature equipped with additional components serving a variety of
mixtures shown in Fig. 11. This is of critical concern for com- functions. Charge storage devices, such as accumulators and
pressor design, especially for those conditions encountered receivers, are used in systems that have large operational en-
at system start-up. Figure 11 also indicates the tempera- velopes and, due to the density differences of the refrigerant at
ture/composition regions (gray shaded) where liquid phase the different operational temperatures, require significantly
immiscibility is encountered. This refrigerant/lubricant pair different amounts of refrigerant at different conditions. Re-
exhibits both a lower consolute temperature of —25 C and an ceivers are employed where liquid flows through the lines, typ-
upper consolute temperature of ~ 15 C. Within the shaded re- ically in the high pressure part of the system between the exit
gion, two liquid phases are present for this mixture. This im- of the condenser and the expansion device. The liquid flowing
miscibility region is usually located from experimental mea- into the expansion device is drawn from the receiver and, be-
400
10 20 30 60
Temperature (C)
FIG. 11—Daniel plot of R-410A/POE-22 mixture.
10000
Liquid
«> 1000
i
I 100
10
50 250 450 1.5 1 1.5 2
Enthalpy (kj/kg) Entropy (kJ/kg-K)
FIG. 12—R-134a P-h diagram. FIG. 13—R-134a T-s diagram.
cause there is a reservoir of liquid to draw from, a system lubricant to return to the compressor, as they would otherwise
equipped with a receiver is more tolerant to transients in the simply absorb all of the oil from the compressor. Because the
condenser. Accumulators, on the other hand, are applied refrigerant density is substantially higher in the high-pressure
where refrigerant vapor flows, typically between the exit of the part of the system, receivers Eire preferred when the size of the
evaporator and the inlet of the compressor. The purpose of the equipment becomes a concern. All cheirge storage devices can
accumulator is twofold; it stores excess charge and also pre- trap substantial amounts of lubricant, particularly when the
vents liquid (which can damage the compressor) from enter- refrigerant-lubricant combination is not fuUy miscible.
ing the compressor. Accumulators act as effective oil separa- Other components utilized in HVAC systems include fil-
tors, and m u s t b e equipped with a m e c h a n i s m to allow ter/dryers, reversing vtJves, and secondary heat exchangers
such as liquid suction heat exchangers. Filter/driers, as the 100 -| r 3

Insufficient Velocity Sufficient Velocity
name imphes, serve the two functions. The fiUering of 90 -
particulates, which can plug the expansion device or damage 80 .
- 2.5
the compressor, is usually accomplished by screens, meshes, -5-
70 -
or felts. Moisture can react with lubricants in the system to -2 %
decompose them back to acids and alcohols, and the dryer & 60 - o.
section of the filter/dryer is designed to remove any residual
moisture from the system. Filter/dryers can be applied in the
•^
•a
1
50 -
40-
\ a - 1-5 Q
\ ^ ^y>€ IS
vapor or liquid portions of the system, but are usually found 30 - r 1
in the liquid flow due to pressure drop concerns. Reversing 20 - s
OH
valves are used in heat pump systems, where the system op- Measured Line Flooding -0.5
10 -
erates part of the time as an air conditioner and part of the
time as a heater. They simply reverse the flow through the 0 i• ^ — — , 1 - 0
heat exchangers, so that the condenser becomes the evapora- 0 1 2 3 A

tor and visa-versa. The lubricant in the system aids the valve Vapor Velocity (m/s)
actuation process, but usually does not impact this compo-
nent in any other way. Liquid suction heat exchangers act to FIG. 14—Minimum velocity for R-410A/POE 68.
further cool refrigerant exiting the condenser (to lower the
entheJpy at the inlet of the expansion device) at the price of
heating the suction vapor to the compressor. velocity condition. The relationship between the pressure
drop, velocity, and flooding (or lubricant holdup) is shown in
Finally, oil separators are sometimes employed to ensure Fig. 14 for the combination of R-410A and POE-68. A num-
adequate lubricant return to the compressor. These devices ber of correlations have been devised to predict when this
are tj'pically applied at the exit of the compressor, and use a condition is reached in practice [67,68]. Under this condi-
variety of methods to separate and return the lubricant to the tion, the lubricant will build up in the section of the system
compressor. experiencing minimum velocity, typically in traps or along
the bottom of lines. This buildup of lubricant in the system is
Equipment Line Sizing referred to as holdup, and can have severe consequences on
system performance. As this buildup continues, the area
The system components are connected by lines, which cdlow available for flow will contract, and thus the velocity will in-
the flow of refrigerant (and lubricant) from component to crease again. Due to pressure and surface tension effects, the
component. The pressure drop through these lines, and also transition from a less than adequate velocity to a sufficient
through the heat exchangers, has a considerable impact on velocity is often dramatic. The pressure buildup behind the
system performance and the tradeoff between system perfor- lubricant obstruction, coupled with the transition to ade-
mance and cost is made in sizing the diameter of these lines quate transport velocity, causes a slug of lubricant to burst
[65,66]. For optimal performance, these lines would be sized from the trap and to be carried to another part of the system
to ensure minimum pressure drop, and this would be a valid [69]. When the lubricant obstruction has been cleared, the
philosophy if the lubricant were not present. In the liquid flow velocity again drops and lubricant again becomes
line, the lubricant flows in suspension (in the case of an im- trapped. This cycle repeats on a frequency dictated by the line
miscible lubricant-refrigerant combination) or as a fully sol- size, vapor velocity, and characteristics of the refrigerant-lu-
uble part of (when fully miscible) the refrigerant. There is briccint pair. In some cases, the slug transport never occurs
typically no lubricant transport issue in liquid lines. In vapor due to the amount of available surface area, such as in a hor-
lines, lubricant transport becomes much more of an issue, as izontal line, or due to extremely high lubricant viscosity.
the lubricant does not vaporize along with the refrigerant.
Lubricant transport in vapor lines occurs by two primary
mechanisms: mist flow and annular flow. In mist flow, the lu- Refrigerant/Lubricant Selection
bricant is atomized into small droplets that are carried in sus-
pension with the vapor refrigerant. In annular flow, the lu- The selection of the refrigerant is based on the operational
bricant builds up along the perimeter of the line and is performance given the envelope of operating conditions, as
dragged along by the velocity of the vapor flow. Mist flow well as, increasingly, the environmental effects of the refrig-
dominates when the lubricant viscosity is low while annular erant. The lubricant selection follows the refrigerant selec-
flow is more prevalent when the lubricant viscosity is high tion, as in most cases, it is based on the refrigerEint selection.
(when the annular flow becomes laminar). The specific compressor type will dictate a minimum opera-
As pressure drop is a function of Reynolds number, (Re = tional viscosity for adequate lubrication given the opera-
tional characteristics. The solubility of the lubricant with the
, where D = tube diameter, v = velocity, fi = viscosity) if chosen refrigerant, at the most severe operational conditions,
the velocity of the vapor flow is decreased, the pressure drop determines the viscosity grade of the chosen lubricant. Other
will also decrease. However, as the velocity is reduced, the considerations for lubricant selection are related to the oper-
shear forces eventually become insufficient to drag the annu- ational envelope of the system, particularly for refrigeration
lar flow of lubricant, and the droplets in the mist flow suc- systems.
cumb to gravity forces and drop out of suspension from the If the refrigerant-lubricant combination exhibits regions of
vapor flow. This condition essentially stops lubricant trans- immisciblity, these must be carefully considered in system
port through the system, and is referred to as the minimum design, particularly for charge storage components. The re-
80 be extremely high. Newer refrigerant-lubricant combina-

Immiscible tions, such as HFC-POEs, have tended to exhibit higher vis-
60
cosities than the older combinations, such as CFC-MOs that
40 Lower CST
have been used for these applications. When the lubricant
20 Miscible viscosity becomes sufficiently high, it becomes similar to
I
E 0
u -20 Upper CST
wax, and transport becomes difficult, if not impossible. As lu-
bricant continues to build u p in the low temperature portion
w -40 of the system (evaporator), this will have a noticeable effect
H Immiscible on heat transfer and pressure drop in the heat exchanger and
-60 thus on performance. The saving grace for these conditions is
-80 often system transients, such as defrost cycles or slugs of rel-
20 40 60 80 atively w a r m refrigerant, which sufficiently decrease the vis-
cosity of the lubricant to allow transport back to the system.
Oil Concentration (%) At the same time, due to the high pressure differences in the
FIG. 15—Critical solution temperatures for R- system, compressor discharge temperatures are higher than
410A/POE-68. at low lift conditions. Both of these conditions lead to con-
tradictory requirements: the desire for a low viscosity lubri-
cant at low temperature, refrigerant dilute conditions; and a
relatively high viscosity lubricant at high temperature, refrig-
erant rich conditions. This is, of course, the same lubricant,
gions of immiscibility are usually defined by the critical (con- and must be chosen carefully.
solute) solution temperature, as shown in Fig. 15 for R-410A
and POE-68. In the immiscible region, two liquid phases will
form, one lubricant rich and one refrigerant rich. These two Lubricant Circulation Rate
phases will have different densities, and in an actual system,
stagnant liquid will tend to separate according to these den- The circulating lubricant concentration has an effect on per-
sity differences. If the lubricant rich phase is less dense than formance and the design of system components; knowledge
the refrigerant rich phase, it will float above the refrigerant of this concentration (referred to as oil concentration rate, or
dense phase. This is the preferred arrangement for most of OCR) can be quite important. The basic methods for deter-
the system lines, as the lubricant rich phase can still be en- mination of OCR can be broken down to invasive and non-in-
trained into the vapor flow. If the situation were reversed, the vasive techniques.
lubricant rich phase could become trapped below the refrig- The easiest method for determination of OCR is by use of
erant rich phase, leading to poor lubricant return to the com- a sampling volume, as outlined by ASHRAE [70]. A sample of
pressor. On the other hand, for receivers the situation can be liquid refrigerant is c a p t u r e d in a volume (previously
reversed, as liquid flow to the expansion valve is generally weighed), which is then weighed. The refrigerant in the
drawn from the bottom of the device. If the lubricant rich volume is next slowly released with care taken not to allow lu-
phase floats above the refrigerant rich phase in this case, it bricant to escape with the refrigerant. After refrigerant evac-
will not be drawn into the remainder of the cycle and will es- uation, the sample volume is weighed again to determine the
sentially become trapped. For accumulators, where vapor residual oil weight. This system determines the instanta-
flows from the exit and only a small a m o u n t of liquid be- neous OCR in the liquid line of the system. This information
comes entrained into this vapor flow through an oil return is of limited vaiue and may be very misleading when signifi-
mechanism, an immiscible system in combination with sys- cant transients, such as lubricant slugging, are occurring.
tem geometry can also produce a situation where lubricant This method, by its nature, is also quite invasive to the system
does not flow back to the compressor. Experiences with this and will result in a loss of charge every time a measurement
situation have led to accumulator designs where the contents is taken. A less invasive technique employs oil separators to
are continuously agitated so as to reduce or eliminate strati- ensure little or no residual CEirryover to the remainder of the
fication. Flooded heat exchangers are also a concern for lu- system [71]. The separated oil flowrate is measured and com-
bricant holdup. These typically shell and tube heat exchanges peired to the flowrate in the remainder of the system to de-
are used in chiller or other liquid heat transfer systems termine OCR. This technique requires two flowmeters and
where, if the lubricant rich phase is less dense than the re- will only work in the vapor region of the system (such as at
frigerant rich phase, oil holdup can occur in portions of the the compressor discharge). It is still invasive as it disrupts the
heat exchanger. normal flow of lubricant through the system and may mask
slugging trouble spots in the system.
There have been a n u m b e r of minimally invasive or non-in-
System Operational Envelope
vasive OCR measurement systems developed recently, which
As the temperature of the lubricant is reduced, its viscosity are much better at identifying problems with system design.
will increase. The degree of solubility of the lubricant with Coriolis flow meters can provide bulk flow density informa-
the refrigerant, coupled with the viscosity index of the lubri- tion. Knowledge of the pressure and temperature at the den-
cant, combine to determine the mixture viscosity. This is sity measurement point coupled with refrigerant and lubri-
shown in Daniel plots, such as the one in Fig. 11. For refrig- cant properties, which are used to d e t e r m i n e p u r e fluid
eration conditions, the evaporation temperature can be very density at the measurement point, can lead to a determina-
low, and the corresponding viscosity in the vapor phase can tion of the OCR [72]. However, liquid refrigerant and lubri-
cant densities tend to be quite similar, requiring the density formance cheiracteristics of the system. This is generally only
measurement accuracy to be high. In some cases, the error of concern when the ratio of lubricant to refrigerant is high.
band associated with the instrumentation accuracy obscures Finally, careful consideration of edl of these system variables
the entire range of measured oil concentrations, although is the challenge given to designers of m o d e m HVAC and re-
some authors have reported success with this technique. A frigeration equipment.
commercially available unit for measurement of OCR by ul-
traviolet (UV) absorption has been on the market for some
time, and some success has been reported in the use of this ASTM STANDARDS
device [73]. Several researchers have been working on index
of refraction type OCR measurement systems, although none No. Title
have yet been commercialized [74]. Acoustic velocity and di- D 97 S t a n d a r d Test Method for Pour Point of
rect fluid viscosity measurement have also been proposed as Petroleum Products
the basis for determining OCR, once again by comparing the D 445 Standard Test Method for Kinematic Viscosity of
known pure fluid properties to the measured bulk property Transparent and Opaque Liquids
values [72]. Both the UV and index of refraction measure- D 664 S t a n d a r d Test Method for Acid N u m b e r of
ments cire optical techniques, and cire thus fully non-invasive, Petroleum Products by Potentiometric Titration
while the density m e a s u r e m e n t technique typically intro- D 891 Standard Test Method for Specific Gravity, Ap-
duces a pressure drop in the liquid line. All of the above men- parent, of Liquid Industrial Chemicals
tioned measurement systems work only in the liquid line of D 892 Standard Test Method for Foaming Characteris-
the system cind are severely influenced by system transients, tics of Lubricating Oils
which bring two-phase flow (bubbles) to the measurement
D 943 Standard Test Method for Oxidation Characteris-
points. In addition, the capability of these devices to measure
tics of Inhibited Mineral Oils
OCR in immiscible mixtures is also in doubt.
D 1169 S t a n d a r d Test Method for Specific Resistance
(Resistivity) of Electric Insulating Fluids
D 2008 Standcird Test Method for Ultraviolet Absorbance
PERFORMANCE EFFECTS and Absorptivity of Petroleum Products
D 2140 Standard Test Method for Carbon-Type Composi-
The lubricant in the HVAC system has distinct performance tion of Insulating Oils of Petroleum Origin
impacts on the compressor, the heat exchangers, and work- D 2270 Standard Practice for Calculating Viscosity Index
ing fluid, all of which combine to affect system performance. from Kinematic Viscosity
The compressor requires a certain lubricant viscosity for ad- D2549 S t a n d a r d Test Method for Separation of
equate protection. If the fluid viscosity drops below this limit, Representative Aromatic and Nonaromatic Frac-
damage to the compressor may occur due to bearing failure. tions of High-Boiling Oils by Elution Chromatog-
On the other hand, if the lubricant is too viscous, the drag on raphy
the bearings as weU as any sealing surfaces will increase, re- D 2670 Standard Test Method for Measuring WeEir Prop-
sulting in an increase in consumed power and a reduction in erties of Fluid Lubricants (Falex Pin a n d Vee
performance. Block Methods)
For the heat exchangers, many of the lubricant impacts D 3233 Standzird Test Method for Measurement of Ex-
have already been discussed. Some studies have suggested treme Pressure Properties of Fluid Lubricants
that trace amounts of lubricant actually aid in heat transfer (FeJex Pin and Vee Block Methods)
properties and thus system performance [75]. However, any- D 5846 Standard Test Method for Universal Oxidation
thing above trace amounts (typically 0.1% OCR) has generally Test for Hydraulic a n d Turbine Oils Using the
been reported to have a negative performance impact. Lubri- Universal Oxidation Test Apparatus
cant in the vapor phase of the heat exchanger introduces a D 6304 S t a n d a r d Test Method for Determination of
contact resistance, which detracts from the overall heat trans- Water in Petroleum Products, Lubricating Oils,
fer coefficient. The degree to which this impacts performance and Additives by Coulometric Karl Fischer Titra-
is a function of the amount of OCR and lubricant hold up. tion
Studies have suggested that the degree of performance degra- E 203 Standard Test Method for Water Using Volumet-
dation caused by the lubricant can be related to the lubricant ric Karl Fischer Titration
viscosity at the exit of the evaporator [76]. Under refrigeration F2161 S t a n d a r d Guide for I n s t r u m e n t and Precision
conditions, the holdup can have a severe performance impact Bearing Lubricants—Part 1 Oils
as the holdup also influences pressure drop. G 125 S t a n d a r d Test Method for Measuring Liquid
Finally, the fluid performance is also impacted due to the and Solid Material Fire Limits in Gaseous Oxi-
displacement of refrigerant from the flow. The lubricant does dants
not aid substantially in the transfer of heat from the heat ab-
sorbing heat exchanger to the heat rejecting heat exchanger.
Thus, for every percent lubricant flowing in the bulk flow, a ANSI/ASHRAE STANDARDS
corresponding percent drop in performance can be expected.
For multi-component refrigersint mixtures (ctny of the R-400 34-1992 Determination of Refrigerant Lower Flammabil-
series of refrigerants), differential solubility effects can cause ity Limit in Compliance with Proposed Adden-
the circulating composition to fractionate, changing the per- d u m p to Standard 34.
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Modeling the Thermodynamic Properties of Refrigerant fix- [72] Baustian, J. J., Pate, M. B., and Bergles, A. E., "Properties of Oil-
tures," International Journal of TherTnophysics,\o\. 16, 1994, p. Refrigerant Liquid Mixtures with Applications to Oil Concen-
1165. tration Measurement," AS//i?AE TmniacfioMs, Vol. 92, lA, 1986,
[57] Gallagher, J., McLinden, M., Morrison, G., and Huber, M., p. 55.
"NIST Thermodynamic Properties of Refrigereints and Refriger- [73] Katsuna, K., Inoue, I., Mizutsini, T., Sudo, E., and Araga, T.,
ant Mixtures (REFPROP)," NIST, Standard Reference Database "Real Time Oil Concentration Measurement in Automotive Air
23, Version 5.1, 1997. Conditioning by Ultraviolet Light Absorption," SAE Paper
[58] Martz, W. L., Burton, C. M., and Jacobi, A. M., "Vapor-Liquid 910222, Society for Automotive Engineers, Warrendale, PA,
Equilibria for R-22, R-134a, R-123 and R-32/R-125 with a Poly- 1991.
olester Lubricant: Measurements and Departure from Ideality," [74] Newell, T. A., "In Situ Refiractometry for Concentration Mea-
ASHRAE Transactions, Vol. 102, 1996, p. 367. surements in Refrigeration Systems," International Journal of
[59] Wilson, G. M., "A New Expression for the Excess Free Energy of HVAC&R Research, Vol. 2, No. 3, 1996, pp. 247-256.
Mixing," JACS, Vol. 86, 1964, p. 127. [75] Worsoe-Schmidt, P., "Some Characteristics of Flow Patterns and
[60] Martz, W. L., Burton, C. M., and Jacobi, A. M., "Local Composi- Heat Transfer of Freon-12 Evaporating In Horizontal Tubes," In-
tion Modeling of the Thermodynamic Properties of Refrigerant ternational Journal of Refrigeration, Vol. 40, 1960, pp. 40-44.
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1996, p. 25. mance," presented at the ASHRAE Seminar 12, Dallas, TX, 2000.
MNL37-EB/Jun. 2003
Gear Lubricants
Vasudevan Bala^
GEAR DESIGN AND THE LUBRICANTS USED FOR THEIR APPLICATION FUNCTION OF GEAR LUBRICANTS
have evolved continuously over the last 200 years [1]. These
improvements were largely attributed to advances in gear de- The basic function of a gear lubricant is to reduce friction
sign, metallurgy, lubricant additives and base oil refining between the gear teeth under contact, which reduces tooth
[1,2]. Global trends in improved end user satisfaction, fuel wear and prolongs its life. Another critical function of the
economy, lower down time, cheaper maintenance, and im- gear lubricant is to dissipate heat generated in the contact
proved equipment durability have provided the necessary zones. In automotive applications, the gear lubricant can re-
motivation for increased competition among Original Equip- duce shock and noise emanating from reeir axles, hence pro-
m e n t Manufacturers (OEMs) [1-3]. As a result of these viding s m o o t h a n d quiet operation during acceleration.
trends, gear lubricants currently are formulated to meet ex- Other important functions of the gear lubricant during ser-
acting standcirds required to lubricate gear boxes and auto- vice are removal, and prevention of corrosion and pitting,
motive drivelines. The following sections cover the basics in while prolonging gear life.
gear lubrication and provide information in the selection of These functions collectively define the properties of gear
proper gear lubricants depending on their end application. lubricants in automotive and industrial applications (de-
scribed later). Gear lubricants meeting viscosity require-
ments, depending on their application, can assist in proper
EARLY GEAR LUBRICANTS start-up and the normal operation of gear boxes and axles.
Gear lubricants with very low viscosities can promote pre-
The history of gear lubrication dates back to Aristotle around mature seizure of gear teeth, while those with high viscosi-
330 B.C. [4]. Since then application of gears in precursors to ties affect the efficiency and operating temperatures in gear
m o d e m timepieces, windmills, and p u m p s were quite com- boxes and axles. In automobiles, the combined effects of
mon. Table 1 summarizes early gear applications and theo- aesthetically pleasing aerod5Tiamics for improved fuel econ-
rists. The early gears were predominantly made of wood that omy and installation of high performance engines, capable
precluded the use of lubricants until cast iron was used to of achieving higher peak torques at lower revolutions per
fabricate gears [5]. In examples recorded during the building minute, collectively have increased sump operating temper-
of the p5Tamids, animal fats were used to lubricate wooden atures and power densities transmitted by the gears used in
rollers that were used to move massive stones [5]. It was, transmissions and axles. As a result of these effects, gear lu-
however, with the introduction of spiral-bevel gears primar- bricants must resist oxidation and be thermally stable un-
ily for increased load-carrying capacities in the mid-1800s der normal and severe service. Gear lubricants can contain
that gear lubrication become severe. This led to the develop- dispersants that can disperse high molecular weight oxida-
ment of extreme pressure (EP) additives and the first patent tion by-products or sludge, promoting clean operation of
issued in 1869, describing the use of lead soap and active sul- the gear boxes. In some instances, build-up of sludge can
fur [6]. The first commercieil gear lubricants were mixtures of affect the performance of wheel-end and axle shaft lip-
animal fats and mineral oils. F r o m the late 1800s to the seals, thus preventing loss of gear lubricant. The use of EP,
1970s, the demands of the gear industry were met with addi- antiwear additives (AW), and friction modifiers (FM) can
tives based on lead, chlorine, zinc, sulfur, and phosphorus. protect the gear and bearing surfaces under boundary lu-
The use of lead oleates, napthenates, dithiocarbamates, and brication. The resulting drop in friction can reduce sump
sulfurized olefins provided the necessary anti-score and cor- temperatures, t h u s prolonging lubricant and equipment
rosion protection. During the 1930s, these additives were (gears, bearings, seals) life. In high-speed operations (in pa-
found to be inadequate for jixles that operated under heavy per and steel mills) or driving, gear lubricants are pumped
loads and high temperatures. This led to the combined use of and splashed incessantly. As a result, foam suppression by
lead soaps, chlorinated paraffins, zinc dialkyldithiophos- gccir lubricants is critical to prevent loss of lubricant deliv-
phates, and sulfurized olefins. By the 1960s, gear additives ery, cavitation, or implosion at the metal contact zones. In
were predominantly based on zinc, chlorine, and sulfur that certain industrial operations, water separation for regular
met Military, OEM, and industry standards. Table 2 illus- maintenance and lubricant top-off is desired. Other func-
trates EP gear chemistry used [7]. tions of gear lubricants include storage stability during
transportation and fuel economy benefits under most driv-
ing conditions.
' Cognis Corporation, 4900 Este Ave., Cincinnati, OH, 45232.
431
Copyright' 2003 by AS'I M International www.astm.org
TABLE 1—Early gear inventors and theorists.

Early Gear Information
Approximate
Name Date Item
Aristotle 330 B.C. Explained gear wheel drives in windlasses; pointed out that the direction of rotation
is reversed when one gear wheel drives another gear wheel.
Otesibius (Greek) 250 B.C. Made water clocks and water organs using gears.
Philo of Byzanitum 230 B.C. Made rack and pinion devise to raise water.
Archimedes 220 B.C. Made devices to multiply force or torque many times; studied spiral.
Vitruvlus 27 B.C. Described the first real use of power gearing in mill drives.
Hero 60 A.D. Described gears (cogwheels) for many uses; ceJculated actual gear ratios; devised
distance (cyclometer) eind angle (dioptra) measurements using gears.
Gear Theorists
Approximate
Name Date Nationality Contribution
Nicholas of Cusa 1451 French Studied cycloidal curve.
Albert Durer 1525 German Discovered epicycloids.
Girolamo Cardano 1557 Swiss Developed first mathematics of gears in print.
Philip de la Hire 1694 French Developed full mathematical analysis of epicycloids; recommended involute
curve for gearing (involute not used in practice until about 150 years later.
Charles Camus 1733 French Expanded on work of la Hire; developed theories of mechanisms; studied
lantern pinion and gear, crown gears, and beveled gears.
Leonard Euler 1754 Swiss Worked out design principles and rules for conjugate action some consider
him the "father of involute gearing."
Abraham Kaestner 1781 German Wrote practical methods for computing tooth shapes of epicycloid and
involute gear teeth; considered 15 degrees to be a minimum pressure angle.
Robert Willis 1832 English Wrote and taught extensively in gear field—a pioneer in gear engineering.
Edward Sang 1852 Scotch Developed generaJ theory of gear teeth; provided theoretical basis on which
all gear tooth generating machines are based.
TABLE 2—Early EP gear oil additives.

S:l S:2 S:3 S:4
Date 1935 1943 1948 1957
Cliemistry Type S, CI S, CI, P Pb, CI, S* Zn, S, CI, P*
Chlorine, % 34 26 4.6 15
Sulfur, % 10 8 4.9 13
Phosphorus, % 0.5 4
Lead, % 7.55
Zinc, % 3.5
Performance Level GL-4'" GL-4* GL-4, GL-5*
Dosage, Wt % 5-10 5-10 28 5-10
Application Automotive Automotive Automotive Automotive
"Some versions of S-3 and S-4 contained limited slip additives.
'API gear oil classification system, Publication 1560.
GEAR TYPES Helical gears are used in applications when higher peripheral
speeds and quieter operations are needed. The resulting eixial
Gears can be classified according to their tooth profile, forces require more complex bearing design. With herring-
shape, loading, and direction of torque transfer [8a]. The bone gears, axial forces are eliminated, but the tooth width is
choice of these different gear types depends on these factors generally twice as large compared to the helical design. Bevel
and is seen in automotive and industrial applications. The gears have intersecting axes, line contact and low slide/roll
basic function of gears is to transmit power along with in- ratios. Cylindrical w o r m gears also have crossed axes, line
creasing or decreasing shaft speed. Gears can also be used to contact, but large slide/roll ratios. They permit the transmis-
deliver the required torque and, depending on the gear design sion of high ratios under quiet, smooth, and low-vibration
used, can be used to change the direction or axis of rotation. operation. The hjrpoid gear design is predominantly used in
In specific automotive applications, gears are used to syn- automotive axles. They have a high center off-set with
chronize shaft speeds in transmissions and change torque crossed axes, elliptical contact, and large slide to roll ratios.
transfer in front and rear axles. Figure 1 illustrates the different types of gears and provides
There are different gear types used in automotive and in- information on their uniqueness and operation. These com-
dustrial applications. The c o m m o n gear types are spur, heli- m o n gears are used in automotive and industrial gear boxes.
cal, herringbone, w o r m , straight, and spiral-bevel a n d The proper selection of gear sets is dependent on gear size al-
hypoid. Spur gears come in straight, helical, and herringbone lowed, load bearing limit, desired gear ratio for torque and
designs. The most c o m m o n type is the straight spur gear type speed transfer. Table 3 provides additional information
that sees no axial forces a n d uses simple bearing design. on the selection of gear sets based on their gear ratio,
CHAPTER 16: GEAR LUBRICANTS 433
HELICAL GEARS
WORM GEARS
• Teeth In Spiral Plane To
The Axis • Extreme Case Of Hypoici @ear
• Smoother Than Spur • Hardened Steel And Bronze
Gears
• Higher Load Capability
• Quiet
• Multiple Tooth Contaot • Smooth Operation
• High Load Capability
SPUR GEARS
• Teeth In Parallel Plane To The HERRINGBONE GEARS
Axis
• Expensive To Manufacture
• Oast Iron Or Steel
• Noisy • Quiet
• Rough Operation • Smoom Operation
• simple And Economical To • Used For High Speed
ManufQeture Gearing
• single Tooth Contaot
• Rolling And Sliding Motion
HYPOID GEARS
BEVEL GEARS
• Form Of Spiral Bevel Gear
• Axis Centers Intersect
• Pinion Axis Does Not Intersect
• Noisy Ring Gear Axis
• Rough Operation • Smooth Running
• Limited To Low Siseeds • Light Weight And Cempoet
• Greater Load Capabiltly • Severe Sliding Action
With Spiral Bevel • Sleel Due To High Tooth
Loading
FIG. 1—Different types of gear sets [8].
TABLE 3- Performance comparison of various types of gear sets.

Maximum Maximum Maximum Maximum
Transmission Peripheral Output Torque
Position of Axes Gear Type Ratio Speed (kN) (kNm)
Parallel Spur 2250
Straight 10 5 7500
Helical 10 25 22500 9000
10 200 22500 2300
10 22500 600
Intersecting Bevel
Straight 7 2.5 375 90
Skew 7 2.5 3750 90
7 60 3750 45
Crossing at 90° Worm 50 60 750 300
Crossed Helical 50 75 170
H5ôid 50 750
Crossing at 80-100° Worm 50 50 115
(not 90°) Crossed Helical 50 170
peripheral speed, load, and torque [9]. The selection of the nation within the lubricating system [8a]. Failures resulting
proper gear lubricant for these c o m m o n gear sets is depen- from these effects cem lead to serious tooth surface damage
dent on the application and requirements set forth to meet such as pitting, spalling, wear, and scuffing. Table 4 provides
certain gear box or axle performance criteria. This is further the basic failure modes encountered in gear lubrication
elaborated later in this chapter under Classification of Gear [10,11a].
Lubricants for automotive and industrial applications. Descriptions of common lubrication related failures in pit-
ting, micropitting, adhesive wear, abrasive wear, polishing
wear, and scuffing and their prevention follow.
METHODS OF GEAR LUBRICATION Pitting is a fatigue phenomenon and occurs when a surface
initiated crack propagates into the metal before turning to-
The c o m m o n modes of gear lubrications are [8a]: wards the surface [10,lla,12]. In some instances, pitting can
• manueJ application with brushes also be initiated from a subsurface defect or inclusion, usu-
• drip feed from reservoir or tubes ally impurities (Fig. 2). When several pits grow together, the
• intermittent or continuous lubrication under pressure or large pit is referred to as a spell. The recommended guide-
splash lines to prevent the onset of pitting and/or spalling in gear
sets are [11a]:
In the selection of gear lubrication, consideration has to be
given to the end application and the prevention of gear failure. • reduce contact stresses by reducing loads
Manual application or drip feed is used for open gear sets • improve material strength of gear metal
where the temperature rises and load and wear on the gear • increase specific film thickness (defined as film thick-
teeth are all low due to the operation, and where the gears can ness/surface roughness)
be lubricated easily by a single application or repeated appli- Micropitting, as the name suggests, is similar to pitting ex-
cations at long intervals [9]. Gears that demand longer service cept that the pit sizes are several orders smaller [10,lla,12].
life operate continuously with high peripheral speeds (0.8-3 Other names used to describe micropitting are gray staining
m/s) under moderate loads during operation require inter-
mittent lubrication. Continuous lubrication via splash, p u m p -
assisted or pressure fed is generally provided for power trans-
mission with closed housings. Oil splash lubrication is by far
the most c o m m o n method of lubricating gears. It combines
the advantages of efficiency, continuous lubrication, and
cooling over a wide range of speeds and loads. Effective splash
lubrication where one of the gears dips into the reservoir and
provides lubrication to the other gears is seen in industrial ap-
plications, automotive transmissions, and axles where closed
gear housings are predominantly used [5].
GEAR FAILURE MODES

C o m m o n gear failures usually can be traced to lack of FIG. 2—Example of common gear failure—
lubrication, improper lubrication for the hardware, use of pitting. Courtesy of AGMA from Standard ANSI/AGMA
incompatible lubricant and/or additives, or possible contami- 1010-E95.
TABLE 4 -—Basic failure modes of gear teeth.

Non-lubrication-related Failures Lubrication-related Failures
Overload Bending Fatigue Hertizan Fatigue Wear ScuiBng
Brittle fracture Low-cycle fatigue Pitting Adhesion Scoring
Ductile fracture (scycles to failure) Initial Running-in Galling
Plastic deformation High-cycle fatigue Superficial Mild Seizing
Cold flow ( a 1000 cycles to failure) Destructive Moderate Welding
Hot flow Spalling Severe Smearing
Indention Micropitting Excessive Initial
Rolling Frosting Abrasion Moderate
Bruising Gray staining Scoring Destructive
Peening Peeling Scratching
Brinelling Subcase fatigue Plowing
Rippling (fish scaling) (case crushing) Cutting
Ridging Gouging
Bending (3aelding) Corrosion
Tip-to-root interference Fretting corrosion
Cavitation
Electrical dischsirge damage
Polishing (burnishing)
and frosting [8a] (Fig. 3). The specific film thickness has been
identified as a key parameter that influences micropitting [8].
The recommended guidehnes to prevent the onset of micro-
pitting in gear sets are [11a]:
• use smooth tooth surfaces produced by grinding or honing
• use adequate amount of gear lubricant of the highest vis-
cosity possible
• use of high speed
• use of carburized steel
Adhesive wear can be classified as mild or severe depending
on the cimount of wear seen on the gear tooth [10,11 a, 12]. Mild
adhesive wear generally occurs during break-in when the tooth
surface asperities are removed to improve the specific film
thickness. Severe wear has occurred when there is a significant
change in the tooth profile. The recommended guidelines for FIG. 4—Example of common gear failure—abrasion.
preventing the onset of adhesive wear in gear sets are [11a]: Courtesy of AGMA from Standard ANSI/AGMA
1010-E95.
• use smooth tooth surfaces
• run-in new gear sets at 1/2 the load before use
• Use higher speeds when possible. Under slow-speed high
loads, use nitrided gears combined with highest viscosity
lubricants
Abrasive wear is usually caused by foreign contamination
or wear debris from run-in of the gear sets [8a, 10,11a, 12]
(Fig. 4). Contamination can originate from inherently un-
clean gear boxes during build-up, ingressed through breather
valves a n d seals. Proper m a i n t e n a n c e of the gear box by
regular visual inspections and analyses of the lubricants can
reduce abrasive wear. The recommended guidelines for pre-
venting abrasive wear in gear sets are [11a]:
1. Remove contamination during build-up with proper flush-
ing and draining of the lubricant.
2. Refill with fresh lubricant and filter where applicable.
3. Use smooth surface hardened gears in combination with FIG. 5—Example of common gear failure—
high viscosity lubricants polishing. Courtesy of AGMA from Standard
4. Adopt regular maintenance schedules ANSI/AGMA 1010-E95.
5. Use filtrating systems with circulating oils
6. Follow OEM recommended drain intervals
7. Conduct used oil analyses to m o n i t o r condition of the in the lubricant [8a,10,lla,12] (Fig. 5). The use of EP and
lubricant antiwear additives can alleviate this type of wear. The recom-
Polishing wear is believed to be caused by continuous re- mendations for reducing polishing wear in gear sets are [11a]:
moval of the reactive boundary layer by fine abrasive material • Use of lubricants with the properly selected gear additives
• Continuous filtration to remove fine abrasive debris pre-
sent in lubricant
Scuffing is defined as localized welding between mating
metal surfaces. This genereJly occurs when the gears operate
under boundary lubrication [8a, 10,11 a, 12] (Fig. 6). Gears are
prone to scuffing, especially during start-up. It is not uncom-
m o n to use gears coated with phosphorus-maganese (lubr-
ited), copper, or silver to prevent scuffing during run-in. Gear
lubricants containing sulfur-phosphorus additives are for-
mulated to reduce scuffing. The following guidelines are
recommended to reduce scuffing [11a]:
1. Use gears with smooth surfaces that were honed.
2. Use gears with coatings to reduce propensity to scuff.
3. Use high viscosity lubricants containing sulfur-phospho-
rus additives.
4. Use heat exchanger to cool the lubricant sump.
FIG. 3—Example of common gear failure— 5. Use nitrided gears.
micropitting. Courtesy of AGMA from Standard Several references [4,5,10,1 la,13] provide further details
ANSI/AGMA 1010-E95. that elaborate on gear failure modes. The American Gear
Manufacturers Association Standard ANSI/AGMA 1010-E95 condition persists between the pinion and ring gears in auto-
[12] provides a common language to describe gear weeir and motive hypoid axles. Under boundary conditions, the addi-
failure and serves as a guide to uniformity and consistency in tive system present in the gear lubricant prevents scuffing,
the use of its language. It describes the appearance of gear metal adhesion, and wear.
tooth failure modes and mechanisms to facilitate the Under higher speeds and/or lighter loads, the gears operate
identification of gear wear and failure. under mixed lubrication. Under mixed lubrication, gear sur-
face asperities still come in contact and wear occurs at a
slower rate than under boundary lubrication. Both the viscos-
GEAR LUBRICATION ity of the gear lubricant and the additive system can influence
optimum gear performance under mix lubrication. Elastohy-
The conforming surfaces of gear teeth in mesh can operate drodjTiamic (EHD) lubrication provides the optimum condi-
under three different modes of lubrication: boundary, mixed, tion under which separation of gear teeth occurs, minimizing
and elastohydrodynamic. Boundary lubrication occurs wear. The lubricant's viscosity is important under EHD lubri-
during start-up or stopping conditions. In certain condi- cation and is affected by proper selection of the lubricant vis-
tions of heavy loads and slow speeds e.g., towing, boundary cosity grade. Table 5 provides the necessary equations that de-
scribe the calculation of film thicknesses under EHD for spur
and bevel gears with straight and helical teeth [9].
Figure 7 shows the typical contact between gear teeth for
spur, helical, and bevel gears [14]. The contact starts with
high sliding and some rolling. The sliding reduces to pure
rolling at the center of the gear tooth or pitch line after which
rolling decreases with increasing sliding. Generally, under
these conditions, the gear teeth undergo boundary to EHD
and back to boundary lubrication. Mixed and boundary lu-
brications generally persist for hypoid gear sets. EHD theory
has shown that film thicknesses of ~1 micron can prevent
surface asperities from coming in contact [15]. Under the
conditions of high pressure, the lubricant can exhibit viscos-
ity increases that maintain film thickness. Increases in the
relative velocities of the gear tooth surfaces, gear lubricant
viscosity, and in the radius of curvature at the point of con-
tact, can lead to gear oil film thicknesses more dramatically
FIG. 6—Example of common gear failure—scuffing.
Courtesy of AGMA from Standard ANSI/AGMA
than proportionate reductions in unit tooth load, or elastic
1010-E95. modulus of the gear metal [9].
Table 5—Symbols used in elasto-hydrodynamic film thickness calculation [9].

Gap parameter
P
Load parameter
Ep
^ = "4
G'=âE
Velocity parameter
Material parameter
^mia Minimum film thickness between surfaces
•Ô Operating viscosity at atmospheric
pressure
a Pressure coefficient of viscosity
« = ! ( « , + uj) Effective peripheral
PI X PI
velocity of two surfaces
p^— — Effective radius of curvature of the
Pi + PJ two surfaces
X £, Effective modulus of elasticity
E ^^>
£2(1 - <î) + £»(! - •'I) of the two materials
«T„ ffj Poisson's ratio for the two materials
w'^FIb Normal tooth force per unit tooth
width
pinion pitch cSroie •
(to) • Pitch point
(•} • First point of contact
(c) L » t point of contact

FIG. 7—Relative motion of meshing gear tooth surfaces. Reprinted with permission of CRC Press, Boca
Raton, FL. [14].
Table 6—Calculation of the effective radius of curvature [9].
I l l 2 i
- = —+ —= -r-r-x
p />! P2 sin/J„ ' V"0. 1 "0. 2 /
Spur gear Bevel gear (90 degrees)
ai sin p„
Straight teeth p = p = /!„ sin P,
(«• ± 1)'
ai sin ^„
Helical teeth Pn = A„
CDS'* Y{i ± 1)^ " ~ cos* 'yAi' + iJ
1 = pinion; 2 = gear; 4- = external teeth; — = internal teeth
p — radius of curvature t = transmission ratio
d^ = pitch diameter P = mesh angle
a — centre distance Y = helix angle
A - cone distance
The methodology for performing m i n i m u m film thickness a=1.030+3.509(logvo)^

calculations applicable to gear pairs (spur and bevel gears) is + 2.412*10-'*mgi'^(logvo)1.5976
provided next [9]. The m i n i m u m film thickness equation is -3.387 (logVo)^°'V"".
Table 5 provides the description of the symbols used in where:

m i n i m u m film thickness equation. The effective values for a = pressure-viscosity coefficient, [10~*Pa~']
velocity, load, modulus of elasticity and curvature are deter- mo = viscosity-temperature property from the ASTM
mined first. Tables 6-8 contain information for calculating Walter equation and equal to (ASTM slope)/0.2
the effective radius of curvature, peripheral velocity, and spe- vo = atmospheric kinematic viscosity at the tempera-
cific normal tooth force, respectively. The viscosity-temperature of interest, [mm^/S]
ture and pressure-viscosity coefficient of the lubriccint at the p = atmospheric density at the temperature of inter-
operating temperature are determined. These are obtained est, [lO^kg/m^]
by the following equations. These values are used to calculate the minimum film thick-
ness. Table 9 provides the variation for the different paired
log log (v + 0.7) = A - B log T
gears of spur and bevel types.
where:
log logarithm to base 10 TYPES OF GEAR LUBRICANTS
V kinematic viscosity, [cSt] or [mm^/s]
T Temperature, [K] or [°R] Most commonly available gear lubricants are blended from
AandB dimensionless constants petroleum basestocks. The following categories briefly de-
Table 7—Calculation of the effective peripheral velocity [9].
At pitch point: u = u, » KJ »«p,tOi = Pico^

Spur gear Bevel gear (90 degrees)
Straight teeth „ = ^ ( ——j sm ^. u= ^ >t„ sin ^„
Helical teeth „= - ^ (^-A.) 3i„ ^„ „= __^^^sin^„
1 = pinion; 2 = gear; + = external teeth; —= internal teeth

n = rotational speed i = transmission ratio
A = cone distance p = mesh angle
a = centre distance Y = helix angle
u = peripheral velocity
Table 8—Calculation of the specific normal tooth force [9].
F
w= -
F
F = —^—; straight teeth
cos fit,
F
P= T-^ 77:; hehcal teeth
(cos ^ i , cos y,)
^ 2M
w = specific normal tooth force M = torque

F = normal tooth force dy, = pitch circle diameter
b — tooth width ^ = mesh angle
Fu = peripheral force 7 = helix angle
Table 9—Calculation of elasto-hydrodjmamic film thickness [9].

ft„,„ = 2.65 X a^'^lnowf >*•**£-*'*'*w-°»^
Spur gear
Straight teeth
, 2.65 X, „0.54 / _„ \0.7 rO.*S
'miB £0.03
Helical teeth
2.65 X a°-^* / nnj^y (a sin ^ J " ^ i°*'
'»mi„- £0.03^0.13 ^^'ô 3 Q J X c o s " « y ( i ± l ) '
Bcpc/ gear
Straight teeth
•0.27
2.65 X « ° ' * / nn,Y\ ^ . „ '•13 '
"mi- = £0.03^0.13 ( ''O -^j i^m Sm P„) (,•2 + j)0.43
Helical teeth
2.65 X a° '* / nnX'' i^m s«n ^ , 1.13
) " ' «, 0 . 2 7
''•»'" £«"H''''M''*' 30; cos''*y (F + l ) ° * '
scribe the Vcirious types of gear lubricants and their general cation in w o r m gear drives where high sliding speeds be-
applications [14,15]. Gear lubricants can fall under any one tween the gear teeth requires lubricity additives to reduce
of these categories and their fined application, whether in- friction and improve torque efficiency. Compounded oils are
dustrial or automotive, is predicated on the meeting of spe- required to operate in the temperature range of 5-120°C.
cific performance requirements that will be discussed later in Constant relubrication of the gear teeth is recommended due
the chapter. to the unique gear mesh that wipes off the oil from the teeth
after contact. Reconditioning of the oil similar to inhibited
oils is quite common.
R u s t a n d O x i d a t i o n I n h i b i t e d ( R & O) O i l s
R & O oils are mineral oils containing rust and oxidation in-
Open Gear Compounds
hibitors, antifoamants, and/or antiwear additives. The rust in-
hibitors prevent corrosion of the metal surfaces by slowing the These oils are used in large gear sets t h a t move at slow
formation of acids and free radicals that are the by-products speeds. These lubricants contain tackifiers that adhere to the
formed at the onset of oxidation. Without oxidation inhibitors, gear teeth that resist being thrown-off or squeezed out of the
these acids and free radicals can form high moleculeir weight mesh. Solvents are sometimes used to help in the application;
sludge and deposits manifesting as viscosity increase [26]. In- they then evaporate leaving behind a thick lubricant film.
hibited oils are used in gear application under light to moder- The normEd operating temperature range for these lubricants
ate loads. This type of gear lubricant can be used to lubricate is 5-120°C. This type of lubricant does not offer any advan-
bearings and gears operating between - 2 0 to 120°C. Inhibited tage that circulating lubricants do for cooling and heat
oils can be reconditioned with filters to ensure cleanliness even removal.
with wear debris and contaminants are present.
Greases
E x t r e m e P r e s s u r e Oils
Greases are usually mineral lubricants that are thickened with
Extreme pressure oils contain additives predominantly of the soaps to a gelatinous consistency. The thickener holds the liq-
sulfur & phosphorus type to reduce destructive wear and uid lubricant and releases it when in use. The advantage of
scoring. These additives combine with the metal surface un- greases is that they do not have to be added continuously.
der frictional heating and provide a sacrificial boundary film Greases can act as sealants to keep contaminants out. Packed
that is easily sheared. EP oils can also contain other surface wheel bearings and small gear boxes in household appliances
active non-sulfur/phosphorus based additives. Examples in- are typical examples where greases are used. Greases are re-
clude graphite, molybdenum disulfide, potassium triborate, stricted to gears or bearings that operate at slow-speeds and
and additives containing bismuth. EP oils are used to lubri- more importantly, light loads. The useful operating tempera-
cate spur, helical, and spiral-bevel gears u n d e r loads too tures for greases are —30 to 120°C, depending on the base oil
heavy for inhibited oils. EP oils with the addition of disper- and soap used. Table 10 summarizes the various types of gear
sants and detergents can b e used in hjrpoid axles that are ex- lubricants and their application [15].
posed to heavy loads or shock loading. Shock loading occurs
under sudden heavy accelerations and decelerations that can
promote scoring at the gear surfaces. These automotive ap- ADDITIVES USED IN GEAR LUBRICANTS
plications will be elaborated later in the chapter. The useful
temperature range for EP oils is generally - 2 0 to 120°C. It is As stated before, the purpose of gear lubricants is to reduce
not u n c o m m o n to see automotive gear lubricants subjected friction and wear between gear teeth, dissipating frictional
to temperatures from —54 to 170°C. heat (not referring to greases), removal and reduction of
sludge and deposits, and prolonging gear tooth life. The ad-
ditives used in gear lubricants impart and enhance the lubri-
C o m p o u n d e d Oils
cating properties of mineral and/or synthetic base oils in
These oils contain fat or tallow as lubricity agents in heavy which they are blended. The general properties of mineral
cylinder basestocks to reduce friction. These oils find appli- and synthetic base oils are described later in the chapter.
TABLE 10—Types of gear lubricant used with various gear applications.

Gear Types
Lubricant Spur Helical Worm Bevel Hypoid
R & O oil (non-EP) Normal loads Normal loads Light loads Normal loads Not recommended
Slow speeds only
EPoil Heavy or shock Heavy or shock Satisfactory for most Heavy or shock Required for most
loading loading applications loading applications
Compounded oil Not normally Not normally Preferred by most Not normally For light loading
(ca. 5% tallow) used used gear manufacturers used only
Heavy-bodied Slow-speed Slow-speed Slow-speeds only Slow-speeds Slow-speeds only
open gear oils Open gearing Open gearing EP additive desirable Open gearing EP additive
required
Grease Slow-speed Slow-speed Slow-speeds only Slow-speeds Not recommended
Open gesiring Open gearing EP additive desirable Open gearing
Gear lubricants can be referred to as nonengine lubricants than the metal itself. The boundary film prevents scoring,
used in noncombustible environments. The additives in gear colding, welding, and seizure of gear surfaces.
lubricants can be classified as chemically active or inert. Ex-
amples of chemiccilly active additives are dispersants, deter-
gents, antiwear, EP, oxidative inhibitors, friction modifiers, Antiwear Agents
rust, and corrosion inhibitors. These additives generally The purpose of antiwear agents is also to reduce frictional
interact, via adsorption and/or decomposition and/or rear- wear, but under conditions of low loads. Typical components
rangement, with surfaces and with polar oxidation bi-prod- t h a t provide antiwear properties are zinc dialkyldithio-
ucts. Examples of chemically inert additives are emulsifiers, phoshates, alkyl phosphates and phosphites, aryl phosphates
demulsifiers, p o u r point depressants (PPDs), seal swell and phosphites, p o t a s s i u m triborate, a n d chlorowaxes.
agents, antifoamants, a n d polymeric thickeners. These Phosphates and phosphites are manufactured by reacting
additives alter the physiccJ properties of the finished gear alcohols with phosphorus pentoxide, or trichloride, respec-
lubricant. tively. Generally, alkyl p h o s p h a t e s a n d phosphites are
Most gear additive systems consist of all or most of the fol- neutralized with amines for enhanced surface adsorption.
lowing additives components: Their function to reduce wear is similar to EP agents via sur-
• extreme pressure agents face adsorption and decomposition under frictional heating
• detergents to form a sacrificial b o u n d a r y film. Generally, antiwear
• dispersants agents are more surface active than EP agents. Thus, their
• friction modifiers content in gear lubricants is generally lesser than EP agents
• oxidation and corrosion inhibitors by comparison.
• antiwear agents
• demulsifiers and emulsifiers
Detergents
• foam inhibitors
• pour point depressants Detergents keep metal surfaces clean of deposits. Tjrpical
These additives and their currently understood mechanism types of detergents are alkali earth metal (sodium, calcium,
of activity are described in the following section. There, it will magnesium) sulfonates, phenates, salicylates, and carboxy-
become apparent that some of these additives Eire multifunc- lates. These additives neutredize organic acids from lubricant
tional and understanding their S5Tiergistic and antagonistic oxidation and also associate with precursors that form sludge
properties towards each other collectively in the gear lubri- and varnish. This has the overall effect of keeping metal sur-
cant will allow formulators the ability to meet their perfor- faces clean of deposits. Consequently, the m a n n e r in which
mance targets. detergents react with oxidation byproducts can result in pro-
longing the use of gear lubricants and maintaining clean
working gear boxes. Neutral and basic metal sulfonates are
Extreme Pressure (EP) Agents formed by reacting alkylbenzenesulfonic acids with metal hy-
The purpose of EP agents is to reduce metal wear from scor- droxides or oxides (calcium, magnesium, sodium types) to
ing, cold welding, and seizure under conditions of high loads. form salts. Neutral salts are formed with correct stoichiome-
Typical c o m p o n e n t s t h a t provide E P properties are zinc try and overbased salts are formed in the presence of carbon
dialkyldithiophosphates (ZDDP), alkyldithiophosphates, sul- dioxide. Neutral and overbased metal phenates and carboxy-
furized olefins, alkylpolysulfides, sulfurized fats, potassium lates are prepared similarly to sulfonates except cJkylphenols
triborate, and chlorowaxes. Other examples are lead, bis- and alkylsalicylic acids, respectively, are used instead of
m u t h , and molybdenum dithiocarbamic and organic acid alkylbenzenesulfonic acids.
derivatives. Lead Etnd chlorine containing EP agents are be-
coming less popular due to their potential environmental and
hazardous impact. Most sulfur and some phosphorus con- Dispersants
taining components can function as good EP agents. Dispersants keep insoluble contaminants dispersed in the
ZDDPs are formed by reacting organic alcohols with phos- bulk lubricant. Typical examples of dispersants used in gear
phorus pentasulfide to form dialkyldithiophosphoric acids, lubricants are of the alkenylsuccinimide, succinate ester,
which are subsequently reacted with zinc oxide to form zinc Mannich derived, and alkenylphosphonic acid derivatives.
salts. Organic dialkyldithiophosphates are made without the The latter is seldom used as the other three types see domi-
last reaction. Sulfurized olefins are m a d e by reacting ele- nant use in crankcase engine lubricants. In manufacturing
mental sulfur with olefins at high temperatures forming a alkenylsuccinimides, succinic anhydride is prepared first by
mixture of sulfur containing compounds. Chlorowaxes are reacting polyalkenes with mzJeic anhydride. The most com-
manufactured via a similar process using chlorine and fatty m o n polyalkene used is polyisobutene. The resulting poly-
paraffins. Zinc, bismuth, emd molybdenum salts of dithiocar- isobutene succinic a n h y d r i d e is then neutralized with
bamic acid are made by reacting the acid derived from react- aJkylenepolyamines to form polyisobutene succinimides.
ing dialkylamine and carbon disulfide with the metal oxide. In some instances, further reaction of polyisobutene
Polysulfides are generally prepared by oxidizing alkyl mer- succinimides with m e t a b o r i c acid is commonly used to
captans. EP agents are relatively surface active and adsorb on impEirt seal compatibility and enhance deposit and Vcimish
metal surfaces. Frictional heat derived from sliding u n d e r control. Alkenylsuccininate esters are formed by reacting
high loads provides enough energy for bond scissation to oc- polyisobutene succinic anhydride with polyhydric alco-
cur, forming a sacrificial boundary film of lower yield stress hols. Mannich derived dispersants are formed by reacting
formaldehyde, pol}dsobutenyl, and alkylenepolyamines. Dis- are edkylated naphthalene and phenolic polymers and poly-
p e r s a n t s associate with p r e c u r s o r s of insolubles, t h u s methacrylates. Alkylated naphthalene is formed by the reac-
controUing deposit formation. The presence of a long hydro- tion of napthalene with chlorowax or olefins in the presence
carbon chain in polyisobutene helps in suspending the pre- of aluminum chloride. Alkylphenolic polymers are also pre-
cursors of insolubles in the bulk lubricant. pcired in similar fashion. These pour point depressants all act
in similar fashion by hindering the formation of wax from the
base lubricant by adsorption on wax crystals.
POLYMERIC THICKENERS
Oxidation Inhibitors
Polymeric thickeners are also c o m m o n l y referred to as
viscosity modifiers a n d viscosity index improvers. They Oxidation inhibitors function to inhibit the oxidation and
function to reduce the lubricant viscosity's dependence on decomposition of the gesir additives and lubricant. Examples
t e m p e r a t u r e . Typical examples of these include poly- of oxidation inhibitors are ZDDPs, polysulfides, hindered
isobutene, polymethacrylates, and copolymers of st5Tene and and sulfurized phenols, and aromatic amines. The prepara-
butadiene. Isobutylene is polymerized to desired molecular tion of ZDDPs and polysulfides has been described. Hindered
weights in the presence of a Lewis acid. Polymethylacrylates phenols are made by Lewis acid catalyzed alkylation of phe-
are prepeired by free radical polymerization of alkyl acrylates nol or aJkylphenol with poljdsobutylene. Sulfurized phenols
and methacrylates. Styrene butadiene polymers are formed are formed by reacting alkylphenol with sulfur monochlo-
by free radical polymerization of styrene-butadiene mixtures ride. Arylamines are prepared by alkylating diphenylamine
in the presence of vanadium based catalysts. Similjir process with a n olefin in the presence of aluminum chloride. Oxida-
is used in the polymerization of olefin block copolymers. This tion inhibitors function to decompose hydroperoxides and
latter type of poljTner is not commonly used due to its high radicals formed during oxidation. The reduction in hy-
manufacturing cost. The molecular weight of these polymers droperoxides and radicals slows down the rate of oxidation of
vary greatly. Due to shear stability constraints imposed by vis- the gear lubricant.
cosity classification for gear lubricants, the molecular weights
(MW) generally range from 5000-50 000, depending on poly-
m e r type. The most c o m m o n tjê of viscosity modifier used Corrosion Inhibitors
for gear lubricants is polyisobutene, whose MW is around
Corrosion inhibitors function to prevent corrosion and rust-
5000. All viscosity modifiers act in similar fashion. At low tem-
ing of metal peirts in contact with the gear lubricant. Com-
peratures, the polymers are tightly coiled cind their effects on
m o n examples of these are ethoxylated phenols, sulfonate
the viscosity are low. As temperature increases, the polymer
based detergents, triazoles, and thiadiazoles. Polyethoxy-
uncoils and occupies more space. This has the overall effect of
lated phenols and amines are formed by reacting ethylene
not reducing the lubricant's viscosity at high temperatures.
oxide, alkylphenols, a n d amines. Benzotriazole is m a d e
from diazotization reaction with nitrous acid. Dimercap-
tothiadiazole (DMTD) derivatives are made of sodium salt
F o a m Inhibitors
of DMTD with Ein alkyl halide. Corrosion inhibitors adsorb
Foam inhibitors act to deter the formation of foam in appli- on the metal surface via their polcir ends. Some of these,
cations where there is substantial a m o u n t of churning and such as DMTD derivatives, can be used to prevent corrosion
p u m p i n g , e.g., automotive axles. Typical c o m p o u n d s are against yellow metals s u c h as synchronizers and brass
polydimethylsiloxanes a n d polyalkylmethacrylates. These washers.
compounds effectively reduce the surface tension of the air-
lubricant interface, thereby facilitating their collapse.
Polydimethylsiloxanes a n d alkyl methylacrylates are pre- Demulsifiers and Emulsifiers
p a r e d by polymerization of dimethylsiloxane a n d alkyl Demulsifiers enhance water separation from the gear lubri-
methylacrylates. cant c o n t a m i n a t e d with water. Emulsifiers promote the
mixing of water and oil to form an emulsion. Examples of
Friction Modifiers demulsifiers cire block polymers of ethylene oxide, or propy-
lene oxide and glycerol, siloxanes, polyamines, and polyols.
Friction modifiers are c o m p o u n d s that act to reduce the Common examples of emulsifiers are hydroxyalkylamines,
coefficient of friction. Certain antiwear and EP agents such amides, a n d ethers. Demulsifiers function oppositely of
as long chain edkyl phosphates and molybdenum compounds emulsifiers. They migrate to the water-lubricant interphase
can be used as friction modifiers. Other examples of friction to create low viscosity zones, thus promoting the cocdescenc-
modifiers are graphite, fatty alcohols, acids, and amides. ing of water or lubricant. On standing, gravity drives the
Friction modifiers adsorb on the metal surfaces with their separation of water from oil. Emulsifiers reduce the surface
polar ends, thus forming a b o u n d a r y film with desired tension of water, thus promoting its mixing with oil.
properties. Tables 11-18 [ 8 a , b , l l b ] provide a s u m m a r y of additive
tjrpes and their function, with examples given for each type.
These tables also provide details on their chemical structure
Pour Point Depressants
and the general mode of sjmthesis. The additives described
These compounds enable the gear lubricant to flow at low are collectively formulated into mineral cind/or synthetic base
temperatures. Tjqjical examples of p o u r point depressants oils. Table 19 summarizes typical properties of base oils that
TABLE 11—Chemically active additives and their function.
Additive Class Purpose Typical Compounds Mechanism of Performance
Antiwear and extreme Reduce Mction and Wear, Zinc dialkyl dithiophosphates, di or These additives react with the metal
presure (EP) agents and prevent scoring and tri-alkyl and atyl phosphites, alkyl surface to form a sacrificisil
seizure phosphoric acid esters and salts, chemical film with lower shear
organic sulfides and polysulfides, strength than the metal itself.
sulfurized fats, dithiocarbamic acid This not only inhibits welding of
derivatives, and chlorowaxes." two surfaces in contact but also
minimized metal removal due to
friction.
Corrosion and rust Prevent corrosion and rusting Ethoxylated phenols, neutral and basic These chemicals adsorb on the
inhibitors of metal parts in contact metal sulfonates, alkanolamines, metal surfaces via their polar
with the lubricant alkenylsuccinic acids, and heterocyclic ends"^ and at the same time
compounds, such as alkyltriazoles associating with the lubricant via
and dimercaptohiadiazole (DMTD their hydrocsirbon groups. This
and their derivatives.)* allows the formation of a durable
lubricant film that acts as a
barrier against corrosion-causing
materials. Some of these are
basic and have the ability to
neutralize corrosive acids as well.
Detergents Prevent metal attack by acidic Neutral and basic (contain base reserve, These additives perform by two
byproducts of combustion usueilly as metal carbonate sodium mechanisms. (1. They neutralize
and oxidation and keep calcium and magnesium sulfonates, organic acids that result from
metal surfaces free of phenales, and carboxylates.) lubricant oxidation. (2. They
deposits associate with sludge and
varnish precursors and keep
them dissolved in oil. Both
these mechanisms prevent
deposit formation, thereby
keeping meteil surfaces clean.
Dispersants Keep insoluble contaminants Alkenylsuccinimides and succinate These chemicals, like detergents,
dispersed in the lubricant esters, Mannich products, and associate with deposit precursors
alkenylphosphonic acid derivatives and prevent their agglomeration
to insolubles. The presence of
long hydrocarbon chains in
dispersants help in suspending
these precursors in the bulk
lubricant.
"Tlieir use is being discontinued due to perceived negative impact of chlorine on the environment.
^Heterocyclic compounds are useful in controlling yellow metal corrosion.
°A11 additives except some viscosity modifiers and pour point depressants have a polar end and a non-polar hydrocarbon chain.
Polarity is due to the presence of a nitrogen, oxygen, sulfur, or phosphourus-containing functional group.
are used to blend automotive and industrial gear lubricants. well [16-18]. The purposes of defining service designations
The two categories of base stocks shown are mineral and and classifications cire:
synthetic. Mineral base stocks typically are solvent refined • to promote a uniform practice for use by marketers of gear
from crude and have viscosities ranging from approximately lubricants and by OEMs in identifying and recommending
4-30 cSt at 100°C. Synthetic base stocks are chemically dif- these lubricants by service designations [16-18].
ferent and cein range widely in viscosities. The selection of • to assist the users of automotive and industrial equipment
these various base stocks (mineral and/or synthetic) is in the selection of gear lubricants for field use [16-18].
dependent on the cost, application, and performance of the The following sections cover specifications to meet com-
gear lubricant. There are no definite rules to follow except m o n automotive and industrial gear lubricant requirements.
that any combination of base stocks can be used to meet the A glossary of test methods covered is provided following this
viscosity and performance targets, e.g., oxidation of the for- section.
mulated gear lubricant.
Automotive Gear Lubricants

CLASSIFICATION AND PERFORMANCE The evolution of gear lubricants to their present composition
TESTING OF GEAR LUBRICANTS and service requirements began with the introduction of hy-
poid gears by Gleason Works in 1925 [5]. This design was
This section covers some commonly used requirements for adopted because it provided automobile manufacturers the
qualifying automotive and industrial gear lubricants. Even advemtages of a lower center of gravity, lower weight, quieter
though the purpose for developing SAE J308 was its appli- operation, and greater load carrying capabilities. However,
cation to automotive and manual transmission lubricants, the lubrication of h5rpoid geeirs proved challenging. They re-
the requirements apply to industrial gear lubricants as quired gear lubricants with enhanced EP performance. At the
TABLE 12—Chemically inert additives and their function.

Additive Cass Purpose Typical Compounds Functions
Metal deactivators Reduce catal5'tic effect Complexing agents, such as These materials have the ability to
of metcils and their ethylenediaminetetraacetic acid (EDTA complex with metal ions to make
salts on the rate of and diseJicylidene-propanediamine) them inactive. This inhibits the
oxidation oxidation-promotion action of
metal salts.
Oxidation inhibitors Inhibit oxidative Zinc dialkyl dithiophosphates, organic These additives have the ability to
decomposition of sulfides and polysulfides, sulfur-coupled decompose hydroperoxides and
lubricant and phenols (phenol sulfides and hindered to make radicals innocuous. Both
additives phenols, and aromatic amines) these species promote oxidation.
Their removal from the reaction
sequence results in a slowdown
of oxidation.
Emulsifiers Promote mixing of Nonionic surfactants, such as hydroxyalkyl These materials facilitate emulsion
water and oil to amines, amides and ethers, and ionic formation by lowering surface
form an emulsion" surfactants, such as sodium carboxylate tension of water and allowing its
and trialkyl-ammonium halides and through mixing with oil.
carboxylates For oil-in-water emulsions, these
chemicals encapsulate oil using
their non-polar ends and keeping
it in solution by associating with
water via their polar ends. For
water-in-oil emulsions, these
additives perform in a reverse
msinner. That is, they associate
with water via their polar ends
and keep it in solution by
associating with oil via their
non-polar ends.
Demulsifiers Enhance water Block polymers of ethylene oxide or Demulsifiers have a function
separation from propylene oxide and glycerol, siloxanes, opposite to that of emulsifiers.
oil contaminated polyamines, or polyols They facilitate water separation
with water from a water-contaminated
lubricant. They concentrate at
the water-oil interface to create
low viscosity zones, thereby
promoting drop coalescence and
gravity-driven phase separation.
Foam inhibitors Prevent lubricant Silicone polymers, such as These additives reduce surface
from forming a polydimethylsiloxane, and organic tension of air or gas bubbles,
persistent foam polymers, such as poly (sJkyl thereby facilitating their
methaciylates) collapse.
Friction modifiers Alter coefficient of Organic fatty alcohols, acids, and amides, These materials associate with
friction linear alkyl phosphites and phosphates metal surfaces via their polar
esters and their salts, molybdenum ends and with lubricant via their
compounds, and graphite hydrocarbon chains. The result
is the formation of a durable
lubricant film of desired frictional
characteristics.
Pour point Enable lubricant to Alkylated naphthalene and phenolic These compounds adsorb
depressants flow at low polymers, polymethacrylates themselves onto wax crystals and
temperatures prevent the formation of
undesirable crystalline networks
that can adsorb leirge quantities
of oil and hinder its flow.
Seal swell agents Swell elastomer seals Organic phosphates and aromatic These additives are adsorbed by the
hydrocarbons elastomer seal material causing
it to swell. This not only assures
the integrity of the seals but it
also prevents them from
cracking and deterioration.
Viscosity modifiers Reduce the rate of Poly (alkyl methaciylates, polyolefins, and The key to the performance of these
viscosity change copolymers of styrene and butadiene additives is their differential
with temperature association* with lubriceint at
different temperatures. At low
temperatures, this association is
low, and at high temperatures, it
is high. The result is a lower loss
in viscosity at high temperatures.
"Desired for some hydraulic and metalworking lubricants tiiat use such emulsions.
''The term solubility is often used to describe this phenomenon. However, the term association may be more appropriate.
Table 13—Ântiwear and extreme pressure (EP) additives.

Compound Structure Methods of Synthesis
Zinc dialkyl These materials are made by reacting alcohols with

dithiophosphates (RO),E^ phosphorus pentasulfide to form dialkyl dithiophosphoric
acids. These acids react with zinc oxide to form zinc salts.
Phosphites and O
Phosphites result when alcohols or phenols are reacted with
phosphates (RO)2P^
phosphorus trichloride or a lower alcohol phosphite, such as
H trimethyl phosphite or dimethyl hydrogen phosphite.
Dialkyl Hydrogen
Phosphite Triaryl Phosphite
o o
Amine phosphates are obtained from amine salting of
R O — P — a RNHj + RO—p—ff RNHj
monoalkyl and dialkyl phosphoric acids. These acids are
OR OH
usually made by reacting alcohols with phosphorus
Amine Salts of Dialkyl and Mono-alkyI pentoxide.
Phosphoric Acids
Organic sulfides and I

CHj CHj Disulfides can be made by oxidative coupling of
polysufides HjC- -c—ss- - C — C H , :—c—sss—c—CH, mercaptans, which can react with sulfur to form higher
CH, GH,
Dialkyl Disulfide
CHJ CHJ
Dialkyl Trisulfide
polysulfides. Polysulfides can also be made by a one step
process involving olefin-hydrogen sulfide-sulfur reaction.
R—CH=CH-CH;
Sulfiirized olefins Sa
s/ s. Olefins can be sulfurized using sulfur at 125''C or higher.
R-CH2-CH—CH2
RCH2'
Usually, a mixture containing a variety of products is
R-CH2-CH—CHJ
obtained.
These products are salts of dithiocarbamic acid. The acid,

R2N—c:^
Dithiocarbamates made from dialkylamine and carbon disulfide, is salted
using zinc oxide.
Zinc Dithiocarbamates
N O T E : R and R2 represent alkyl groups.
Table 14—Detergents.
Alkybenzenesulfonic acids are reacted with stoichiometric
Neutral and basic
metal sulfonates '<r
S05)2M
Neutral Metal
•<r
S0j)»M^003
Basic Metal
amount of lime (calcium hydroxide) or magnesium oxide to
form neutral salts. One can use excess of these reagents if
Sulfonate Sulfonate carbon dioxide is used as a co-reactant. The materials thus
M = Ca or Mg obtained, called basic or overbased salts, contain excess
base as metal carbonate.
.0J2M oynôoj
Neutral and basic The process for making these materials is the same as that
metal phenates for metal sulfonates, except that the starting acid is an
Neutral Metal Basic Metal alkylphenol instead of an alkylbenzenesulfonic acid.
Phenate Phenate
Neutral and basic M = Ca or Mg The process for making these compounds is the same as
metal carboxylates
-CCs - -ex,.. that for metal sulfonates and phenates. The starting
material for these products is alkylsalicylic acid. This acid
o o
Neutralc Metal Salicylate results when a phenol is reacted with a strong base, such as
sodium or potassium hydroxide, and carbon dioxide
,QH
(Kolbe's process).
Basic Metal Salicylate
M=Ca or Mg
Table 15—Dispersants.
These materials are made by reacting alkylenepolyamines
Alkenylsuccinimides NCHjCHjNHCHjCHiN
./ with polyisobutenylsuccinic anhydride. Succinic
\ anhydride is an ene reaction product of polyisobutylene
Polyisobutenvlsyccinimtde
and maleic anhydride.
Alkenylsuccinate esters Polyisobutenylsuccinic anhydride is reacted with

polyhydric alcohols, such as neopentyl glycol and
L (
penterythritol, to form these esters.
Polvisobutenytsuccinate Ester
These products result from the condensation of an

Mannic products 1^ CHjNHCHjCHNHCHjCHzN alkylphenol, formaldehyde, and alkylenepolyamines.
"^1^5^ Polyamtnomethylalkylphenol
When these products are designed for use as dispersants,
the alkyl group in alkylphenol is polyisobutenyl.
These materials can be obtained by reacting olefin-
Alkenylphosphonic acid PIB—P—OCHjCH-CW phosphorus pentasulfide adduct with polyhydric alcohols.
derivatives OCHiCH-OH Usually, the adduct is first hydrolyzed using steam and
CH, then reacted with an alkylene oxide, such as propylene
Bis-hydroxypropyl oxide, to form these esters.
Alkenvlohosohonate
Table 16—Oxidation inhibitors.

These materials are made by reacting alcohols with
Zinc dialkyl phosphorus pentasulfide to form dialkyl dithibphosphoric
dithiophosphates acids. These acids are reacted with zinc oxide to form
zinc salts.
Monosulfides can be obtained by reacting a mercaptan

Organic sulfides and CH,
with an olefin. Disulfides can be made by oxidative
polysulfides H,C—C—SS-
f HjC—C—SSS-
coupling of mercaptans, which can react with sulfur to
CHj CHj CH, CH, form higher polysulfides. Polysulfides can also be made
Dialkyl Sulfide Dialkyl Trisulfide by a one step process involving olefm-hydrogen sulfide-
sulfur reaction.
Sulfur-coupled phenols, or phenol sulfides, can be
Sulfur-coupled phenols prepared by reacting an alkylphenol with sulfiir
(phenol sulfides) and monochloride.
hindered phenols
Hindered phenols are made by Lewis acid-catalyzed
alkylation of phenol or alkylphenol with an olefin, usually
isobutylene.
Diphenylamine is aklylated with an olefin in the presence
Aromatic amines of a Lewis acid, such as aluminum chloride, to yield these
products.
Arylamine
Table 17—Viscosity index improvers.

CH,
Polyolefins I Isobutylene polymerizes in the presence of Lewis acids to
•CHj-C— form these polymers. Higher olefins also polymerize to
CH,
^3 J n
yield analogous materials.
Polyisobutylene
Olefin copolymers These polymers are prepared from mixtures by vanadium-

CH,
based Ziegler-Natta catalysis. In these polymers, the ratio
of different olefins in the monomer mixture determines
-fCH2-CH2^ -CH—CHj-
the polymer's low and high temperature properties. Two
common polymers of this type are EPRs and EPDMs.
Ethyiene-propylene Copolymer
EPRs are made fiôm ethylene-propylene mixtures.
EPDMs, on the other hand, contain butadiene or isoprene
Styrene diene CH3 as the third monomer. These materials result from free
copolymers radical polymerization of styrene-butadiene mixtures.
CH-CH2- -CH2—CH=C-CH2-
Because of the presence of unsaturation (double bond),
these polymers are more susceptible to oxidation. Their
Styrene-diene Polymer oxidation resistance can be improved by removing the
double bonds through hydrogenation.
Alkyl methacrylate CH,

Free radical polymerization of alkyl acrylates and
polymers CH2-C-
methacrylates results in these polymers. In addition to
COORJj, being good viscosity modifiers, these polymers have the
ability to lower pour point. Hence, they are also used as
Alkyl Methacrylate Polymer
pour point depressants.
RO^
Styrene ester -Cô These esters are prepared by reacting styrene-maleic
polymers -CH-CHj-CH-CH anhydride polymer with alcohols. Styrene reacts with
0=0
maleic acid in the presence of fi-ee radical initiators to
/ yield this polymer.
RO
Styrene Ester Polymer
automobile manufacturers request, b o t h t h e additive a n d Petroleum Institute (API), developed test methods a n d
petroleum industries initiated the development of gear lubri- service designations for qualifying gear lubricants under low
cants to meet hypoid gear performance. Gear lubricants speed, high torque a n d high speed-shock load conditions.
based on sulfur-chlorine additives were then developed for This led to the development of MIL-L-2105A. These tests and
passenger car rear axles for high speed a n d moderate loads. service designations were able to differentiate the load-
Chlorinated paraffins, sulfurized fatty acids, a n d olefins are carrying capacities of automotive gear lubricants.
examples of sulfur-chlorine additives used for this purpose. The 1960s, with improved aerodynamics a n d demand for
As the popularity of hypoid axles increased into t h e mid- further increases in load-carrying requirements of hypoid
1930s, they were incorporated into trucks, which operated at axles, led to increasing thermal and oxidative problems in the
low speeds a n d higher loads. This led to the development of field. This along with environmental concerns over lead and
sulfur-phosphorus-chlorine based gear lubricants for both chlorine use prompted the use of advemced sulfur-phospho-
passenger cars and light duty truck applications. This was ev- rus and later, borate based additives (in the 1970s), which are
ident during World War II, where gear lubricants designated still in use today. The U.S. Military revised their specifica-
by MIL-L-2105 were plagued with persistent problems asso- tions to incorporate thermal and oxidative requirements into
ciated with truck axles operating under high torques and low MIL-L-2105B. Later, other tests for power divider, fatigue
speeds. These problems were relieved with the use of phos- spalling, a n d corrosion were incorporated by the industry
phorus containing additives in zinc dithiophosphates, alkyl from the 1970s to 1980s. Table 20 highlights some of the im-
phosphates, a n d phosphates. After World W a r II, MIL-L- portant milestones affecting automotive gear lubricants.
2105 gear lubricants were becoming inadequate in meeting The corroborative efforts of API, ASTM, SAE, Military, and
the requirements of new hypoid axles, which were subjected CRC led to the complete description of gear lubricants meet-
to higher torques. ing viscometrics and performance requirements for various
By the 1950s, the U.S. Military, working closely with the service designations. ASTM a n d CRC were responsible for
Coordination Research Council (CRC) a n d t h e American defining the different service categories, while SAE defined
Table 18—Miscellaneous additives.

Compound Structure Methods of synthesis
CH2CH2OH
Corrosion and rust Neutral and basic calcium sulfonates are made by reacting
Ca R—N^
inhibitors \ alkylbenzenesulfonic acids with lime in the absence or the
CH2CH2OH presence of carbon dioxide. In basic detergents, the reserve
Neutral Calcium Sulfonate Diethanolamine base is usually in the form of calcium carbonate.
O
SO3
R—CH—C—OH
Polyethoxylated phenols and amines result from the reaction
^€f CaxCaCOs I
CH—C—OH
II
of ethylene oxide with alkylphenols and amines.
O Alkenylsuccinic acid is a hydrolysis product of alkenylsuccinic

Basic Calcium Sulfonate Alkenylsuccinic Acid anhydride.
0(CH2CH2)xCH2CH20H Dimercaptothiadiazole (DMTD) derivatives are made either by

reacting sodium salt of DMTD with alkyl halide or by reacting
^ ^ ^ Polyethoxvlated Phenol
DMTD with mercaptans in the presence of an oxidizing agent.
RS. SR DMTD is manufactured by reacting hydrazine with carbon
disulfide.
N—N
Oimercaptothiadiazole Alkylbenzotriazole Benzotriazole is usually made from o-phenylenediamine via a
Derivative diazotization reaction (reaction with nitrous acid).
CH2OOOH
N=CH-
CH2CX30H
Metal deactivators Ethylenediaminetefraacetic acid is made from base-catalyzed
-CH2COOH reaction of ethylenediamine and chloroacetic acid.
W
\ HO
CH2COOH Sahcylaldehyde reacts with 1,2-propanediamine to form the
Ettivlenediaminetetraacetic N, N-Disalicylidene-1,2- salicylidene.
Acid Propanediamine
Emulsifiers and
demuisiflers Hydroxyalkyl and polyhydroxyalkyl derivatives are prepared
by reacting amides, amines, and alcohols with alkylene oxides.
\ R0(CH2CH20)xCH2CH20H
Ethylene oxide is most often used for this purpose.
NH(CH2CH2);P
N-Hydroxyalkvlamide Polymhoxylated Alcohol
IHydraxyalkyI Etherl Sodium carboxylate is prepared by reacting a carboxylic acid
CH2CH2OH with sodium hydroxide.
R—N'^
\ V
CH2CH2OH ONa'*' The reaction of amines with mineral acids yield
alkylammonium salts. When amines are reacted with organic
Diethanolamine Sodium
R' Cartoxylate
halides, quatemary ammonium salts are obtained.
R'
I Tetraalkylammonium carboxylate is a product of chloroacetic
R—N^-CHjCHjC
R—N—H X acid with trialkylamines.
i R"
\
R"
Trialkylammonium Tetraalkylammonium
Salt Carboxylate Siloxane polymers are products obtained from the reaction of
Foam inhibitors
CH3 CH, 1 CH, CH3 dimethylsilyl chloride with water.
O—Si- O—Si—O-j-Si-
I
•CHj-C—
I Alkyl methacrylate polymers result from free radical
CH, CH, COORj n
CH; polymerization of alkyl methacrylates.
Alkyl Methacrylate
Dimethylsiloxane Polymer
Polymer
OH Alkylnaphthalenes form when naphthalene is reacted with
Pour point chlorowax and or olefins in the presence of a Lewis acid, such
depressants as aluminum chloride.
R'
Alkylnaphthalene Alkylphenol
Alkylphenols are products of Lewis acid-catalyzed reaction of
CH, phenol with waxy olefins and or chlorowaxes.
I
-CH2-C
I Alkyl methacrylate polymers result from free radical
COORj
AlkylMethacrylate polymerization of alkyl methacrylates.
Polymer
R, R' Waxy Alkyl Groups

4 4 8 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK
TABLE 19—Physical properties: mineral oils versus synthetic base stocks [8b].
(A) Mineral Oils
Kinematic Viscosity, cSt Dynamic Viscosity, Viscosity Pour Point COC Flash
Type 40°C 100°C at -40°C (cP) Index (X) Point (°C)
90 Neutral 17,40 3,68 Solid 92 -15 190
100 Neutral 20,39 4,11 Solid 101 -13 192
200 Neutral 40,74 6,23 Solid 99 -20 226
350 Neutral 65,59 8,39 Solid 97 -18 252
650 Neutral 117,90 12,43 Solid 96 -18 272
150 Bright Stock 438,00 29,46 Sohd 95 -18 302
(B) Synthetic Base Stocks
Alkylated aromatic 26,84 4,99 9047 119 -18,3 224
Olefin oligomer 16,77 3,87 2371 126 -43,0 221
Dibasic acid ester 18,2 3450 176 -15,6 232
(Dioctyl sebacate)
Trimethylolpropane
Ester (C7 Acid) 13,94 3,4 2360 -18.3 232
Polyglycol 45,69 150 177
TABLE 20—Chronological changes in automotive gear lubricants. TABLE 21—API gear oil service designations [5,8,17,21].
Year Performance Demands Reasons and Consequences API
Classification Type Applications
1925 Hypoid Axle introduced Lower center of gravity,
weight, quieter operation GL-1 Straight mineral oil. Truck manual
1940s Service Classification By API and Military transmissions.
1950s MIL-L-2105A updated Wear and EP limits GL-2 Usually contains fatty Worm gear drives.
incorporated materials. industrial gear oils.
1962 MIL-L-2105B revised Oxidation & thermeJ stability GL-3 Contains mild EP Manual transmissions
limits incorporated Additives. and spiral bevel
1975 Mack GO-G Power divider & Spalling final drives.
Tests introduced GL-4 Equivalent to obsolete Manual transmissions
1976 MIL-L-2105C Low temperature, cross- MIL-L-2105; usually and spiral bevel a n d
grades, corrosion limits satisfied with 50% hypoid gears in
incorporated GL-5 additive level. moderate service.
1987 MIL-L-2105D Quality issues: MSDS GL-5 Virtually equivalent to Moderate and severe
1994 MT-l/PG-1 HD transmission specification present MIL-L-2105D; service in hypoid
introduced primary field service and other types of
1995 MIL-PRF-2105E MIL-L-2105D + MTl/PG-1 recommendation of gears. May cdso be
introduced most passenger car used in manual
1996 Extended Service OEM specifications by Eaton, a n d truck builders transmissions.
Mack, Meiitor worldwide.
1998 SAE J306 Revised viscosity classification GL-6 Obsolete. Severe service
2001 MIL-PRF-2105E Extended field testing involving high
Modified offset hypoid gears
MT-I Contains t h e m a l Nonsynchronized
stability and EP manual
additives transmissions in
heavy-duty service.
viscosity grades and service designations for axle cind manual
trEinsmission lubricants. Today's automotive gear lubricants
are classified by several designations:
defoamants, and PPDs may be used under this service
• API Service Designation category. Use of EP, emtiwear, or friction modifiers are not
• SAE Viscosity Classification (SAE J306) permitted.
• US Military MIL-PRF-2105E and SAE J2360 [19,20] API GL-2 designates the type of service typical of automo-
• OEM Specifications tive worm gear axles operating under conditions of load,
These different classifications will be discussed next. temperature, and sliding velocities, which lubricants satis-
factory for API GL-1 service will not suffice. Use of antiwear
and very mild EP additives are permitted under this service
API SERVICE DESIGNATION category.
API GL-3 designates the type of service typical of manual
There are six service designations defined by API, summa- transmissions and spiral-bevel axles operating under mild to
rized in Table 21. API GL-1 designates the type of service moderate to severe conditions of speed cmd load. These con-
t3rpical of manual trEmsmissions operating under mild condi- ditions require the gear lubricant to have greater load car-
tions of low unit pressures and minimum sliding velocities. rying capabilities required for GL-1 and GL-2, but not meet-
Mineral oils treated only with oxidation smd rust inhibitors. ing the requirements for GL-4. Generally, gear lubricants
TABLE 22—Proposed light duty manual transmission fluid standard [22].

Characteristic Test Method Conditions/Modifications Limits
Synchomesh SSP 180 CEC L-66-X-96 Under development No clash at 100 000 cycles
Wear ASTMD5182 90°C, 3600 rpm 10 load stage pass
Thermal Oxidation GFC Procedure A 160°C, 192 hours 50% vis inc. max
2.5 m g KOH/g
Viscosity after shear CEC-L-45-T-93 20 hrs, 60°C, 5000 N 25% max
loss 5.8 cSt m i n at lOOX
Pour Point ASTM D 97 Less t h a n - 3 9 ° C
Brookfield Viscosity ASTM D 2983 -40^ 50 000 cP max
Cold Crank Simulator ASTM D 5293 -30°C 5000 cP max
Foam ASTM D 892 Seq I, II, III 20,50,20/0 ml
ASTM D 6082 SeqIV 100/0 ml
Rust Prevention ASTM D 665 (Method A) Pass
Copper Corrosion ASTM D 130 3 hrs, 1 2 r C l lb max
Seal Compatibility ASTM D 5662 Pass
TABLE 23—API GL-5 tests [21,23]. • SAE J2360 Lubricating Oil, Gear Multipurpose Military
Test Characteristics Use
Designation Type Measured
• Or equivalent MIL-PRF-2105E
L-33 Gear test using axle Resistance to
components. corrosion in the
API GL-6 designates the tjrpe of service characteristic of
presence of gears designed with very high pinion offset. Such designs re-
moisture. quire score protection in excess of that required by GL-5.
L-37 Gear test using Resistance to This service category is almost obsolete, as equipment re-
complete axle gear distress quired for testing is no longer commercially available.
assembly. under the
conditions of The API GL-5 service category is currently the most
low speed high popular worldwide. In 1994, a new category for service in
torque. non-synchronized manual transmissions used in buses and
L-42 Gear test using Resistance to heavy-duty trucks was approved (API MT-1). Gear lubricants
complete axle gear distress meeting API MT-1 were approved against performance tests
assembly. (scoring) under
conditions of for improved deposit control, oxidation and thermal stability,
high speed and and seal compatibility beyond those required by lubricants
shock loads. meeting GL-1 through GL-5. Comparisons between API GL-
L-60 Bench test using Thermal oxidation 4, GL-5, and MT-1 are given in Table 24.
spur gears. stability.
ASTM D 892 Bench test. Foaming
tendencies. SAE J306 Viscosity Classification
ASTMD 130 Bench test. Stability in the
presence of Axle a n d m a n u a l transmission lubricants were originally
copper alloys.
classified by their viscosities described in SAE J306c - Rec-
ommended Practice, published in 1978. In this classification
system the ' W designates 'Winter' operation and defines low
meeting this service category 2U"e not intended for hypoid temperature viscosity limits for 75W to 85W grades. This was
axles. to alleviate pinion bearing failures when axles operated at
API GL-4 designates the type of service typical of spiral- temperatures when viscosities were greater than 150 000 cP.
bevel and hypoid gears in axles operating under moderate From 1996 through 1998, the following changes were made
speeds and loads. Gear lubricants under this service designa- to SAE J306:
tion m a y be used in selected m a n u a l transmissions and • Title change to "Automotive Gear Lubricant Viscosity
transaxles. While this service category is commercially used, Classification"
some original equipment for qualifying against this service • Labeling requirements similar to SAE J300 in format and
designation is n o longer available. ASTM is currently investi- content
gating the possibility of redefining this service designation • Viscosity grade must be preceded by "SAE"
using m o d e m test equipment. This service category is called • W grade precedes non-W grade
Passenger Manual Transmission (PM-1). A summary of the • Only the lowest W grade satisfied to be used
proposed tests for PM-1 is given in Table 22. • Two additional grades added (SAE 80 and SAE 85) with
API GL-5 designates the tjrpe of service typical of hypoid viscosity limits at 100°C
gears, operated u n d e r high-speed and/or low speed with • Footnote regarding low temperature performance of man-
high-torque conditions (see Table 23). Lubricants formerly ual transmission lubricants
qualified u n d e r MIL-L-2105D satisfy the requirements for • Incorporation of stay-in-grade shear stability requirement
API GL-5 service category. Details of API GL-5 performance using CEC-L45-T93
tests [21] are contained in the following publications: The requirement for shear stability was incorporated be-
• ASTM STP-512A: Laboratory Performance Tests for Auto- cause m o d e m gear lubricants may contain high molecular
motive Gear Lubricants intended for API GL-5 Service. weight polymers that may shear, resulting in a loss in viscos-
TABLE 24—API GL-4, GL-5 and MT-1 performance comparisons (5,23).

Performance API GL-4 (MIL-L-2105) API GL-5 (MIL-L-2105D) API MT-1
Scoring resistance u n d e r CRC L-19'' test or FTM L-42 test: gear/pinion coast side No requirement.
high speed shock load 6504T; equal to or better scoring equal to or better
conditions t h a n RGO-105. thanRGO-110
Resistance to gear CRC L-20 test; no tooth L-37 test; no tooth disturbance No requirement.
distress under high disturbance such as such as rippling, ridging,
torque, low speed rippling, ridging, pitting, pitting, or severe wear.
conditions. or severe wear.
Corrosion resistance in 1. CRCL-13 or FRM 5313.1 L-33 test: n o evidence of rusting No requirement.
the presence of water. 2. CRCL-21 after 7 day's exposure on any
No evidence of rusting. working surface; m a x i m u m
0.5 in.^ rust on cover plate
( 1 % surface area).
Thermal and oxidation No requirement. L-60-1 test; 100% max. viscosity L-60-1 test; 100% max. viscosity
stability/component increase; 3 % max. pentane increase; 3 % max. pentane
cleanliness. insolubles; 2% max. toUuene insolubles; 7.5 min. carbon/
insolubles. varnish ration on large gear;
9.4 min. sludge rating on all
gears.
Antiwear No requirement. No requirement. FZG (A/8.3/90); minimum 10
stage pass.
High temperature No requirement. No requirement. Mack Transmission Test
lubricant stability. T-2180: equal to or better
than reference
Antifoaming CRC L-12 test: readings ATSM D892: readings taken ATSM D892: readings taken
characteristics taken immediately immediately after 5 min. immediately after 5 min.
after 5 min. aeration; aeration; Sequence 1 —20 mL aeration; Sequence 1—20 mL
Sequence 1 -23.9°C, max; Sequence 2 - 5 0 mL max; max; Sequence 2—50 mL;
650 mL; Sequence Sequence 3 - 2 0 mL max. Sequence 3 - 2 0 mL max.
2 -93.3°C, 650 mL
Cooper corrosion ASTMD130:3bmax. ASTM D130: 3 max. after 3 hr. ASTM D130: 2A max. after 3 hr.
after 1 hr. at 1 2 r C . at 12rc. at 1 2 r C .
Channeling No requirement. FTM 3456.1 Modified: SAE 75, No requirement.
characteristics - 4 5 ^ max; SAE 80W90, - 3 5 ° C
max; SAE 85W-140, - 4 0 ° C max.
Compatibility with SS&CFED-STD-791 SS&CFED-STD-791 SS&CFED-STD-791
existing gear
lubricants
Solubility—measure FTM 3430: 0.25 wt. % FTM 3430: 0.25 wt. % max of FTM 3430: 0.25 wt. % max of
separated material max of original original nonpetroleum original nonpetroleum
after centrifuging oil nonpetroleum material in sample material in sample
stored for 30 days at material in sample
room temperature
(29.4 ± 9.5°C).
Compatibility—same FTM 3440: 0.50 wt. % FTM 3440: 0.50 wt. % max of FTM 3440: 0.50 wt. % max of
solubility except max of original original nonpetroleum original nonpetroleum
mixed 50/50 with each nonpetroleum material in sample. material in sample.
of six reference oils. material in SEimple.
"Equipment no longer available; impossible to conduct test per original procedure.
TABLE 25—Viscosity classifications for SAE J306 and MIL-PRF-2105E [18,19,23].

SAE Viscosity Classification
Properties 70W 75W SOW 85W 80 85 90 140 250
Vis at 100°C
Min (cSt) 4.1 4.1 7.0 11.0 7.0 11.0 13.5 24.0 41.0
Max (cSt) None None None None <11.0 <13.5 <24.0 <41.0 None
Vis of 150,000 cP
Max Temp, °C -55 -40 -26 -12 None None None None None
iUilitary Specification
Properties 75W 80W90 85W140
Viscosity at 100°C
Min (cSt) 4.1 13.5 24.0
Max (Cst) <24.0 <41.0
Vis of 150,000 cP -40 -26 -12
Max Temp, °C
Channel Point, min. "C -45 -35 -20
Flash Point, min °C 150 165 180
TABLE 26—Chemical and physical property requirements of MIL-PRF-2105E [19].

Property ASTM Method SAE 75W SAE 80W-90 SAE 85W-140
Viscosity D445 As per SAE J306 As per SAE J306 As per SAE J306
Channel Point, °C, max FTM 3456 -45 -35 -20
Flash Point, "C, min D92 150 165 180
API Gravity D287 Report Report Report
Viscosity Index D2270 Report Report Report
Pour Point, "C D97 Report Report Report
Pentane Insolubles, wt% D893 Report Report Report
Sulfur, wt% D1552 Report Report Report
Sulfur from Additive, wt% D 1552 Report Report Report
Phosphorus, p p m D 1091 Report Report Report
Chlorine, p p m D808 Report Report Report
Nitrogen, p p m D3228 Report Report Report
Zinc, p p m D4951 Report Report Report
Boron, p p m D4951 Report Report Report
Potassium, p p m D4951 Report Report Report
Organo-metals, ppm D4951 Report Report Report
ity. In order to ensure that the designated high temperature TABLE 27—Bench and rig test requirements for
viscosity grade is retained during use, gear lubricants must MIL-PRF-2105E [19].
meet viscosity limits at 100°C after shear. The permanent loss Test Method Passing Requirements
in viscosity may be detrimental to the gears and bearings as Copper Corrosion, Not to exceed 2a rating
film thicknesses may decrease. ASTM D 130,
12rC, 3 h
Foam Tendency, Seq Max Vol. at end of Blowing
U.S. Military MIL-PRF-2105E ASTM D 892
I 20 ml
In August 1995, MIL-L-2105D was superceded by MIL-PRF- II 50 ml
2105E. Most of the requirements needed for API MT-1 were in- III 20 ml
corporated into MIL-L-2105E. In 1998, at the U.S. Mihtary's
Oxidative and Viscosity Incr. at 100°C <100%
request, SAE adopted the SAE J2360 Standard equivalent to Thermal Stability, Pentane Insolubles < 3 wt%
MIL-PRF-2105E. The viscosity requirements are shown in ASTM D 5704, Toluene Insolubles < 2 wt%
Table 25 along with the SAE J306 Standard. The requirements 50 hrs, 163°C Carbon Varnish Rating >7.5
for stay-in-grade also apply to the military viscosity grades. Ta- (L-60-1) Sludge Rating >9.4
bles 26-29 summarize key performance tests as required by Gear Wear Test, No severe surface distress to gears
MIL-PRF-2105E. Field tests using light duty trucks or passen- ASTM D 6121,
ger cars and heavy duty Class 8 trucks are also required to 24 h, 275°F,
Green and
demonstrate no heirm performance in light and heavy duty Lubrited Gears
axles and heavy duty non-synchronized manual transmis- (L-37)
sions. The gear lubricants covered by MIL-PRF-2105E or SAE Cyclic Durability Better than reference oil
J2360 are intended for automotive gear units, heavy-duty in- Test, ASTM 5579
dustrial type enclosed gear units, steering gear units, heavy
Seal Compatibility, Polyaciylate, 150°C, 240 h
duty non-s3rnchronized Class 7 and 8 manual transmissions,
ASTM D 5662
and fluid lubricated universal joints of automotive equipment. Parameters Min Max
The lubricants covered by this specification are intended for Elongation change, % No limit -60
use as defined by appropriate lubrication orders when ambi- Hardness change, points -35 +5
Volume change, % -5 + 30
ent temperatures are above -54°C. In addition, API GL-5/MT-
1 tests, field tests in both light emd heavy-duty vehicles, are re- Fluoroelastomer, 150°C, 240 h
quired for meeting MIL-PRF-2105E. Axles from the light and Parameters Min Max
heavy-duty vehicles along with the transmissions from the Elongation change, % No limit -75
heavy-duty vehicles are inspected for cleanliness, surface dis- Hardness change, points -5 + 10
tress to gears, bearings, and shifting mechanisms. The gear lu- Volume change, % -5 + 15
bricant's condition is also monitored at periodic intervals. API L-33 Gear No rust on ages, < 1% on cover plate"
Corrosion
API L-42 Gear Lower % scoring than reference on gears.
OEM Specifications Scoring Test
"Rating being modified for better consistency.
Many OEMs have developed their own performance classifi-
cations for standard and extended drain services. These fac- yellow metal corrosion, frictional durability for limited slip
tory and service fill requirements generally meet API GL-5 axles, and power divider transaxles [25-47].
performance requirements [1,24]. In addition, performance Other enhanced performance considerations include im-
considerations for these lubricants meet specific perfor- proved oxidative stability, reserve performance for extreme
mance targets in the areas of improved fuel economy, tem- pressure [2], and wear. These requirements ensure that the
perature reduction, improved fatigue performance, enhanced axles and transmissions are protected under the increased
TABLE 28—Light and heavy-duty field test requirements of MIL-PRF-2105E [19,20].
Field Test Type Number of Vehicles Needed Test Mileage Sampling Interval
Heavy Duty Service Minimum of three Class 8 100 000 miles (previous) 4 oz, every 20 000 miles
(Axles and Transmissions) Trucks 200 000 miles (current)
Light/Moderate Duty Service Minimum of five light 50 000 miles (previous) 4 oz, every 10 000 miles
trucks and/or sedans 100 000 miles (current)
TABLE 29—Field test oil analyses requirements of

MIL-PRF-2105E [19].
Property ASTM Method
Viscosity at 40 and 100°C, cST D445
Phosphorus, p p m D 1091
Sulfur, wt% D1552
Chlorine, ppm D808
Nitrogen, p p m D3228
Zinc, p p m D4951
Boron, p p m D4951
Potassium, p p m D4951
Organo-metals, p p m D4951
Total Acid Number D664
Total Base Number D4739
Insolubles, wt% D983
TABLE 30—Current/future OEM axle specifications [1]."

Specification SAE Viscosity
OEM No. Grades Performance Requirements Recommended Drain Period (miles)
Mack GO-J 80W-90, 85W-140 Mil-PRF-2105E 250 000
Seal immersion test
Mack spalling test(*)
GO-J Plus 500 000 mile field test 500 000
100 h o u r L-60-1
Extended Mack cycling testC)
Eaton/Dana PS-163/ 75W, 80W-90, 85W-140 Mil-PRF-2105E 500 000
SHAES-256 Copper & bronze corrosion tests
Dynamic seal tests
Spalling test
500 000 mile field test
Wet L-37 Test
ArvinMeritor 076-D & A 80W-90, 85W-140 MiL-PRF-2105E 100 000 miles without p u m p and filter
to 500 000 miles with p u m p , filter
a n d appropriate additives
Mercedes Benz 235 90, 85W90, 85W140 API GL-5 60 000 (long haul)
In-house axle tests for all without flexible service system
(FSS)
220 000 for FSS
Mercedes Benz 235.6 80W90 API GL-5 60 000 (long haul)
85W90,90 In-house axle tests for all without flexible service system
(FSS)
Dynamic seal tests 220 000 for FSS
50 p p m CI max.
Volvo 97 310 75W, SOW, 90, 85W140, API GL-5 75 000 (long haul)
80W140
97 312 75W90 API GL-5/Pitting test/field test 110 000 current (long haul)
250 000 target
MAN 342N 90 API GL-5 50 000
342ML 80W90 API GL-5 100 000 (long haul)
FZG PITS field test
342SL 75W90 API GL-5 200-250 000
80W90 FZG PITS field test
Iveco 90 API GL-5 75 000
85W140
ZF TEML05 90 API GL-5 50 000
In-house axle and FZG tests
"This oil is used for axles and transmissions.
^Test currently not available.
driving durability they are currently being subjected to. Cer- TABLE 31—ÂISE 224 requirements lead free EP gear oil [16].
tain OEMs rely on extended versions of the L-60-1 test to de- Test Limits
fine improved performance for oxidation [1]. Gear lubricants API Gravity, ASTM D 287 25 min
are also required to perform in power dividers. Interaxle and Viscosity Index, ASTM D 567 95 min
interwheel power dividers transfer torque between front-rear
Precipitation Number, ASTM D 91 Trace
axles and wheels, respectively. Most conventional sulfur-
phosphorus and borate based gear lubricants are not capable Pour Point, ASTM D 97 - 9 ° C max (based
on viscosity)
of providing improved frictional durability required for
Flash Point, ASTM D 92
performance in power dividers. These require the use of ISO Grade 150 and higher 232.2°C min
friction modifiers for enhancing the proper lubrication of ISO Grade 68 and 100 203.4°C min
gears, cams, and bearings found in power dividers. Similar Copper Corrosion, ASTM D 130 l b max
frictional performance for light-duty vehicles is seen in
Rust Test (A & B), ASTM D 665 Pass
limited-slip axles. These serve to transfer torque equally
S-200 Oxidation—312 hrs, 121.1°C
between the rear wheels. The friction plates of these limited- Viscosity Increase, 98.9°C 6% max
slip clutch packs are made of steel plates that are manganese- Precipitation N u m b e r after test 0.1% max
phosphate, molybdenum, or paper coated. The frictional Demulsibility, ASTM D 2711
requirements for power dividers and limited slip axles allow Free Water 80 ml min
for conventional sulfur-phosphorus and borate chemistries Emulsion 1.0 ml max
to be compatible with friction modifiers with no compromise Water in Oil 2.0% max
to the gear lubricant's GL-5 performance. Table 30 summa- 4 Ball EP, ASTM D 2783
rizes several major U.S. and European heavy-duty OEM cur- Load Wear Index 45 kg min
rent and future specifications [1]. Weld Point 250 kg m i n
4 Ball Wear, ASTM D 2266
20 kg, 1800 rpm, 1 hr Scar Diameter of
0.35 m m max
INDUSTRIAL GEAR LUBRICANTS Timken Load Arm Test, ASTM D 2782 O.K. 60 lbs min
FZG Four Square Test 1 1 * Stage min
In general, industrial gear lubricants are used under condi-
tions of moderate loading. These lubricants are applied in en-
closed and open gearboxes. Industrial gear sets are more
diverse than automotive gear sets and are generally lubri- combines enclosed and open gearing superceding AGMA
cated by manual application, drip feed, spray, and splash lu- standards 250.04 and 251.02. It also covers the use of
brication. Typical uses of industrial gear lubricants are in synthetic industrial gear lubricants. Specifications of EP oils
steel mills, construction and mining sites, kilns, and have been upgraded to reflect advances in additive technol-
furnaces. The main function of industrial gear lubricants are ogy. Table 31 summarizes requirements for U.S. Steel 224
to prevent corrosion of rust and yellow metcJs, EP, as anti- (AISE 224). Table 32 compares several industrial require-
wear agents, for foam suppression, to prolong oxidation, to ments for EP gear lubricants. Tables 33-35 are specifications
demulsify, and to be able to lubricate under some level of for compounded, EP, and synthetic gear lubricants, respe-
contamination. Examples of specifications for industrial ctively, from AGMA 9005-D94. Table 36 specifies the viscos-
gear lubricants cire: ity ranges for AGMA gear lubricants.'^
• AISE 224 (formerly known as U.S. Steel 224)
• American Gear Manufacturers Association 9005-D94 [16]
T E S T IMETHODS F O R EVALUATING G E A R
• General Motors LS-2
LUBRICANTS
• David Brown ET 33/80
• DIN 51517/3
Precipitation Number ASTM D 91
• Flenders
• Cincinnati Milacron P-35, P-59, P-63, P-74, P-77, P-78 This test method covers the determination of precipitation
The two most common industrial specifications among the number of lubricating oils including steam cylinder stocks
ones hsted are AISE 224 and AGMA 9005-D94. AGMA and black oils. Fully refined petroleum oils normally contain
formed the lubrication committee in 1938 to study gear no naphtha insoluble material. Semi-refined or black oils fre-
lubrication problems. This committee was responsible for quently contain some naphtha insoluble material, sometimes
the adoption of the standard AGMA 250.01—Lubrication of referred to as asphaltenes. This test measures the amount of
Enclosed and Open Gearing in 1946. Several revisions culmi- naphtha insoluble material in oil. This quantity is reported as
nated in the standard AGMA 250.04 pubhshed in 1981, which the precipitation number. The ASTM precipitation number,
eliminated lead napthenate as an EP additive and modified n, is the number of milliliters of precipitate formed when 10
the AGMA lubricant numbering to coincide with the viscos- mL of lubricating oil are mixed with 90 mL of naphtha and
ity ranges in ASTM 2422 and the British Standard Institute centrifuged between 600-700 rpm.
(BS.4231) and International Standards and Organization
(ISO 3448). The elimination of open gearing where bearings ^ The original material is printed with permission of the copyright
were lubricated separately led to the adoption of AGMA Sta- holder, the American Gear Manufacturer's Association, 1500 King
Street, Suite 201, Alexandria, Virginia 22314. Statements presented
ndcird 251.01 approved in 1963. This standard was revised are those of the author and may not represent the position of the
again in 1974. The current AGMA standard 9005-D94 again American Gear Manufacturer's Association.
TABLE 32—Comparison of industrial gear oil specifications [23].

Tests AGMA 9005-D94 E P DN 51517 Part 3 (CLP) AISE 224
Timken OK Load, ASTM D 2782 60 lbs min 60 lbs min
FZG A/8.3/90, Pass Stage, min 12 11 11
4 Ball EP, ASTM D 2783
Weld Point 250 kg min
Load Wear Index 45 min
4 Ball Wear, ASTM D 2266 Scar Diameter—0.35
120 kg, 1800 rpm, 1 hr max
Corrosion Protection
ASTM D 130, 3 hrs/100°C lb max lb max
ASTM D 665, min PassB Pass A Pass A & B
Oxidation Stability
ASTM D 2893 (121°C), % Vis Incr 6 max
S 200, % Vis Incr 6 max
Precipitation Number 0.1 max
Foam Suppression, ASTM D 892
Seq I Tendency/Stability, ml max 75/10
Seq II Tendency/Stability, ml max 75/10
Seq III Tendency/Stability, ml max 75/10
Table 33—Minimum physical and performance specification for inhibited and compounded gear lubricants.
Courtesy of AGMA from Standard ANSI/AGMA 9005-D94.
Property Test Procedure Criteria for Acceptance
Viscosity ISO 3104 Must be as specified in Table 36

ASTM D 445
Viscosity ISO 2909 90 minimum
Index ASTM D 2270
Oxidation ISO 4263 Hours to reach a neutralization number of 2.0 ")
Stability ASTM D 943 AGMA Grade Hours (minimum)
0,1,2 1500
3,4 750
5,6 500
Rust ISO 7120 No rust after 24 h with synthetic sea water
Protection ASTM D 655B
Corrosion ISO 2160 #lb strip after 3 h at 12rC (250°F)
Protection ASTM D 130
Foam ASTM D 892 Must be within these limits:
Suppression Max volume of foam (ml) after
Temperature n. blow 10 min. rest
Sequence I 24°C (75°F) 75 10
Sequence II 9 3 . 5 ^ (200°F) 75 10
Sequence III 24°C (75''F) 75 30.0 ml
Demulsibility ASTM D 2711 *Must be within these limits:
Max percent water in the oil after 5-hour test 0.5%
Max cuff after centrifuging 2.0 ml
Min total free water collected during entire test 30.0 ml
Cleanliness None Must be free of visible suspended or settled contamination.
"The criteria for acceptance indicated for oxidation stability and demulsibility is not applicable to compounded gear oils.
Flash a n d Fire Points b y Cleveland O p e n Cup Pour Point ASTM D 97

ASTM D 92
This test m e t h o d m e a s u r e s the lowest t e m p e r a t u r e of a
This test method describes the determination of flash and fire petroleum specimen to determine its utility in certain low
point of petroleum products by a m a n u a l or a u t o m a t e d t e m p e r a t u r e applications. After preliminary heating, the
Cleveland open cup apparatus. Approximately 70 mL of the sample is cooled at a specified rate and examined at intervals
test specimen is filled into the test cup. The temperature of of 3°C for flow characteristics. The lowest temperature at
the specimen is increased rapidly at first and then at a slower which movement of the specimen is observed is recorded as
rate as the flash point is approached. At specified intervals a the pour point.
test flame is passed across the cup. The flash point is the low-
est liquid temperature at which the vapors from the specimen
will ignite. To determine the fire point, the test is continued Copper Strip Tarnish Test ASTM D 130
until the test flame causes the specimen to ignite a n d sustain The sulfur from the base oil and EP additives can have a cor-
burning for a m i n i m u m of 5 s. roding action on various metals but is not related to the total
Table 34—Minimum physical and performance specification for ep gear lubricants.
ASTM D 445
Viscosity ISO 2909 90 minimum (applies to viscosity grades 2 EP thru 8 EP only)
Index ASTM D 2270
Oxidation ASTM D 2893 Increase in kinematic viscosity of an oil sample at 121°C (250°F)
Stability should not exceed 6%°)
Rust ISO 7120 No rust after 24 hours with synthetic sea water")
Protection ASTM D 655B
Corrosion ISO 2160 # l b strip after 3 hours at 100°C (212°F)
Protection ASTMD 130
Foam ASTM D 892 Must be within these limits:
Suppression Max volume of foam (ml) after:
Temperature 5 min. blow 10 min. rest
Sequence I 2 4 ^ (75°F) 75 10
Sequence 11 93.5°C (200°F) 75 10
Sequence III 2 4 X (75°F) 75 10
Demulsibility ASTMD 271IMOD *Must be within these limits'):
AGMA Grades
2EPto7EP 8 EP to 13 EP
Max percent water in the oil 2.0% 2.0%
after 5-hour test
Max cuff after centrifuging 1.0 ml 4.0 ml
Min total free water collected 80.0 ml 50.0 ml
during entire test (start with
90 ml of water)
Cleanliness None Must be free of visible suspended or settled contamination.
Load carrying property ASTM D 2782 (Timken Test) An oil must meet both; a 60 pound Timken OK lad, and fail stage
and DIN 51 354 (FZG Test) greater t h a n 12 on the FZG machine with A/8.3/90°C parameters
for acceptance").
Filterability None Must be filterable to 25u (microns) (wet or dry) without loss of EP
additive (b25 = 200 fiher rating)
"Acceptance criteria has been upgraded.
Table 35—Minimum physical and performEince specification for synthetic gear lubricants.
ASTM D 445
Viscosity Index ISO 2909 120 minimum "
ASTM D 2270
Oxidation Stability ASTM D 2893 Increase in kinematic viscosity of oil sample at 121°C (250°F)
should not exceed 6%
Rust Protection ISO 7120 No rust after 24 h with synthetic sea water.
ASTM D 665B
Corrosion Protection ISO 2160 # l b strip after 3 h at 1 2 r c (250°F)
ASTMD 130
Foam Suppression ASTM D 892 Must be within these limits:
Max Volume of foam (ml) after:
Temperature 5 min. blow 10 min. test
Sequence I 24°C (75°F) 75 10
Sequence II 93.5°C (200°F) 75 10
Sequence III 2 4 X (75T) 75 10
Demulsibility ASTMD 2711 MOD Must be within these limits*).
Max percent water in the oil after 5 hour test 1.0%
Max cuff after centrifuging 2.0 ml
Min. total free water collected during entire 60.0 ml
test (start with 90 ml of water)
Cleanliness None Must be free of visible suspended or settled contaminants.
Mciximum Pour Point ISO 7120 - 3 2 ° C (22°F)
ASTM D 665
Load Carrying Property DIN 51 354 An oil must meet 11 stage fail (10 stage pass) on FZG machine with A/8.3/90°C
parameters for acceptance.
Filterability None Must be filterable to 25/i (microns) wet or dry without loss of additives
(/325 = 200 filter rating).
" Esters having a lower viscosity index and meeting all other requirements of this specification may be used in specific applications where proper viscosity at
operating temperature has been verified.
* Polyglycols which will not pass the demulsibility test, but meet all other requirements of this specification, may be used in specific applications where there
is no danger of water contamination.
Table 36—Viscosity ranges for AGMA gear lubricants. Courtesy of AGMA from Standard ANSI/AGMA 9005-D94.
Rust and Oxidation Viscosity Extreme Pressure
Inhibited Gear Oils, Range " mm'^/s Equivalent Gear Lubricants * Synthetic Gear Oils °
AGMA Lubricant No. (cSt) at 4000 ISO Grade" AGMA LubricEint No. AGMA Lubricant No.
0 28.8-35.2 32 OS
1 41.4-50.6 46 IS
2 61.2-74.8 68 2EP 2S
3 90-110 100 3EP 35
4 135-165 150 4EP 4S
5 198-242 220 5EP 5S
6 288-352 320 6EP 6S
7, 7 Comp'' 414-506 460 7EP 7S
8, 8 Comp'' 612-748 680 8EP 85
8A Comp'' 900-1100 1000 8AEP
9 1350-1650 1500 9EP 95
10 2880-3520 10 EP 10 S
11 4140-5060 11 EP US
12 6120-7480 12 EP 12 5
13 190-220 cSt at 13 EP 13 S
100°C (212°F)
Residual compounds'^ Viscosity ranges"
AGMA Lubricant No cStatl00°C(212°F)
14R 428.5-857.0
15R 857.0-1714.0
"per ISO 3448, Industrial Liquid Lubricants - ISO Viscosity Classification, Also ASTM D 2422 and British Standards Institution B.S. 4231.
''Extreme pressure lubricants should b e used only w h e n recommended b y the gear manufacturer.
"Synthetic gear oils 9S -13S are available but not yet in wide use.
''Oils marked Comp are compounded with 3 % to 10-% fatty or synthetic fatty oils.
"Viscosities of AGMA Lubricant N u m b e r 13 and above are specified at 100°C (212°F) as measurement of viscosities of these heavy lubricants at 40°C (lOOT)
would not be practical.
l i e s i d u a l compounds - diluent type, commonly knows as solvent cutbacks, are heavy oils containing a volatile, no-flammable diluent for ease of applications.
The diluent evaporates leaving a thick film of lubricant on the gear teeth. Viscosities listed are for the base compound with diluent.
CAUTION: These lubricants may require special handling and storage procedures. Diluent can be toxic or irritating to the skin. Do not use these lubricants
without proper ventilation. Consult lubricant supplier's instructions.
sulfur level in the gear lubricant. The effect varies pending on Acid N u m b e r ASTM D 6 6 4
the activity of sulfur. This test is designed to assess the rela-
tive degree of corrosivity of lubricants. A polished copper This method determines the acidic constituents in gear lu-
strip is i m m e r s e d in a specified quantity of sample a n d briceints that are present as additives or as degradation prod-
heated at a temperature for a specified time. At the end of this ucts during service. It is applicable for the determination of
period the copper strip is removed, washed, and compared acids whose dissociation constants in water are Isirger than
with ASTM Copper Strip Corrosion Standards. Generally, in- 10~^; extremely weaJs acids whose dissociation constants are
dustrizJ and automotive gear lubricants are tested at 100 and smaller t h a n 10~^ do not interfere. Salts react if their hydrol-
121°C for 3 h, respectively. ysis constants are larger than 10"*. The sample is dissolved in
a mixture of toluene a n d propan-2-ol containing a small
amount of water and titrated potentiometrically with alco-
A P I Gravity A S T M D 2 8 7 holic potassium hydroxide (KOH). The acid n u m b e r is re-
ported as mg KOH/g of sample. Since a variety of oxidation
This test covers the determination by means of a glass hy- products contribute to the acid n u m b e r and the organic acids
drometer of the API gravity of crude petroleum products. vary widely in corrosion properties, this test method cannot
Gravities are m e a s u r e d at 60°F (15.56°C) or converted to be used to predict corrosiveness of the geeir oil u n d e r service.
values at 60°F, by means of standard tables. This test method
relies on the principle that gravity of a liquid varies directly
with the depth of immersion of the floating API hydrometer. Rust Inhibition ASTM D 6 6 5
This method evaluates the ability of oils to prevent rusting of
Kinematic Viscosity ASTM D 445 ferrous parts if water mixed with the oil. A mixture of 300 mL
of the oil under test is stirred with 30 mL of distilled water
This method specifies a procedure for determining the kine- (Method A) or synthetic seawater (Method B) at 60°C in the
matic viscosity of lubricants by measuring the time of flow presence of a completely immersed cylindrical steel rod. The
under gravity through a calibrated glass capillary viscometer. duration of the test is 24 h. At the end of 24 h, the test rod is
The viscometer is placed in a heated bath at typically 40 and inspected for signs of rust.
100°C. The kinematic viscosity is the product of the measured
flow time and the calibration constant of the viscometer. The
F o a m Characteristics ASTM D 892
correct operation of equipment, such as gearboxes, axles and
transmissions, depends on the appropriate viscosity of the This method covers the determination of foaming charac-
gear lubricant. teristics of oils at 24°C and 93.5°C. The tendency of oils to
foam can be serious in systems such as high-speed gearing, Water Content ASTM D 1744
high volume pumping, and splash lubrication. Inadequate
lubrication, cavitation, and overflow loss of oil can lead to This method covers the determination of water in the con-
m e c h a n i c a l failure. The s a m p l e is m a i n t a i n e d at 24°C centration from 50-1000 mg/kg in oil. The new or used oil is
while air is blown into it at a constant rate for 5 m i n a n d titrated with standard Karl Fischer reagent to an electromet-
allowed to settle for 10 min. The volume of foam is mea- ric end point. Knowledge of the water level can be used to
sured at the end of both periods. The test is repeated on a predict performance and quality of oils, especially used oils.
second sample at 93.5°C a n d t h e n after collapsing the High levels of water of > 2 wt% cem cause equipment failure
foam, at 24°C. and may necessitate an oil drain.
F o u r BaU W e a r ASTM D 2 2 6 6
Insolubles in U s e d Oils ASTM D 8 9 3
This method covers the determination of the weetr chciracter-
This m e t h o d covers the d e t e r m i n a t i o n of p e n t a n e a n d
istics in sliding steel on steel applications only. This test Ccin
toluene insolubles in used oils. Procedure A covers the
be used to determine the antiwear properties of industrial
determination of insolubles without the use of coagulant in
gear lubricants relative to each other. No correlation has
pentane. Procedure B determines insolubles of oils contain-
been established between this test and field service. A steel
ing detergents and employs a coagulant for both the pentane
bcdl is rotated under load against three stationary balls. The
and toluene. In both procedures, a representative amount of
diameters of the wear scars on the stationeiry balls are mea-
sample is mixed with pentane and centrifuged. The solution
sured at the end of the test.
is decanted and washed with either pentane and/or toluene.
The "wet" insolubles are dried and weighed.
Viscosity Index ASTM D 2270
Chlorine Level ASTM D 808 This method specifies the procedures for calculating the Vis-
cosity Indices (VI) of oils from 40°C and 100°C. Described
This method covers the determination of chlorine in new and Procedures A and B determine the VI of oils u p to 100 and
used oils in the rzinge of 0.1-50 wt%. The procedure assumes greater than 100, respectively. The VI is a widely accepted
that compounds containing halogens other than chlorine are measure of the variation in kinematic viscosity due to the
not present. Knowledge of the level of chlorine in oils CEin be changes in temperature. The higher the VI of the oil is, the
used to predict performance or handling of gear oils. The oil less the dependence of viscosity on temperature. JCnowledge
is oxidized by combustion in a b o m b containing oxygen un- of a gear lubricant's VI can be used to predict performance
der pressure. The liberated chlorine c o m p o u n d s are ab- and quality.
sorbed in a sodium carbonate solution. The level of chlorine
present is determined gravimetrically by precipitation as
silver chloride. T i m k e n M e t h o d for E P ASTM D 2 7 8 2
This method covers the determination of the load-carrying
Phosphorus Level ASTM D 1091 capacity of oils by means of the Timken EP Tester. The tester
is operated with a steel test cup rotating against a steel test
This test method determines the level of phosphorus in un- block. The rotating speed is 123.71 ± 0.77 m/min or 800 ±
used and used oils and is independent of the type of phos- rpm. Oil samples Eire preheated to 37.8°C before starting the
p h o r u s compounds. This is because of the conversion to a n test. Two determinations are made: the minimum load (score
aqueous solution of orthophosphate ion by oxidation of value) that will compromise the lubricant film between the
the sample during the course of the analysis. Knowledge of rotating cup and stationary block and cause seizure or scor-
the phosphorus level can be used to predict performance ing; and the maximum load (OK value) at which the rotating
a n d quality of oils. The organic material in oils is de- cup will not compromise the lubricant film.
stroyed and the p h o s p h o r u s is converted to phosphate ion
by oxidation with sulfuric acid, nitric acid, and hydrogen
peroxide. The residual hydrogen peroxide is removed by Four Ball E P ASTM D 2 7 8 3
diluting with water and evaporation. The level of phospho-
This method also determines the load carrying properties of
r u s is t h e n d e t e r m i n e d by p h o t o m e t r i c or gravimetric
lubricating oils. This method differentiates between lubricat-
methods.
ing oils having low, medium, emd high level of EP properties.
The tester is operated with one steel ball under load rotating
Sulfur Level ASTM D 1552 against stationary three balls. The rotating speed is 1760 ± 40
r p m . The test lubricant is b r o u g h t between 18.33-35°C
This method covers three procedures for determining total (65-95°F) and a series of 10 s durations are made at increas-
sulfur content in oils and is applicable to samples boiling ing loads until welding occurs.
above 177°C and containing not less than 0.06 wt% sulfur.
One procedure uses infrared detection following pyrolysis.
DemulsibUity ASTM D 2711
The other two procedures use iodate detection followed by ei-
ther a n induction furnace or resistance furnace following py- This method determines the ability of oil and water to sepa-
rolysis. Knowledge of the sulfur level can be used to predict rate from each other. It is intended for oils with medium and
performeince and qucdity of oils. high viscosity. The test provides a guide for determining the
demulsibility of gear lubricants that are prone to water con- oils and additive packages. A small portion is weighed and
tamination and may encounter the turbulence of pumping diluted with solvent such as xylene. Internal and calibration
and circulation capable of producing water-in-oil emulsions. standards are weighed into the test specimen. The mixture is
The ability to separate water is desired in applications where then fed into an ICP instrument. By comparing the emission
it is relatively easy to perform maintenance without draining intensities of the elementals against the calibrated standards,
the oil sump completely. the concentrations of elements in the sample oil are
calculated. This test method can be used to confirm whether
the additive packages or oil meet specifications with respect
Oxidation of EP Oils ASTM D 2893 (S-200) to elemental composition.
This widely used method determines the oxidation charac-
teristics of EP gear oils. The oil sample is subjected to a
FZG Scuffing Test ASTM D 5182 or DIN 51354
temperature of 95°C in the presence of dry air for 312 h. The
oil is then tested for precipitation number and viscosity This test method, developed by the Forschungstelle fur Zah-
increase. nrader und Getriebebau (Research Site for Gears and
Transmissions), is commonly referred to as the FZG Visual
Method. It is intended to measure the scuffing load capac-
Low Temperature Brookfield Viscosity ASTM D
ity of oils used to lubricate hardened steel gears. High EP
2983
gear lubricants that meet API GL-4 and 5 easily exceed the
This test method describes the use of the Brookfield vis- capacity of the test rig. An FZG Gear Test Machine is oper-
cometer for the determination of the low-shear rate viscosity ated at constant speed (140 rpm) for a fixed period (15
of gear lubricants in the temperature range from - 5 to min.) at successively increasing loads (12 max) until the
-40°C. The viscosity range is 1000-1 000 000 cP. A lubricant failure criteria is reached. The test gears are examined ini-
sample is cooled in an air bath at test temperature for 16 h. It tially and after each load stage for cumulative damage
is carried in an insulated container to a nearby Brookfield (scuffing) to the gear tooth flanks. This test method can be
viscometer where its viscosity is measured at the temperature used to screen the scuffing load capacity of oils used to lu-
of the bath. The low temperature properties of gear lubri- bricate spur and helical gear units. The FZG Four Square
cants are critical for equipment starts that may be subjected Test is required for AISE 224 that stipulates no greater than
to low temperatures. The lack of lubrication can cause severe 10 mg between stages.
catastrophic distress to the gears and bearings.
Cold Crank Simulator ASTM D 5293
Nitrogen Level (Kjeldahl Method) ASTM D 3228
This test method provides the determination of the apparent
This test method determines the level of nitrogen for concen- viscosity of a lubricating oil at temperatures between —5 and
trations between 0.03 and 0.1 wt%. The sample is digested in -30°C at shear stresses between 50 000 to 100 000 Pa and
a mixture of concentrated sulfuric acid, potassium sulfate, shear rates of iC—10^ sec^ An electric motor drives a rotor
mercuric oxide, and copper sulfate. After digestion, sodium that is closely fitted inside a stator. The space between the ro-
sulfate is added to the mixture to precipitate the mercury, tor and stator is filled with the test oil. The test temperature
and the mixture is made alkali with caustic. Nitrogen in the is measured near the stator inner wedl. The speed of the sta-
form of ammonia is then titrated to determine the level of ni- tor is calibrated against viscosity. The test oil's viscosity is de-
trogen present. The concentration of nitrogen is a measure of termined from this calibration and measured motor speed.
the presence of nitrogen containing additives. Knowledge of
nitrogen levels can be used to predict performance.
Thermal and Oxidation (L-60-1) ASTM D 5704
Base Number ASTM D 4739 This test method determines the oil-thickening, insoluble-
formation and deposit-formation cheiracteristics of axle and
This method covers a procedure to determine the basic com- transmission oils, especially when subjected to high temper-
ponents in oils. This method resolves these components into ature oxidation. A sample of the oil is placed in a heated gear
groups having weaJi-base and strong-base ionization proper- case containing two spur gears, a test bearing, and a copper
ties. Base numbers of up to 70 are covered by this method. catalyst. The test oil is heated to 163°C for 50 h. Air is bubbled
The sample is dissolved in a mixture of toluene, isopropyl al- through the test oil at a constant rate. Parameters used to
cohol, chloroform, and water. The mixture is then titrated evaluate oil degradation after testing are: viscosity increase,
potentiometrically with alcoholic hydrochloric acid. The end insolubles, and gear cleanliness. The deterioration of the oil
point is selected from a titration curve and used to calculate in the transmission or axles can lead to serious seal failures
a base number in units of mg KOH/g sample. The base num- with deposit formation at the seal-shaft interface.
ber can provide information on the performance and quality
of new and used oils.
Cyclic Durability Test ASTM D 5579
Elemental Content ASTM D 4951 This test method evaluates the thermal stability of heavy-duty
gear transmission lubricants when operated under high
This method quantifies the levels of barium, boron, calcium, temperatures. The gear lubricant's performance is measured
copper, magnesium, phosphorus, sulfur, and zinc in unused by the number of shifting cycles that can be performed with-
out failure of synchronization when the transmission is GFC Oxidation

operated while continuously cycling between high and low
ranges. Field correlation with truck transmission service has This test method measures the oxidative stability of gear lu-
not been established, however, this method has shown to bricants under high temperatures. A quantity of sample
discriminate between satisfactory and unsatisfactory trans- placed in a flask is heated at a specific temperature with air
mission lubricants in the one petrticular transmission. After bubbled throughout the duration of the test. At the end of the
the transmission is rebuilt emd flushed with the test lubricant, test, the viscosity increase, wt% insolubles, and acid number
it is started and operated at low range until the sump tem- are reported.
perature reaches 250°F. This temperature is maintained
throughout the duration of the test. The transmission is Synchronizer SSP 180 Test
automatically cycled between low and high range until two
unsynchronized shifts occur or the desired length of time is This test measures the ability of a transmission lubricant to
reached. At the conclusion of the test, parts are rated for provide proper synchronized shifts at a specified tempera-
wear. ture and synchronizer friction material. The test rig uses
cone t)rpe synchronizers of several friction types. The indus-
try is currently conducting round robin testing to formulize a
Seal Compatibility ASTM D 5662 test procedure for PM-1.
This method evaluates the compatibility of nitrile, fluoroe-
lastomer, and polyacrylate seals in lubricants. Seal failure in Shear Stability CEC-L45-T-93
gearboxes, axles, and transmissions is caused by excessive
The test procedure eveJuates the shear stability of lubricants
seal hardening, elongation loss, and volume swelling. This
containing polymeric additives. Polymeric additives are usu-
method tests the likelihood of premature seal failure caused
ally used for thickening and improving low temperature flow
by the lubricant's effect on seals. The seal materials are
properties. A specified quantity of oil is placed in a tapered
placed in the test oil and subjected to the specified duration
roller bearing fixture that is motored by the Four Ball Ma-
and temperature. At the end of the test, changes in elonga-
chine. The temperature is controlled at 60°C for 20 h with a
tion, volume, and hardness are determined.
load of 5000N. At the end of this duration, the percent change
in viscosity at 100°C is determined. SAE J306 has shear sta-
High Temperature Foam Inhibition ASTM D 6082 bility requirements for gear lubricants to not shear out of
grade. Loss in viscosity can caused compromise to lubricant
This method describes the procedure for determining the films for proper bearing and gear performance.
foaming characteristics of oils at 150°C. By comparison,
ASTM D 892 determines foaming characteristics of up to
93.50C. A measured quantity of oil is heated to 49°C for 30 FZG (Forschungsstelle fur Zahnrader und
min and allowed to cool to room temperature. The oil is Getriebebau) Pits C 180 TS
transferred to a 100 mL graduated cylinder and heated to This test procedure evaluates the influence of oil aging on the
150°C and aerated at 200 mL/min with dry air for 5 min. The pitting life of gears under conditions of variable load, speed,
amount of static foam at the end of aeration and the stability and high temperature. The results are compared to a refer-
after specific times are recorded. ence oil in the same test. The failure criterion is to report less
than 4% of the active flank area of one single tooth at the
L-37 Low S p e e d High Torque Hypoid Test ASTM end of the test. The pitting performance of gear lubricants is
D6121 critical
This test evaluates the load carrying capacity of gear lubri-

cants under low speed and high torque conditions. The gears Channel Point FTM 3456
are conditions for 100 min at 440 wheel r/min and 394 Ibf-ft This test method is used to determine the channeling charac-
wheel torque, maintaining the sump at 297°F. The gears are teristics of oils at low temperature. The test consists of stor-
inspected and the second phase is commenced. The duration ing the oil sample for 18 h at the temperature required by the
of the second phase is 24 h and the sump temperature is con- specification, cutting a channel in the oil with a metaJ strip,
trolled at 275°F. The wheel r/min and wheel torque are 80 and and determining whether the lubricant flows together to
1742 Ibf-ft, respectively. The gears are inspected for wear and cover the bottom of the container within IDs. The ability of
various forms of other distress. This test measures the gear a lubricant to resist channeling at low temperatures provides
lubricant's ability to protect final drives from abrasive wear, adequate lubrication at startup conditions.
adhesive wear, plastic deformation, and surface fatigue. Lack
of protection can lead to premature gear or bearing failure,
or both. This test procedure is followed for both coated and Gear Scoring Test L-42
non-coated gears to evaluate gear lubricants against MIL- This test method evaluates the anti-scoring characteristics of
PRF-2105E requirements. The Wet L-37 test differs in the a gear lubricant under high-speed and shock loading condi-
temperature during the second phase: a specified amount of tions using a hypoid axle. The axle is driven by a 5.7 liter V8 en-
water is added and the axle is motored for 12 h at tempera- gine that drives the test axle, a 4-speed truck transmission, and
tures below 175°F. The axle is then motored for another 12 h two inertia dynamometers at a rate to simulate hard accelera-
at a temperature of 325°F. tion to approximately 100 mph. After break-in, the axle is ac-
celerated through the gears to a speed of lOSOrpm, then decel- at room temperature and centrifuging thereafter to quantify
erated to 530 rpm. This cycle is repeated five times. The high- the level of incompatibility from the amount of insolubles.
speed sequence is followed by ten shock loadings. The gear lu-
bricant is required to equal or better the scoring on the coast
Storage Solubility of Gear Lubricants FTM 3440
side of the pinion Eind ring gears of a passing reference oil.
This method is used for determining the storage stability
characteristics of gear lubricants. The gear lubricant is
Gear Corrosion Test L-33
heated at 120°C for 20 min and observed for separation of ad-
This test evaluates the rust and corrosion inhibiting proper- ditive material after storage at room temperature for a period
ties of a gear lubricant when subjected to water contamina- of 30 days. The level of incompatibility is determined from
tion and elevated temperatures. The test utilizes an unloaded the amount of insolubles weighed at the end of storage.
hypoid axle unit mounted on a test stand, which enables the
unit to be motored over with heat lamps. The axle is filled
Air R e l e a s e A S T M D 3 4 2 7 o r D I N 5 1 3 8 1
with 1200 mL of oil and 30 mL of water and motored for 4 h
at 82.2°C. On completion of this motoring phase, the axle is This method covers the ability of the gear oil to separate
stored for 162 h for 51.7°C in an environmental oven. At the entrained air. Compressed air is blown through the test oil,
end of storage, the axle is disassembled and rated for corro- which has been heated to 25, 50, or 75°C. After the air flow is
sion, sludge, and other deposits. topped, the time required for the entrained air in the oil to
reduce in volume to 0.2% is recorded as the air bubble
separation time.
Dynamic Seals Test
This test method evaluates the seal compatibility during op-
eration at a specified temperature and high shaft speed of FUTURE TRENDS IN GEAR LUBRICANTS
2500 r p m for 1000 h. The lip shaft seals are inspected for wear
and deviations from original dimensions at the end of test. Automobile manufacturers are competing for consumers by
Modifications to this test specific to OEM seal materials and claiming improved vehicle performance. Promoting vehicle
shaft diameters can be made. This test attempts to simulate performance in the areas of "Fill for Life" or extending drain
seal performance and the gear lubricant's effect in the field. intervals, seamless shifting, aerodynamic changes for aes-
thetics, and improved fuel economy are some examples. Ta-
bles 37 Eind 38 summarize the consequences of these trends
Compatibility of Gear Lubricants FTM 3430
to automotive gear lubricants.
This test procedure is used to determine the compatibility of As a result of these trends, automotive gear lubricants are
gear lubricant when blended with a reference gear lubricant required t o have improved performance in fatigue, seal
by observing for precipitation of additive matericd after stor- compatibility, oxidative and thermal stability, reduced chlo-
age. The test consists of storing the blended oils for 30 days rine, lower friction, lower cross grades in SAE 75W-90, EP,
Table 37—Âxle trends and consequences [1].

• Trend ' Consequences • Lubricant Effect
• Extended Drain Improved Component • Improved
Durability Pitting
Performance
• Improved
Synchronizer
Performance
Improved Seal
Compatibilty
•> Reduced Airflow Higher Bulk Oil Better
• Use of Retarders Temperatures Thermal/Oxidative
• Reduced Noise Stability
(Use of insulation)
• Higher Unit Power/Wt
Ratio
• Improved Efficiency - Lower Oil Viscosity at • Lower Viscosity Grades

• Improved Shiftability Start and Lower - Increased Use of
Temperatures Under 'Synthetics'
Normal Operation • Lower Friction
Additive
Technology
Table 38—Transmission trends and consequences [1].
• Trend • Consequences • Lubricant Effect

Extended Drain • Improved Component improved Pitting
Durability Performance
• Use of Filters? Improved Seal
I Higher Speeds
< Reduced Airflow
> Higher Bulk Oil Temperatures Z Compatibilty
Improved
Thermal/Oxidation
I increased Unit Loading Stability
I iVIore Environmentally • Easier Disposal • Reduced Chlorine

Friendly (Target 50 ppm Max)
< improved Fuel Economy ' Improved Axle • Lower Friction Additive
Efficiency Technology
• Lower Viscosity Grades
80W-90 and 75W-90
• Component Cost Reductioi I Simplified • IMore Robust

Technology Performance
I Reduction in Use of Doubl< < Hypoid Axle With • Improved EP

Reduction Axles Heavier Loadings Performance
< Reduced Noise
antiwear, and cost effectiveness. E n d users of industrial gear mance requirements. Last, a section on future trends for gear
lubricants are requesting reduction in inventory and cost. It lubricants was dedicated to acknowledge the industry's in-
is not u n c o m m o n to see the use of advanced gear additive tention to constantly upgrade gear lubrication specifications
chemistries to rationalize or minimize inventory. Gear addi- to meet its changing needs.
tive systems capable of meeting both industrial (low treats of
1.4 to 2.5 wt%) and automotive (treat levels of 4.0 to 15.0
wt%) performances are being used today. Other trends for in- ASTM STANDARDS
dustrial gear lubricants are improved oxidative stability, im-
proved demulsibility, and lower additive treat cost. Unless otherwise indicated all of the following standards are
It is becoming more evident, as these trends for gear current.
lubricants are materializing, that the additive and lubricant
industries are meeting these challenges with improved tech- No. Title
nology in refinement, additive development, and formulation. D 91 Test Method for Precipitation Number for Lubri-
cating Oils
D 92 Test Method for Flash and Fire Points by Cleveland
CONCLUSIONS Open Cup
D 97 Test Method for Flash Point by Pensky-Martens
This chapter described gear lubricants and summarized their Closed Cup Tester
requirements for automotive a n d industrial gear applica- D 130 Test Method for Detection of Copper Corrosion
tions. Lubricating gears in axles or gearboxes is challenging, from Petroleum Products by the Copper Strip Tar-
as gear lubricants are required to provide efficient operation nish Test
with minimized maintenance. Gear lubricants collectively D 287 Test Method for API Gravity of Crude Petroleum
provide various attributes such as: scuffing resistance, ex- and Petroleum Products (Hydrometer Method)
treme pressure (EP), antiwear, corrosion resistance against D 445 Test Method for JCinematic Viscosity of Transpar-
ferrous and yellow metals, compatibility with various elas- ent and Opaque Liquids (and the Calculation of Dy-
tomeric seals, oxidative and thermal stability, possession of namic Viscosity)
varying degrees of demulsibility depending on application, D 664 Test Method for Acid N u m b e r of Petroleum Prod-
low and high temperature film strength, good low tempera- ucts by Potentiometric Titration
ture fluidity, cost effectiveness, and environmental safety. D 665 Test Method for Rust-Preventing Characteristics of
Commonly used gear sets were described in this chapter Inhibited Mineral Oil in the Presence of Water
along with some tjîcal gear failure modes. A list of typical D 808 Test Method for Chlorine in New a n d Used
additives used to formulate gear lubricants were also given. Petroleum Products (Bomb Method)
Current classifications for automotive and industrial gear lu- D 892 Test Method for Foaming Characteristics of Lubri-
bricants were compared along with their testing and perfor- cating Oils
D 893 Test Method for Insolubles in Used Lubricating Oils SAE J306—Automotive Gear Lubricant Viscosity Classification
D 1091 Test Method for Phosphorus in Lubricating Oils SSP 180 or CEC L-66-T-99—Evaluation of the Sychromesh
and Additives E n d u r a n c e Life using the FZG SSP 180 Synchromesh
D 1552 Test Method for Sulfur in Petroleum Products Test Rig
(High-Temperature Method)
D 1744 Test Method for Determination of Water in Liquid
Petroleum Products by Karl Fischer Reagent REFERENCES
D 2266 Test Method for Wear Preventive Characteristics of
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Meeting of National Lubricating Grease Institute, Carlsbad, Oct.
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D 3228 Test Method for Total Nitrogen in Lubricating Oils
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Petroleum Oils Annual Meeting of National Lubricating Grease Institute, Naples,
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Between-5 and-30°C Using the Cold-Cranking zol Corporation's Additive Ready Reference for Lubricant and Fuel
Simulator Performance. Lubrizol, Wickliff, OH, 1998.
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Manual Transmission Publications, Ltd., London, 1993.
Lubricants in a Cyclic Durability Test [10] Benedict, G. H., "Gears," Ch. 20, Standard Handbook of Lubri-
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[12] ANSI/AGMA 1010-E95: Appearance of Gear Teeth—Terminol-
D 6082 Test Method for High Temperature Foaming Char-
ogy of Wear and Failure, AGMA, Alexandria, VA.
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D 6121 Test Method for Evaluation of the Load Carrying bology, CRC Press Ltd., Boca Raton, FL, 1996.
Capacity of Lubricants Under Conditions of Low [14] Stucker, J. B., "Rear Axle and Gear Box Lubricants," CRC Hand-
Speed and High Torque Used for Final Hypoid book of Lubrication, Vol. I, CRC Press, Boca Raton, FL, 1992.
Drive Axles [15] Radovich, J. L., "Gears," CRC Handbook of Lubrication, Vol. II,
CRC Press, Boca Raton, FL, 1992.
[16] AGMA 9005-D94: Industrial Gear Lubrication, AGMA, Alexan-
OTHER STANDARDS dria, VA, August 1994.
[17] SAE J308: Axle and Manual Transmission Lubricants, Society
AGMA 9005-D94—Industrial Gear Lubrication of Automotive Engineers, Warrendale, PA, 1989.
Federal Test Method 3456—Channel Point of Federal Test [18] SAE J306: Automotive Gear Lubricant Viscosity Classification,
Method Std. No. 791 Society of Automotive Engineers, Warrendale, PA, 1998.
FZG-PITS Test C 180 TS—Test Method for Evaluating the [19] MIL-PRF-2105E: Lubricating Oil, Gear Multipurpose (Metric)
Influence of Oil Ageing on the Pitting Load Capacity of Military Use, U.S. Military, Aug. 1995.
Lubricants [20] SAE J2360: Lubrication Oil, Gear Multipurpose Military Use,
Society of Automotive Engineers, Warrendale, PA, 1998.
GFC (Groupement Francais De Coordination) or CEC L-48-A-
[21] Laboratory Performance Tests for Automotive Gear Lubricants in-
00—Oxidative Stability of Lubricating Oils Used in Automo- tended for API GL-5 Service, ASTM STP 512A, ASTM Interna-
tive Transmissions by Artificial Ageing (Laboratory Test) tional, West Conshohocken, PA, 1991.
MIL-PRF-2105E or SAE J2360—Lubricating Oil, Gear Multi- [22] Proposed Specification for Passenger Manual Transmission,
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SAE J308—Axle and Manual Transmission Lubricants TN, Nov. 2000, ASTM International, West Conshohocken, PA.
[23] Ethyl Petroleum Additives Lubrication Specification Handbook, [36] Moat, N. W., "Canadian Experience with Multigrade Gear Oils,"
Ethyl Petroleum Additives, Inc., Richmond, VA, June 2000. SAE Paper No. 811204, Society of Automotive Engineers, War-
[24] Goodhead, J. W. and Cook, S. P., "High-Temperature PerformEince rendale, PA, 1981.
Needs of Gear Oils: A Comparison of Current and Future Tech- [37] Watts, R. F. and Willette, G. L., "Newtonian Multigrade Gear
nologies," 4th CEC Symposium, Birmingham, UK, May 1993. Lubricants: Formulation and Performance Testing," SAE Paper
[25] Bala, V. and Saathoff, L., "Oxidative Stability of Automotive No. 821180, Society of Automotive Engineers, Warrendale, PA,
Gear Lubricants," NLGI Paper No: 9821, Presented at The 65"' 1982.
Annual Meeting of National Lubricating Grease Institute, Naples, [38] Adams, J. H., Frost, K. A., Hartmann, L. M., and Painter, L. J.,
Oct. 1998. "The Effect of Gear Lubricant on Fuel Economy as Measured in
[26] Bala, V., Hartley, R. J., and Lawrence, J. H., "The Influence of a Line Haul Truck Fleet," SAE Paper No. 810179, Society of Au-
Chemical Structure on the Oxidative Stability of Organic Sul- tomotive Engineers, Warrendale, PA, 1981.
fides," Presented at The 1995 STLE Annual Meeting, May 1995. [39] Greene, A. B. and Risdon, T. J., "The Effect of Molybdenum
[27] Bala, V. and Pietras, J. M., "Enhanced Performance Considera- Containing Oil Soluble Friction Modifiers on Engine Fuel Econ-
tions for Automotive Gear Lubricants," Presented at the 2"'' In- omy and Gear Oil Efficiency," SAE Paper No. 811187, Society of
ternational Symposium on Fuels and Lubricants, New Delhi, 2000. Automotive Engineers, Warrendale, PA, 1981.
[28] Pinkus, O. and Wilcock, B. K., "Strategy for Energy Conserva- [40] Devlin, M. T., Naumann, J. K., Saathoff, L. D., and Walters, D.
tion Through Tribology," Presented at the 33rd ASLE Annual K., "Predicting the Fuel Economy Properties of Gear Oils Using
Meeting, Dearborn, April 1978. Laboratory Friction Tests," GFC Conference, Paris, Nov. 1999.
[29] Bartz, W. J., "Fuel Economy Improvement by Engine and Gear [41] Adamo, R. and Corso, S., "Frictional and Antiwear Behavior of
Oils," 5th CEC International Symposium on the Performance Fuel Efficient Gear Lubricants," presented at the 36th ASLE An-
Evaluation of Automotive Fuels and Lubricants, Goteborg, Swe- nual Meeting, Pittsburgh, May 1981.
den, May 1997. [42] Porrett, D., Miles, S., Werderits, E., and Powell, D., "Develop-
[30] Bartz, W. J., "Some Considerations Regarding Fuel Economy m e n t of a Laboratory Axle Efficiency Test," SAE Paper No.
I m p r o v e m e n t s by Engine and Gear Oils," presented at t h e 800804, Society of Automotive Engineers, Warrendale, PA,
ASLE/ASME Conference, New Orleans, LA, Oct. 1981. 1980.
[31] Chamberlin, W. B. and Sheahan, T. J., "Automotive Fuel Sav- [43] Bala, V., Brandt, G., a n d Walters, D. K., "Fuel Economy of
ings Through Selected Lubricants," SAE Paper No. 750377, So- Multigrade Gear Lubricants," presented at the 12th Interna-
ciety of Automotive Engineers, Warrendale, PA, 1975. tional Colloquium Tribology, Esslingen, Germany, 2000.
[32] Richardson, L. P., Schiemann, L. F., and O'Connor, B. M., "Eco- [44] Bala, V., RoUin, A. J., and Brandt, G., "Rheological Properties af-
nomic and Energy Benefits through use of Multigraded Gear fecting the Fuel Economy of Multigrade Automotive Gear Lu-
Oils," presented at the NPRA Fuels and Lubricant Meeting, Hous- bricants," SAE Paper No. 2000-01-2051, Society of Automotive
ton, Nov. 1977. Engineers, Warrendale, PA, 2000.
[33] O'Connor, B. M., Graham, R., and Glover, I., "European Experi- [45] Bala, V., Guidry, K. L., and Kuhlman, R. E., "Fuel Economy
ence with Fuel Efficient Gear Oils," SAE Paper No. 790746, So- Considerations of Multigrade Automotive Gear Lubricants,"
ciety of Automotive Engineers, Warrendale, PA, 1979. NLGI Paper No: 0016, Presented at 67th Annual Meeting of Na-
[34] Naman, T. M., "Automotive Fuel Economy—Potential Improve- tional Lubricating Grease Institute, Asheville, NC, Oct. 2000.
ment through Selected Engine and Gear Lubricants," SAE Pa- [46] Bala, V. and Pietras, J. M., "Fuel Economy Evaluation of Multi-
per No. 800438, Society of Automotive Engineers, Warrendale, grade Automotive Gear Lubricants," Presented at the PetroTech
PA, 1980. Conference, New Delhi, January 2001.
[35] Stambaugh, R. L., Galluccio, R. A., and KoUer, R. D., "Multi- [47] Bala, V., Guidry, K. L., and Kuhlman, R. E., "Enhanced Perfor-
grade Gear Lubricants in Truck Fleet Testing—Ânalysis for Fuel mance Properties of Multigrade Automotive Gear Lubricants,"
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MNL37-EB/Jun. 2003
Automotive Lubricants
Shirley E. Schwartz, ^ Simon C. Tung,^ and Michael L. McMillan'
LUBRICANT TYPES Defoamers are agents that spread over a fluid surface and
reduce surface tension, so that air bubbles can easily escape.
MANY TYPES OF LUBRICANTS ARE USED IN A VEHICLE. Engine oil Viscosity index (VI) improvers are long-chain chemical
and transmission fluid, on a volume basis, provide a major c o m p o u n d s t h a t change shape u n d e r various conditions.
portion of the lubricants in a typical car or truck, and a great When the oil is hot, the VI improvers stretch out and, in the
n u m b e r of standard tests are associated with these fluids. process of stretching out, they make the oil behave as if it was
Greases provide a variety of highly specialized functions and more viscous. When the oil is cold, the VI improvers fold in
are found in many locations within a vehicle (for example, in upon themselves, and as a consequence, they exhibit lower
door locks, gears for seat adjustments and windshield wipers, viscosity than would be the case if they didn't curl up.
bearings, electrical contacts, and numerous other places). The lubricant base stock has the important function of
For some automotive lubrication applications, standard transporting the various protective chemical additives to the
tests are not available. An example is automotive air condi- sites in which they are needed and transporting waste prod-
tioning systems, which require a specialized lubricant that ucts away from the sites in which the waste is generated. For
can be transported by the air conditioning medium. Those example, engine oil t r a n s p o r t s anti-wear surface-active
who use lubricants for which standard tests are not available agents to the nose of the cam on a camshaft, a region in
must devise their own procedures to ensure that the lubricant which chemical agents are essential for wear protection
performs acceptably. when a lifter slides over a cam nose. Protective anti-wear
agents are not as critical when a roller follower is used, rather
than a sliding contact.
Functions of Automotive Lubricants The wearing surfaces in a newly manufactured vehicle may
Various issues influence the choice of lubricant composition have burrs or rough spots, which are smoothed during use.
for optimum performance in automotive applications. The The lubricant transports these burrs or residues away from
lubricant must protect the automotive components that it lu- the rough spots in which they originated. The burrs can then
bricates. In some cases this protection is in the form of a fluid be transported to a filter, or they may be dropped to the bot-
film that keeps opposing surfaces separated. In other cases, tom of the oil reservoir.
the lubricant provides weair protection by forming a wear- The diversity of function of automotive c o m p o n e n t s
resistant fllm on a surface, to generate boundary lubrication strongly influences the characteristics of the lubricant re-
protection. quired for use with the component. That is, different vehicle
During exposure of a lubricant to high temperature in the components require different lubricant base stocks, fluid vis-
presence of oxygen, there is a risk that the lubricant will re- cosities, and type and quantity of additive treatment for the
act with the oxygen to form organic acids, which can be cor- component to function properly. Thus, a variety of special-
rosive and can cause varnish to form on engine components. ized lubricants are required for automotive applications.
Automotive lubricants eire protected against this oxidation by Engine oil must remain effective despite the fact that fuel
virtue of antioxidant additives, which are sacrificial agents and combustion products can condense in the oil under con-
that react with oxygen and thus reduce the probability of oxy- ditions such as short trips and cold starts in a winter climate,
gen attacking the oil's base stock. during which fuel and water may accumulate in engine oil at
In addition, alkaline additives (detergents) in the oil neu- concentrations greater than five percent [1,2]. During high
tralize acids that may be formed. Detergents are chemicals temperature operation, engine oil must not evaporate or de-
consisting of a hydrocarbon tail and a polar head, such that grade excessively. Transmission fluid must withstand high
the polar head will be attracted to the products of oil oxida- temperatures and loads. Various types of bearings require
tion and nitration and will inhibit the formation of varnish or the presence of a fluid film that separates a rotating shaft
deposits, which otherwise could build u p on engine surfaces. from its opposing bcciring surface. Brake fluid must continue
to provide appropriate braking force, even if the vehicle
' Materials Engineer, General Motors Powertrain, 3003 Van Dyke drives through pouring rain or encounters puddles or slush
Ave., Warren, MI 48090-9060. on the road.
^ Senior Staff Research Engineer and Principal Research Engineer,
respectively. Chemical and Environmental Sciences Laboratory, During high load, high temperature conditions, such as the
General Motors Research and Development and Planning, 30500 those experienced by piston rings at the top of the cylinder
Mound Road, Warren, MI 48090-9055. under the influence of the burning fuel, fluid film lubrication
465
may not be sufficient to provide complete wear protection. In are formed by combining small hydrocarbon building blocks
such cases, the lubricant must contain additives that interact to form longer chains of a desired composition that tends to
with r u b b i n g surfaces to form chemical anti-wear films. be more resistant to chemiccd attack than is the case for oils
These protective chemical films form on hot iron surfaces produced by a refining process.
during vehicle operation as long as the lubricant has not de- Additives are blended into a base stock to provide desirable
graded excessively. However, these chemical films may be properties such as optimum friction characteristics for the
partially removed during severe engine service [3]. Once the desired application, anti-wear and antioxidant capability, de-
additives that provide this chemical film (typically, zinc di- foaming capability, and corrosion inhibition. The chemical
alkyl dithiophosphate, ZDP, and other anti-wear agents) are nature of the additives for a given application are chosen on
sufficiently degraded during use, the engine oil needs to be the basis of their ability to perform their desired function,
changed; otherwise engine wear can accelerate. withstand the conditions u n d e r which they must operate,
In addition to providing a fluid film and a chemical surface and be compatible with the base stock in which they are used.
film, automotive lubricants must also inhibit corrosion. For
example, partially burned fuel can be acidic, and these fuel- Test M e t h o d s for Automotive Lubricants
derived acids can condense in engine oil, especially during
very short trips in exceedingly cold weather. An example of A variety of tests are needed to guarantee that a given auto-
this effect is shown later in this chapter in the section on test motive lubricant performs as it should. These tests include:
methods for automotive lubricants. Engine oil itself, when • Engine and component tests that mimic different driving
exposed to hot spots in the presence of oxygen, can also form or operating styles under a variety of test conditions,
acids (due to oil oxidation) that promote varnish formation • Physical and chemical properties of the lubricant,
and engine corrosion, especially if the oil's alkaline anti- • Corrosivity of a used lubricant,
corrosion additives have been degraded as a consequence of • Wear protection provided by the lubricant,
extended use without an oil change. • Remaining effectiveness of the lubricant's additive package.
A lubricant typically reduces friction, but in some cases an Additional desired information with regard to lubricant
automotive lubricant is designed to provide a desired amount characterization includes: tendency to form deposits, rate
of friction, as is the case for proper clutch engagement in au- and extent of oil oxidation, fuel efficiency, and emission sys-
tomatic transmissions. A desired amount of traction may be tem protection, including limits on phosphorus in engine oil,
needed, as is the case for traction fluid in a continuously since phosphorus can adversely affect the performance of the
variable transmission. Traction fluids have a chemical struc- catalyst that reduces automotive emissions [6-9].
ture that, under stress, forms a three-dimensional network For some lubrication functions, standard test methods are
that resists flow [4,5]. available to ensure that the various products in the market-
The lubricant associated with air conditioning fluid must place provide the desired protection. For other lubrication
be sufficiently compatible with the air conditioning medium functions, there are no standard tests, but a vehicle manu-
that the air conditioning fluid can transport the lubricant to facturer may require that the lubricant of choice must pass
the wearing surfaces. In addition, the mixture of lubricant the memufacturer's (or some other) designated tests.
and air-conditioning fluid must have sufficient lubricating Each different type of automotive lubricant has its own
properties to protect the air-conditioning p u m p , b u t the unique test methods that address the issues relevant to the
fluid/lubricant combination must not become aggressive to service needs of that particular lubricant. For example, en-
hoses or to other materials in the air-conditioning system. gine tests are used to determine whether a new candidate
These examples illustrate the complexity of the issues that engine oil formulation meets current certification require-
must be addressed when attempting to provide adequate au- ments. These certification requirements must be passed be-
tomotive lubrication. In some cases, standard test methods fore an oil container is allowed to show the "starburst" label
document whether a lubricant provides appropriate protec- that indicates the oil is acceptable for use in current vehicles.
tion to the hardware. In other cases, vehicle, component, or Bench tests can often be used to indicate whether certain
lubricant manufacturers designate the lubricant that, in their fundamental lubricant properties are within a desired range
estimation, best fits a given application. (for example, tests for viscosity, pour point, volatility, shear
stability, wear rate, wear depth, etc.). Chemical and physical
tests measure the composition and properties of a lubricant,
COMPOSITION OF AUTOMOTIVE the changes that occur as the lubricant ages, and the charac-
LUBRICANTS teristics of any contaminants or wear debris that may have
entered the lubricant.
In general, automotive lubricants consist of a base stock and The following sections describe issues relative to various
various additives. The choice of base stock depends on the types of automotive lubricants and test methods that have
function of the lubricant. In the case of engine oil, various been developed to address those issues. As is t5?pically the
types of organic oils may be used: paraffinic, naphthenic, and case, older test methods are periodically upgraded, and new
synthetic. Paraffinic hydrocarbons consist of hydrogen and methods are developed. Thus, some of the tests described in
carbon atoms that are chemically bonded together in the any given list of standard methods may be out of date. An ex-
form of branched chains. Naphthenic hydrocarbons contain ample of this evolutionary process is seen with regard to a low-
carbon atoms that are bonded together in the form of rings. temperature engine test, ASTM D 5844, Test Method for Eval-
Paraffinic and naphthenic hydrocarbons are typically de- uation of Automotive Engine Oils for Inhibition of Rusting
rived by refining oil from oil wells. Synthetic hydrocarbons (ASTM Sequence IID). This engine test has recently been re-
CHAPTER 17: AUTOMOTIVE LUBRICANTS 467
placed by a bench test, ASTM D 6557, Standard Test Method was dissolved in 1999, it was replaced by a new organization—
for Evaluation of Rust Preventive Characteristics of Automo- the Alliance of Automobile Manufacturers (the Alliance),
tive Engine Oils, also known as the "BEJI Rust Test." During which includes the former members of AAMA plus six other
the creation of the Ball Rust Test, extensive testing was con- manufacturers. The Alliance, however, is not actively involved
ducted to identify appropriate chemiccJ reagents and test con- in development of automotive lubricant standards.
ditions to ensure that the bench test would provide the same An early attempt at classifying engine oils was initiated in
useful information as was gleaned from the engine test. 1911, when the Miscellaneous Division of the Society of Au-
tomotive Engineers (SAE) introduced Specification No. 26,
which specified that specific gravity, flash and fire points,
AUTOMOTIVE E N G I N E OILS carbon residue, and viscosity (resistance to flow at a given
temperature) should be used to describe oil properties. In
Introduction 1923 the specification was expanded to include specific
Identifying appropriate test methods for engine oils repre- ranges for the various measured properties of the engine oils.
sents one of the most difficult challenges facing automobile The designation of engine oils on the basis of performance
and lubricant manufacturers. The reason for the difficulty is began in 1947. API (American Petroleum Institute) adopted a
not because of any inherent characteristic of engine oil. The classification system based on the intended use of the oil.
challenges in the development of test methods for engine oil Three types of oil were defined: Regulcir (termed ML), Pre-
arise because the environment in which engine oils must op- m i u m (MM), and Heavy Duty (MS). The performance cate-
erate can be exceedingly harsh and difficult to control. Com- gories for gasoline engine oils (ML, MM, and MS) imply mo-
bustion gases, fuel and water in the oil, and outside contam- tor oil ("M" in the designation) suitable for light (L in the
inants (dirt, sand, other airborne materials) accelerate oil designation), moderate (second M in the designation), and
degradation, cause unique filtration problems, and result in severe (S in the designation) service. Regular oils generally
m u c h shorter change intervals compared to other typical au- were straight mineral oils. Premium oils contained some ox-
tomotive lubricants. Engine oil properties and composition idation inhibitor (but no other performance additives), and
also affect vehicle fuel economy (as is the case for transmis- Heavy Duty oils were blended with oxidation inhibitors and
sion fluids and rear axle lubricants). Engine oil influences detergents/dispersants. This system was modified in 1952 to
vehicle emissions as a consequence of emission system con- create different performance requirements for diesel oils
tamination and catalyst poisoning. Engine oil can escape than those for gasoline engine oils and to rank the severity of
from the engine via mist exiting the exhaust system. In addi- the service.
tion, small amounts of engine oil or oil mist can b u m when Performance categories for diesel engine oils were DL, DM,
exposed to a flame front, which can create particulate emis- and DS, where D stands for diesel, and M, L, and S are the
sions containing charred hydrocarbons and degraded oil ad- same as for gasoline engine-oil categories.
ditives. Even though these designations (ML, MM, MS, DL, DM,
It is for these reasons that engine oil is the focus of much and DS) indicated the quality of the engine oil, many vehicle
attention in the technical literature as well as in the standard and engine manufacturers found it necessary to add addi-
test-development arena. The following sections describe tional performance requirements to ensure adequate pro-
standard test methods for evaluating engine oil performance tection for their engines. This led to the development of lu-
(including both engine and bench tests) and the terminology bricants tailored to a given manufacturer, and complicated
used to describe engine oil performance, from both historical the manner in which engine manufacturers informed their
and current perspectives. The discussions are limited pri- customers which oils were currently recommended. Finally,
marily to performance designations a n d associated test in 1969 three organizations, API (American Petroleum Insti-
methods commonly used in North America. Oils described by tute), ASTM (was American Society for Testing and Materi-
other means and defined by different test methods are used als, now called ASTM International), and SAE (Society of
in various other areas of the world, for example Europe and Automotive Engineers, now called SAE International), coop-
Japan. However, these international test methods are not ad- erated to establish a performance designation system, which
dressed in detail in this chapter. is still being used. In this system, two series of engine oil
performance and service categories were established. The "S"
series, in which S designates service, is used with gasoline-fu-
E n g i n e Oil P e r f o r m a n c e S t a n d a r d s - - P a s t eled, 4-stroke-cycle, spark ignition engines. The "C" series de-
and Present notes commercial, intended for use in compression-ignition
Over the years, many organizations have contributed to the diesel engines, both 2-stroke-cycle and 4-stroke-cycle).
development of engine oil performance standards. Among Table 1 shows the evolution of light-duty gasoline engine
these organizations are ASTM International (ASTM), the oil performance designations. The "~" symbol means that
American Petroleum Institute (API), the Engine Manufactur- the terminology for API SA and API SB oils was created after
ers Association (EMA), the Coordinating European Council those oils were no longer considered adequate for current ve-
(CEC), the Japan Automobile Manufacturers Association hicles. A similar evolution occurred for heavy-duty diesel en-
(JAMA), and the International Lubricant Standardization and gine oil performance. A detailed description of the history of
Approval Committee (ILSAC). ILSAC includes automotive both gasoline and diesel engine oil performance categories
and engine builders JAMA, EMA, and the former American can be found in SAE (Society of Automotive Engineers)
Automobile Manufacturers Association (AAMA, whose mem- Standard J183, "Engine Oil Performance and Engine Service
bers were General Motors, Ford, and Chrysler). When AAMA Classification."
TABLE 1—Historical evolution of engine oil performance designations.

Performance Designation Period of Use
ML, MM, MS ~1950s and later
API SA (designation created after this oil was already obsolete) -1900-1930
API SB (designation created after this oil was already obsolete) -1931-1964
APISC 1964-1967
APISD 1968-1971
APISE 1972-1979
APISF 1980-1988
APISG 1988-1992
API SH / ILSAC GF-1 1993-1996
API SJ / ILSAC GF-2 1996-2001
API SL / ILSAC GF-3 2001 and beyond
The API SA through API SD designations Hsted in Table 1 Motors, Ford, and DaimlerChrysler) retained membership in
were adopted in 1971 to describe oils that had been available ILSAC when AAMA was dissolved.
previously. API Category SA was adopted to describe oils gen- The first ILSAC engine oil standard (ILSAC GF-1, where
erally available in North America between 1900 and 1930. GF stands for gasoline-fueled engines) was published in
These oils contained no performance additives. Such oils had 1993, as indicated in Table 1. ILSAC standards apply only to
previously been designated as "Regular" or "ML." API SA and certain viscosity grades, namely SAE OW-XX, 5W-XX, and
SB oils can still be found in some retail establishments, lOW-XX viscosity grades, in which "XX" represents a viscos-
where a n uninformed customer (who may need to add make- ity designation such as 20, 30, 40, etc. ILSAC standards also
u p oil) may purchase an SA oil that is sadly deficient with re- include m i n i m u m levels of fuel economy performance and
gard to engine protection. contain other requirements (most notably a maximum phos-
API Category SB was adopted to describe oils for gasoline- phorus level) to address emission system compatibility and
fueled engines that were generally available in North Amer- other issues. Even though API (American Petroleum Insti-
ica between 1931 and 1963. These oils were comparable in tute) engine-oil categories apply to all viscosity grades and do
performance to oils known as "Premium" or "MM" prior to not include fuel economy requirements, an ILSAC GF-1 oil is
1971. They contained a minimal level of performance addi- roughly equivalent to an API SH quality oil, but in addition
tives. API Category SC described oils typically available be- the GF-1 engine oil also meets requirements allowing the GF-
tween 1964 and 1967 in North America. These oils were prob- 1 oil to be classified as energy conserving. The ILSAC GF-2
ably the first oils to contain a full range of performance standard for engine oils is roughly equivalent to API SJ, but
additives. They had been designated "MS" prior to 1971. API also includes fuel economy requirements. The ILSAC GF-3
Category SD described oils of the performance level generally standard is similar to API SL, but again, GF-3 oils must sat-
available in 1971. Although these oils were also described as isfy fuel economy requirements, which GF-2 and API SL-
"MS" prior to 1971, they generally contained a higher addi- quality engine oils are not required to meet. A well-stocked
tive treatment level than API SC oils. automotive supply store may have a dozen different brands
API "S" categories (API SE through API SL) were developed of engine oil, many choices of viscosity grades, and several
as needs arose for greater engine protection. API SE oils ad- choices of oil quality from which a customer may select the
dressed high-temperature engine oil thickening problems in oil of his choice.
the field. API SF oils addressed customer concerns related to The ML, MM, a n d MS Categories, as well as API SA
engine wear. API SG oils addressed oxidation and sludge for- through API SG, have been declared technically obsolete by
mation concerns that had arisen in the field. Throughout this SAE (Society of Automotive Engineers). This was done be-
period (1972-1992), automotive engines had undergone cause many of the engine tests necessary to demonstrate that
tremendous changes to accommodate increasingly more strin- oils meet the performance requirements of these categories
gent emission control requirements, both nationwide and in cannot be conducted, since reference fuels, reference oils,
California beginning in 1972, and U.S. Corporate Average Fuel and engine parts for these tests are no longer available. In ad-
Economy (CAFE) requirements originating in 1978. dition, oils with recent designations (API SH, SJ, and SL) can
The desire of vehicle manufacturers to specify oils which be used in applications for which earlier oil designations (SA
might help them address these requirements, as well as their through SG, which are now considered technically obsolete)
desire to have a greater voice in establishing engine oil per- were required. API SH, while not technically obsolete, is gen-
formance specifications, led to the formation of ILSAC (In- erally not used except in combination with a "C" Category, to
ternational Lubricant Standardization and Approval Com- describe oils intended for mixed fleet (that is, diesel and gaso-
mittee) in 1987. Originally a u n i o n between the Motor line) service. In such cases, the "C" Category designation usu-
Vehicle Manufacturers Association (MVMA) and the Japan ally precedes the "SH" designation on a label.
Automobile Manufacturers Association (JAMA) for the pur-
pose of establishing lubricant standards, ILSAC expanded to
include the Engine Manufacturers Association (EMA). E n g i n e Oil P e r f o r m a n c e T e s t s
MVMA later became the American Automobile Manufactur- Beginning with oils designated as API SB, all of the oil per-
ers Association (AAMA), and subsequently became the Al- formance categories described in Table 1 were or are defined
liance of Automobile Manufacturers (the Alliance) in 1999. by a series of engine dynamometer performance tests (usu-
However, only the original three members of AAMA (General ally termed engine sequence tests) and bench tests. The com-
plete description of each of these performance categories • The temperatures and loads of the test should be appropri-
(both the current categories and those declared technically ate for the tjrpe of service being emulated.
obsolete) is provided in SAE Standard J183, Engine Oil Per- For a given test method, a desired chemical environment is
formance and Engine Service Classification. Only the tests created by utilizing an appropriate fuel (including its degra-
used to define the current performance categories (API SJ dation products) and generating oil degradation products
and ILSAC GF-2) and the tests used in the categories effective that are similar to those generated in the driving style of in-
in 2001 (API SL and ILSAC GF-3) are discussed in this sec- terest. A desired materials environment is created by using
tion. Some of these tests have been developed into ASTM engine and hardware materials that are representative of the
Standard test methods, and others are in the process of being engines that the test method is designed to protect. In addi-
developed into ASTM Standards. It is not a requirement that tion, hardware should be chosen for the test such that inter-
all tests used to define a n engine performance category be
actions between hardware surfaces and chemicals used or
ASTM Standards. However, those tests that are not ASTM
generated in the tests (such as fuels, lubricants, and their
Standards are usually advanced to ASTM Standards during
degradation products) are similar to those in the real world.
the lifetime of a given category. ASTM Subcommittee D02.B0
A desired t h e r m a l environment m e a n s that test tempera-
on Automotive Lubricants maintains a section devoted ex-
tures, even if they are severe, are not so severe that funda-
clusively to converting test methods developed for new lubri-
mental mechanisms of damage have changed.
cant performance categories into ASTM Standards.
Creating an appropriate test environment, but also finding
test conditions such that the test does not require an inordi-
nate a m o u n t of test time, is often difficult to achieve. An ex-
Issues Addressed in Test Method Development
ample of this difficulty is as follows. If a lubricant test
Examples of the types of questions that need to be addressed method is designed to determine the corrosive effects of fuel
to ensure that a given engine oil will protect an engine in var- degradation products on engine materials, the test must be
ious t5rpes of service are as follows: conducted at a temperature such that those corrosive fuel ox-
1. If the engine is run at high engine speed and high oil tem- idation products will not boil off, but will remain in the en-
perature, gine oil to create corrosive conditions. If a test temperature
differs significantly from operating temperatures, an investi-
• Will the engine oil thicken excessively?
gator must determine whether or not any apparent correla-
• Will there be sufficient wear protection?
tion is accidental. In addition, leaded fuel tjrpically contains
• Will harmful deposits form?
chlorine and bromine compounds that can contribute to en-
2. If the engine is driven in city service, will the oil provide gine corrosion. If leaded fuel is used in an engine test that
sufficient sludge protection? simulates a given type of vehicle operation, but current vehi-
3. If the engine is driven in extreme short trips in a winter cli- cle operation uses unleaded fuel, one m u s t determine
mate, will the oil provide adequate corrosion protection whether any correlations observed between the leaded-fuel
when water, fuel, and fuel oxidation products condense in test and actual vehicle operation are real or accidental. That
the engine oil? is, the investigator must determine whether the chemical en-
Each numbered item in the previous paragraph represents vironment in the engine test simulates an accelerated version
a different driving style: high temperature high-load, city ser- of reality. Such correlation is often difficult to prove.
vice with oil fully warm, and extreme short trip service in Thus, chemical, thermal, and materials properties all in-
which the engine oil never warms completely. Each of these fluence the outcome of a test, and it is important to ensure
driving styles is associated with a specific ASTM standard that these properties, as utilized in a given test, are providing
test method to ensure that an engine oil provides sufficient a realistic representation of actual operating conditions. In
protection for that particular type of service. An engine oil addition, when bench tests are used in place of engine tests to
must pass all of these tests before its manufacturer is allowed measure a given performance parameter, great care must be
to display a label indicating that the oil meets current speci- taken to ensure correlation between the bench test and en-
fications. Freeway driving (an additional driving style) is con- gine effects.
sidered to be mild on engine oil and is not represented in a
standard test, since it is assumed that the tests representing
the other driving styles are sufficient to characterize lubri- Gasoline Engine-Oil Performance Categories and
cant properties. Associated ASTM Standard Test M e t h o d s
A test method must mimic the oil degradation and engine As of the year 2001, only four designations were widely used
damage that occurs as a consequence of a given style of driv- to describe gasoline engine oil performance: API SJ and SL,
ing. That is, a test must exhibit the same fundamental mech- and ILSAC GF-2 and GF-3. As stated previously, the engine
anisms that occur during real-world operating conditions. A test and bench test performance requirements for API SJ and
given engine test environment must be related to real-world ILSAC GF-2 are similar with regard to engine test methods,
driving conditions in at least three ways: but in addition ILSAC GF-2 oils must meet the stricter En-
• The chemical changes that talce place in the test should be ergy Conserving fuel efficiency requirements. Similarly, API
comparable to those that occur in real-world driving. SL requirements as well as Energy Conserving requirements
• The materials used in the test (for example, engine, piston must be passed before an engine oil can be designated as
rings, seals, bearing materials) should not create an envi- ILSAC GF-3.
ronment that might cause a test to provide misleading in- The appropriate test methods for engine oils must be con-
formation. ducted in accordance with the requirements outlined in the
American Chemistry Council (ACC) Product Approval Code in the CRC L-38 Spark-Ignition Engine. This test evaluates
of Practice. These requirements include test registration of bearing weight loss and oil deterioration under high-temper-
all tests and use of only calibrated equipment and facilities. ature, high-load service conditions. According to Section 1.4
These requirements were implemented when API SH and IL- of the test method, "correlation of test results with those ob-
SAC GF-1 designations for engine oil were adopted in 1993. tained in automotive service has not been established."
Test operating conditions include an engine speed of 3150
revolutions per min, fuel flow of 2.15 kg/hour, and gallery oil
ILSAC GF-2 A N D API SJ STANDARD TESTS temperature of 143.5°C for SAE 20, 30, 40, 50, and multi-
grade oils. There is a 4-hour run-in period and a half-hour
H i g h T e m p e r a t u r e Oil O x i d a t i o n a n d E n g i n e flush at the start of the test, followed by four 10-hour test seg-
Wear, ASTM S e q u e n c e HIE ments. Any fuel that has entered the engine oil during the test
is stripped (removed) before viscosity is determined. Strip-
During high speed, high load service, an engine oil becomes ping is accomplished by heating the oil at 120°C under vac-
very hot. Engine deposits may form. The oil's viscosity may u u m in a nitrogen a t m o s p h e r e for 1 h after the oil has
increase excessively as a consequence of any or all of the fol- warmed to the test temperature. ASTM D 445, Standard Test
lowing: evaporation of the lighter ends of the oil, base stock Method for Kinematic Viscosity of Transparent and Opaque
polymerization, oxidation, and nitration of the oil. In addi- Liquids (the Calculation of Dynamic Viscosity), is used to
tion, engine c o m p o n e n t s m a y exhibit unacceptable wear. evaluate the viscosity stability of multiviscosity oils such as
These issues are addressed in ASTM D 5533, Standard Test SAE lOW-40.
Method for Evaluation of Automotive Engine Oils in the
Sequence HIE Spark-Ignition Engine. In this test a 3.8L V-6 The change in acidity of the engine oil is determined, since
engine and a specified fuel are used, test preparation and op- oil acidity increase is a measure of oil degradation. Acidity
eration are described in great detail, engine components are may be evaluated either by ASTM D 974, S t a n d a r d Test
measured before and after a test, and oil samples are taken Method for Acid and Base N u m b e r by Color-Indicator Titra-
every 8 h and checked for viscosity increase. After a break-in tion, or by ASTM D 664, S t a n d a r d Test Method for Acid
period, the test is conducted for 64 h at an engine speed of Number of Petroleum Products by Potentiometric Titration.
3000 revolutions per m i n and an oil temperature of 149°C. The extent of varnish a n d sludge deposits is determined.
Additional operating parameters are also specified. At the Weight loss of copper-lead bearings is determined. Bearing
end of the test, oil properties and engine components are weight loss should be no greater than 40 mg. Additional spec-
rated for viscosity increase, sludge, varnish, deposits, lifter ifications are listed in the test method. ASTM D 974 indicates
sticking, scuffing, ring sticking, and wear. that "the method does not measure an absolute acidic or ba-
sic property that can be used to predict performance of an oil
Terminology used in ASTM D 5533 is defined in ASTM D under service conditions. No general relationship between
4175, Standard Terminology Relating to Petroleum, Petroleum bearing corrosion and acid or base n u m b e r s is known."
Products, and Lubricants, in which the standard's test number ASTM D 664 indicates approximately the same thing.
and ASTM committee associated with the test are also listed.
Limiting values for this and other tests are provided in
ASTM D 4485, Standard Specification for Performance of City Service Engine Sludge and Valve Train Wear,
Engine Oils. For SJ quality engine oil, limiting values indi- ASTM Sequence VE
cate that kinematic viscosity increase at 40°C should not be The Sequence VE test, ASTM D 5302, is titled Standard Test
more than 375% after 64 h of testing. There should be n o Method for Evaluation of Automotive Engine Oils for Inhibi-
stuck lifters and no oil-related ring sticking. There should be tion of Deposit Formation a n d Wear in a Spark-Ignition
n o c a m or lifter scuffing. Combined cam plus lifter wear Internal Combustion Engine Fueled with Gasoline and Oper-
should average less than 30 fim, with a maximum of no more ated Under Low-Temperature, Light-Duty Conditions. The
than 64 |xm. Engine sludge is rated according to CRC (Coor- purpose of the test is to ensure that a given engine oil protects
dinating Research Council) Sludge Rating Manual No. 12. an engine under city driving conditions.
Piston skirt varnish and oil ring land deposits are rated by The test is r u n in three stages. Stage 1 lasts for 120 min at
comparing the engine components to CRC Varnish Rating an engine speed of 2500 revolutions per min. The engine load
Manual No. 14. These merit rating measurements should be is listed as 33.5 brake horsepower, at an engine oil inlet tem-
higher t h a n a specified limiting value. perature of 155°F (note that English units are listed. 155°F is
In addition, a homogeneity and miscibility test. Federal 68.3°C and 33.5 brake horsepower is 25 kW). Stage 2 lasts 75
Test Method Standard No. 79IC, Method 3470, is used to de- m i n at 2500 revolutions per m i n at an oil temperature of
termine whether an engine oil is compatible with standard 210°F (98.9''C) and an engine load of 33.5 brake horsepower
test oils. This test ensures that if a vehicle owner adds a liter (25 kW). Stage 3 lasts 45 min at an engine speed of 750 revo-
(quart) of make-up oil to a different oil that is already in the lutions per min, a load of 1.0 brake horsepower (0.746 kW),
oil pan, n o adverse effects will occur, assuming both oils and an engine oil inlet temperature of 115°F (46.1°C). Sev-
meet current specifications. enty two repetitions of this four-hour test cycle are con-
ducted, to provide a total of 288 h of test time. The fuel used
High Temperature Copper-Lead Bearing Wear, is Phillips J unleaded gasoline. Rocker arm cover, valve deck,
CRC L-38 cylinder block, camshaft baffle, front seal housing, and the
An additional high temperature engine test method is ASTM oil pan are rated for sludge using CRC No. 12, Sludge Rating
D 5119, Standard Test Method for Evaluation of Engine Oils Manual. Varnish on the piston skirt is rated using CRC Man-
ual No. 14. Parts other than piston skirts are rated by com- Engine Oil Volatility
paring the engine parts to color chips. Piston undercrown de-
Engine oil volatility (evaporation loss) has been correlated to
posits axid ring land deposits Etre EJSO evaluated.
engine oil consumption [10-12]. In ein effort to limit oil con-
The extent of clogging of vEirious components is rated: oil sumption, reduce its effects on emission systems, and im-
screen, oil ring, PCV (positive crankcase ventilation) valve, prove customer satisfaction, volatility limits are incorporated
and camshaft lobe orifice clogging. Oil screen clogging in both API SJ and ILSAC GF-2 categories. Volatility can be
should be n o greater than 20%. The n u m b e r of stuck rings measured by ASTM D 5800 (Noack Volatility method) or by
and hydraulic lifter plungers is recorded. There should be no ASTM D 5480 or ASTM D 6417. Both of these are gas chro-
hot-stuck compression rings. Various wear measurements matography methods in which the temperature of a sample
are tciken, including: camshaft lobes, rocker arm, connecting of fluid is raised, the various components that Eire pEirt of the
rod bearing, and cylinder bore. Piston ring gap increase is fluid mixture boil off, and the composition of the compo-
also used as a measure of wear. Average cam wear should be nents that have volatilized off is determined.
no greater than 127 /xm. Maximum cam wear should be no
greater t h a n 380 /am. The following oil analyses are con-
Foaming Tendency
ducted: iron, copper, and silicon in engine oil, kinematic
viscosity (ASTM D 445), and pentane insolubles in oil (ASTM Oils that foam excessively can cause valve lifters in engines to
D 893 B). collapse and oil pumps to lose pressure. Test methods ASTM
D 892 (foaming characteristics) and ASTM D 6082 (high-
Short-Trip-Service Engine Rusting, ASTM Sequence IID temperature foaming characteristics) measure the tendency
of an oil to foam and the stability of any foam created. In
ASTM D 5844, Standard Test Method for Evaluation of Au- ASTM D 892 a lubricant at 24°C is blown with air for 5 min,
tomotive Engine Oils for Inhibition of Rusting, is an engine then allowed to settle for 10 min. The volume of foam is mea-
test conducted with a 1977 5.7L Oldsmobile engine. The test sured at both the five-min point and the ten-min point. A sec-
uses leaded gasoline, and a warning message is provided that ond fluid sample is measured at 93.5''C, and again, after col-
indicates "The method may not be applicable for the evalua- lapsing the foam, at 24°C.
tion of engine oils if unleaded gasoline is used." In Stage I (28
h) the engine speed is 1500 revolutions per min, engine load In ASTM D 6082, foam is generated with a diffuser. "Cor-
is 25 brake horsepower (18.6 kilowatts) at an oil temperature relation between the amount of foam created or the time for
of 120°F (48.9 °C) in the filter block. In Stage II (2 h) coolant foam to collapse, or both, and actual lubrication failure has
temperature is increased. In Stage III (2 h) the engine speed not been established."
is 3600 revolutions per min, engine load is 100 brake horse-
power (74.6 kW), and the oil temperature is 260°F (126.7°C). Phosphorus Content
Additional operating parameters are listed in the test proce- Phosphorus in engine oil has been shown in numerous stud-
dure. Various engine c o m p o n e n t s are evaluated for such ies [6-8] to be related to poisoning of catalytic converters and
measurements as rust formation on valve lifter bodies, valve other emissions system components. For this reason, phos-
lifter plungers, valve lifter balls, oil p u m p relief veJve, and phorus content of ILSAC GF-2 and certain viscosity grades of
pushrods. Lifter plunger sticking, oil p u m p relief valve stick- API SJ oils must remain below a designated value. Phospho-
ing, and oil consumption are also measured. rus content is measured either by ASTM D 4951, Standard
Test Method for Determination of Additive Elements in Lu-
Energy Conserving Characteristics, bricating Oils by Inductively Coupled Plasma Atomic Emis-
ASTM Sequence VIA sion Spectrometry or by ASTM D 5185, S t a n d a r d Test
Method for Determination of Additive Elements, Wear Met-
In addition to the engine performance r e q u i r e m e n t s deals, and Contaminants in Used Lubricating Oils and Deter-
scribed above, ILSAC GF-2 oils must meet fuel efficiency re- mination of Selected Elements in Base Oils by Inductively
quirements according to the test procedure described in Coupled Plasma Atomic Emission Spectrometry.
ASTM Standard D 6202 (Sequence VIA). In this engine dy-
namometer test, the fuel consumption associated with a test
oil is measured and compared to the fuel consumption when Additional Requirements
using a standard reference oil. For the test oil to be called
"Energy Conserving," it must exceed the fuel efficiency of the Several additional requirements must be satisfied before an
reference oil by a given percentage, based on its SAE viscos- oil can claim to be either ILSAC GF-2 or API SJ. These re-
ity grade. The m i n i m u m percent improvement for ILSAC GF- quirements include:
2 oils is 1.4% for SAE OW-20 and 5W-20 viscosity grades, • Flash Point either by ASTM D 93, Standard Test Methods
1.1% for other OW and 5W multiviscosity grades, and 0.5% for Flash-Point by Penske-Martens Closed Cup Tester, min-
for SAE l o w multiviscosity and all other viscosity grades. imum flash point of 200°C or by ASTM D 92, Standard Test
API SJ oils are not required to meet fuel efficiency require- Method for Flash and Fire Points by Cleveland Open Cup,
ments, although oils satisfying the above Sequence VIA re- m i n i m u m flash point of 185°C,
quirements can be designated as "Energy Conserving" in the • Gelation Index (a measure of low-temperature oil gelling
bottom half of the API (American Petroleum Institute) ser- tendency) by ASTM D 5133, Standard Test Method for Low
vice symbol, which appears on many oil containers. Ameri- Temperature, Low Shear Rate, Viscosity/Temperature
can Petroleum Institute publication API 1509 provides infor- Dependence of Lubricating Oils Using a Temperature-
mation on this subject. Scanning Technique,
• TEOST-33 (Thermo-Oxidation Engine Oil Simulation Test, gine oil (the same groupings of viscosity grade as were de-
protocol 33, a deposit control test, with a maximum defined in the ILSAC GF-2 requirements for the Sequence VIA
posit weight of 60 mg), Test, as described previously). Sequence VIB fuel efficiency
• Homogeneity and Miscibility by Federal Test Method 791c requirements apply only to ILSAC GF-3 oils, not to API SL
(Method 3470.1), oils, although oils satisfying the Sequence VIB requirements
• Engine Oil Filterability and Water Tolerance as deter- for GF-2 can use the "Energy Conserving" label of the bottom
mined by the Engine Oil Filterability Test (EOFT) half of the API service symbol, as was previously mentioned
• Engine Oil Water Tolerance Test (EOWTT). under the topic "Energy Conserving Characteristics," Se-
As of the year 2001, the latter two tests are in the process of quence VIA.
being elevated to ASTM standards by ASTM Subcommittee
D02.06 (Analysis of Lubricants). Bench and Other Test Requirements
Most of the same bench and chemical property requirements
ILSAC GF-3 and API SL Standard Tests that exist for ILSAC GF-2 and API SJ categories also exist for
The five new engine performance tests that define ILSAC GF- ILSAC GF-3 and API SL (although in some cases the limits
3 and API SL categories, at the time of this writing, are in the associated with the tests for ILSAC GF-3 and API SL are dif-
ferent from those required for ILSAC GF-2 and API SJ).
process of being advanced to ASTM Standards by ASTM
These requirements include:
D02.B0 Committee on Automotive Lubricants. These engine
tests include the following. • Volatility loss as determined either by ASTM D 5800 or by
ASTM D 6417,
Sequence IIIF • Filterability criteria as measured by the Engine Oil Filter-
The Sequence IIIF Test replaces the Sequence HIE Test ability Test and the Engine Oil Water Tolerance Test,
(ASTM D 5533) and measures high-temperature engine oil • Foaming tendency by ASTM D 892 and D 6082,
thickening and piston deposits. It also provides information • Homogeneity and Miscibility by Federal Test Method 791c,
on camshaft and valve lifter wear. Method 3470.1,
• Gelation Index by ASTM D 5133, and
Sequence VG • Maximum phosphorus content as measured either by
The Sequence VG Test is a partial replacement for the Se- ASTM D 4951 or by ASTM D 5185.
quence VE Test (ASTM D 5302). Sequence VG measures the There are, however, two new bench test requirements for
sludge and deposit control tendency of engine oils under en- ILSAC GF-3 and API SL oils: the Ball Rust Test and the
gine conditions which simulate stop-and-go city service in ve- TEOST MHT-4 test.
hicles.
Ball Rust Test
SequenceIVA ASTM D 6557, Standard Test Method for Evaluation of Rust
Sequence IVA is also a partial replacement for the Sequence Preventive Characteristics of Automotive Engine Oils, was
VE Test (ASTM D 5302). Sequence IVA measures the ability developed to replace the Sequence IID Engine Test, which
of an oil to provide overhead cam and slider-follower wear measures the ability of an oil to prevent rust and corrosion in
protection under stop-and-go engine conditions such as are engines operating on leaded gasoline under short-trip driving
experienced in city driving. conditions. ASTM D 6557 is also known as the Ball Rust Test,
since it uses a steel ball (lifter check ball) as a test specimen
Sequence VIII that is representative of a typical ferrous engine component.
Sequence VIII replaces the CRC L-38 Test (ASTM D 5119). It A ball and a measured sample of an engine oil that is to be
measures the same parameters as the L-38 Test did: copper- evaluated are placed in a test tube. If more than one oil sam-
lead bearing weight loss under high-temperature operating ple is to be tested, additional test tubes, each containing a ball
conditions and permanent viscosity loss due to shearing. and an oil sample are prepared. The test tubes are placed in
However, the Sequence VIII Test utilizes unleaded fuel, a shaker in which shaker speed and temperature are con-
whereas the L-38 test utilizes leaded fuel. trolled. Air and a corrosive fluid are fed into the test tube to
create a corrosive environment. The corrosive fluid consists
Sequence VIB of representative samples of the type of chemicals that can be
Sequence VIB replaces the Sequence VIA Test (ASTM D generated during the combustion process in short-trip winter
6202) for measuring the fuel-efficiency properties of an driving. After 18 h, the steel test specimens (balls) are evalu-
engine oil. Like its predecessor, the Sequence VIB Test mea- ated for the extent of rusting, using a computerized scanning
sures the improvement in fuel efficiency of a test oil com- system with optical imaging. Excellent correlation between
pared to an ASTM standard reference oil. Unlike its prede- results obtained in the Ball Rust Test and Sequence IID has
cessor, however, the Sequence VIB Test not only measures been achieved with a wide variety of oil compositions. How-
the fuel efficiency of the oil when the oil is relatively new ever, the method indicates that, in comparison with the re-
(after only 16 h of aging in the engine), but also the fuel effi- sults of ASTM D 5844 (Standard Test Method for Evaluation
ciency after 96 h of aging, which corresponds to approxi- of Automotive Engine Oils for Inhibition of Rusting (Se-
mately 4000-5000 miles (6500-8000 km) of vehicle opera- quence IID), "correlation between these two test methods
tion. Different levels of fuel efficiency improvement are has been demonstrated for most, but not all, of the test oils
required, depending upon the SAE viscosity grade of the en- evaluated."
TEOSTMHT-4 include the CRC L-38 (ASTM D 5119) test, which has already
A new version of the Thermo-Oxidation Engine Oil Simula- been described, and the Detroit Diesel 6V92TA test (ASTM D
tion Test (TEOST), the MHT-4, was developed for ILSAC GF- 5862). ASTM D 5862, Standard Test Method for Evaluation
3 and API SL specifications. The TEOST MHT-4 test is in- of Engine Oils in Two-Stroke Cycle Turbo-Supercharged
Detroit Diesel 6V92TA Engine, is a two-stroke cycle diesel en-
tended to provide additional high-temperature piston deposit
gine test that measures such parameters as high-temperature
control in m o d e m engines that are designed for improved
stability of engine oil, cylinder liner scuffing, piston ring face
driveability and in addition must meet federal emissions and
distress, plugging of liner ports, and slipper bushing distress.
fuel economy requirements.
Removal of tin from the cylinder liner is also eveduated. En-
gine components are measured before and after the test to
D i e s e l E n g i n e Oil P e r f o r m a n c e C a t e g o r i e s a n d determine the extent of wear or degradation. The test is con-
Associated ASTM Standard Test M e t h o d s ducted under two different modes of operation: torque mode
and power mode. In the torque mode, engine speed is 1200
When diesel engines are operated at high temperature, the revolutions per m i n and the oil gallery temperature is 102°C.
viscosity of the engine oil can increase due to oil oxidation In the power mode, the engine speed is 2300 revolutions per
and nitration, base stock polymerization, evaporation of the min, at an oil gallery temperature of 111°C. Additional pa-
lighter ends of the oil, and accumulation of soot in the oil. As rameters are listed in the test procedure. A non-ASTM Stan-
was the case for gasoline-fueled vehicles, diesel engine oil ad- dard test requirement for this category is the Caterpillar IM-
ditives can degrade during long-term use. If the engine oil de- PC method described under the API CF category.
grades to the point at which it becomes acidic, acidic reaction
products that form on a metal surface can be scraped off by
moving components, resulting in undesirable wear. In addi- API CF-4
tion, soot accumulation can adversely affect engine wear by The API CF-4 category describes the tests that are used for
two fundamentally different mechanisms. Soot can interact high-speed service in four-stroke cycle diesel engines. The
with a n d sequester a n engine oil's antioxidant/anti-wear category includes tests that m e a s u r e bearing weight loss,
agent so that the anti-wear capability of the engine oil be- ASTM D 5119 (the L-38 test, which measures oil degradation
comes diminished [13]. Soot can also abrade away a protec- and bearing corrosion—including a mEiximum limit of 50 mg
tive anti-wear film that has formed on heavily loaded regions bearing weight loss). Piston deposits, viscosity increase, and
of an iron surface [3]. These oil-related concerns are ad- brake specific oil consumption are rated according to the
dressed using various standard tests. Mack T-6 test. Average rate of kinematic viscosity increase in
At the t i m e of this writing, there were five active API the last 50 h according to the Mack T-7 test and oil con-
(American Petroleum Institute) diesel engine oil perfor- sumption and wear in the Cummins NTC-400 test ctre also
mance categories, designated as API CF, API CF-2, API CF-4, measured. In addition, the Caterpillar IK engine test is used
API CG-4 and API CH-4. Each of these categories has at least to measure piston and ring groove deposits, piston scuffing,
two engine performance tests t h a t m u s t be conducted to ctnd oil consumption.
demonstrate compliance with category requirements. Vari-
ous bench tests are also included. A complete description of API CG-4
each of these categories, including engine and bench tests, as API CG-4 oils are intended for use in high-speed, four-stroke-
well as associated test limits for each requirement, is docu- cycle diesel engines operating in both highway and off-road
mented in ASTM D 4485, Stcindard Specification for Perfor- conditions, with fuels in which the sulfur content may VEiry
mance of Engine Oils and in SAE J183, Engine Oil Perfor- from less than 0.05% sulfur by weight to less than 0.5 weight
memce and Service Classification. It is anticipated that these % sulfur, as described in ASTM D 4485. These oils provide
five categories will be reduced to three: API CF-2, API CG-4, effective control of deposits and wear in engines designed to
and API CH-4. Thus, API CF and API CF-4 will no longer be meet 1994 exhaust emission standards. ASTM Standard tests
used. A description of each of these diesel engine-oil perfor- include the Mack T-8 engine test (ASTM D 5967), ASTM Se-
mance categories is as follows. quence HIE engine test (ASTM D 5533), CRC L-38 bearing
test (ASTM D 5119), the roller follower wear test (ASTM D
APICF 5966), and a corrosion bench test (ASTM D 5968). Foaming
API CF oils are intended for use in off-road indirect-injection tendency according to ASTM D 892 is also included. ASTM D
diesel engines using a broad range of fuel types, including 5533, ASTM D 5119, and ASTM D 892 are described previ-
those with high sulfur content. The only ASTM Standard ously in this chapter.
test in the performance definition of this category is the CRC ASTM D 5966, Standard Test Method for Evaluation of
L-38 Test (ASTM D 5119), which measures bearing weight Engine Oils for Roller Follower Wear in Light-Duty Diesel
loss a n d oil deterioration, as described previously. Non- Engine, was developed to address soot accumulation in en-
ASTM tests include the Caterpillar IM-PC test (PC stands for gine oil, which can contribute to engine wear [3,13]. This test
Pre-Chamber), which measures piston deposits and ring is conducted at 1000 revolutions per min and a m a i n oil
sticking in a single cylinder diesel engine. gallery temperature of 120°C. Roller follower shaft wear is
evaluated. Kinematic viscosity at 100°C cind soot content are
API CF-2 also monitored.
API CF-2 oils are intended for use in two-stroke-cycle en- ASTM D 5967, Standard Test Method for Evaluation of
gines, which require cylinder and ring-face scuffing resis- Diesel Engine Oils in T-8 Diesel Engine (the Mack T-8 Test),
tance and deposit control. ASTM standard test requirements eveJuates both viscosity increase and soot accumulation in
474 MANUAL i7: FUELS AND LUBRICANTS HANDBOOK
the engine oil of a Mack E7-350 diesel engine. Oil consump- United States Federal Exhaust Emissions Standards with fu-
tion is also monitored. The test is conducted at an engine els containing less than 0.05% sulfur by weight. The Cater-
speed of 1800 revolutions per min, a fuel rate of 63.3 kg/hour, pillar IK engine test measures the same performance param-
an engine oil temperature of 100-107°C, and an inlet mani- eters as the Caterpillar IP engine test, but for engines in use
fold temperature of 43.3°C. Additional test conditions are prior to 1989, using aluminum pistons and fuel that has 0.4
listed in the test procedure. The viscosity should not increase weight % sulfur. The Cummins Mil High Soot Diesel Engine
by more than 11.5 centistokes at a soot content of 3.8%. Test measures soot-related valve-train wear. Engine sludge
ASTM D 5968, Standard Test Method for Corrosiveness of and oil filter plugging tendency are measured. The Engine Oil
Diesel Engine Oil, measures the extent to which non-ferrous Aeration Test (EOAT), mentioned in the API CG-4 specifica-
metals are susceptible to corrosion as a consequence of inap- tion, is also conducted.
propriate engine oil formulation (rather than oil degradation
or contamination). Test coupons (lead, copper, tin, and phos- Additional Tests Used to Describe Engine Oil
phor bronze) are cleaned and placed in the test oil. Air is Performance and Properties
allowed to flow into the oil for 168hat 121°C. Test coupons
are evaluated for corrosion and discoloration, and the oil is The use of a bench test, if it can be shown to correlate to an
evaluated for the presence of metals that have entered the oil engine test, can be considerably less labor intensive and less
as a consequence of corrosion of the metcil samples. costly than an engine test. Bench tests for engine oil are of
Non-ASTM tests used in defining the API (American several types. Some, such as the Ball Rust Test, ASTM D 6557
Petroleum Institute) CG-4 specification include the Caterpil- (described previously), produce fundamental information
lar IN engine test, which measures piston deposits in a four- about a specific aspect of the protection provided by an en-
stroke-cycle, direct injection diesel engine operating on fuel gine oil. Other bench tests measure various properties of the
containing less than 0.05 percent sulfur by weight. API CG-4 engine oil such as viscosity, alkalinity, acidity, extent of oil
also includes the Engine Oil Aeration Test (EOAT), which has oxidation, presence of oil additives, and the presence of oil
been correlated with oil aeration in diesel engines equipped contaminants such as engine-wear debris or corrosion prod-
with hydraulically actuated, electronically controlled unit in- ucts. Many of these bench tests are included as part of the
jectors. specified analysis procedure for an engine test. In other
words, a bench test often provides necessary documentation
API CH-4 to evaluate the results of a dynamometer test. Various tests
that are used to ascertain the performance of automotive lu-
API CH-4 oils are intended for use in high-speed, four-stroke- bricants in general and engine oils in particular are described
cycle diesel engines designed to meet 1998 exhaust emissions in the following sections.
standards. ASTM Standard tests include CRC L-38 (ASTM D
5119, Standard Test Method for Evaluation of Automotive
Engine Oil Acidity and Alkalinity
Engine Oils in the CRC L-38 Spark-Ignition Engine), ASTM
Sequence HIE test (ASTM D 5533), Mack T-8 (ASTM D 5967), Automotive lubricants typically contain oil-soluble alkaline
and a high temperature corrosion bench test (ASTM 5968) agents that provide corrosion protection, since corrosion is
were described previously. less likely to occur in a moderately alkaline environment.
The Mack T-9 (ASTM D 6483) is described below. The tests Acids can be generated from fuel combustion or from oxida-
use diesel fuels with sulfur content up to 0.5 weight %, as de- tion of engine oil in hot spots. For example, if engine oil be-
scribed in ASTM D 4485. Foaming tendency (ASTM D 892), comes acidic as a consequence of exposure to heat or if acidic
volatility (ASTM D 5800 or ASTM D 6417), and sheared vis- combustion by-products from the fuel condense in the engine
cosity (ASTM D 6278) requirements are also included. oil during short-trip, low temperature service, engine corro-
sion may occur. If oil alkalinity is too high, a lubricant or
ASTM D 6483 (Standard Test Method for Evaluation of
other fluid may also become aggressive to a metal surface.
Diesel Engine Oils in T-9 Diesel Engines, known as the Mack
T-9 test) evaluates diesel engine oil for various performance Several techniques are available to assess oil acidity and re-
characteristics, including resistance to lead corrosion and maining alkalinity protection, for example:
wear of piston rings and cylinder liners. The test uses a Mack • ASTM D 664, Standard Test Method for Acid Number of
E7-350 V-MAC II diesel engine. The test starts with a one- Petroleum Products by Potentiometric Titration
hour break-in, followed by a two-phase test that includes 75 • ASTM D 974, Standard Test Method for Acid and Base
h at 1800 revolutions per min and 425 h at 1250 revolutions Number by Color-Indicator Titration
per min. Oil samples are taken during the testing and are an- • ASTM D 1093, Standard Test Method for Acidity of Distil-
alyzed for increase in viscosity and for weeir metals in the oil. lation Residues or Hydrocarbon Liquids
The extent of engine-component wear is also assessed. For • ASTM D 2896, Standard Test Method for Base Number of
example, the maximum allowed cylinder liner wear is an av- Petroleum Products by Potentiometric Perchloric Acid
erage value of 25.4 \xxn at a soot content of 1.75%. The maxi- Titration
mum allowed average-top-ring weight loss is 120 mg, and the • ASTM D 4739, Standard Test Method for Base Number De-
maximum allowed increase of lead content in the engine oil termination by Potentiometric Titration.
is 25 parts per million. In each of these tests, a sample of the oil or residue of in-
Non-ASTM standard tests used in defining the API CH-4 terest is titrated (that is, reacted) with the desired test
category include the following. The Caterpillar IP engine test reagent. Different reagents used in the various tests yield dif-
measures piston and ring groove deposits in four-stroke- ferent values for an acid number or base number. An investi-
cycle, direct injection diesel engines calibrated to meet 1998 gator will have to determine which test best meets his needs.
For Acid Number according to ASTM D 664, the following Corrosiveness of Diesel Engine Oil
qualification is listed: "The test method may be used to indi- ASTM D 5968, Standard Test Method for Coirosiveness of
cate relative changes that occur in an oil during oxidizing Diesel Engine Oil, was described previously, under section
conditions — The test method is not intended to measure an API CH-4.
absolute acidic property that can be used to predict perfor-
mance of an oil under service conditions. No general rela- Entry of Water into Engine Oil
tionship between bearing corrosion and acid number is In addition to condensation of acids, water can condense in
known." ASTM D 974 has a nearly identical notice. ASTM D engine oil during short-trip, winter operation. ASTM D 1744,
1093 indicates: "The results obtained by this method are Standard Test Method for Determination of Water in Liquid
qualitative expressions." Thus, an investigator would be wise Petroleum Products by Karl Fischer Reagent (Discontinued
to determine which type of analysis suits his needs. in January, 2000), has been used to determine the water con-
An example of transient engine-oil acidification due to content of engine oil. The amount of water that condenses in the
densation of partially burned fuel is shown in Figure 1 (de- engine oil during very cold short-trip operation is directly re-
rived from information available in Ref. 2), in which an oil lated to the amount of water-per-kilometer produced by a
sample was taken on a day when the outside temperature was given fuel [2]. M85 fuel (85 percent methanol plus 15 percent
-20°C. The test vehicles had been given 3-km trips three gasoline) produces approximately four times as much water-
times a day. During this interval of bitter cold, the engine oil per-kilometer as gasoline. This influence of fuel type on wa-
acidity spiked in all the vehicles that were on short-trip test ter in oil is shown in Fig. 2 (which was derived from infor-
that day. Two representative examples are shown in Fig. 1. mation available in Ref. 2). Differences in oil analysis results
The weather later warmed, so that the volatile fuel-derived due to differences in engine type and oil type are negligible in
acids that had condensed in the oil were removed. comparison to the fuel effect. With longer trips or warmer
weather, the water is removed via evaporation.
Ambient temperature
Near -20° C, 3-km trips Viscosity
Viscosity is a measure of the resistance to flow. Two types of
3.1LV-6 engine
viscosity measurements are typically used, kinematic and dy-
namic. Kinematic viscosity is measured by determining the
time required for a fluid to flow past the marks on a specicd
tube at a specified temperature, assuming that the flow is
laminar, and not turbulent. Kinematic viscosity is described
mathematically in terms of mm^/s. Dynamic viscosity is
:i=^^ equal to kinematic viscosity multiplied by the density of the
fluid of interest.
Engine oils operate most effectively when their viscosity is
100 200 300 400 500 600 within an optimum range for a given type of engine and a
Distance on oil, l(m
given set of driving conditions. Temperature influences
FIG. 1—Condensation of volatile acids into engine viscosity. Higher oil temperature causes a reduction in oil
oil (per ASTM D 664), due to partial oxidation of fuel viscosity, and lower oil temperature causes oil viscosity to
during exceedingly cold weather, and removal of the increase.
acids with warmer weather.
Ml • I ' T • 11 ' 1 '

JA N FEB MAR APR MAY
A longer trip in May

lUBSfuel- caused water to
25 evaporate from oil
65 % msthanol
+ 1 5 % gasoline
Percent water
In engine oil, 20
Karl Fischer
method ^ ^
15
Engine Fuel Oil ' <1

10
—•- 3.1L MSSfuel A
—^ 3.1L MBS fuel B
—o- 3.1L gasoline A

5
—»— 4.5L gasoline B
—"— 4.5L gasoline B

1 '
200 400 600 800 1000
Distance traveled, km
FIG. 2—Influence of type of fuel on the amount of water that can ac-
cumulate in engine oil during short-trip, cold-start driving, according to
ASTIM D 1744.
150 • 1 • 1 • '• 1 1 If the viscosity vEiries significantly with sheeu", different re-
85% methanol fuel, short trips, emulsion formation sults may be obtained from viscometers of different diame-
V
Viscosity of 1 Evaporation of water ter. ASTM D 446 gives specifications and operating instruc-
engine oil at ^ — o and methanol during
\ warm weather tions for glass kinematic viscometers.
40°C, cSt
ASTM D 4683 measures viscosity at high temperature and
100 high shear a n d carries the warning, "applicability to
petroleum products other than engine oils has not been de-
termined." Engine oil at very low temperature can become
i \ highly viscous, per ASTM D 4684 (which carries the same
warning as is found with ASTM D 4683). In ASTM D 4684, an
Gasoline fuel in engine oil,
50 short trips, solution formation engine oil is cooled from 80°C at a programmed rate to a fi-
___x_ ' ned low temperature (between -15°C and -35°C). Yield stress
and apparent viscosity are measured.
SAE 10W-30, API SG-quality engine oil

I . I . I ^ 1 ^
200 400 600 800 1000 EXTENT OF OIL OXIDATION

Distance on oii, Icm
As engine oil is used in a vehicle, the ability of the engine oil
FIG. 3—Influence of solution-forming and emulsion-forming to resist oxidation becomes diminished as a consequence of
fuel contamination on engine oil viscosity (per ASTIVI D 445). exposure to heat and to contamination from fuel and fuel re-
action products. This degradation can be monitored using test
methods such as ASTM D 5483, Standard Test Method for Ox-
In addition to the changes in viscosity due solely t o tem- idation Induction Time of Lubricating Greases by Pressure
perature effects, operation at a given high temperature will Differential Scanning Calorimetry. The test method indicates
cause the oil's viscosity to increase (in comparison to viscos- that, "This test method can be used for research and develop-
ity of the fresh oil at the same temperature) due to oil oxida- ment, quality control and specification purposes. However,
tion and to evaporation of the lighter ends of the engine oil. n o correlation has been determined between the results of this
Various low-temperature viscosity cheinges can also be ob- test method and service performance." Information found in
served. Low engine-oil temperature causes an increase in vis- tests such as those illustrated in Fig. 4 suggest a very useful
cosity. However, at low outside temperatures, hydrocarbon correlation between oil oxidation in road tests and DSC oil
fuel can condense in engine oil, which causes a decrease in analysis results as described in Refs. 14 and 15.
oil viscosity. Condensation of methanol (alcohol) fuel in en- In this method, a small cimount of lubricant is placed in a
gine oil formed an emulsion and caused a significant viscos- cup, the cup is placed in a chamber which is filled with oxy-
ity increase. An example of these opposite viscosity effects is gen and heated rapidly to the desired test temperature, and
shown in Fig. 3, which is derived from information available held at that temperature for the duration of the test. The time
in Ref. 2. from the start of the test until the onset of rapid oxidation is
Thus, fuel-in-oil measurements can provide information measured. An alternative procedure is to r a m p the tempera-
about the nature of viscosity changes and the nature of con- ture u p in a series of stages and observe the effects of elevated
taminants in the engine oil. However, these effects only occur temperature on oil oxidation.
if the engine oil remains at low temperature during short-trip
operation, otherwise once the oil t e m p e r a t u r e rises suffi-
ciently, m u c h of the fuel will evaporate from the oil, and the
oil viscosity will revert to a more typical value. 1( SAE 10W-30 engine oil, API SF quality
Standard ASTM viscosity tests include:
4I -
• ASTM D 445, Standard Test Method for Kinematic Viscos- Oxidation
• ^ % v
NS^ *
1.
ity of Transparent and Opaque Liquids (the Calculation of induction •
Djoiamic Viscosity), time by

3 . No trailer
• ASTM D 446, Standard Specifications and Operating In- differential /
scanning o\.
structions for Glass Capillary Kinematic Viscometers, calorimetry, 0 N
\ * » ^^
X
• ASTM D 4683, Standard Test Method for Measuring Vis- natural 2
cosity at High Temperature and High Shear Rate by Ta- logarithm of o \
pered Bearing Simulator, DSC NO «BP*
With trailer
• ASTM D 4684, Standard Test Method for Determination of 1 \ o VNA
Yield Stress and AppcUênt Viscosity of Engine Oils at Low
Temperature.
ASTM D 445 measures the time it takes for a liquid to flow 0 • ^-0 0^^- '
through a standard capilleiry tube. This test method has the 5000 10000 15000
Distance on oil, km
wzuning, "The result obtained from this test method is de-
pendent u p o n the behavior of the sample cind is intended for FIG. 4—Differences in loss of oxidative stability of engine oil
application to liquids for which primarily the shear stress (natural logarithm of the DSC value) as a consequence of type
and shear rates are proportional (Newtonian flow behavior)." of service, determined using ASTM D 5483.
Even though this method was developed for greases, it can resistance, wear resistance, friction characteristics, and re-
be used for other lubricants. An example is found in Figure 4, sistance to foaming. Additional tests measure performance
which shows differences in the rate of engine oil oxidation during selected duty cycles, as defined by the manufacturer.
between similar vehicles, driving over identical terrain, but For example, major automotive producers in North America
two of the vehicles were not pulling a trailer (dark circles), have their own specifications for transmission fluids. Thus,
and one of the vehicles pulled a 1000-kg trailer (open circles) in retail establishments that sell transmission fluids, one can
[14,15]. As can be seen, the constant-temperature version of see labels on transmission fluid bottles indicating "meets the
the differential scanning calorimetry technique (abbreviated specifications for XXX a n d YYY", in which XXX and YYY
as "DSC") was able to document statistically significant dif- represent the brand names of a specific automobile manu-
ferences in the chemical status of the engine oil from the ve- facturer. Transmission fluid test requirements published by a
hicle that pulled the trailer. The natural logarithm of the DSC given automobile m a n u f a c t u r e r include GM-6417M for
value was plotted. This figure indicates that oxidative stabil- Dexron®-III (General Motors) a n d Mercon®-V (Ford).
ity can be a reliable measure of severity of service. The theo- A n u m b e r of standard ASTM tests for transmission fluids
reticcil explanation for this effect is provided in Ref. 14. are listed in the SAE International Surface Vehicle Informa-
The various ASTM standard test procedures described in tion Report, SAE J311 (revised 2000-02): ASTM D 130 (Cop-
this section list a great n u m b e r of related test methods. Ref- per Strip Corrosion), ASTM D 665 (Rust Preventing Charac-
erenced Documents from these test methods are provided in teristics), ASTM D 892 (Foaming Characteristics, as
Tables 2 and 3 at the end of this chapter, so that the reader described previously in the Engine Oil section), ASTM D
will have a comprehensive list of the various tests associated 1275 (Corrosive Sulfur in ElectriccJ Insulating Oils, which is
with engine oil. not listed in the 2001 ASTM a n n u a l book of standards),
ASTM D 1748 (Rust Protection by Metal Preservatives in the
Humidity Cabinet), and ASTM D 2882 (Wear Characteristics
TRANSMISSION FLUIDS of Hydraulic Fluids in a Constant Volume Vane Pump). Ad-
ditional ASTM tests are also provided in the Annual Book of
Composition and Performance of ASTM Standards. The tests listed here are described below.
Transmission Fluids Referenced d o c u m e n t s in these transmission-related test
methods are provided in Tables 4 and 5 at the end of the
Transmission fluids lubricate a vehicle's transmission. They chapter.
may be composed of synthetic or mineral oil. S5Tithetic oil
typiccilly shows enhanced resistance to deterioration from ex-
posure to heat. However, synthetic and mineral oil both con-
High Temperature, High Load Testing
tain additives that help maintain the desired friction proper-
ties, minimize wear, and provide corrosion inhibition to the ASTM D 5579, S t a n d a r d Test Method for Evaluating the
transmission components. In addition, antioxidant additives Thermal Stability of Manual Transmission Lubriccints in a
are required to prolong the life of the transmission fluid. Cyclic Durability Test, evaluates the thermal stability of flu-
Maintaining stable friction properties is highly important, ids used in heavy duty manual transmissions during high-
since any change in shift characteristics or generation of temperature (121°C) operation. This test measures the num-
shudder (objectionable vibration) after prolonged or severe ber of shifting cycles, between a high and a low gear, that can
use is sure to be noticed by a vehicle owner. To provide the be performed without failure of synchronization in a manual
desired shift properties, one of the additives present in a transmission being operated at high temperatures. The test is
transmission oil is typically a long-chain hydrocarbon that terminated when the transmission experiences two shifts in
has a polar group on one end. The polar end group of the ad- which the clutch teeth produce a loud noise. According to
ditive is attracted to the metal surface, and the long-chain hy- Section 1.3 of the test method, "Correlation of test results
drocarbon portion associates with the oil, thereby forming a with truck transmission service has not been established.
durable, low-friction oil film on the metal surface. Too m u c h However, t h e procedure has been shown to appropriately
friction reduction will cause transmission components to sepEirate two transmission lubricants, which have shown sat-
slip, b u t too little friction reduction will not allow the trans- isfactory a n d unsatisfactory field performance in the trucks
mission to shift smoothly cind will cause wear. of one manufacturer."
In addition to appropriate friction characteristics, it is also ASTM D 5704, Standard Test Method for Evaluation of the
essential to reduce wear a n d promote long transmission life. Thermal a n d Oxidative Stability of Lubricating Oils Used for
Wear protection is provided to a great extent by oil additives. Manual Transmissions and Final Drive Axles (commonly re-
If suitable anti-wear additives were not present, there would ferred to as the L-60-1 test), measures oil thickening and for-
likely be excessive weeir of the transmission components un- mation of insolubles and deposits in a manual transmission
der severe operating conditions. Thus, fluid degradation dur- oil and final drive axle lubricating oil.
ing prolonged service should not be extensive enough to com- ASTM D 5182, Standard Test Method for Evaluating the
p r o m i s e transmission performance, a n d wear rates m u s t Scuffing Load Capacity of Oils (FZG Visual Method), mea-
remain low so that excessive loss of material does not cause sures the scuffing load capacity of oils used to lubricate hard-
shift characteristics to deteriorate. ened steel gears. Scoring (abrasive wear) is also assessed. An
Various standard test methods are available to ensure sus- FZG Gear Test Machine is operated at a constant speed of
tained transmission performance. Tests for automatic trans- 1450 revolutions p e r min. The test starts at 90°C at a prede-
mission fluids include measurement of physical eind chemi- termined load. The severity of the test is increased (using a
cal properties: viscosity, flash point, pour point, corrosion designated test cycle) until failure occurs. The n u m b e r of
shifting cycles to failure of synchronization is determined. ASTM D 5662, Standard Test Method for Determining Au-
Shifter fork wear is also measured. Examples of various types tomotive Gear Oil Compatibility with Typical Oil Seal Elas-
of wear patterns that may be observed during the testing (pol- tomers, measures whether the properties (hardness, volume,
ishing, abrasive wear, moderate abrasive wear, and scuffing) and elongation in a stretch test) of selected oil-seal elas-
are provided in the test method to help the investigator inter- tomers (nitrile, polyacrylate, and fluoroelastomer) are
pret test results. In the introduction, the following warning is changed on exposure to automotive gear oils.
listed: "High EP (extreme pressure) type oils, for example, Additional transmission-related tests referenced in the
those oils meeting the requirements of API GL-4 and GL-5, standard methods described here are listed in Tables 4 and 5
generally exceed the capacity of the test rig and, therefore, at the end of this chapter.
cannot be differentiated with this test method." "EP" in this
statement stands for "Extreme Pressure," which typically
represents extreme temperature. STANDARD TEST METHODS FOR GREASES
ASTM D 5760, Standard Specification for Performance of
Manual Transmission Gear Lubricants, lists the methods and Introduction to Greases
performance criteria for deciding whether a lubricant ex- Greases provide a great n u m b e r of highly specialized func-
hibits acceptable behavior in nonsynchronized heavy-duty tions in an automobile, such as lubrication of door locks,
manual transmissions. The limiting criteria are provided in electrical connections, various t3rpes of bearings, gears, and
ASTM D 5704, Standard Test Method for Evaluation of the levers. There may be more than 50 different types of grease
Thermal and Oxidative Stability of Lubricating Oils Used for specified by the manufacturer for use in a given vehicle.
Manual Transmissions and Final Drive Axles. The limits in-
Greases typically are composed of oil (synthetic or mineral,
clude a viscosity increase of no more than 100% (per ASTM D
representing 70 or more percent of the total composition of
445) and a pentane insolubles content of no more than 3 %
the grease), a thickening agent, and various additives to pro-
(per ASTM D 893). Limiting values for elastomer (seal) prop-
vide wear protection, corrosion protection, and stability.
erties are also listed. For example, elastomer hardness should
Thus, standard test methods for automotive greases focus on
not decrease by more than 20% nor increase by more than 5%.
such parameters as physical and chemical properties, sepa-
ration of the thickener from the oil, oxidation resistance,
B e n c h a n d Analytical Tests Related t o wear protection, water tolerance, and ability to retain the de-
Transmission Fluids sired properties even after exposure to severe operating con-
Various bench methods are used to help characterize trans- ditions such as high temperature.
mission fluid properties a n d performance. ASTM D 130,
Standard Test Method for Detection of Copper Corrosion Physical and Chemical Properties of Greases
from Petroleum Products by the Copper Strip Tarnish Test,
is used to determine whether a fluid of interest will tarnish Chemical Properties, Stability, and Contamination
copper. In this test, a polished copper strip is immersed in the A number of tests are available to ensure that a grease has the
test fluid at a temperature and for a time appropriate for the appropriate composition and that its properties have not de-
test fluid. At the end of the test, the copper strip is cleaned teriorated excessively during service. ASTM D 128, Standard
and compared to a stemdard. Test Methods for Analysis of Lubricating Grease, describes
ASTM D 1748, Standard Test Method for Rust Protection techniques for analyzing the chemical constituents of a con-
by Metal Preservatives in the Humidity Cabinet, uses steel ventional grease that is composed primarily of petroleum oil
panels which are dipped in the test lubricant, removed and and soap, a n d in addition may contain water, fatty acids,
allowed to drain, and are then suspended in a humidity cab- alkaline agents for corrosion inhibition, fat, glycerin, and
inet at 48.9°C for a designated n u m b e r of hours. The size and insoluble c o m p o n e n t s . The method states, "Composition
n u m b e r of rust spots that form on the panel are determined. should not be considered as having any direct bearing on ser-
There should be n o more than three dots of rust, each of vice performance unless such correlation is established."
which should be smaller than 1 m m in diameter. During hot operation, lighter components of a grease can
ASTM D 2882, Standard Test Method for Indicating Wear evaporate. ASTM D 972, Standard Test Method for Evapora-
Characteristics of Petroleum and Non-Petroleum Hydraulic tion Loss of Lubricating Greases and Oils, is a test method de-
Fluids in Constant Volume Vane Pump, measures the total signed to provide a quantitative measurement of the mass loss
mass loss from the twelve vanes used in the p u m p and from that occurs during this evaporation process. A sample of
the cam ring on which the vanes ride. Good lubricants show grease or oil is weighed a n d then maintained at a desired tem-
very little wear in this test. Fluid cleanliness before and after perature in the range of 100-150°C for 22 h. Heated air is
the test, initial flow rate, and final flow rate are also mea- passed over the sample. At the end of the test the mass loss as
sured to determine the extent of damage to hardware and a consequence of exposure to heat is determined. The method
degradation of the fluid. indicates that "correlation between results from this test
Additional tests pertinent to transmissions include mea- method and service performance has not been established."
surement of the torque required to overcome the friction that An additional test method for evaporative loss of a grease
occurs between clamped clutch plates at high and low slip is also available. ASTM D 2595, Standard Test Method for
speeds and assessing the tendency to shudder (which occurs Evaporation Loss of Lubricating Greases Over Wide-Tem-
as a consequence of stick-slip motion between mating sur- perature Range, can be conducted at a t e m p e r a t u r e any-
faces). Measurement of "shift feel" aJso provides useful infor- where from 93-316°C. Heated air is passed over a weighed
mation to an investigator. sample of grease, emd the loss of weight of the grease is mea-
sured. The method indicates that "correlation between re- to soften, swell, or to react adversely to the presence of the
sults from this test method and service performance has not grease c o m p o n e n t s . Alternatively, the grease may extract
been established." elastomer additives such as plasticizers, which will result in
ASTM D 942 (Reapproved 1995), Standard Test Method for changes in the stability of the elastomer. ASTM D 4289, Stan-
Oxidation Stability of Lubricating Greases by the Oxygen dard Test Method for Elastomer Compatibility of Lubricat-
Bomb Method, measures the ability of a grease to resist oxi- ing Greases a n d Fluids, measures the extent to which a
dation in an oxidizing atmosphere at elevated temperature. A grease is compatible with various types of elastomeric or
sample of grease is oxidized in a sealed b o m b that is filled polymeric materials. The hardness of a standard-sized
with oxygen at 110 psi (758 kPa) at 99°C. Pressure is recorded coupon of the elastomer to be tested is measured in the fol-
during the test. The extent of oxidation is determined by mea- lowing way. Three standard sized coupons are cut out of a
suring the decrease in oxygen pressure. The method carries sheet of elastomer of specified thickness. The hardness of the
the notification that this test method "predicts neither the stack of three coupons is measured with a standard indenter.
stability of greases under dynamic service conditions, nor the Density and volume are also determined. The coupons are
stability of films of greases on bearings and motor-parts. It immersed in the grease of interest for 70 h at the test tem-
should not be used to estimate the relative oxidation resis- perature that is designated for the elastomer of interest. After
tance of different grease types." the immersion period, the elastomer is re-tested for changes
ASTM D 1743, S t a n d a r d Test Method for Determining in volume and hardness, to determine the extent of changes
Corrosion Preventive Properties of Lubricating Greases, in these properties. The test method carries the notice that:
measures the ability of a grease to protect a bearing against "Some lubricant specifications m a y require different test
corrosion in the presence of water. A bearing is r u n for a conditions, such as longer d u r a t i o n s or lower or higher
short time and is then exposed to water. After 48 h at 52°C temperatures. In such instances, the repeatability and repro-
and 100% humidity the bearing is inspected for corrosion. ducibility values stated in Section 12 do not apply, and the
In ASTM D 4048, Standard Test Method for Detection of user and supplier should agree on acceptable limits of preci-
Copper Corrosion from Lubricating Grease, a copper strip is sion." The method also states that "the volume and hardness-
immersed in a sample of grease and heated for a period of change values determined by this test method do not dupli-
time. Typical time and temperature conditions are 100°C for cate similar changes that occur in elastomeric seals under
24 h. At the end of the test the copper strip is washed and actual service conditions."
compared to copper strip standards to provide a measure of
the severity of corrosion. The method states, "no correlations Viscosity and Penetration Effects
with actual field service, most of which are under djmamic The viscosity of the base oil in a grease has a significant in-
conditions, have been established. It does not measure either fluence on the properties of a grease. ASTM D 445 (men-
the ability of the lubricant to inhibit copper corrosion caused tioned previously) describes the measurement of the base oil
by factors other than the lubricant itself nor does it measure viscosity by determining the time required for the base oil to
the stability of the grease in the presence of copper." flow through a calibrated glass tube.
ASTM D 1742, Standard Test method for Oil Separation The thickening agent in a grease uses surface tension and
from Lubricating Grease During Storage, measures the ten- molecular attractions to help hold the grease's oil in the place
dency of a grease to separate into distinct fractions during in which it is supposed to provide protection. The thickening
storage. A sample of grease is placed on a sieve and is subject agent can consist of fibers, platelets, or spheres, which are in-
to 1.72 kPa (0.25 psi) at 25°C for 24 h. The amount of mate- soluble or only slightly soluble in the grease. Thickeners can
ricJ that seeps into a beaker is weighed. The test represents also be complex polymer-like chains such as complex
separation during storage rather than separation under dy- polyureas. ASTM D 1092, Standard Test Method for Measur-
namic operating conditions. The following warning is pro- ing Apparent Viscosity of Lubricating Greases, determines
vided: "This test method is not suitable for greases softer than the viscosity of the grease over the range of —53 to 37.8°C. A
NLGI No. 1 grade." In addition, the m e t h o d states, "this sample of the grease is forced through a capillary, using a
method is not intended to predict oil separation tendencies of floating piston that is controlled by a hydraulic system. Vis-
the grease under dynamic conditions." The method does in- cosity is calculated from the flow rate and the force devel-
dicate oil separation that occurs during storage. oped in the system.
ASTM D 1404, Standard Test Method for Estimation of ASTM D 1263, Standard Test Method for Leakage Tenden-
Deleterious Particles in Lubricating Grease, measures the cies of Automotive Wheel Bearing Greases, measures the
presence of abrasive or inappropriate particles in a grease. A leakage of a grease from a modified front wheel h u b and
small sample of grease is placed between two standard plas- spindle assembly. The wheel is rotated at a speed of 660 rev-
tic plates, and pressure is applied to the plates. The presence olutions per min for 6 h at a temperature of 105°C. The extent
of inappropriate abrasive peirticles produces a characteristic of leakage is determined, and the condition of the bearing
scratch pattern. The n u m b e r of such scratch patterns on the surface is noted at the end of the test. The method carries the
plates is determined. "The significance of the n u m b e r of notice that "it is not the equivalent of longtime service tests,
scratches as far as correlation with field performance is con- n o r is it intended to distinguish between wheel bearing
cerned has not been established." greases showing similar or borderline leakage."
If a grease comes into contact with an elastomer, several ef- A related leakage test is ASTM D 4290, S t a n d a r d Test
fects may occur. Components of the grease may be suffi- Method for Determining the Leakage Tendencies of Automo-
ciently compatible with the elastomer that grease compo- tive Wheel Bearing Grease Under Accelerated Conditions. In
nents enter the elastomer structure and cause the elastomer this test, grease is placed in a modified version of an auto-
mobile front wheel hub-spindle-bearings assembly. The hub test method indicates that "unworked penetrations do not
is rotated at 1000 revolutions per min at the same time that generally represent the consistency of greases in use as effec-
the bearings are thrust-loaded to 111 N. The spindle temper- tively as do worked penetrations."
ature is maintained at 160°C for 20 h. Leakage of the grease,
or the oil in the grease (or both), is measured. In addition, the
condition of the bearing surface is noted. The method "is not Grease Performance
the equivalent of long-term service tests." Some of the issues related to grease performance include the
ASTM D 566, Standard Test Method for Dropping Point of ability of the grease to resist washout from water, effects of
Lubricating Grease, determines the temperature at which ma- low-temperature operation on grease performance, wear pro-
terial falls through a hole in the bottom of a cup while a sam- tection provided, and determination of the useful life of the
ple of grease is being heated. This type of test helps determine grease.
whether a particular grease is suitable for a given application. ASTM D 1264, Standard Test Method for Determining the
The following notice is given: "This test method is not recom- Water Washout Characteristics of Lubricating Greases, mea-
mended for use at bath temperatures above 288°C." sures the resistance of a grease to being washed out of a bear-
ASTM D 2265, Standard Test Method for Dropping Point ing due to the presence of water. In the test, a grease is
of Lubricating Grease Over Wide Temperature Range, mea- packed into a ball bearing. Water impinges on the bearing
sures the temperature at which the first drop of material falls housing, and the amount of grease washed out is measured
from a test cup and reaches the bottom of a test tube (as cor- by weighing the bearing before and after the test. "No corre-
rected by a term related to the oven temperature). This test lation with field service has been established."
method can differentiate between different types of thicken- ASTM D 4049, Standard Test Method for Determining the
ers such as simple soaps, complex soaps, stearate soaps, and Resistance of Lubricating Grease to Water Spray, also mea-
urea-based thickeners. The elapsed time and the temperature sures the influence of water on grease. In this test grease is
that the grease withstood in the dropping-point test indicate applied within a scribed area on a panel. The panel is
how well the thickener can hold the base oil within its matrix weighed, and water is sprayed onto the grease at a pressure
or within its complex lattice structure before the energy from of 276 kPa at 38°C. At the end of the test, any grease that is
the heat is able to weaken the internal energy of the lattice. outside the scribed area is wiped off, and the panel is re-
The information derived from this test is used to maintain weighed to determine the amount of grease that remains.
quality control of the grease and does not necessarily relate ASTM D 1478 (reapproved 1997), Standard Test Method
to performance of the grease. for Low-Temperature Torque of Ball Bearing Grease, deter-
In ASTM D 217, Standard Test Method for Cone Penetra- mines the extent to which a grease retards the rotation of a
tion of Lubricating Grease, the consistency (or resistance to slow-speed ball bearing by measuring starting and running
flow) of a grease is measured by observing the depth to which torques at temperatures below —20°C. In this test a ball bear-
a cone penetrates the grease, using a device called a pen- ing is packed completely full with the test grease. The ambi-
etrometer. Properties of the grease may be influenced by the ent temperature is lowered to the test temperature and held
manipulation that the grease has experienced. Thus, the test there for 2 h. At the end of this time the ball bearing is ro-
method defines four test conditions: unworked penetration, tated, and the restraining force on the outer ring is measured
worked penetration, prolonged worked penetration, and (both at starting time and after one hour). The test procedure
block penetration for grease that holds its shape. indicates that: "This test method has proved helpful in the se-
Unworked penetration means penetration is tested at 25°C lection of greases for low-powered mechanisms — . The suit-
without shearing the grease beforehand. The cone assembly ability of this test method for other applications requiring
of the penetrometer is released and is allowed to drop freely different greases, speeds, and temperatures should be deter-
into the grease for 5 s. The worked condition represents prop- mined on an individual basis."
erties after the grease has been sheared during 60 double ASTM D 4693, Standard Test Method for Low-Tempera-
strokes at 25°C in grease-working equipment. In the condi- ture Torque of Grease-Lubricated Wheel Bearings, measures
tion of penetration after prolonged work, the grease has ex- the extent to which a grease retards the rotation of a spe-
perienced more than 60 double strokes in a grease worker at cially-manufactured, spring-loaded, automotive-type wheel
a temperature of 15-30°C, plus 60 additional strokes at 25°C. bearing assembly when subjected to low temperatures. In the
Penetration is then measured immediately. The block pene- test, a freshly stirred and worked sample of the grease is
tration test is used for a grease that is rigid enough to hold its packed into the bearings of an automotive-type spindle-
shape. A cube of grease is cut from the bulk of the grease, and bearings-hub assembly. The assembly is heated, then cooled
penetration is measured at a grease temperature of 25°C. In and held at -40°C (or other desired temperature). The spin-
each of these ASTM D 217 methods, three determinations of dle is rotated at 1 revolution per min. The torque required to
penetration are conducted, and the results are averaged. This prevent rotation of the hub is measured. "It is the responsi-
test method is not "considered suitable for the measurement bility of the user to determine the correlation with other
of the consistency of petrolatums by penetration." types of service."
ASTM D 1403, Standard Test method for Cone Penetration ASTM D 1831, Standard Test Method for Roll Stability of
of Lubricating Grease Using One-Quarter and One-Half Scale Lubricating Grease, is a low-speed, high-surface-area tum-
Cone Equipment, determines cone penetration for small bling procedure at low shear. Cone penetration (ASTM D
samples of grease, including both worked and unworked pen- 1403) is first measured, then the grease is subjected to low
etration. The test is conducted at 25°C, and a smaller cone shear for 2 h, and the cone penetration is again measured.
than that described in ASTM D 217 is used in the test. The This method is used to assess shear stability of the grease.
The following warning is listed, "Although this test method is method description. F r o m such graphs, one can evaluate
widely used for specification purposes, the significance of the product life, for example, expected n u m b e r of hours before
roll stability test has not been determined." 10% of the greases will have failed, or hours to 50% failure.
ASTM D 2266, Standard Test Method for Wear Preventive ASTM D 3337, Standard Test Method for Determining Life
Characteristics of Lubricating Grease (Four-Ball Method), and Torque of Lubricating Greases in Small Ball Bearings,
measures the ability of a grease to resist wear in sliding steel- measures grease life and torque in a shorter time period than
on-steel contacts. It does not address wear in materials other those tests that evaluate field performance. A single row of
than steel on steel, nor does it evaluate the extreme pressure ball bearings, lubricated by the grease of interest, is rotated at
characteristics of a grease. In this test a steel ball is rotated high speed at the desired test temperature. The end of the test
while in contact with three additional balls. The diameter of is determined when one of the following conditions occurs:
the wear scar on each of the non-rotating balls is measured. • An instantaneous torque Ave times the minimum torque
The test method indicates that "No correlation has been es- occurs.
tablished between the four-ball wear test and field service." • A temperature 11 °C above the test temperature occurs at
ASTM D 2509, Standard Test method for Measurement of the outer race of the test bearing.
Load-Carrying Capacity of Grease (Timken Method), uses a • There is a noise level increase that persists for more than 1
steel cup that rotates against a steel block at a rotation speed min at start-up or when running at high speed.
of 123.71 m per min. The m i n i m u m load needed to rupture
An example of the graphing procedure (WeibuU plot) for
the lubricant film that lies between the rotating cup and the
cumulative life of the grease is provided as part of the test
block is determined. A determination is also made of the
procedure.
m a x i m u m safe load such that the lubricant film will not be
ASTM D 3527, Standard Test Method for Life Performance
ruptured by the rotating cup, and abrasion will not occur be-
of Automotive Wheel Bearing Grease, evaluates the life per-
tween the rotating cup and the block. The test procedure in-
formance of a wheel-bearing grease at high temperature. A
dicates that: "The test method is used widely for specification
modified automobile front-wheel hub-spindle-bearing as-
purposes and is used to differentiate between greases having
sembly is used in the test. Bearings are thrust-loaded to 111
low, medium, or high levels of extreme pressure characteris-
Newtons, the h u b is rotated at a speed of 1000 revolutions per
tics. The results may not correlate with results from service."
min, and the spindle temperature is held at 160°C for 20 h.
ASTM D 2596, Measurement of Extreme Pressure Proper- The test is terminated when the pre-set torque limit is ex-
ties of Lubricating Grease (Four-Ball Method), determines ceeded. The test "is not the equivalent of long-time service
the load-carrying properties of lubricating grease. Two prop- tests, nor is it intended to distinguish between the products
erties are measured: the diameter of the wear scar (for the having similar high-temperature performance properties."
case in which welding or seizure does not occur) and the load
ASTM D 3704, Standard Test Method for Wear Preventive
at which welding occurs. Two warnings are provided: 1) "The
Properties of Lubricating Greases Using the (Falex) Block on
results do not necessarily correlate with results from service"
Ring Test Machine in Oscillating Motion, uses a steel test
and 2) "Lubricating greases that have as their fluid compo-
ring oscillating against a steel test block. The test speed, load,
nent a silicone, halogenated silicone, or a mixture compris-
angle of oscillation, time, hardness, and surface finish of the
ing silicone fluid and petroleum oil, are not applicable to this
test specimen can be chosen to represent the field conditions
method of test."
of interest. The width of the wear scar on the test block is de-
ASTM D 3336, Standard Test Method for Life of Lubricat- termined. The method evaluates the amount of wear protec-
ing Greases in BeJl Bearings at Elevated Temperatures, eval- tion provided by a given grease. "The user of this method
uates the performance of lubricating greases operating at el- should determine to his own satisfaction whether results of
evated temperatures (up to 371°C) in ball bearings, at a speed this test procedure correlate with field performance or other
of 10 000 revolutions per min, but under light load. If the test bench test machines."
temperature is 149°C or below, the test cycle is operated at
Fretting is surface damage that results from oscillation
test temperature for 21.5 h per day, with 2.5 h of shut-down
over a short distance. ASTM D 4170, Standard Test method
per day in which heat is not applied. If the test temperature
for Fretting Wear Protection by Lubricating Greases, is a test
is r u n at a temperature greater than 149°C, the test is run for
method that documents the protection provided by a grease
20 h per day at the desired test temperature, with 4 h per day
that is subjected to oscillation (30 Herz) between two ball
of shut-down in which n o heat is applied. Tests are con-
bearings through a small arc (12°). The test lasts 22 h at a
ducted until failure or until a specified n u m b e r of hours is
load of 2450 Newton. Mass loss of the bearings is determined.
reached. The grease has failed the test when one of the fol-
According to the method, "Test results do not necessarily
lowing conditions has occurred:
correlate with results from other t5ês of service. It is the re-
• Spindle output power increases to a value of three hundred sponsibility of the user to determine whether test results cor-
percent above the steady state condition at test temperature. relate with other types of service." Tables 6 and 7 show addi-
• An increase in temperature of 15°C over the test tempera- tional standard test methods related to greases.
ture occurs (but the daily start-up temperature rise is not
to be construed as a test failure).
• There is loading of the test bearing or belt slippage at start- GEAR AND AXLE LUBRICANTS
u p or during the test cycle.
Introduction to Gear Lubricants
Hours to failure are plotted in terms of cumulative per-
centage of the tests conducted. Examples of these plots Gears must be designed to withstand high loads that are con-
(known as WeibuU plots) are provided as part of the test- centrated on gear surfaces. As a consequence, high tempera-
tures may be generated at the point of contact. Despite the ASTM D 5182, Standard Test Method for Evaluating the
h a r s h environment, the gear lubricant must provide suffi- Scuffing Load Capacity of Oils (FZG Visual Method), was de-
cient wear and extreme pressure protection to prevent mate- scribed under transmission fluids. In this test, a gear test de-
rial failure of the gears, and the gear lubricant must remain vice is rotated at increasing loads until scuffing occurs. The
functional for extended periods of time. following statement is provided, "The test method is limited
If the gear materials are not sufficiently robust and the lu- by the capabilities of the equipment (test rig and gears), and
bricant is not sufficiently protective, irreversible damage may the performance observed may not directly relate to scuffing
occur to the gear, which typically means that the equipment performance observed with spiral bevel on hjrpoid gearing. It
in which the gear is located will not perform as designed. Per- is also limited to discriminating between oils with mild EP
formance criteria for gear lubricants include such factors as additives or less."
ability to withstand the required loads and continuing ability ASTM D 4172, Standard Test Method for Wear Preventive
to transmit power. Gear surface finish and gear tooth con- Characteristics of Lubricating Fluid (Four-BeJl Method), ro-
tour must not deteriorate. In addition, the properties of the tates one steel ball against three stationary steel balls that are
gear lubricant must remain stable, including oxidative stabil- immersed in the test lubricant. The test method measures the
ity, anti-wear protection, maintenance of appropriate fric- extent of the wear scar on the three stationairy balls. "The user
tion characteristics, low-temperature viscosity, corrosion of this test method should determine to his own satisfaction
protection, and resistance to foam formation. Various stan- whether results of this test procedure correlate with field per-
dard tests address these concerns. formance or other bench test machines."
ASTM D 2783, S t a n d a r d Test Method for Extreme-
Standard Tests for Gear Lubricants Pressure Properties of Lubricating Fluids (Four-Ball
ASTM D 5579, S t a n d a r d Test Method for Evaluating the Method), rotates one steel ball against three stationary steel
Thermal Stability of Manual Transmission Lubricants in a balls. Lubricant covers the stationary balls. Increasing load is
Cyclic Durability Test, was described previously in the sec- applied until welding occurs. The following notice is pro-
tion on Transmission Lubricants. This test evaluates a gear vided, "The user of this test method should determine to his
lubricant's performance, since a transmission cycles through own satisfaction whether results of this test procedure corre-
a continuing sequence of gear shifts. Shifter fork wear is late with field performance or other bench test machines."
measured, and deterioration of shift performance is the cri- An alternative test for measurement of extreme pressure
terion for termination of the test. properties is ASTM D 3233, Standard Test Methods for Mea-
ASTM D 5760, Standard Specification for Performance of surement of Extreme Pressure Properties of Fluid Lubricants
Manual Transmission Gear Lubricants, was also described in (Falex Pin and Vee Block Methods). A steel journal is rotated
the section on manual transmissions. Performance require- at 290 revolutions per min against two stationary V blocks
ments include a maximum of n o more than 100% viscosity in- that are immersed in the lubricant sample. Increasing load is
crease and limits on the generation of insoluble contaminants applied, a n d the load at which failure occurs is noted. "The
in the lubricant. Elastomers must not deteriorate excessively, user should establish any correlation between results by ei-
and scuffing should not occur at a specified high load. ther method and service performance."
ASTM D 2670, Standard Test Method for Measuring Wear An additional topic of interest is whether a given gear oil is
Properties of Fluid Lubricants (Falex Pin and Vee Block compatible with the elastomers it touches. ASTM D 5662,
Method), evaluates the wear-resistant properties of fluid lu- Standard Test Method for Determining Automotive Gear Oil
bricants. In this test, a rod is rotated while being squeezed be- Compatibility with Typical Oil Seal Elastomers, addresses
tween two V-shaped blocks. Load is applied to the V blocks, this issue. In ASTM D 5662, an elastomer test specimen is ex-
and the amount of wear is determined. "The user of this test posed to the gear oil for 240 h. The test temperature depends
m e t h o d should determine to his or h e r own satisfaction on the composition of the elastomer to be tested. Nitrile is
whether results of this test procedure correlate with field per- tested at 100°C. Polyacrylate and fluoroelastomers are tested
formance or other bench test machines. If the test conditions at 150°C. Hardness, volume changes, and elongation are
are changed, wear values may change and relative ratings of measured and compared to the start-of-test measurements of
fluids may be different." these same properties. The method states: "This test method
The load-carrying capacity of a lubricant is the amount of addresses only those failures caused by excessive elastomer
load a lubricant can withstand, without rupturing the oil hardening, elongation loss, and volume swell and attempts to
film. ASTM D 2782, Standard Test Method for Measurement determine the likelihood that a n oil might cause premature
of Extreme-Pressure Properties of Lubricating Fluids sealing system failures in field use."
(Timken Method), measures this property. In this test a steel Another important characteristic of a gear lubricant is the
test cup is rotated against a steel test block. The rotation ability to release water rapidly, in case water should enter the
speed is 123.71 m per min. Fluid samples are pre-heated to gear lubricant. ASTM D 2711, Standard Test Method for
37.8°C. Two measurements are obtained: the minimum load Demulsibility Characteristics of Lubricating Oils, measures
required to rupture the lubricant film and the maximum load the ability of water and oil to separate from each other. A
at which the rotating cup will not rupture the fluid film and sample of the test oil and a designated amount of water are
cause scoring or seizure. The u s e r is notified: "This test stirred together for 5 min at a temperature of 82°C. The ex-
method is used widely for the determination of extreme pres- tent of separation of water and oil is measured after 5 h.
sure properties for specification purposes. Users are cau- ASTM D 892, which measures the amount of foam that can
tioned to carefully consider the precision and bias statements form and the stability of the foam, was described previously,
herein when establishing specification limits." in the engine oil section. ASTM D 130, which measures the
CHAPTER 17: A UTOMOTIVE LUBRICANTS 483
extent of corrosion of a copper strip, was described in the sec- such that the brake shoes are pressed onto the rotating drum.
tion on transmission fluids. The friction of the shoe against the d r u m stops the wheel.
Test methods for gear oils are also available from CRC A disk brake has a metal disk, and flat shoes or pads are
(Coordinating Research Council). The CRC L-37 method is a pressed against the disk to provide the force to stop the vehi-
24-hour dynamometer test that is conducted at high torque cle, using the force supplied by the hydraulic action of the
and low speed and that assesses gear distress. CRC L-42 is a brake fluid.
24-hour dynamometer test incorporating high speed shock Thus, the motion of a braking mechanism is controlled by
loading, designed to measure resistance to gear scoring. CRC a hydraulic system that includes a pump, a fluid, and lines
L-33 is a 7-day motored rust test in which geeirs are exposed (tubes) that transmit the hydraulic force to the brake compo-
to humidity in an oven. CRC L-60-1 is a test for oxidation and nents. The brake fluid must not react with components of the
deposits, using motored gears over a period of 50 h. brake system, and it must be able to withstand wide varia-
Viscosity characteristics of axle lubricants are measured actions in temperature while still performing effectively.
cording to ASTM D 445, Standard Test Method for Kinematic Requirements for the brake fluid are described in the 2001
Viscosity of Transpsirent eind Opaque Liquids (the Calculation SAE Handbook, Standards Development Program, Volume
of Dynamic Viscosity), as described under the section on en- 2, Parts and Components and on-Highway Vehicles (Part I),
gine oils. Low temperature viscosity is measured using ASTM "Motor Vehicle Brake Fluid-SAE J1703 Jan95", page 25.49,
D 2983, Standard Test method for Low-Temperature Viscos- and "Borate Ester Based Brake Fluids-SAE J1704 Jan97",
ity of Automotive Fluid Lubricants Measured by Brookfield page 25.59.
Viscometer. In this test, viscosity is measured in the tempera- SAE J1703 and SAE J1704 specify such measurements as
ture range from 5 to —40°C, using a rotating spindle. boiling point, fluid stability, viscosity, reserve alkalinity, cor-
rosion resistance, low-temperature fluidity, evaporation,
water tolerance, low temperature stability, resistance to oxi-
Axle Lubricants dation, and effect on rubber materials such as seals. A num-
An additional area of concern related to gear lubricants is the ber of standard ASTM methods related to these tests are
topic of axle lubricants. Requirements for axle lubricants are listed at the end of this chapter.
described in the American Petroleum Institute API-GL-5 re-
quirements for gear lubricants. However, two of the tests
listed in API-GL-5 (CRC L-37 and CRC L-42) are not required SOLID LUBRICANTS
for axle lubricants. Desirable properties for axle lubricants
Solid lubricants are used where it is important for the lubri-
include viscosity in an appropriate range (for example, near
cant to stay in place. Solid lubriccints are typically composed
14 or 15 centistokes at 100°C). Performance of an axle lubri-
of a solid, a binder, and additives such as corrosion inhibitors
cant must not degrade excessively during service. The axle lu-
or solvents. Examples of c o m m o n solid lubricants include
bricant must not damage metal components, nor should the
molybdenum disulfide, graphite, a n d polytetrafluoroethy-
metal components accelerate an axle lubricant's degradation.
lene (PTFE) or other fluorine-containing polymers. Molybde-
In addition, axle lubricants must not damage seals. Desirable
n u m disulfide and graphite have a chemical structure that is
axle-lubricant attributes include fuel efficiency, thermal
like flat plates such that an upper plate can easily slip eilong
stability, long life, and appropriate limited-slip differential
the surface of the next plate beneath it. PTFE has a chemical
performance.
structure that typically does not attract or hold a variety of
Referenced documents related to geeir and axle lubricant common fluids such as water or oil, as witnessed by the fact
test methods are provided at the end of this chapter. Tables 8 that the fluid tends to bead u p on the PTFE surface, rather
and 9. than spreading over the surface. In contrast, if a drop of oil
touches an iron surface, the oil spreads over the surface.
Solid lubricants typically have a temperature range over
BRAKE FLUIDS which they are effective. Above the optimum reinge, they may
degrade chemically or physically. For example, according to
Brake fluid typically behaves like a hydraulic fluid, since fluid information in the Tribology Data Handbook, molybdenum
power is used to apply force to the brakes, therefore generat- disulfide has a n u p p e r t e m p e r a t u r e limit in the range of
ing enough friction to slow and stop the forward motion of 400°C, but it can withstand high loads [16]. Graphite can
the vehicle. Fifty years ago, if water got into brakes during a withstand 650°C and moderate loads.
heavy rain, the brakes might not work properly, and an acci- If PTFE (polytetrafluoroethylene) is used in a high-temper-
dent might result. Today, with better technology, such occur- ature application, care must be taken to ensure that the tem-
rences are rare. However, someone who is servicing a brake p e r a t u r e does not exceed the point at which PTFE is no
system must make sure to instcill the appropriate brake fluid longer stable. On the other hand, use of low-friction materi-
for that brake, otherwise there is risk that the brakes will not als is an advantage with regard to fuel conservation in auto-
function as they should. motive vehicles.
Two types of braking systems are typically used in vehicles: ASTM D 2714, Standard Test Method for Calibration and
drum brakes and disk brakes. In a d r u m brake, a drum ro- Operation of the Falex Block-on-Ring Friction and Wear
tates with the wheel. Curved brake shoes are inside the drum, Testing Machine, provides a test method for determination of
separated by a slight air gap from the drum. When a driver friction coefficient of a solid lubricant. Friction coefficient is
steps on the brake, brake fluid, acting like a hydraulic fluid to defined as the ratio of the friction force, F, that resists move-
apply force where it is needed, is sent to the braking system ment to the normal force, N, that presses the two bodies to-
gether. A steel test ring rotates against a steel test block. The ADDITIONAL FLUIDS THAT EXHIBIT
specimen assembly is immersed in the lubricant. A normEil LUBRICATING PROPERTIES
load of 65 kg is applied. The velocity of the test ring is 7.9
m/min. The test method contains the warning that "The user Several additional fluids within a vehicle (coolant and fuel)
of this test method should determine to his or her own satis- must provide some lubrication, even though lubrication is
faction whether results of this test procedure correlate with not their primeiry function. Engine coolant must not allow
field performance or other bench test machines. If the test excessive corrosion to occur in the coolant system. The
conditions are changed, wear values can change and relative coolant typically incorporates a mixture of ethylene glycol
ratings can be different." a n d water (to lower the freezing point, so that the coolant re-
mains fluid) and corrosion inhibitors (to reduce corrosion of
the coolant system).
AUTOMOTIVE AIR CONDITIONING If engine coolant leaks from the coolant system and enters
LUBRICANTS the engine oil, the oil properties can degrade, which can dam-
age or destroy an engine if too much coolant has entered the
In the 1930s, chlorine-containing refrigerants were intro- engine oil. Thus, standard ASTM tests associated with effects
duced, since they were considered to be safer than other re- of the coolant on the engine lubrication system are related to
frigerant fluids that had been in use prior to 1930 [17]. How- detection of coolant (ethylene glycol) in engine oil. ASTM D
ever, in the late 1970s it was observed that, in some places, 4291, Standard Test Method for Trace Ethylene Glycol in
the protective ozone layer had been depleted as m u c h as 30 Used Engine Oil, measures the amount ethylene glycol in the
or 40% at an altitude of 40 km. As a consequence, the United range of 5-200 parts per million by mass. A sample of oil is
States, Canada, Norway, Sweden, and others passed legisla- mixed with water, the ethylene glycol migrates to the water
tion prohibiting the use of these chlorofluorocarbon refriger- phase, and the amount of glycol present is determined by gas
ants in spray cans [17]. chromatography.
In 1985 investigators found that there had been a 40% loss ASTM D 2982, Standard Test Methods for Detecting Gly-
of protective ozone during springtime in the antarctic. It was col-Based Antifreeze in Used Lubricating Oils, measures the
also found that a chlorofluorocarbon could be thousands of glycol content of lubricating oils by extracting the glycol from
times worse than carbon dioxide in promoting global warm- the oil using an acid solution. The glycol is oxidized to form
ing. Thus, a search was initiated to find a replacement for the formaldehyde, which is then reacted to form a colored solu-
chlorofluorocarbons used in automotive air-conditioning tion that can be analyzed colorimetrically.
systems [17]. One of the authors of this chapter was involved The fuel supply system must not wear out and must not be
in the effort to find a replacement for the refrigerants that excessively corroded or eroded by the fuel. Corrosiveness, lu-
had been used in automotive air-conditioning systems. bricity, and material compatibility properties of a fuel such
Automotive air conditioning systems require a lubricant. as gasoline can differ significantly from those of an oxy-
However, n o standard tests h a d been created that were spe- genated fuel such as alcohol, as shown in Figs. 2 and 3. The
cific for this application. It was necessary to address several lower volatility and higher viscosity of diesel fuel, in compar-
issues relative to the search for these chlorine-containing re- ison to gasoline, can provide greater film thickness for lubri-
frigerants. cation of injectors. Standard tests that describe relationships
• Can a lubricant be identified that is compatible with the re- between the fuel system and the engine lubrication system in-
frigerant? clude measurement of fuel in oil and fuel economy.
• Will the lubricant that is compatible with the refrigerant In S t a n d a r d Test Method for Gasoline Diluent in Used
have enough lubricity to provide long life to the pump? Gasoline Engine Oils by Distillation, ASTM D 322, used en-
• Will it be necessary to modify the composition of seals in gine oil (which may be contaminated with fuel) is mixed with
the air conditioning unit to ensure that the seals are not de- water. Several vaporizations are conducted to separate the
graded by the new refrigerant and its associated lubricant? fuel from the oil and from the water. The volume of fuel that
• Which refrigeration-system materials should be used, such was extracted is measured.
that they will not be degraded by the refrigerant or its lu- In ASTM D 3525, Standard Test Method for Gasohne Dilu-
bricant? ent in Used Gasoline Engine Oils by Gas Chromatography, a
Extensive testing showed that, for an air conditioning com- known amount of internal standard is placed in the engine
pressor to work properly, the air conditioning fluid must be oil. The amount of fluid boiled off at a temperature below
able to transport the air conditioning lubricant to the work- that of the internal standard is used to obtain a quantitative
ing components of the p u m p . In other words, there had to be assessment of how much fuel was in the oil.
a chemical compatibility between the lubricant and the air
conditioning medium, in addition to the normal lubrication
requirements such as providing a protective lubricating film SUMMARY AND FUTURE DIRECTIONS
and inhibiting corrosion. Thus, in order to have a viable air-
conditioning system, it was not sufficient to remove the orig- As illustrated by these examples, automotive lubrication en-
inal air-conditioning fluid and put another air-conditioning compasses a wide range of fluid properties, fluid functions,
fluid into the system. and component composition and design within a vehicle. The
This example indicates that whenever changes are made to great diversity of vehicle lubrication requirements mandates
any component of a lubrication system, testing must be per- that many different kinds of lubricants, specifications, and
formed to ensure that no incompatibilities have arisen. standards Eire needed.
Various issues arise on a continuing basis, with regard to Such issues will receive increased attention in the future.
automotive lubricants: Displacing current power sources (gasoline and diesel en-
• Can further improvements be m a d e in vehicle fuel econ- gines), however, will be difficult to accomplish, since current
omy by developing more efficient engine oils, transmission systems have worked exceedingly effectively for m a n y
fluids, cixle lubricants, etc.? decades. Incremented improvements have occurred, but rev-
• Can changes in automotive design be implemented such olutionary changes in design have not yet been sufficiently
that power eind performance are not compromised, but en- problem-free to reduce or eliminate use of the intemEd com-
ergy consumption during operation is reduced? bustion engine. It will be left to future generations to find vi-
• Can suitable alternative automotive power sources (fuel able alternatives.
cells, hydrogen, batteries) be developed?
• To w h a t extent can vehicle weight be reduced without LIST OF REFERENCED DOCUMENTS
compromising occupant safety? A List of Referenced Documents is included with most of the
• Can lighter metals such as aluminum be used in engines standard test methods described previously. The referenced
to replace iron, and thus reduce energy consumption, documents are listed below (Tables 2 through 10), so that the
since less energy will be required to keep the vehicle in reader will have a comprehensive tabulation of standard test
motion? methods associated with each category of automotive lubri-
• What types of lubricants are effective for use with alterna- cant. In addition, abbreviations a n d terms are defined in
tive materials? Table 11.
• Can the amount of lubriccint required for a given applica-
tion be reduced, so that oil reserves will last longer? Acknowledgment
• Can the useful life of ciny given automotive lubricant be in- The a u t h o r s t h a n k Brent Calcut, Robert Olree, Jill Cum-
creased? mings, Robert Stockwell, Jim Linden, James Spearot, Cole-
• To what extent ccin automotive lubricants be recycled? m a n Jones, John Flaherty, and Jeff Knight of General Motors
• Are biodegradable automotive lubricants feasible? for their contributions, suggestions, and corrections.
TABLE 2—Referenced documents in ASTM standard test methods related to engine oil.
ASTM No. Test Method or Document Title
C 1109 Analysis of Aqueous Leachiates from Nuclear Waste Materials Using Inductively Coupled Plasma-Atomic Emission
Spectrometry
D 16 Definitions of Terms Relating to Paint, Varnish, Lacquer, and Related Products
D56 Flash Point by Tag Closed Tester
D86 Distillation of Petroleum Products
D91 Acidity of Hydrocarbon Liquids and Their Distillation Residues
D92 Flash and Fire Points by Cleveland Open Cup
D93 Flash Point by Penske-Martens Closed Tester
D97 Pour Point of Petroleum Products
D117 Guide to Sampling Test Methods, Standard Practices, and Guides for Electrical Insulating Oils of Petroleum Origin
D 129 Sulfur in Petroleum Products (General Bomb Method)
D 130 Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test
D 140 Practice for Sampling Bituminous Materials
D 156 Saybolt Color of Petroleum Products (Saybolt Chromometer Method)
D235 Specification for Mineral Spirits (Petroleum Spirits) (Hydrocarbon Dry Cleaning Solvent)
D240 Heat of Combustion of Liquid HydrocEirbon Fuels by Bomb Calorimeter
D287 API Gravity of Crude Petroleum and Petroleum Products (Hydrometer Method)
D323 Vapor Pressure of Petroleum Products (Reid Method)
D341 Viscosity-Temperature Charts for Liquid Petroleum Products
D381 Existent Gum in Fuels by Jet Evaporation
D445 BCinematic Viscosity of Transparent and Opaque Liquids (the Calculation of Dynamic Viscosity)
D446 Standard Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers
D482 Ash from Petroleum Products
D524 Ramsbottom Carbon Residue of Petroleum Products
D525 Oxidation Stability of Gasoline (Induction Period Method)
D613 Cetane Number of Diesel Fuel Oil
D664 Acid Number of Petroleum Products by Potentiometric Titration
D873 Oxidation Stability of Aviation Fuels (Potential Residue Method)
D892 Foaming Characteristics of Lubricating Oils
D893 Insolubles in Used Lubricating Oils
D974 Acid and Base Number by Color-Indicator Titration
D 1078 Distillation Range of Volatile Organic Liquids
D1133 Kauri-Butanol Value of Hydrocarbon Solvents
D1193 Specification for Reagent Water
D 1217 Density and Relative Density (Specific Gravity) of Liquids by Bingham Pycnometer
D1250 Standard Guide for Petroleum Measurement Tables
(continues)
TABLE 2—(continued).
D 1266 Sulfur in Petroleum Products (Lamp Method)
D 1298 Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid Petroleum Products by
Hydrometer Method
D1310 Flash Point and Fire Point of Liquids by Tag Open-Cup Apparatus
D 1319 Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption
D 1353 Nonvolatile Matter in Volatile Solvents for Use in Paint, Lacquer, and Related Products
D1480 Density and Relative Density (Specific Gravity) of Viscous Materials by Bingham Pycnometer
D1481 Density and Relative Density (Specific Gravity) of Viscous Materials by Lipkin Bicapillary Pycnometer
D1552 Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry
D2170 Kinematic Viscosity of Asphalts (Bitumens)
D2171 Viscosity of Asphalts by Vacuum Capillary Viscometer
D2422 Standard Classification of Industrial Fluid Lubricants by Viscosity System
D2500 Cloud Point of Petroleum Products
D2509 Measurement of Load-Carrying Capacity of Lubricating Grease (Timken Method)
D2622 Sulfur in Petroleum Products by X-Ray Spectrometry
D2699 Research Octane Number of Spark-Ignition Engine Fuel
D2700 Motor Octane Number of Spark-Ignition Fuel
D2709 Water and Sediment in Distillate Fuels by Centrifuge
D2782 Measurement of Extreme-Pressure Properties of Lubricating Fluids (Timken Method)
D2887 Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
D2896 Base Number of Petroleum Products by Potentiometric Perchloric Acid Titration
D2982 Detecting Glycol-Base Antifreeze in Used Lubricating Oils
D3120 Trace Quantities of Sulfur in Light Liquid Petroleum Hydrocarbons by Oxidative Microcoulometry
D3231 Phosphorus in Gasoline
D3237 Lead in Gasoline by Atomic Absorption Spectrometry
D3244 Standard Practice for Utilization of Test Data to Determine Conformance with Specifications
D3338 Estimation of Heat of Combustion of Aviation Fuels
D3339 Acid Number of Petroleum Products by Semi-Micro Color Indicator Titration
D3525 Gasoline Diluent in Used Gasoline Engine Oils by Gas Chromatography
D3606 Determination of Benzene and Toluene in Finished Motor and Aviation Gasoline by Gas Chromatography
D3829 Predicting the Borderline Pumping Temperature of Engine Oils
D3941 Flash Point by the Equilibrium Method with a Closed-Cup Apparatus
D4052 Density and Relative Density of Liquids by Digital Density Meter
D4057 Standard Practice for Manual Sampling of Petroleum and Petroleum Products
D4175 Standard Terminology Relating to Petroleum, Petroleum Products, and Lubricants
D4177
Standard Practice for Automatic Sampling of Petroleum and Petroleum Products
D4206
Sustained Burning of Liquid Mixtures by the Setaflash Tester (Open Cup)
D4294
Sulfur in Petroleum Products by Energy-Dispersive X-Ray Fluorescence Spectroscopy
D4307
D4626 Standard Specification for Performance of Engine Oils
D4628 Calculation of Gas Chromatographic Response Factors
D4636 Analysis of Barium, Calcium, Magnesium, and Zinc in Unused Lubricating Oils by Atomic Absorption Spectrometry
Corrosiveness and Oxidation Stability of Hydraulic Oils, Aircraft Turbine Engine Lubricants, and Other Highly
Refined Oils
D4683 Measuring Viscosity at High Shear Rate and High Temperature by Tapered Bearing Simulator
D4684 Determination of Yield Stress and Apparent Viscosity of Engine Oils at Low Temperature
D4737 Calculated Cetane Index by Four Variable Equation
D4739 Base Number Determination by Potentiometric Titration
D4741 Measuring Viscosity at High Temperature and High Shear Rate by Tapered-Plug Viscometer
D4863 Determination of Lubricity of Two-Stroke-Cycle Gasoline Engine Lubricants
D4927 Elemental Analysis of Lubricant and Additive Components-Bcirium, Calcium, Phosphorus, Sulfur, and Zinc by Wave-
length-Dispersive X-Ray Fluorescence Spectroscopy
D5119 Test Method for Evaluation of Automotive Engine Oils in the CRC L-38 Spark-Ignition Engine
D5133 Low Temperature, Low Shear Rate, Viscosity/Temperature Dependence of Lubricating Oils Using a Temperature
Scanning Technique
D5134 Detailed Anedysis of Petroleum Naphthas Through n-Nonane by Capillary Gas Chromatography
D5185 Determination of Additive Elements, Wear Metals and Contaminants in Used Lubricating Oils by Inductively-Coupled
Plasma Atomic Emission Spectrometry
D5186 Determination of the Aromatic Content and polynuclear Content of Diesel Fuels and Aviation Turbine Fuels by Super-
critical Fluid Chromatography
D5290 Measurement of Oil Consumption, Piston Deposits, and Wear in a Heavy-Duty High-Speed Diesel Engine-NTC-400
Procedure
D5302 Evaluation of Automotive Engine Oils for Inhibition of Deposit F o r m a t i o n and Wear in a Spark-Ignition Internal
Combustion Engine Fueled with Gasoline and Operated Under Low-Temperature, Light-Duty Conditions
D5480 Engine Oil Volatility by Gas Chromatography
D5481 Measuring Apparent Viscosity at High-Temperature and High-Shear Rate by Multicell Capillary Viscometer
D5533 Evaluation of Automotive Engine Oils in the Sequence HIE, Spark-Ignition Engine
D5800 Evaporation Loss of Lubricating Oils by the Noack Method
D5844 Evaluation of Automotive Engine Oils for Inhibition of Rusting (Sequence IID)
(continues)
CHAPTER 17: A UTOMOTIVE LUBRICANTS 487
TABLE 2—(continued).
D 5862 Evaluation of Engine Oils in Two-Stroke Cycle Turbo-Supercharged 6V92TA Diesel Engine
D 5966 Evaluation of Diesel Engine Oils for Roller Follower Wear in Light-Duty Diesel Engine
D 5967 EvcJuation of Diesel Engine Oils in the T-8 Diesel Engine
D 5968 Evaluation of Corrosiveness of Diesel Engine Oil
D 6074 Guide for Characterizing Hydrocarbon Lubricant Base Oils
D 6082 High Temperature Foaming Characteristics of Lubricating Oils
D 6202 Measurement of the Effects of Automotive Engine Oils on the Fuel Economy of Passenger Cars and Light-Duty Trucks
in the Sequence VIA Spark Ignition Engine
D 6278 Shear Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus
D 6299 Applying Statistical Quality Assurance Techniques to Evaluate Analsîcal Measurement System Performance
D 6300 Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products and Lubricants
D 6335 Determination of High Temperature Deposits by Thermo-Oxidation Engine Oil Simulation Test
D 6417 Estimation of Engine Oil Volatility by Capillary Gas Chromatography
D 6483 Evaluation of Diesel Engine Oils in the T-9 Diesel Engine
D 6557 Evaluation of Rust Preventative Characteristics of Automotive Engine Oils
E 1 Specification for ASTM Thermometers
E 29 Standard Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
E 77 Inspection and Verification of Thermometers
E 128 Maximum Pore Diameter and Permeability of Rigid, Porous Filters for Laboratory Use
E 135 Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
E 178 Practice for Dealing With Outlying Observations
E 191 Specification for Apparatus for Microdetermination of Carbon a n d Hydrogen in Organic and Organo-Metallic
Compounds
E 270 Terminology Relating to Liquid Penetrant Examination
E 300 Practice for Sampling Industrial Chemicals
E 344 Terminology Relating to Thermometry and Hydrometry
E 355 Gas Chromatographic Terms and Relationships
E 380 Use of the International System of Units (SI) (The Modernized Metric System)
E 473 Terminology Relating to Thermal Analysis
E 502 Selection and Use of ASTM Standards for the Determination of Flash Point of Chemicals by the Closed Cup Method
E 594 Testing Flame Ionization Detectors Used in Gas Chromatography
E 691 Conducting an Inter-Laboratory Study to Determine the Precision of a Test Method
E 1119 Specification for Industrial Grade Ethylene Glycol
E 1500 Installing Fused Silica Open Tubular Capillary Columns in Gas Chromatographs
G 40 Terminology Relating to Wear and Erosion
TABLE 3—Referenced documents to non-ASTM methods for engine oils.
Organization Test Method or Document Title
ANSI (American National Standard MC96.1 Temperature Measurement—Thermocouples
Standards Institute)
API (American Petroleum API 1509 Engine Service Classification and Guide to Crankcase Oil Selection
Institute) Standard
Chemical Manufacturers CMA Petroleum Additives Product Approval Code of Practice
Association Code
Coordinating Research CRC Rust Rating (CRC Manual No. 7)
Council (CRC) Motor Rating CRC Sludge Rating Manual (CRC Manual No. 12)
Method Manuals CRC Varnish Rating Manual (CRC Manual No. 14)
CRC Techniques for Valve Rating (CRC Manual No. 16)
Deutsches Institut fiir DIN 51.581 Noack Evaporative Test
Normunge DIN 1725 Specification for Aluminum Alloys
DIN 12785 Specification for Glass Thermometers
Federal Test Method Standard No. 791b, Lubricants Liquid Fuels and Related Products, Methods of Testing
No. 791C, Method 3470
No. 791, Method 5308.7
General Motors Corporation GM9099-P Engine Oil Filterability Test (EOFT)
Engineering Standard
lEEE/ASTM (Institute of SI-10 Standard for Use of International System of Units (SI): The M o d e m Metric System
Electrical and Electronic
Engineers)
Institute of Petroleum IP 17 Colour by the Lovibond Tintometer
IP 139 Neutralization Number by Color Indicator Titration
IP 146 Test for Foaming Characteristics of Lubricating Oil
ISO Guide 25-General Requirements for the Calibration and Testing Laboratories
Guide 34 Quality Systems Guidelines for the Production of Reference Materials
Guide 35 Certification of Reference Material-General and Statistical Principles
3104, Petroleum Products—Transparent and Opaque Liquids-Determination of Kinematic Vis-
cosity and Calculation of Dynamic Viscosity
ISO 3105, Glass CapHlaiy Kinematic Viscometers—Specification and Operating Instructions
ISO 3696 Water for AnalyticEil Laboratory Use—Specification and Test Methods
ISO 9000 Quality Management and Quality Assurance Standards-Guidelines for Selection and Use
Military Specification MIL-L-2104, Lubricating Oil, Internal Combustion Engine, Combat/Tactical Services
SAE (Society of Automotive J183, Engine Oil Performance and Engine Service Classification (Other Than "Energy Conserving")
Engineers) Standards J254, Instrumentation and Techniques for Exhaust Gas Emissions Measurement
J300, Engine Oil Classification
J304, Engine Oil Tests
J726, Air Cleaner Test Code (Includes Piezometer Ring Specifications)
J1423, Passenger Car and Light-Duty Truck Energy-Conserving Engine Oil Classification
J1995, Engine Power Test Code - Spark Ignition and Compression Ignition—Gross Power Rating
U.S. Federal Test Method No. 791, Method 5308.7 Corrosiveness and Oxidative Stability of Light Oils (Metal Squares)
Standards No. 791b Lubricants Liquid Fuels and Related Products; Methods of Testing
TABLE 4—Referenced documents in ASTM standard test methods for transmission fluids.
A108 Specification for Steel Bars, Carbon, Cold-Finished, Standard Quality
A 109 Specification for Steel, Strip, Carbon, Cold-Rolled
A 240/A 240 M Specification for Heat-Resisting Chromium and Chromium-Nickel Stainless Steel Plate, Sheet, and Strip for
Pressure Vessels
B224 Classification of Coppers
D91 Precipitation N u m b e r of Lubricating Oils
D130 Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test
D235 Specification for Mineral Spirits (Petroleum Spirits) (Hydrocarbon Dry Cleaning Solvent)
D396 Specification for Fuel Oils
D412 Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic Elastomers—Tension
D445 Kinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
D471 Test Method for Rubber Property-Effect of Liquids
D512 Chloride Ion in Water
D516 Sulfate Ion in Water
D664 Acid Number of Petroleum Products by Potentiometiic Titration
D893 Insolubles in Used Lubricating Oils
D975 Specification for Diesel Fuel Oils
D 1193 Specification for Reagent Water
D1217 Density and Relative Density (Specific Gravity) of Liquids by Bingham Pycnometer
D 1401 Water Separability of Petroleum Oils and Synthetic Fluids
D1480 Density and Relative Density (Specific Gravity) of Viscous Materials by Bingham Bicapillary Pycnometer
D 1481 Density and Relative Density (Specific Gravity) of Viscous Materials by Lipkin Bicapillary Pycnometer
D 1655 Specification for Aviation Turbine Fuels
D 1838 Copper Strip Corrosion by Liquefied Petroleum (LP) Gases
D2170 Test Method for JCinematic Viscosity of Asphalts (Bitumens)
D2240 Rubber Property-Durometer Hardness
D2422 Classification of Industrial Fluid Lubricants by Viscosity System
D3603 Rust-Preventing Characteristics of Steam Turbine Oil in the Presence of Water (Horizontal Disk Method)
D4057 Manual Sampling of Petroleum and Petroleum Products
D4175 Terminology Relating to Petroleum, Petroleum Products, and Lubricants
D4177 Automatic Sampling of Petroleum and Petroleum Products
D5182 Evaluating the Scuffing (Scoring) Load Capacity of Oils (FZG Visual Method)
D5579 Evaluating the Thermal Stability of Manual Transmission Lubricants in a Cyclic Durability Test
D5662 Determining Automotive Gear Oil Compatibility with Typical Oil Seal Elastomers
D5704 Evaluation of the Thermal and Oxidative Stability of Lubricants Used for Manual Transmissions and Final
Drive Axles
D5760 Performance of Manual Transmission Gear Lubricants
D6074 Guide for Characterizing Hydrocarbon Lubricant Base Oils
El Specification for ASTM Thermometers
E77 Inspection and Verification of Thermometers
E527 Practice for Numbering Metals and Alloys
G40 Terminology Relating to Erosion and Wear
ASTM Adjuncts ASTM Copper Strip Corrosion Standard Engineering Drawings PCN ADJD5704
TABLE 5—Âdditional standards or specifications related to transmission fluids.

ANSI/ISA (Instrument Society of America)-S7.3 Quality Stsindard for Instrument Air
DIN51354Teill FZG Zahnrad Verspannungs Priif Maschine-Allgemeine Arbeitsgrundlagen
Federal Specification RRS-366 (Method 5329 of W-L-791e) Test Sieve Sizes
QQ-S-698 Steel Sheet and Strip, Low Carbon
PD-680 Standard Solvent
JAN-H-792 Operations of Humidity Cabinet
Federal Specifications Standard No. 79IC Method 3430.2 Compatibility Characteristics of Universal Gear Lubricants
Method 3440.1 Storage Solubility Characteristics of Universal Gear Lubricants
Federal Standard No. 791C, Method 3440.1 Storage Solubility Characteristics of Universal Gear Lubricants
Institute of Petroleum Specifications-IP Standard Thermometers, Appendix A
Specifications for IP Standard Reference Liquids, Appendix B
BS 871 Specification for abrasive papers and cloths
BS 970: Part 1: Carbon and Carbon Manganese Steels Including Free Cutting
Steels
ISO Guide 25—General Requirements for the Calibration and Testing Laboratories
3104 Petroleum Products-Transparent and Opaque Liquids-Determination of
Kinematic and Calculation of Dynamic Viscosity
3105 Glass Capillary Kinematic Viscometers-Specification a n d Operating
Instructions
3696 Water for Analytical Laboratory Use-Specification and Test Methods
4021 Hydraulic Fluid Power-Particulate Contamination Analysis-Extraction of
Fluid Samples from Lines of an Operating System
4406 Hydraulic Fluid Power-Fluids-Method for Coding Level of Contamination
by Solids Particles
9000 Quality Management a n d Quality Assurance Standards-Guidelines for
Selection and Use
Mack Trucks Oil, Gear Multi-Purpose (GO-H)
Military Standard MIL-L-2105 and 2105D, Lubricating Oil, Gear, Multipurpose
MIL-C-15074C, Corrosion Preventive Compound Finger Print Remover
MIL-C-16173D Corrosion Preventive Compound, Solvent Compound Cutback,
Cold Application
SAE Standard J308, Axle and Manual Transmission Lubricants
J 405 Chemical Composition of SAE Wrought Stainless Steels
1009C Tee Reducer, Bulkhead on Side, Flareless Tube
Table 6—Referenced documents in ASTM standard tests for greases.

D88 Saybolt Viscosity
D95 Water in Petroleum Products and Bituminous Materials by Distillation
D97 Pour Point for Petroleum Oils
D130 Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test
D 156 Saybolt Color of Petroleum Products (Saybolt Chromometer Method)
D217 Cone Penetration of Lubricating Grease
D235 Specifications for Mineral Spirits (Petroleum Spirits) Hydrocarbon Dry Cleaning Solvent
A 240/A 240M Specification for Heat-Resisting Chromium and Chromium-Nickel Stainless Steel Plate, Sheet, and Strip for
Pressure Vessels
D297 Rubber Products—Chemical Analysis
D329 Specification for Acetone
D412 Vulcanized Rubber and Thermoplastic Elastomers-Tension
D445 BCinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
D446 Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers
D471 Rubber Property—Effect of Liquids
D473 Sediment in Crude Oils and Fuel Oils by the Extraction Method
D566 Dropping Point of Lubricating Grease
D770 Specification for Isopropyl Alcohol
D785 Rockwell Hardness of Plastics and Electrical Insulating Materials
D937 Cone Penetration of Petrolatum
D972 Evaporation Loss of Lubricating Greases and Oils
D 1078 Distillation Range of Volatile Organic Liquids
D 1310 Flash Point and Fire Point of Liquids by Tag Open-Cup Apparatus
D 1353 Nonvolatile Matter in Volatile Solvents for Use in Paints, Varnish, Lacquer, and Related Products
D1403 Cone Penetration of Lubricating Grease Using One-Quarter and One-Half Scale Cone Equipment
D 1480 Density and Relative Density (Specific Gravity) of Viscous Materials by Bingham Pycnometer
D 1481 Density and Relative Density (Specific Gravity) of Viscous Materieds by Lipkin Bicapillary Pycnometer
D2170 BCinematic Viscosity of Asphalts (Bitumens)
D2265 Dropping Point of Lubricating Grease Over Wide Temperature Range
D2500 Cloud Point of Petroleum Oils
D2595 Evaporation Loss of Lubricating Greases Over Wide Temperature Range
D2714 Calibration and Operation of the Falex Block-on-Ring Friction and Wear Testing Machine
D3182 Practice for Rubber-Materials, Equipment, and Procedures for Mixing Standard C o m p o u n d s and Preparing
Standardized Vulcanized Sheets
D3183 Practice for Rubber-Preparation of Pieces for Test Purposes from Products
D3244 Practice for Utilization of Test Data to Determine Conformance with Specifications
D3527 Life Performance of Automotive Wheel Bearing Grease
D4289 Elastomer Compatibility of Lubricating Greases and Fluids
D4290 Determining the Leakage Tendencies of Automotive Wheel Bearing Grease under Accelerated Conditions
D4693 Low-Temperature Torque of Grease-Lubricated Wheel Bearings
D4950 Classification of and Specification for Automotive Service Greases
D5483 Oxidation Induction Time of Lubricating Greases by Pressure Differential Scanning Calorimetry
D5706 Determining Extreme Pressure Properties of Lubricating Greases Using a High-Frequency, Linear Oscillation
(SRV) Test Machine
D5707 Measuring Friction and Wear Properties of Lubricating Grease Using a High-Frequency, Linear Oscillation (SRV)
Test Machine
D5969 Corrosion-Preventive Properties of Lubricating Greases in Presence of Dilute Synthetic Sea-Water Environments
D6138 Corrosion-Preventive Properties of Lubricating Greases Under Dynamic Wet Conditions (Emcor Test)
D6184 Oil Separation from Lubricating Grease (Conical Sieve Method)
D6185 Practice for Evaluating Compatibility of Binary Mixtures of Lubricating Greases
E 11 Specification for Wire-Cloth Sieves for Testing Purposes
E77 Inspection and Verification of Thermometers
E220 Calibration of Thermocouples by Comparison Techniques
E230 Temperature-Electromotive Force (EMF) Tables for Standardized Thermocouples
E563 Practice for Preparation and Use of Freezing Point Reference Baths
E585 Specification for Sheathed Base-Metal Thermocouple Materials
E608 Specification for Metal-Sheathed Base-Metal Thermocouples
E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
G 15 Terminology Related to Corrosion and Corrosion Testing
Adjunct ASTM Adjunct: Copper Strip Corrosion Standard, Adjunct PCN 12-401300-00
ASTM Test Methods for Rating Motor, Diesel, and Aviation Fuels; Motor Fuels (Section I), Reference Materials and
Blending Accessories (Annex 2), Reference Materials (A2.7), and Table 32; (Specification for ASTM Knock Test
Reference Fuel, n-heptane)
TABLE 7—Âdditional standards or specifications related to greases.

ABMA (American Bearing Manufacturers Standard 4. Tolerance Definitions and Gaging Practices for Ball and Roller Bearings
Association)
AFBMA (Anti-Friction Bearing Manufacturers Standard 19 1974 (available from ANSI, American National Standards Institute,
Association) B.3.19-1975)
ANSI (American National Standards Institute) Specification B3.12 for Metal Balls
ANSI/AFBMA Standard 20-1987 Radial Bearings of Ball, Cyhndrical, Roller, and
Spherical-Roller Type-Metric Designs (AFBMA Code 20BCO2JO)
British Standards Institute BS970: 1983 Part I, Section S
Compressed Gas Association Booklets G-4 and G-4-1
Federal Test Method Standard 791C, Method 3603.5, Swelling of Synthetic Rubbers
IP (Institute of Petroleum) Specification for Standard IP Thermometers
Institute of Petroleum 50, Method of Testing for Cone Penetration of Lubricating
Grease
ISO (American National Standards Institute) Guide 25-General Requirements for the Calibration and Testing Laboratories
3104 Petroleum Products-Transparent and Opaque Liquids-Determination of
Kinematic Viscosity and Calculation of Dynamic Viscosity
3105 Glass Capillary Kinematic Viscosmeters-Specification and Operating
Instructions
3696 Water for Analytical Laboratory Use-Specification and Test Methods
9000 Quality M a n a g e m e n t and Quality Assurance Standards-Guidelines for
Selection and Use
Military Standard MIL-G-10924F, Specification for Automotive and Artillery
NLGI (National Lubricating Grease Institute) Grease Consistency Specification
SAE (Soc. Automotive Engineers) Standard AMS (Aerospace Materials Specification) 3217A Standard Elastomer Stocks-Test
Slabs
AMS 3217/2A Test Slabs, Acrylonitrile
AMS 3217/3A Test Slabs, Chloroprene (CR)-65-75
Butadiene (NBR-L)-Low Acrylonitrile, 65-75
U.S. Air Force Specification 539, Specification Bulletin for Standard Elastomer Stocks
TABLE 8—^Referenced documents in ASTM stzmdards related to gear lubricants.
B16 Specification for Free-Cutting Brass Rod, Bar, and Shapes for Use in Screw Machines
D96 Water and Sediment in Crude Oil by Centrifuge Method (Field Procedure)
D 130 Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test
D235 Specification for Mineral Spirits (Petroleum Spirits) (Hydrocarbon Drycleaning Solvents)
D329 Specification for Acetone
D341 Viscosity-Temperature Charts for Liquid Petroleum Products
D396 Specification for Fuel Oils
D412 Vulcanized Rubber and Thermoplastic Rubbers and Thermoplastic Elastomers—Tension
D446 Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers
D471 Rubber Property-Effect of Liquids
D484 Specification for Hydrocarbon Drycleaning Solvents
D975 Specification for Diesel Fuel Oils
D 1480 Density and Relative Density (Specific Gravity) of Viscous Materials by Bingham Pycnometer
D 1481 Density and Relative Density (Specific Gravity) of Viscous Materials by Lipkin Bicapillary Pycnometer
D1655 Specification for Aviation Turbine Fuels
D1796 Water and Sediment in Fuel Oils by Centrifuge Method (Laboratory Procedure)
D1838 Copper Strip Corrosion by Liquefied Petroleum (LP) Gases
D2170 Viscosity of Asphalts (Bitumens)
D2266 Wear Preventive Characteristics of Lubricating Fluid (Four-Ball Method)
D2509 Measurement of Load-Carrying Capacity of Extreme Lubricating Grease (Timken Method)
D2670 Wear Properties of Fluid Lubricants (Falex Pin and Vee Block Method)
D2783 Measurement of Extreme Pressure Properties of Lubricating Fluids (Four-Ball Method)
D5182 Evaluating the Scuffing (Scoring) Load Capacity of Oils
D5579 Evaluating the Thermal Stability of Manual Transmission Lubricants In a Cyclic Durability Test
D5662 Determining Automotive Gear Oil Compatibility with Typical Oil Seal Elastomers
D5704 Evaluation of the Thermal and Oxidative Stability of Lubricating Oils Used for Manual Transmissions and Final Drive
Axles
D5760 Specification for Performance of Manual Transmission Gear Lubricants
E 128 Maximum Pore Diameter and Permeability of Rigid, Porous Filters for Laboratory Use
G40 Terminology Relating to Erosion and Wesir
ASTM Three Glossy Prints of Test Blocks Showing Scars (D 2780)
Adjuncts ASTM Copper Strip Corrosion Protection
TABLE 9—Additional standards related to gear lubricants.

Organization and Test No. Test Method or Document Title
ANSI (American National Specification for Metal Balls
Standards Institute) B3.12
DIN (Deutsch Industries Norm) FZG Zahnrad Verspannungs Pruef Maschine—AUgemeine Arbeitsgrundlagen
51 354 Teil (Part) 1
Federal Standard No 791 C Method 3430.2 Compatibility Characteristics of Universal Gear Lubricants
Method 3440.1 Storage Solubility Characteristics of Universal Gear Lubricants
Institute of Petroleum Standards Color measured using the Lovibond Tintometer
IP 17
ISO Guide 25-General Requirements for the Calibration and Testing Laboratories
3104 Petroleum Products-Transparent and Opaque Liquids-Determination of Kinematic
Viscosity and Calculation of Dynamic Viscosity
3105 Glass JCinematic Capillary Viscometers-Specifications and Operating Instructions
3696 Water for Analyticeil Laboratory Use-Specification and Test Methods
9000 Quality Management and Quality Assurance Standards-Guidelines for Selection
and Use
Mack Trucks, Inc. GO-H, Oil, Gear: Multi Purpose
Military Standard MIL-L-2105, Lubricating Oil, Gear, Multipurpose
SAE (Society of Automotive Engineers) J308 Axle and Manual Transmission Lubricants
TABLE 10—ASTM standard test methods related to brake fluids.

D91 American Automobile Manufacturers Association
D260 Standard Recommended Practice for General Gas Chromatography Procedure
D344 Method of Test for Relative Dry Hiding Power of Paints
D395 Aerospace Materials Specification
D412 Rubber Properties in Tension
D445 K n e m a t i c Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
D664 Neutralization Number of Potentiometric Titration
D746 Brittleness
D 1120 Method of Test for Boiling Point of Engine Antifreezes
D1209 Color of Clear Liquids (Platinum-Cobalt Pigments)
D 1364 Water in Volatile Solvents (Fischer Reagent Titration Method)
D 1415 Method of Test for International Hardness of Vulcanized Natural Rubber and Synthetic Rubbers
D2240 Rubber Property—Durometer Hardness
D3182 R e c o m m e n d e d Practice for Rubber-Materials, E q u i p m e n t and Procedures for Mixing S t a n d a r d Compounds a n d
Preparing Standard Vulcanized Sheets
D3185 Methods for Rubber-Evaluation of SBR (Styrene-Butadiene Rubber) including Mixtures with Oil
El Specification for ASTM Thermometers
E 145 Specification for Gravity-Convection and Forced-Ventilation Ovens
E 260-73 Standard Recommended Practice for General Gas Chromatography Procedure
TABLE 11—Definition of terms and abbreviations used in the text.

AAMA American Automobile Msinufacturers Association
AMS Aerospace Materials Specification
ANSI American National Standards Institute
API American Petroleum Institute
ASTM American Society for Testing and Materials
CEC Coordinating European Council
CF, CF-2, CF-4, "C" represents a category for engine oils that are used in compression ignition (diesel) engines. F, CF-2, CF-4, G,
CG, CG-4 and G-4 represent a particular oil quality.
CR Chloroprene Rubber
CRC Coordinating Research Council
CRC Press Chemical Rubber Company Press
CVT Continuously Variable Transmission
cSt Centistokes, a measure of viscosity
DIN Deutsch Industries Norm (German industry standard)
EMA Engine Manufacturers Association
EOAT Engine Oil Aeration Test
EOFT Engine Oil Filterability Test
EOWTT Engine Oil Water Tolerance Test
EP Extreme Pressure (used for lubricants that experience high pressure or high temperature)
FZG Fahrzeug (German word for motor vehicle)
GF-1, GF-2, Terms represent an engine oil quality that is defined by a series of tests that the oil must pass. GF indicates the
GF-3, GF-4 oils are used with gasoline fuel. GF-1 corresponds to API-SH quality engine oil.
ILSAC International Lubricant Standardization and Approval Committee
ISA Instrument Society of America
ISO Represents a standard from the American National Standsirds Institute
JAMA Japan Automobile Manufacturers Association
MIL Military specification
NBR-L Acrylonitrile-Butadiene Rubber with Low Acrylonitrile
PC Pre chamber, associated with engine oil tests for diesel engines
psi Pounds per square inch. 550 psi equals 3.8 million N/m^
rpm Revolutions per min
SAE Society of Automotive Engineers
SF, SG, SH, "S" represents a category for engine oils that are used in spark ignition engines. Each successive final letter
SJ, SL represents a more recent category. (SL is more recent than the others listed.)
TEOST Thermo Oxidation Engine Oil Simulation Test
ZDP or ZDDP Zinc dialkyl-dithio phosphate, an antioxidant and an anti-wear agent used as an additive in engine oil
REFERENCES Engine Vehicles," SAE International Paper No. 940745, Society

of Automotive Engineers, Warrendale, PA, 1994.
[1] Younggren, P. J. and Schwartz, S. E., "The Effects of Trip [9] Ueda, F., Sugiyama, S., Arimura, K., Hamaguchi, S., and
Length and Oil Type (Synthetic Versus Mineral Oil) on Engine Akiyama, K., "Engine Oil Additive Effects on Deactivation of
Damage and Engine-Oil Degradation in a Driving Test of a Ve- Monolithic Three-Way Catalysts and Oxygen Sensors," SAE In-
hicle with a 5.7L Engine," SAE International Paper No. 932838, ternational Paper No. 940746, Society of Automotive Engineers,
Society of Automotive Engineers, Warrendale, PA, 1993. Warrendale, PA, 1994.
[2] Schwartz, S. E., "A Comparison of Engine Oil Viscosity, Emul- [10] Deane, B. C, Choi, E., and Crosthwait, K., "The Relationship of
sion Formation, and Chemical Changes for M85 and Gasoline- Base Oil Volatility to Oil Loss in Automotive Application,"
Fueled Vehicles in Short-Trip Service," SAE International Paper NPRA Paper No. AM 97-40, National Petroleum Refiners Asso-
No. 922297, Society of Automotive Engineers, 1992. ciation, Washington, DC, 1997.
[3] McGeehan, J. A., Alexander, III, W., Ziemer, J. N., Roby, S. H., [11] Choi, E. and Deane, B., "Base Stock Volatility and Oil Con-
and Graham, J. P., "The Pivotal Role of Crankcase Oil in Pre- sumption," NPRA Paper No. AM-98-47, National Petroleum Re-
venting Soot Wear and Extending Filter Life in Low Emission finers Association, Washington, DC, 1998.
Diesel Engines," SAE International Paper No. 1999-01-1525, So- [12] Manni, M., Gommellini, C, and Sabbioni, G., "Effect of Physi-
ciety of Automotive Engineers, 1999. cal Characteristics of Lubricating Oils on Emissions, Fuel Econ-
[4] Machida, H. and Karachi, N., "Prototype Design and Testing of omy and Oil Consumption in a Light Duty Diesel Engine," SAE
a Half Toroidal CVT," SAE International Paper No. 900552, So- International Paper No. 952552, Society for Automotive Engi-
ciety of Automotive Engineers, WEirrendale, PA, 1990. neers, Warrendale, PA, 1995.
[5] Hata, H. and Tsobuchi, T., "Molecular Structure of Traction Flu- [13] Rounds, F. G., "Effect of Lubricant Additives on the Prowear
ids in Relation to Traction Properties," Tribology Letters, Vol. 5, Characteristics of Synthetic Diesel Soots," Lubrication Engi-
1998, pp. 69-74. neering, Vol. 43, No. 4, 1987.
[6] CuUey, S. A. and McDonnell, T. F., "The Impact of Passenger Car [14] Schwartz, S. E., "A Model for the Loss of Oxidative Stability of
Motor Oil Phosphorus Levels on Engine Durability, Oil Degra- Engine Oil During Long-Trip Service, Part I: Theoretical Con-
dation, and Exhaust Emissions in a Field Trial," SAE Interna- siderations," STLE (Society of Tribologists and Lubrication Engi-
tional Paper No. 952344, Society of Automotive Engineers, War- neers) Tribology Transactions, Vol. 35, No. 2, 1992, pp. 235-244.
rendale, PA, 1995. [15] Schwartz, S. E., "A Model for the Loss of Oxidative Stability of
[7] CuUey, S. A., McDonnell, T. F., Ball, D. J., Kirby, C. W., and Engine Oil During Long-Trip Service, Part II: Vehicle Measure-
Hawes, S. W., "The Impact of Passenger Car Motor Oil Phos- ments," STLE Tribology Transactions, Vol. 35, No. 2, 1992, pp.
phorus Levels on Automotive Emissions Control Systems," SAE 307-315.
International Paper No. 961898, Society of Automotive Engi- [16] Gresham, R. M., Tribology Data Handbook, CRC (Chemical Rub-
neers, Wcirrendale, PA, 1996. ber Company) Press, Boca Raton, FL, 1997, pp. 600-607.
[8] Drury, C. and Whitehouse, S., "The Effect of Lubricant Phos- [17] Crutzen, P. J. and Ramanathan, V., "The Ascent of Atmospheric
phorus Level on Exhaust Emissions in a Field Trial of Gasoline Sciences," Science, Vol. 290, pp. 299-304.
MNL37-EB/Jun. 2003
Metalworking and
Machining Fluids
Syed Q. A. Rizvi:\
METALWORKING IS THE PROCESS OF CONVERTING BULK METAL into except at very low temperatures. At these temperatures, the
a component or apart and primarily involves two types of op- lubricant gains viscosity, w h i c h can interfere with the
erations: those that produce metal debris and those that pro- smooth operation of the equipment. Internal friction is im-
duce no debris. The former type is classified as metal removal portant when considering a lubricant's intrinsic properties,
operations and the latter type is classified as metal forming such as viscosity (ASTM D 445, D 2983, D 3829, D 4684, and
operations. Cutting and grinding are examples of the first D 5293) and pour point (ASTM D 97).
type and drawing, stamping, and bending are examples of the All metal surfaces, irrespective of their finish, contain
second type. All metalworking operations involve bringing ridges, valleys, asperities, and depressions. When two metal
two solids, a tool and a work piece, together to create a new surfaces come in contact, solid friction, sometimes called
part or a shape. The process involves high friction, high tem- static or adhesive friction, ensues and the surfaces undergo
peratures, and tool wear; and it is the job of the lubricant, or adhesion and cold welding. The strength of such an associa-
the metalworking fluid, to control them. Metalworking fluids tion depends upon the hardness of the materials, the cleanli-
accomplish this by providing cooling, lubrication, and pro- ness of the surfaces, and the electronic structure of the met-
tection against corrosion. Therefore, they improve the effi- als as related to their tendency to form metal-metal solutions,
ciency of the operation, and hence increase productivity. or alloys [4,5]. As soon as the surfaces start to move, kinetic
friction comes into play. Kinetic friction results from the
plowing of the asperities of one surface across the other sur-
FUNDAMENTAL CONCEPTS face, plastic deformation or elastic hysteresis, and wear de-
bris getting lodged between the moving surfaces [5]. Static
Lubrication friction is larger than kinetic friction. This is because of the
extent and the duration of contact. Friction is also related to
Friction is c o m m o n to all surfaces in contact and is usually the tjTDe of motion of the bodies. Sliding motion, for instance,
represented by the friction coefficient, signified by the sym- leads to higher friction than rolling motion and hence results
bol /JL. The coefficient of friction (/x) is a unit-less ratio that in more wear. This is primarily a consequence of the larger
equals 0/N, where 0 represents the frictional force experi- contact zone of the sliding surfaces.
enced by the two contacting bodies in motion and N repre-
Applications that encounter metal-to-metal contact involve
sents the n o r m a l force pressing the same two bodies to-
either no lubrication (dry), solid lubrication, or liquid lubri-
gether. Its value ranges from zero (0) to one (1). The higher
cation. Wear resistance in equipment designed to operate
the value, the higher the frictional force or the resistance of
without lubrication is introduced by the use of low-wear met-
the contacting bodies towards motion. Under boundary lu-
als and/or surface treatment, such as hardening or coating.
brication conditions, ^l approaches 1.
Solid lubrication is c o m m o n where liquid lubrication is
Minimizing friction is one of the fundamental functions of u n w a n t e d or is difficult because of equipment design or
a lubricant. If friction is not controlled, it can lead to wear extremely high operating temperatures. Such lubricants, ex-
and surface damage, and ultimately to catastrophic failure of emplified by graphite and molybdenum disulfide, have multi-
the equipment. Because of a generally direct correlation be- layered structures with low shear strength in some direc-
tween friction a n d wear [1,2], p r o p e r lubrication of the tions. Movement in such directions is therefore facilitated.
equipment is important if its integrity is to be preserved over These lubricants are applied to equipment in a number of
its designated lifetime. However, it is important to note that ways such as b o n d e d dry films, sputtered films, or loose
the correlation between friction and wear is a function of the flakes. In metalworking applications, we are primarily inter-
system and is not always direct [3]. ested in liquid lubrication. The purpose is either to separate
In lubricant-related applications, we are concerned with contacting surfaces by introducing a liquid film or to mini-
three types of friction, that is, the solid friction, fluid friction, mize wear by delivering wear control additives to surfaces in
and internal friction [12]. The main function of a lubricant is contact.
to minimize solid friction, which it achieves by forming a
The relationship of coefficient of friction (/x) and the rela-
fluid film between two contacting (often metal) surfaces.
tionship of oil film thickness (p) to lubricant viscosity (Z),
Usually, a fluid's internal friction is not of any major concern
equipment speed (N), and equipment load, or pressure (P), are
' Research and Development Manager, Lubricant Additives Divi- graphically represented in Fig. 1, Part A [6]. This graph is com-
sion, King Industries, Inc., Science Road, Norwalk, CT 06852. monly referted to as the Streibeck Curve. As one can see, the
497

W^Y^/.iA^^.i'VÂ^lU*^
Lubricant
Firm
FLUID-FILIVI LUBRICATION
Surfaces well separated by
the bulk lubricartt film
Lubricant-
Film
MIXED-FILM LUBRICATION
Both the bulk lubricant and
the boundary film play a
role
BOUNDARY LUBRICATION
Performance essentially
depends upon the quality of
the boundary flim
(A) RELATIONSHIP OF VISCOSITY {2), {By GRAPHIC REPRESENTATION OF

SPEED (W), AND LOAD {P) TO LUBRICANT FILM THICKNESS IN
FRICTION AND FILM THICKNESS DIFFERENT LUBRICATION REGIMES
FIG. 1—Lubrication regimes in mechanical equipment.
ratio of ZN/P relates directly to oil film thickness (p), but in- cation is depicted in Fig. 2. The crosshatched area in the fig-
versely to coefficient of friction (/U,). This implies that high lu- ure indicates solid lubricant film that causes elastic defor-
bricant viscosity (Z), high equipment speed (N), and low mation of the metal surfaces.
equipment load (P) will allow the formation of a thick lubri- Boundary lubrication represents the other extreme of the
cant film, 2ind hence the equipment will encounter little or no lubricating environment. Under this kind of lubrication, high
friction. Conversely, low lubricant viscosity, low equipment loads and very slow speeds produce extreme pressures that
speed, and high equipment load will create a situation where can lead to a lack of effective lubrication, and hence promote
film thickness will be inappropriate and the equipment will maximum metal-to-metal contact. The lubricant film thick-
encounter high friction. The initial drop in the coefficient of ness in this type of lubrication is in the order of 0.0-2.0 fjun.
friction, shown in the figure, while moving from fluid-film to If not controlled, the resulting dry metallic friction will cause
mixed-film lubrication, reflects a decrease in viscous drag due extensive wear and ultimately total seizure. Reactive chemi-
to a decrease in lubricant viscosity and or equipment speed. cals, called antiwear and extreme pressure agents, provide
Mechanical equipment experiences three types of lubrica- protection in this kind of lubricating environment. Mixed-
tion environments: fluid-film, boundary, and mixed-film. film lubrication falls between the two extremes mentioned
These are depicted in Fig. 1, Part B [6]. Fluid-film lubrica- above and contains the characteristics of both the fluid-film
tion, also known as hydrodynamic lubrication, is of the most lubrication and the boundary lubrication. There are regions
desirable type. This type of lubrication depends upon the vis- of no metal-to-metal contact and of metal-to-metal contact.
cosity of the lubricant and is effective only when the load in Metalworking operations are designed to have at least
the contact zone is low. Under these circumstances, the slid- some metal-to-metal contact. This is because total separation
ing surfaces are separated by a lubricant film several times of surfaces will make the process inefficient. For example, in
the thickness (2-100 ;nm) of the surface roughness. metal removal operations, separation will lead to poor
Another type of hydrodynamic lubrication, referred to as tool-work piece contact, which will interfere in chip forma-
elasto-hydrodynamic lubrication or EHD [7-9], commonly tion. In metal forming operations, this will lead to low fric-
occurs in parts with rolling motion. In this type of lubrication and hence loss of control. This implies that in metal-
tion, the lubricant is exposed to high contact pressures and working, the lubricant must be designed to perform in
undergoes a large viscosity increase. See Viscosity section mixed-film and boundary lubrication regimes. In general,
and Fig. 4. This results in an extremely rigid lubricant film metal removal operations require boundary lubrication and
(0.01-5.0 /xm thick), which causes elastic deformation of the metal forming operations require mixed-film lubrication.
surfaces in the lubricating zone. Elasto-hydrodynamic lubri- Metal removal operations, therefore, involve little or no lu-
CHAPTER 18: METALWORKING AND MACHINING FLUIDS 499
Mutually Flattened Elastlcally Deformed

Areas Under Load Metal Strip Areas
FIG. 2—Elasto-hydrodynamic lubrication.
bricant film and metal forming operations involve a fairly
t
thin lubricant film, as shown in Fig. 1, Part B.
Lubricant film in metal forming operations is of two types:
wedge and squeeze. Wedge type films occur when two non-
parallel surfaces in motion converge and squeeze type films
occur when parallel surfaces in motion come together [10].
(A
In forming operations, wedge type films are more common M Naphthenic Oil
than the squeeze type. As the lubricant enters the converging E
zone, there is an increase in pressure that causes an increase E
in lubricant viscosity. This is a consequence of the lubricant
molecules coming closer. The increase in viscosity changes
(0
the nature of lubrication in the contact zone from being hy- o
drodynamic to elasto-hydrodynamic. As the lubricant exits, o
(A
the gap widens and there is a decrease in viscosity cind an in-
crease in velocity. This causes a reversal from elasto-hydro- Paraffinic Oil
dynamic lubrication to hydrodynamic lubrication (Fig. 1,
Part A). The result is separation of the surfaces and minimal m
metal-to-metal contact. A d r o p in viscosity is a consequence E
of the widening gap that permits lubricant molecules to move c
away from one another. '2.
The quality of the lubricant film determines the metal
forming efficiency. The higher the operation speed, the
Temperature ( C)
higher the film thickness; similarly, the higher the viscosity, FIG. 3—Viscosity-temperature relationship.
the higher the film thickness (Fig. 1). Both these conditions
therefore force the converging surfaces to move away from
each other (the gap widens), which improves the operation such as upsetting. The film thickness increases due to fast ap-
efficiency. For example, in rolling operations, the speed of proaching surfaces and the lubricant viscosity increases be-
strip determines the film thickness. Since temperature and cause of an increase in pressure. Both factors hinder lubri-
pressure also impact viscosity, hence lubricant film thick- cant flow out of the contact zone, which results in a squeeze
ness, these factors also affect the efficiency of the metal form- film. Deformation of the work piece during the operation re-
ing operations. Different base fluids have differing responses sults in a flatter surface, thereby making the squeeze film
to temperature and pressure, and therefore their properties thinner. The thickness of the squeeze films depends on lubri-
can influence the properties of the metal forming lubricants cant viscosity, speed, and load (force) in the same way as that
as well. Naphthenic basestocks are usually preferred over of the wedge films, but for the reasons described.
paraffinic basestocks. This is because they not only experi- Lubrication regime defines a lubricant's ability to support
ence a faster viscosity decrease with an increase in tempera- load (modify friction and reduce metal transfer) and can be
t u r e (have a lower viscosity index), they also u n d e r g o a determined by taking into account film thickness and com-
greater viscosity increase with a n increase in pressure. See bined surface roughness. The ratio of the two, represented by
Figs. 3 and 4. These factors make lubricants derived from A, equals film thickness (p) divided by the combined rough-
these basestocks extremely effective in high-pressure appli- ness of the surfaces (S), or p/5. The combined roughness is the
cations, such as rolling. roughness amplitude of two surfaces relative to their average
As mentioned earlier, squeeze films form when two paral- levels. The value of A equal to 0.5 implies boundary regime;
lel surfaces converge, a situation that occurs in operations the value of A between 0.5 and 3.0 implies mixed film regime;
Solid
Paraffinic Oil
Naphthenic Oil
0 20 40 60 80 100 120 140

Pressure (1,000 psi) •
FIG. 4—Viscosity-pressure relationship.
and the value of A greater than 3 implies fluid-iilm or hydro- (SUS), and Saybolt Furol Seconds (SFS) are now obsolete.
dynamic regime [10]. Unlike metal removal operations that The methodology to convert these units into Stokes is de-
primarily involve boundary lubrication regime, metal form- scribed in the ASTM Standard D 2161 [13].
ing operations start in the boundary regime but move into A number of factors affect viscosity. These include temper-
mixed-film and hydrodynamic regimes as the operation picks ature, pressure, time, and the structures of organic com-
up speed. Lubricant properties, such as viscosity and the pounds present in the fluid and their response to shear forces
presence of film-forming additives play a role in boundary [12]. The two variables whose effect primarily pertains to
and mixed-film regimes. Film-forming additives include fric- metalworking fluids eire temperature and pressure. Mineral
tion modifiers, antiwear agents, and extreme pressure oils and synthetic oils both experience a viscosity decrease
agents. These additives protect surfaces against extensive with an increase in temperature. In general, the viscosity of
friction and wear. They do so by forming low shear protective naphthenic oils decreases at faster rate than that of the paraf-
films either via physical adsorption, chemical adsorption, or finic oils (Fig. 3). The viscosity-temperature relationship of a
through chemical reaction. See the Film-forming Agents sec- fluid is expressed in terms of its viscosity index (VI) (DIN ISO
tion for further details. 2909 [14], ASTM D 2270 [13]). Viscosity index, based upon
kinematic viscosities at 40°C and 100°C, when originally in-
troduced had a scale ranging from 0 (zero) to 100. The two
Viscosity oils that were used to establish this scale no longer exist, but
The role of viscosity in forming effective lubricating films their viscosities are still used to compute viscosity indexes.
makes it one of the most important properties of a fluid [11]. Many modem oils have viscosity indexes that extend well be-
Viscosity is defined as a fluid's resistance to flow and is pri- yond 100. Such oils are made by isomerizing the low VI hy-
marily a consequence of the internal friction of the fluid [12]. drocarbons in oil to high VI hydrocarbons, via a process
The viscosity is of two tjfpes: absolute or dynamic viscosity called hydrocracking. The process involves treating the oil
and kinematic viscosity. Absolute viscosity is commonly ex- with hydrogen in the presence of a proprietary catalyst at
pressed in poise (P) or Pascal-seconds (Pa-s) [1 Pa-s =10^ high temperatures. Oils whose viscosities have a high sensi-
centipoise (cP)]. Kinematic viscosity is measured under the tivity to temperature have a low VI, and oils whose viscosities
accelerating influence of gravity and equals absolute viscos- have a low sensitivity to temperature have a high VI. Unlike
ity of the fluid divided by its density. It is expressed in centis- temperature, which has an inverse relationship to viscosity,
tokes (cSt), or square meters per second (m^/s) [1 m^/s =10* pressure bears a direct relationship. That is, when pressure
centistokes (cSt)]. Absolute viscosity is often not used for increases viscosity increases (Fig. 4). However, the effect,
metalworking fluids, but kinematic viscosity is. Previously which is a function of the chemical structure of the fluid, is
used units of kinematic viscosity, Saybolt Universal Seconds not as dramatic as in the case of temperature [12].
Lubricant viscosity is measured by the use of instruments, • Semisynthetic Fluid (oil-in-water emulsion concentrate;
called viscometers. Of many types that are available for this diluted prior to use)—more likely to support bacterial
purpose, capillary viscometers are used to measure kine- growth. The fluids belonging to this class contain oil and
matic viscosity. The lubricant is allowed to flow down a cap- additives emulsified in water. These preformed emulsions
illary and the viscosity is calculated by taking into account when diluted further are used to provide lubrication, cool-
flow time and the viscometer constemt. This constant is sup- ing, and corrosion protection.
plied by the standardization laboratory along with the in-
strument constant. Dynamic viscosity is determined by mul-
tiplying kinematic viscosity with fluid density. This is Oil-based Fluids
described in the ASTM D 445 procedure [13]. These lubricants, commonly referred to as straight oils, are
Viscosity is critical to determining the quality of the lubri- mineral oil-based. These primarily utilize hydrotreated naph-
cant film. In metal-forming applications, it determines the ef- thenic basestocks and contain polyol esters and fatty oils as
fectiveness of the film in separating the tool from the work lubricity agents, and sulfur, chlorine, and phosphorus-de-
piece and therefore controlling friction and wear. Metal re- rived extreme pressure additives. However, there is a growing
moval operations, on the other hand, have diverse lubrication trend towards the use of paraffinic basestocks because the
needs, and hence optimum lubricant viscosity must be esti- derived fluids have a lower tendency to produce mist. The
mated for each operation. This is accomplished by consider- cooling ability of these fluids is not as good as that of the wa-
ing the ability of the lubricant to enter and remain in the con- ter-based systems, but it is respectable. Because of this and
tact zone, the durability of the lubricant film, the desired rate their excellent lubricating ability, these lubricants are often
of spreading, and its cooling capability. These parameters are used in high temperature operations that involve high unit
evaluated by the use of film-strength tests, such as the pressures and high spot temperatures. That is, those involv-
Timken Test (ASTM D 2782), the Four-Ball Tests (ASTM D ing slow machine speeds. These oils are labeled active if they
2783 and D 4172), and the SAE #1 Test.
contain additives capable of releasing active sulfur (see dis-
cussion under extreme pressure agents). Otherwise, they
are classified as inactive. Sulfur-releasing ability is high
FLUID CLASSIFICATION BASED ON when sulfurized olefins and sulfurized fats used as additives
BASE FLUID are of high sulfur content (sulfur to olefin ratio of greater
than 1). Active fluids are commonly used in machining steel.
Metalworking and machining fluids fall under three general However, some metal removal operations, such as blanking,
classes: oil-based, water-based, and solid suspensions [15]. do employ inactive fluids. Inactive fluids contain fatty oils,
Oil-based fluids are mineral oils with or without additives. and fatty oil - mineral oil mixtures and or inactive sulfur ad-
Water-based fluids, on the other hand, are micellar solutions ditives.
of oil and/or additives in water. These fluids are of three
types: soluble oils, semisynthetic fluids, and synthetic fluids.
The worldwide use of oil-based fluids is estimated at 45% and Water-based Fluids
that of water-based fluids is estimated at 53%; with synthet- These fluids are emulsions consisting of an organic phase
ics, semisynthetics, and soluble oils, having a share of 4%, and an aqueous phase. In emulsions, one phase is considered
16%, and 33%, respectively. Solid suspensions make up the a dispersed phase and the other a continuous phase (usually
rest. The ASTM Standard D 2881 [15] and the European the larger of the two). When the organic material (oil and/or
Standard DIN 51 385 [14] classify metalworking lubricants additives) is the dispersed phase and water is the continuous
according to their nature and functions. Classes of metal- phase, the emulsions are called normal, or oil-in-water emul-
working fluids are described below. The essential difference sions. If, however, water is the dispersed phase and organic
between various classes is that as one moves from straight oil material is the continuous phase, the emulsions are called in-
to semisynthetic fluid, the amount of water increases and the
vert, or water-in-oil emulsions. The two types of emulsions
amount of oil decreases. See Table 9.
are depicted in Fig. 5.
• Straight Oil (not dilutable)—not supportive of microbial Metalworking and machining fluids are usually oil-in-wa-
growth. ter tjrpe emulsions. The emulsions are of transient stability
• "Soluble" Oil (oil-based emulsifiable concentrate, diluted (ASTM D 3342, D 3707, and D 3709). Their stability depends
with water at the point of use)—more likely to support bac- upon a variety of factors. These include the nature of the oil
terial growth. It primarily contains oil, emulsifiers, and phase, the amount and the type of emulsifier/s, the pH, the
other additives. When diluted (typical dilution ratio is be- operating temperatures (ASTM D 3707), the nature and the
tween 5 to 20 parts of water to 1 part of concentrate) it pro- amount of additives, and the impurities, either present or in-
duces an emulsion. Oil provides lubrication and corrosion troduced into the system. All these factors can lead to coales-
protection and water provides cooling. In some grinding cence of fine droplets into larger ones and lead to oil-water
applications, the dilution ratio can be as high as 200:1. sepciration.
• Synthetic Fluid (water-based solution concentrate; diluted In general, emulsions that are used as metalworking fluids
prior to use)—more likely to support fungal growth. It con- are kinetically stable but thermodynamically unstable (10).
tains no oil but is a solution of corrosion inhibitors and This means that such emulsions maintain their integrity dur-
friction reducing additives in water. These fluids provide ing use but have the tendency to phase separate when not in
cooling and corrosion protection, but their lubrication use. While phase separation in bulk is undesired, the emul-
properties arise from sjrnthetic lubricity components. sions must phase separate on surfaces to release oil/additives
HjO
HoO
OIL
"^,
IL ./wOO'^^'^^ .~N<00«~> OIL ^^2*^ 0~«v 'VwO '^2*'
OIL OIL
OIL
HoO
(a) (b)
FIG. 5—A representation of (A) water-in-oil emulsion (B) oll-in-water emulsion.
that improve lubrication. Oil availability depends u p o n its TABLE 1—Metalworking fluid monitoring techniques.
amount being present in the formulation and the emulsion Appearance and Color PH Odor Reserve alkalinity (ASTM
stability. As a rule, the higher the oil content and the lower (ASTM D 1293) D974)
the emulsion stability, the greater the oil availability. The Emulsion stability Low-shear foam (ASTM D 3601)
problem is that the two essential properties of emulsions, (ASTM D 1479)
Corrosion inhibition Microbial load (ASTM D 3946)
namely lubricating ability and cooling capacity, are inversely (ASTM D 4627)
related. Emulsions of high oil content (lower water content) Relative bio-resistance
not only have poor cooling ability, but they are also of lower (ASTM D 3946)
stability, which decreases their useful life. To further compli-
cate matters, some metalworking operations, such as rolling,
tend to destabilize these high oil-based emulsions. In other It is important to periodically check the organic (oil) con-
words, there is a lubrication-cooling tradeoff when emulsion tent of the emulsion by breaking it. An acid or a salt, such as
tjrpe metalworking fluids are used. sodium chloride, is used for this purpose. Alternatively, one
Emulsions are usually supplied as concentrates, which can use a refractometer to determine the oil content. If the oil
need to be diluted with water prior to use. In addition to cool- content is too low, it may be appropriate to top u p the fluid
ing and lubricity (ASTM D 2782, D 2783, D 4172, and D with fresh concentrate. Since contaminants, such as tramp
5619), these fluids possess inherent rust prevention proper- oils, metal debris, and microbes, can destroy the integrity of
ties (ASTM D 4627), and detergency. Another attribute of emulsions, they should either be removed or controlled.
these fluids is the ability to incorporate additional perfor- Tramp oils are removed via skimming and metal debris is re-
mance additives. The main disadvantages are their sensitivity moved via filtration. As mentioned above, microbes are con-
towards hard water, susceptibility to microbial attack, and trolled by the periodic addition of the antimicrobial agents.
skin sensitivity. Foaming is another problem (ASTM D 892) with emulsions
Water-based fluids cire susceptible to microbial attack, pri- that relates to the presence of emulsifiers. Foaming not only
marily because of low organic (high water) content. Bacterial leads to poor lubrication, but it also impairs the fluid's heat
infestation of the fluid can lead to an objectionable odor due transfer properties. While new emulsions are more stable
to the formation of hydrogen sulfide, a change of color to than old emulsions, the lubricating ability (ASTM D 2782, D
gray, the formation of black stains on the work piece, and 2783, D 4172, and D 5619) of emulsions improves with use.
foaming. Fungal growth can produce slime and is more diffi- This is because debris resulting from metalworking opera-
cult to control than bacterial growth. The major side effect of tions and the decomposition products from additives, espe-
microbial attack is the emulsion's tendency to phase sepa- cially EP agents, tend to destabilize emulsions via nucleation.
rate. Monitoring and control of emulsion quality are there- Ultimately, a complete breakdown of emulsion occurs and a
fore important. The common techniques used for this pur- new batch must be used. The life of an emulsion during use
pose are summarized in Table 1. The quality of emulsions in is called its "batch life." In general, less stable emulsions have
metalworking fluids is maintained by: a shorter batch life.
• the use of biocides. While emulsions contain a variety of chemicals (discussed
• maintaining p H (bacteria are d o r m a n t at pH of greater in the Additive section), the chemical types that are critical to
than 8.8; 8.8-9.2 is a good range). their formation and stability are emulsifiers and coupling
• controlling dissolved oxygen levels. agents. Emulsifiers are key to the formation of emulsions,
• periodic removal of contaminants, such as tramp oil. and coupling agents help improve their stability. Emulsifiers
• the use of filtration equipment. are surfactants that reduce surface tension of the oil-water
interface, thereby promoting miscibility and leading to col- levels. Despite the listed advantages, microemulsions suffer
loidal dispersions. In many cases, a combination of emulsi- from the disadvantages of being expensive, difficult to dis-
fiers is used and its selection depends upon the type of base pose of, and an extensive tendency to foam (ASTM D 892).
oil to be emulsified and the nature of other additives present
in the formulation [10].
Emulsions are made by mechanically mixing the organic Classification of Water-based Fluids
phase t h a t comprises additives and emulsifier/s, called a Water-based fluids are classified as soluble oils, synthetics,
"concentrate," with water. Since the amount of water in wa- a n d semisynthetics, depending u p o n their oil content and
ter-based fluids can be as high as 95%, its quality not only de- emulsion t3rpe. Soluble oils are macroemulsions containing
termines initial stability of the emulsion but also its "batch about 2-10% naphthenic or paraffinic oil. Semisynthetic flu-
life." The presence of greater than 200 p p m calcium or mag- ids are microemulsions containing less than 2% oil. Synthetic
nesium carbonate (ASTM D 511 and D 513) can lead to emul- fluids contain no oil and are predominantly solutions of wa-
sion stability problems. And the presence of chloride and or ter-soluble organic compounds or polymers in water. The
sulfur levels (ASTM D 512 and D 516) of greater than 150 cooling ability of each tj^De is related to its water content.
p p m will promote corrosion, instability, and rancidity. Soft Therefore, synthetic fluids, with the highest water content,
water of less than 50 p p m hardness (ASTM D 1126), on the are extremely effective in operations, such as grinding, that
other hand, leads to foaming in many formulations. While generate a lot of heat. As mentioned earlier, the appeareince
regular water is usually acceptable, the use of distilled, de- of an emulsion is related to its droplet size. When the droplet
ionized, or reverse osmosis water is recommended if prob- size is small, as in the case of microemulsions, the fluids ap-
lems are encountered. pear transparent, and when it is relatively large, as in the case
Emulsion appearance can vary from transparent to milky of macroemulsions, the fluids appear translucent. The for-
white, depending upon the droplet size. Table 2 shows emul- m a t i o n of microemulsions generally requires a higher
sion appearance as a function of the droplet size. Oil-in-wa- amount of emulsifier.
ter emulsions with droplet sizes of approximately 0.1-0.2 um, The terms S5mthetic and semisynthetic, used to describe
sometimes referred to as microemulsions, are preferred in metalworking fluids, have a different meaning than the same
some metalworking applications. This is because their terms used to describe automotive lubricants. In the case of
smaller droplet size makes them both kinetically and ther- metalworking fluids, these terms pertain to water-based sys-
modynamically more stable. Macroemulsions with droplet tems, such as micellar solutions and emulsions. In the case of
sizes in the range of 0.2-10 u m are only kinetically stable. automotive lubricants, however, the terms synthetic and
This means that microemulsions prefer the dispersed form semi-synthetic pertain to the t3rpe of base fluid used to for-
and are therefore less likely to phase separate. Of course, the mulate these lubricants. Synthetic implies the use of syn-
droplet size depends upon factors such as the nature of the thetic basestocks, such as polyolefins, polyglycols, carboxylic
oil and the amount and the type of emulsifier used. Despite esters, etc., and semi-S3mthetic implies a combination of syn-
greater kinetic and thermodynamic stability, pH (ASTM D thetic basestocks and petroleum basestocks. Despite this dif-
1293), oil-water ratio, and temperature have a profound ef- ference, both types of fluids meet the general definition of
fect on the stability of microemulsions. The larger droplet synthetic as being man-made materials [20].
size and the tendency to coalesce are not always undesired.
Hence, m a c r o e m u l s i o n s are often used in m a n y once-
Soluble Oils (Macroemulsions)
through applications, where immediate breakdown is de-
sired to release oil for superior lubrication. The same prop- These lubricants are emulsions of mineral and/or fatty oils in
erties are useful for effluent treatment. water. An emulsifying agent or a surfactant is necessary to
form these emulsions. Fatty oil-based lubricants have excel-
As mentioned earlier, emulsions for metalworking use are lent lubricating properties due to the friction reducing char-
usually produced prior to use by mechanically mixing the ad- acteristics of such oils (ASTM D 2670, D 5183, and D 5619).
ditive concentrate with water. The concentrate comprises oil, Because of the high oil content ( > 2.0%), these emulsions are
emulsifier/s, and a variety of additives. The concentrate-to- milky in appearance and are easily destabilized by salts, bac-
water ratio in such dilutions is between 1:10 (10%)-1:60 teria, and other materials that can deactivate emulsifiers.
(1.5%). However, this ratio is changed if the operation re- Sulfur, chlorine, and phosphorus-containing additives (Fig.
quires a greater degree of cooling or more lubricity. Metal- 16) are used to make these oils suitable for more severe met-
working fluids for operations requiring more cooling contain alworking operations, such as broaching, tapping, and
a higher percentage of water than those requiring more lu- threading. They may also contain rust and foam inhibitors.
brication. Microemulsions are stable (ASTM D 3342, D 3707, In view of their excellent cooling and lubricating properties,
and D 3709), are resistant to microbial attack (ASTM D soluble oils are used for operations that involve high speeds,
3946), and are effective coolants. These attributes are pri- low pressures, and generate high temperatures.
marily due to their low organic content and high emulsifier
Synthetic Fluids (Micellar Solutions)
TABLE 2—Droplet size versus emulsion appearance. Micelles are aggregates of emulsifier molecules that occur in
Droplet Size in Microns Appearance water. These result from the tendency of the lipophilic por-
>1 Milky white tion of the molecule to avoid highly polar water solvent and
0.1-1 Blue white of the hydrophilic portion of the molecule to associate with
0.005-0.1 Translucent to semi-transparent water, as is depicted in Fig. 6. Synthetic metalworking fluids
< 0.005 Transparent to translucent do not contain any oil, petroleum or synthetic, and are sim-
Nonpolar Group Polar Group

(Lipophilic) (Hydrophilic)
Sodium Dodecylbenzenesulfonate - A Common Emulsifier
H,0
H,0 H,0
îm
Micelle
FIG. 6—Micellar structure of emulsifier.
ply solutions of organic additives in water. Since most or- greater tendency to foam. The higher cost and the greater
ganic materials are hard to dissolve in water, high polarity of tendency to foam relate to the higher amount of emulsifiers
additives is necessary for solubility. Soaps and other surfac- and coupling agents used to formulate them. F o a m is usuEilly
tants are often added to facilitate solubilization. Because syn- controlled by the use of foam inhibitors. Sjfnthetics, in addi-
thetic fluids are oil-free, they have poor lubricating ability tion, are difficult to dispose of because it is not easy to sepa-
but excellent cooling ability. These fluids are therefore ideal rate organics from water without sophisticated sepciration
for high speed machining (metal removal) operations that techniques. Sodium nitrite (NaN02) corrosion inhibitor in
generate a substemtial a m o u n t of heat. In these operations, water is a true solution. It was previously used for applica-
these fluids are more effective than straight oils. Synthetics tions where effective cooling was the only consideration. The
contain fatty amines, fatty amides, or fatty carboxylic acid use of sodium nitrite is being discontinued because of toxic-
salts for rust inhibition (ASTM D 665) and TEFLON® and ity concerns. Because additives used to formulate these fluids
poly(alkylene glycols) for lubricity. Since these fluids are so- are synthetic in origin, these fluids are appropriately called
lutions and not emulsions, they do not suffer from destabi- sjTithetic lubricants, or chemical coolants. Synthetics, like
lization problems and are useful for high-speed machining emulsions a n d microemulsions, a r e obtained by diluting
applications. Higher stability is due to their small micelle size the additive concentrate with water, typically in 1:10 to 1:50
(which also makes them appear cleeir) and low organic con- ratio.
tent. The micelle size in these fluids typically ranges between
0.005 and 0.015 um. The fluids that do not contain any metal Semisynthetic Fluids (Microemulsions)
or amine carboxylates eire suitable for use in combination These fluids fall in between soluble oils and synthetic fluids
with h a r d water. in terms of their oil content. In every other aspect, they re-
Synthetics cem be formulated to shed t r a m p oil, i.e. unde- semble soluble oils. Because of the low oil content, these flu-
sirable contaminant oil, for easy skim-off. These fluids cire re- ids also appecir clear. However, some semisjrnthetic fluids of
sistant to bacterial degradation (ASTM D 3946) because of high oil content contain greater t h a n 3.0% oil and are
low organic content and have good work piece visibility be- translucent. As mentioned earlier, emulsion appearance is a
cause of clarity. The disadvantages include reduced lubricity function of the droplet size: the larger the droplet size, the
due to the absence of petroleum oils; tendency to leave hard milkier the appearance. These fluids consist of fine colloidal
crystalline residues; a n d high alkalinity, higher cost, a n d dispersions of organic and inorganic materials in water. The
advantages of these fluids include the abihty to incorporate threading, reaming, boring, and sawing. The primary func-
both the oil-soluble and the water-soluble chemicals, good lutions of the lubricant are to cool and to facilitate debris re-
bricity, improved wettability, and easy waste treatment/dis- moval. Metal forming fluids Eire lubricants that are used in
posal. operations where metal in the work piece is plastically de-
formed to obtain the desired shape. Such operations involve
molding of metal by the process of bending, stretching, Eind
Solid Dispersions pounding. The primary function of a lubricant in these oper-
These lubricants contain solids suspended in water or oil. ations is to reduce friction. Lower friction helps in increasing
Most solids are inorganic in origin, although at times orgEtnic tool life and in lowering energy usage. Metal forming opera-
polymers are also used. Dispersions are made by mechani- tions include hot rolling, cold rolling, foil rolling, forging,
cally agitating finely divided solids in the presence of a high wire drawing, tube drawing, deep drawing, ironing, extru-
molecular weight dispersant. Common solids used to formu- sion, and spinning.
late these lubricants include graphite, molybdenum disulfide Heat removed has an effect on surface finish and cold weld-
(M0S2), metal powders, metal oxides, metal halides, mica, ing of the tool to the work piece, which affects tool life. The
and tetrafluoroethylene or TEFLON®. Dispersions are hard frictional heat generated during some metalworking opera-
to maintain because solid particles are quite large and hence tions, depending u p o n meted hardness, can reach tempera-
have an increased tendency to settle. During use, these lubri- tures of 1000°C or higher. In addition, extensive cutting pres-
cants form low-shear solid films (films that are easily re- sures at points of contact can lead to specific surface loads of
moved when two contacting surfaces slide) at the tool-work u p to 5000 N/mm'^. Both these factors can cause local weld-
piece interface, which protect surfaces against metal-to- ing during cutting. Shearing of welded spots will not only in-
metal contact. The use of these fluids is limited to certain crease the roughness of surfaces, but it will also expose fresh
metal forming operations, such as extrusion a n d forging. surfaces that are more prone to welding. Consequently, addi-
They are reirely used in metal removal lubricants because of tional frictional heat will be generated. The function of the
their propensity to settle in the presence of debris. Lubricants fluid is to dissipate this heat and reduce the number and the
derived from the use of commercial passive EP (PEP) agents, size of the welding spots. Lubrication effectiveness depends
which are colloidal dispersions, can also be considered to be- upon the properties of the oil and the presence or absence of
long to this class. the friction reducing additives. Cooling ability, on the other
hand, is a function of the amount of water present in the lu-
bricant.
FLUID CLASSIFICATION BASED

ON END-USE Metal Removal Fluids
Metalworking operations generate a lot of heat, which, if not Metal removing operations are of two types: those where the
controlled, will lead to tool damage and inefficiencies in met- work piece is moved against the stationary tool and those
edworking operations. Metalworking fluids generally cool as where the tool is moved against the stationary work piece. In
well as lubricate; hence, they Eire often called metalworking both cases, the tool cuts into the work piece, resulting in chip
coolants, or lubricant coolants. These fluids are formulated formation. These fluids, eJso called metal cutting fluids, are
to fulfill cooling and weeir control needs of specific opera- utilized in operations that are used to remove excess metal on
tions because each differs in these requirements. This meikes the way to manufacturing a new part. Both oil and water-
formulation or selection of a m o d e m metalworking lubri- based fluids are used for these operations. Oil-based fluids
cant, which meets all process and product requirements, a can be of petroleum, synthetic, or biological (vegetable and
complicated task. In addition to cooling a n d lubrication, animal) origin. These fluids are designed to perform four key
other properties sought in a metalworking fluid include ap- functions:
propriate viscosity (ASTM D 445), ability to wet and adhere • cooling to prolong tool life
to surfaces (ASTM D 2782 ASTM D 5183, D 2783, a n d D • lubrication to minimize friction, and hence improve sur-
4172), and non-corrosivity to ferrous and non-ferrous metals face finish
(ASTM D 665 and D 130). Metalworking fluids are sprayed or • facilitate removal of chips eind metal debris
poured at the metal-tool interface to dissipate heat, lubricate, • protect freshly exposed surfaces against rust and corro-
protect freshly exposed metal surfaces against corrosion, and sion.
remove debris away from the critical areas. Heat produced during metal removal is primarily frictioneJ
Metalworking lubricants, based on the mode of their oper- and the most is generated during chip formation. Additional
ation, can be classified as meted forming fluids, metal reheat results from deformation of the metal and during travel
moval fluids, and miscellaneous others. Others include meted of the chip across the tool surface [10,16]. The primary func-
protecting fluids, meted treating fluids, and slideway lubri- tion of the lubricant in metal removed operations is to reduce
cants. Because these fluids are not directly involved in metal- friction as well as remove heat quickly. It must eJso remove
working, present discussion will largely deal w i t h metal meted debris, resulting from cutting and grinding operations,
forming and metal removal fluids, which are of the most pre- away from the work piece. Otherwise, extensive tool wear
dominant type. Metal removal fluids are lubricants that are will occur. While water is an excellent coolant, it lacks the
used in applications where metal is removed from the work ability to reduce friction and wear. Therefore, water-based
piece in order to obtain the desired shape. Such applications fluids contain friction reducing and wear control additives.
include drilling, broaching, turning, grinding, milling. Friction reducing additives primarily generate protective sur-
face films via physical interaction. Wear control additives, on either straight cutting oils; which are mineral oils containing
the other hand, generate such films via chemical reaction. active chemical ingredients, oil/water emulsions with or
The former type includes fatty materials, such as vegetable without these ingredients; or aqueous solutions.
oils and animal fats, and the latter type includes sulfur, chlo- The test elements of the most commonly used film strength
rine, a n d p h o s p h o r u s derivatives. The presence of these machines are shown in Fig. 7. Machines used for these tests
additives also minimizes welding of the generated metal de- measure the effect of load and temperature on the film-form-
bris onto the tool edge, called the "built-up" edge. This not ing ability of the lubricant, as reflected by the friction coeffi-
only reduces blemishing, but it also improves surface finish cient and the wear. Results for the newly formulated oils Eire
of the work piece. compared with those of the reference oils to measure their
The material used for cutting tools is selected to facilitate relative effectiveness.
metal (chip) removal. Vibration, metal feed rate, cutting Because of the differences in test conditions, the results
speeds, and lubricant availability (in the cutting zone) also from different machines are not directly comparable. The Al-
play a roll in this process. These factors must therefore be men-Wieland, Falex, Timken, and Four-Ball test machines
taken into consideration when selecting tool material. For examine the effects of sliding friction only. The SAE #1 tester,
high speed cutting operations, steel, special cutting alloys, ce- on the other hand, evaluates a lubricant's performance both
ramics, and cermets are commonly used. Cermets are com- under sliding and under rolling conditions.
posites that contain ceramics and metals bonded together. The Almen-Wieland rig employs a soft steel pin that rotates
The material hardness increases in the order listed and so in a soft steel split bushing at a constant speed. The load is in-
does the generated temperature, from ~ 600°C to 1200°C. creased in stages until either seizure occurs or the maximum
The geometrical shape of the cutting edge also determines load is reached. The Falex tester also uses a soft steel pin ro-
chip formation, which in turn affects the deformation and tating at a constant speed b u t differs from the Almen-
friction zones. That is where the cutting fluid plays a roll by Wieland machine in that the pin rotates between two hard V-
providing lubrication and cooling, hence controlling wear. shaped bearing blocks, instead of in a soft steel bushing. The
The selection of a proper lubricant is therefore important be- test includes a run-in stage and two stages with increasing
cause it will affect cutting speed, tool life, surface finish, and loads.
precision of the work piece. Tool shape, the depth of cut, and The Timken machine consists of a rotating cylindrical steel
temperature are also important considerations. ring pressed against a steel block. The machine is operated
A cutting fluid's ability to reduce friction can be tested by for 10 min to determine the highest pressure at which there
the use of traditional film-strength test machines. These in- is no scoring of the rotating ring or the block.
clude the Almen-Wieland rig, the Falex Pin-and-vee Block In the Four-Ball tester, a one-half inch rotating steel ball is
tester (ASTM D 2660 and D 3233), the Timken Wear and Lu- pressed against three stationary balls of the same size and
bricant Testing machine (ASTM D 2782), the Four-Ball Test quality. The system of balls is in a holder that contains
rig (ASTM D 5183, D 2783, and D 4172), and the SAE #1 Test enough lubricant to cover the three stationary balls. This
rig [13,17]. However, a correlation with field performance is setup provides three small jireas of initial point contact. Be-
lacking. Thread tapping tests (ASTM D 5619), used by some cause of this, high specific pressures are created at low loads,
additive suppliers, may also be meaningful in assessing the which lead to the deformation of the contact surfaces. The
efficiency of cutting oils. For cutting operations, one can use load is increased until frictional heat welds the balls together.
Lubricant
Lubricant
Timken IVIachine Four-ball EP Machine
Lubricant
SAE Machine
FIG. 7—Film-forming test machines.

Test Geais Helicai Gears
Hydrostatic Pressure
Hydrostatic Pressure
Spur Gears
Ryder Machine
r Test Gears
I X
Locl(ed-up Torque
Spur Gears
Coupling
Gleason Machine
FIG. 8—Test elements of Ryder and Gleason machines.
Weld load and wear scar diameter as a function of load are Extreme pressure agents used in metal removal fluids in-
measured. Wear-reducing additives tend to form scars of clude chlorine, sulfur, and phosphorus compounds. Film-
smaller diameter, and welding occurs at higher pressures. forming additives create physical and chemical protective
The SAE #1 tester consists of two cylindrical rollers that films. For materials of moderate hardness and for operations
are rotated against each other at different relative speeds. involving high speeds, friction reducing agents provide the
The test oil lubricates the lower roller, which is mechanically necessary performance. These chemicals react with metal ei-
driven. The load is increased progressively until failure oc- ther at ambient temperature or at high temperatures to form
curs. The SAE machine simulates both the rolling friction metal carboxylate films (see the Film-forming Agents section
and the sliding friction. The ratio of the two types of friction for a detailed discussion). However, for difficult-to-cut mate-
can be changed by changing the rotating speeds of the cylin- rials and operations involving high pressures and slow
ders. speeds, extreme pressure agents are needed. These additives
These tests are the only way to assess the suitability of lu- form protective films via chemical reaction.
bricants for equipment where mixed and boundary lubrica- The selection of a proper lubricant depends upon the na-
tion conditions predominate. However, the data obtained ture of the metal and the severity of the cutting operation. In
from these tests are subjective. For slideway lubricants, the general, operations that employ low cutting speeds place a
data from these tests can be substantiated by testing in FZG higher demand on the lubricant than those that employ high
(ASTM D 5182), Gleason, and Ryder Gear Tests [17]. The test cutting speeds. Figure 9 shows the relative severity of differ-
elements of Gleason and Ryder machines are shown in Fig. 8. ent cutting operations and the demand they place on the lu-
Metal removal operations by their very nature (high pres- bricant [10,18].
sures and temperatures) do not permit hydrodynamic lubri-
cation. Hence, lubricants containing film-forming additives Tool Wear
are usually required. Such additives include friction reducing Besides the severity of the machining operation, tool wear is
agents and extreme pressure agents. The former tj?pe in- also a function of the quality of the cutting fluid and the
cludes fatty acids, their metal salts (soaps), and their esters. machinability of the metal. Cutting fluid is essential to mini-
TABLE 3—Attributes of tool materials.

BROACHING
Tool Material Attribute
TAPPING Carbon steel Short service, limited effectiveness, loses

hardness at relatively low temperatures
THREADING High-speed Maintains high cutting edge at high
steel (HSS) temperatures, contains tungsten (W),
GEAR SHAPING molybdenum (Mo), chromium (Cr),
cobalt (Co), vanadium (V)
REAMING Cast alloys Cobalt-based, more brittle than HSS, fills
the gap between HSS and carbide tools
Cermets Carbide-based, extremely hard, lack
DRILLING strength and toughness (need good
support), not used where there is heavy
MILLING vibration or shock
Ceramics Cemented metallic oxides, hardness close
TURNING to diamond, do not pick up heat, are
brittle and therefore chip easily
FIG. 9—Relative severity of metal-removal operations. Diamonds Hardest of all abrasives, large stones are
used in dressing tools, small stones are
used in grinding wheels
mizing wesir and equipment damage. Common types of wear Of the metals listed, ferrous metals such as carbon steel,
that can occur in cutting tools due to lubricant failure are as low alloy steel, and stainless steel, and eduminum are the
follows. largest volume metals machined. Copper, brass, and tita-
• Adhesive wear—Welding between the tool surface and the n i u m are the next group, followed by nickel-based alloys,
work piece surface can occur due to high local tempera- cobalt-based alloys, magnesium, zinc, tin, beryllium, zirco-
tures. On shear, these spots Ccin either produce metal de- nium, tungsten, molybdenum, tantalum, uranium, and vana-
bris or result in metal transfer from the tool to the work dium. The order with respect to ease of machinability, from
piece. This kind of damage is more likely to occur at low the easiest to the most difficult, is as follows:
cutting speeds.
Magnesium (Mg) and its alloys < zinc (Zn) and its alloys
• Abrasive wear occurs when fragments of cutting or wear
debris embedded in the chip abrade the rake face of the < brass < aluminum (At) and its alloys < cast iron (Fe)
tool. < bronze < copper (Cu) < carbon steel < alloy steels
• Diffusive wear occurs when metal atoms from one crystal < stainless steel < nickel (Ni) alloys
lattice diffuse into the crystal lattice with lower atomic
density (concentration). This type of wear is likely when < titanium (Ti) and its alloys
tools m a d e of h a r d material are used to machine softer Because metalworking operations involve both the p u r e
metals, for example during the use of tungsten carbide metals and the alloys, selection and use of an appropriate lu-
tools. bricant is a complex process.
• Corrosive wear results from the attack of atmospheric oxy- Operation severity is a function of the cutting speed. In
gen or of the decomposition products from antiwear and general, operations with low cutting speeds, such as broach-
extreme pressure additives on the tool surface. Such addi- ing and tapping, are more severe than those that have high
tives include chlorine, sulfur, and phosphorus-containing cutting speeds, such as turning and milling. Drilling a n d
chemicals. reaming fall in between the two extremes in terms of sever-
• Premature wear is the progressive loss of tool material at ity. High severity at low speeds is because at these speeds
the tool-work piece interface and occurs due to plastic flow metal-to-metal contact is more extensive (boundary lubrica-
of metal at high temperatures. tion) than at high speeds, which promote hydrodynamic lu-
Machinability primarily relates to metal hardness, al- brication. Consequently, there is a greater need for extreme
though other factors, such as cutting speed, tool strength, pressure agents a n d anti-weld additives in the former case
and p o w e r consumption, also play a role. In general, the than in the latter case, where either lubricant viscosity or fric-
harder the metal, the greater the tool wear. It is therefore im- tion-reducing additives suffice. Since good cooling and good
portant to select proper tool material for the job at hand. lubrication are not easy to obtain in the same fluid, water or
Commonly machined materiEils include steels, both alloy and microemulsions (semisynthetic fluids) are used for opera-
stainless; cast iron; aluminum and its alloys; magnesium and tions that require more cooling. And, the use of straight oils
its alloys; copper and its alloys; nickel and its alloys; heat reis preferred for operations that require better lubrication.
sistance alloys that contain nickel, chromium, molybdenum, The majority of operations require both cooling and lubri-
tungsten, and titanium; and plastics. Tool materials include cation. Hence, macroemulsions (soluble oils) that contain
carbon steel, high-speed steel, cast cJloys, ceramics, cermets, substcinticJ amounts of both organic and aqueous portions
and diamonds. The attributes of various tool materials are are often employed. The operating range of these fluids is en-
provided in Table 3 and the characteristics of the metals ma- hanced by the supplemental use of fatty additives. For a cut-
chined are provided in Table 4. ting fluid to perform effectively, a careful consideration of its
TABLE 4—Machining characteristics of machined metals. heavy tool wear. Therefore the lubricants for these opera-
Machined Metal Characteristics tions require the use of extreme pressure additives [19a]. A
Steels new technique, called dry machining, is presently being ex-
Free Machining Modified for machinability with added plored. The purpose is to eliminate purchase, handling, use,
phosphorus or sulfur and disposal costs. Since this technique does not use any lu-
Alloy steels Contain chromium (Cr), cobalt (Co), bricant, it involves high temperatures. Thus far, the tech-
nickel (Ni), molybdenum (Mo), nique has been applied to boring operations. Efforts are un-
tungsten (W), vanadium (V), singly
or in combination; more difficult to derway to extend it to drilling operations [19b].
machine The depth of cut and surface finish are additional consid-
Stainless steel Difficult to machine because of high erations for fluid selection. Low-speed operations where cuts
chromium (Cr) and or nickel (Ni) are deep and good work piece finish is important; the lubric-
that work harden
ity of the fluid is critical. The use of straight oils is therefore
Cast Iron appropriate. For high-speed operations that involve shallow
Gray cast iron Machines easily
Malleable cast iron Machines easily cuts, quick heat dissipation is desired. This makes mi-
Nodular iron Machines easily croemulsions or micellar solutions the lubricants of choice.
White cast iron Hard to machine In most cases, the fluid is applied under pressure into the cut-
Wrought iron Hard to machine ting zone, which is to reduce friction, minimize metal trans-
Machine easily relative to carbon steel; fer, and maximize cooling.
Aluminum and its alloys pure aluminum may be gummy
Excellent machinability; chemically
Magnesium and its alloys reactive hence use of water or acidic Metal Forming Fluids
materials in the fluid must be
avoided These fluids are used for operations that depend on plastic
Copper and its alloys flow of the metal. Such operations include rolling, extrusion,
Single phase alloys, such Hard to machine drawing (drawing tubes, tube bending, deep drawing, wire
as bronze, copper- forming), forging, and sheet metal forming. Some of these
nickel, copper-silicon
operations involve both ambient temperatures (cold work-
Alloyed copper, lead- Medium machinability
bronze, tin-bronze, ing) and high temperatures (hot working). Metal forming
naval brass, aluminum- processes can be distinguished as being steady-state or non-
bronze steady-state [16], each type with different lubrication re-
Alloys that contain Free machining quirements. In steady-state processes, such as rolling, it is
substantial amounts of possible to lubricate the surface of the work piece during its
alloy materials
approach to the deformation zone. However, in non-steady-
Nickel and its alloys
Pure nickel state processes, such as sheet metal forming, the lubrication
Incone (nickel-chromium- Good machinability is not usually possible because of the nature of the operation,
iron alloy) and one must depend upon the pre-applied lubricant film.
Hast alloy (nickel-copper Some processes, such as long billet extrusion, have cheirac-
alloy containing small teristics of both; that is, n o lubricant application during cer-
amounts of iron,
molybdenum and tain parts of the operation and lubrication during other parts
chromium) of the operation.
Monel (nickel-copper The primary functions of a lubricant during metal forming
alloy)
Nickel-silver aDoy Draggy and difficult to machine operations are to reduce friction, which lowers energy con-
sumption; and to minimize wear, which increases tool life.
Heat Resistant alloys
Contain nickel, chromium, Hard to machine and hence need Friction reduction, in addition, facilitates the release of the
molybdenum, and heavily additized cutting fluids forged part from the die and improves surface finish of the
titanium work piece. However, too m u c h friction reduction is unde-
Plastics Thermoplastics melt and thermosett sired because it can lead to slippage and hence make the op-
plastics char at low temperatures, eration inefficient.
hence cooling is most important. Common metal forming lubricants include:
Soluble oils are often used.
• mineral oils—compounded oils (blends of mineral oils and
fatty oils)
• synthetic oils and esters—fatty acids and their derivatives
cooling and lubricating requirements is essential. High-speed • lanolin, tallow, and paraffin waxes—aqueous solutions and
cutting operations, such as turning, milling, and drilling, re- emulsions
sult in higher temperatures, hence cooling ability of the fluid • polymer solutions—dispersions containing graphite,
is critical. Water is an excellent coolant but has little or no lu- molybdenum disulfide (M0S2), salts, glass, bentonite, lime,
bricating ability. However, this deficiency is overcome by the mica, and talc
use of friction reducers and EP agents, which are entrained Additives for these lubricants include fatty acids and fatty
into water by the use of wetting agents and emulsifiers. On compounds, extreme pressure agents (sulfurized and sul-
the other hand, low-speed operations such as broaching and fochlorinated fats and oils), emulsifiers, coupling agents, in-
tapping experience high friction, and consequently lead to organic solids, and dispersants.
Miscellaneous Fluids a n oil circulating system may also b e used to deliver the lu-
bricant at different points along the slide.
Metal Protecting Fluids
These fluids, also called preservative oils, help protect freshly
exposed metaJ surfaces against air, water, and corrosive ma- FLUID COMPOSITION
terials. While most of these fluids cire oil-based, the use of wa-
ter-based fluids is gaining popularity because of the lower Metalworking fluids are composed of a base fluid and a col-
cost, ease of disposal, environmental compatibility, and re- lection of chemicals. While base fluid makes u p the bulk of
duced volatile carbon content. the formulation, it lacks the properties necessary to act as an
effective lubricant. Hence, chemical compounds, called addi-
Metal Treating Fluids tives, are used to either fortify the base fluid's existing prop-
These fluids Eire used for heat-treating operations, such as erties or add new properties [20]. Because of the diversity of
quenching and tempering. They act as heat transfer agents lubrication requirements in metalworking operations, the
and can be oil-based or water-based. The base oils to formu- type and the quantity of additives differ from operation to op-
late these fluids can be synthetic or petroleum in origin. The eration. The quality and quantity of additives cdso depend
performance specifications of these fluids are established by upon the type and properties of the base fluid.
OEMs Eind the end-users. Synthetic fluids, due to their supe-
rior fire resistcmce and fewer disposed concerns, Eire replacing
oil-based formulations. Base Fluid
The base fluid in metalworking lubricants can be biological
Slideway Lubricants (animal or vegetable) in origin, petroleum-based (mineral
These lubricants are used to lubricate slideways and the ac- oil), synthetic-based, or water. Structures of some of the
companying pneumatic equipment. Slideways are guiding basestocks used to formulate metalworking fluids are shown
surfaces on the bed of a machine along which a table or a car- in Fig. 10. The detailed description of these basestocks is pro-
riage moves. Since surfaces that slide over each other are flat, vided in Chapters 7 and 10 of this manual.
the area of contact is large. This leads to increased adhesive Straight oils use severely refined and hydrotreated mineral
wear. These devices in addition experience motion of varying oils and synthetics, such as polyalphaolefins (PAOs), poly-
speeds, which causes sticking and slipping of the sliding sur- butenes, ethylene oxide-propylene oxide polymers (polyalky-
faces. After wear-in, opposing surfaces form an even closer lene glycols or PAGs), and organic esters. For water-based
fit, which squeezes out and wipes away any lubricant that is fluids, naphthenic oils are preferred because of ease of emul-
in the path of motion. Essentially, a boundary lubrication sibility and because of their superior viscosity-pressure rela-
condition exists. This type of lubrication to a degree is by de- tionship (discussed earlier). For straight oils, however, paraf-
sign; otherwise, excess lubricant would form a hydrodynamic finics are the base oils of choice. Synthetic basestocks are less
wedge that will interfere with the motion of the plane. popular than mineral oils, primarily due to their higher cost.
BoundEiry lubricated surfaces will adhere to each other, es- However, the use of these stocks is increasing in fluids where
pecially during slow speed operations. Adhesion occurs when tailored properties are desired and petroleum basestocks are
the static friction either equals or exceeds the force of mo- not effective.
tion. If adhesion is followed by movement due to the applied Polyalkyleneglycols, prepared by polymerizing ethylene
force, the p h e n o m e n o n is called stick-slip. Regular occur- oxide-propylene oxide (EtO/PrO) mixtures [21], are exten-
rence of stick-slip causes not only vibration Eind noise but sively used in metal removal lubricant formulations. Desir-
also damage to the work piece, tool, and rider and way. able properties Eire obtained by controlling molecular weight,
Slideway lubricants perform at extreme t e m p e r a t u r e s , altering terminal groups, and the EtO/PrO ratio. Higher
high loads, moisture, and poor ambient air quality. They molecular weight materials have higher viscosities a n d
must therefore possess both the EP activity EUid the rust and higher EtO/PrO ratio products have higher water solubility.
corrosion-inhibiting properties. These lubricants are formu- One can even alter the EtO/PrO ratio to devise materiEils that
lated with friction reducers, primarily fatty carboxylic acid are water-soluble at low temperatures but are water-insolu-
derivatives that minimize stick-slip, and extreme pressure ble at high temperatures. This property is useful in formulat-
agents that control wear damage resulting from boundary lu- ing fluids that are clear during circulation but separate
brication conditions. Operation at extreme t e m p e r a t u r e s polyalkylene glycol (and additives) at the hot tool-work piece
leads to oxidative breakdown of the lubricant. This must be interface during use.
avoided; otherwise, poor lubrication and corrosion will re- Polyisobutylenes, obtained by polymerizing isobutylene
sult. This is accomplished by the use of oxidation inhibitors. [21], have the tendency to depolymerize at high tempera-
It is important to note that stick-slip control requires com- tures. This makes them useful in rolling and drawing oils for
bining proper machine design and superior lubricant quality. ferrous and nonferrous metals, where petroleum oil derived
Since the oil is removed due to the wiping action of the lubricants cause staining during subsequent annealing pro-
slide, lubricant is supplied at different points along the slide cess. Polyalphaolefins, often not used in metalworking fluids,
route. Suspended metcJlic fines or chips in the lubricant can possess certain attributes that make t h e m desirable. These
lead to scratching, gouging, or abrading of the ways. The use include effectiveness over a wider temperature range and
of a properly formulated lubricant can minimize this type of lower hydrocarbon (HC) emissions t h a n petroleum oils of
damage, as well as control friction, chatter (noise), and stick- similar viscosities. Polyalphaolefins are also highly resistant
slip. Despite the fact that lubrication is often once through. to oxidative and thermal degradation.
H2 H2 H2 H2 H2 H2 H2
^'Cv^ /C>^ ^C^ / ^ \ /^"^ C^
^C CH CH, Paraffinics
H, H, H,
CH, CH. H,C.
H,C ^CH, ^CH,
CH3
H2 H2 H2 H2 I H2
,C^ ^ C ^ ^C^ Ô^ CH. ^C~^
H3C' CH CH CH CH CH CH3
Naphthenics
CH3 HoCs. ^^''2 H2C CH
CH \
/ H2C Crl2
H,C\ A
HoC CHo
CH, \
/ CH3
H,C
CH3
CH, — C H -(-CH2 — C H -^CHj -CH,
I
-ca—c—
R R R
CH3 R = C4H11; CgH-is; C8H17
Polyisobutene
Polyalphaolefins
O O CH20C^
// II
RO —C—(CH2)n — C — O R I -^ ' , R=C5 TO C10
CH3CH2C — CH2OC R
R=C8 TO C-13
//
CH2OC
R
Alkyl Carboxylate Ester Polyol Ester
R = Linear or Branched Alkyl Group

RO (CH2 — C H — 0 ) n — H
R=C2 TO C3
Polyalkylene Glycol
FIG. 10—Basestocks used in metalworking fluids.
Polyalkylated cyclopentanes are a new class of synthetic Additives

hydrocarbons that are promising in terms of future formula-
tions [10]. Their properties can be varied over a wide range Additives used in metalworking fluids can be broadly clas-
by varying the number euid the nature of the alkyl groups. sified into chemically inert and chemically active. Chemi-
They have low pour points, high viscosity indexes, and ex- cally inert additives primarily alter the physical properties
ceptionally low volatility. Other types of synthetic basestocks of the fluid, such as lubricity and surface tension. Such ad-
find limited use in metalworking applications. ditives include emulsifiers, coupling agents, friction reduc-
ers, rust and corrosion inhibitors, foam inhibitors, and an- Emulsifiers are classified as nonionic or ionic, depending
timicrobial agents. Chemically active additives, on the other upon whether the polar part is uncharged or charged. Ionic
hand, alter the chemical properties of the fluid, such as ox- c o m p o u n d s can be subdivided further into cationic if the
idation susceptibility. This group of additives includes some charge is positive, and anionic if the charge is negative [22].
friction reducers, extreme pressure/antiwear agents, and Nonionic emulsifiers that are often used in metalworking flu-
oxidation inhibitors. Common types of additives that are ids include carboxylic acid a m i d e s and esters, polymeric
typically used in metalworking fluids are provided in Table ethers (polyglycol ethers), esters of polyhydric alcohols, and
5. Their chemistry and mode of their action are also sum- alkoxylated alkylphenols. Anionic emulsifiers include metal
marized. salts, primarily sodium, of carboxylic acids, alkyl phosphoric
acids, and sulfonic acids (both natural and sjmthetic). Be-
Emulsion Promoters cause of the lower cost, these emulsifiers aire used as general-
These additives facilitate the formation of emulsions and purpose additives. Cationic emulsifiers include mineral acid
contribute to their stability. These include emulsifiers and salts of amines and imidazolines. It is important to note that
coupling agents. only the charge on the functional group attached to the car-
Emulsifiers are chemicals that are used to emulsify (solu- bon chain is used in this classification. The charge on the
bilize) organic additives and or mineral and synthetic oils in counterion, which is usually inorganic in origin, is ignored.
water. These are used to create soluble oils, synthetics, and The term amphoteric applies to a group of additives, which
semi-synthetics, all of which are water-based lubricants. contain cationic and anionic groups of organic origin, prefer-
Emulsifiers contain functional groups that have the capabil- ably within the same molecule. They possess structural fea-
ity to associate with water as well as oil. These additives tend tures and properties of both the cationic and the anionic ma-
to be situated at the boundary between oil and water (the terials grouped together. These surfactants are practically
oil-water interface), where they help reduce the interfacial never utilized in metalworking fluid formulations. Com-
tension and make the two phases miscible to form a stable pounds that find extensive use as emulsifiers include:
emulsion. Emulsion formation requires some kind of mixing • alkali metal (primarily sodium) sulfonates, both petroleum
or stirring. and synthetic
TABLE 5—Metalworking fluid additives

Additive Type Function Typical Compounds
Water-based fluids
Alkalinity buffers/pH Control bacteria-derived acidity Amines and inorganic bases
Antifoam agents Prevent foam Silicones, silicates, and stearates
Antifungal agents Control fungal growth Sodium omadine
Antimicrobials/preservatives Control microbial growth Triazines, omadine, phenol, oxazolidines,
and imidazolines
Metal passivators Prevent staining and leaching of yellow metals Triazoles
Couplers Emulsion stability Glycols, glycol esters, and alcohols
Emulsifiers Emulsify organics in water Sodium and lithium sulfonates;
poly-ethoxylated phenols, alcohols and
acids; metal and amine carboxylates
(soaps of fatty acids)
Extreme pressure/lubricity agents Form heat-resistant chemical films that Fatty acids, fatty amides, fatty esters, and
reduce friction fatty acid salts (soaps); phosphates; sulfur
and chlorine containing compounds
Odor masks Suppress odor Natural and synthetic aromatic compounds
Thickeners Improve viscosity Polyacrylate esters and glycol esters
Corrosion and rust inhibitors Control oxidative and corrosive damage to Carboxylic acid salts, amides, and amines
metal surfaces and tools
Oil-based fluids
Antifoam agents Prevent foam Silicones, polymethacrylates, and stearates
Anti-misting agents Suppress mist formation Polyisobutenes and other natural and
synthetic polymers
Corrosion and rust iniiibitors Control oxidative and corrosive damage to Metal sulfonates and phosphates; organic
metal surfaces and tools acids and esters; and triazoles
Demulsifiers Facilitate water separation and facilitate Cationic and non-ionic polymeric surfactants
removal of tramp oil via skimming
DispersEints Prevent agglomeration of material particles Polyamides and metal sulfonates
that result during cutting and grinding
Extreme pressure/lubricity agents Form heat-resistant chemical films that Fatty acids, fatty amides, fatty esters, and
reduce friction fatty acid salts (soaps); phosphates; sulfur
and chlorine containing compounds; basic
sulfonates
Odor masks Suppress odor Natural and synthetic aromatic compounds
Thickeners Improve viscosity Polyacrylate esters
Solid lubricants Improve film strength Graphite, molybdenum disulfide,
Poly(tetrafluoroethylene)-PTFE
(TEFLON®)
• alkali metal carboxylates Some emulsifiers show mild anti-rust performance (ASTM
• alkoxylated alcohols, phenols, fatty amines, fatty acids, and D 665). Since emulsification is a liquid phase phenomenon
fatty amides and the rust inhibition occurs at the liquid-solid interface,
• sulfated fatty oils optimizing both these properties is not easy. One can obtain
both the emulsification and the anti-rust performance by al-
Generalized structures of some of the common emulsifiers
tering the hydrocarbon chain length in the emulsifier
are given in Fig. 11.
molecule. However, in many cases, this strategy is not very
Emulsifiers reduce the interfacial tension of the water-or-
effective and it is necessary to improve the anti-rust perfor-
ganic (oil) interface therefore facilitating thorough mixing of
mance by the use of supplemental additives. The common
oil and water to form an emulsion. The efficiency of an emul-
ones include sodium nitrite, borax, boric acid amides and es-
sifier depends upon its molecular weight (usually less than
ters, alkanolamines, and alkanolamides. The use of sodium
2000), its HLB (hydrophile-lipophile balance) value, water
nitrite is decreasing because it can form nitrosamines, which
pH and hardness, the nature of the oil, and the operating con-
are suspected carcinogens (cancer-inducing agents).
ditions, such as temperature. HLB scale spans zero (0) to
greater than 30. The higher numbers mean oil compatibility
Coupling Agents (Couplers)
decreasing and water compatibility increasing. Emulsifiers
of HLB of greater than 13 generally lead to clear water solu- Some additives that need to be emulsified have greater solu-
tions. Emulsifiers with an HLB of 3 to 6 are suitable for wa- bility in water than in oil. Consequently, they are not easy to
ter-in-oil emulsions and those with an HLB of 8 to 18 are suit- formulate into emulsifiable oil concentrate (package) with-
able for oil-in-water emulsions. The manner in which these out the presence of a large amount of water (as much as
additives form emulsions is shown in Fig. 5. 50%). Coupling agents facilitate emulsification of water into
the base oil, emulsifier system, and other additives. In the
Water-in-oil emulsions form when these additives associ-
long term, these additives maintain emulsion stability. Com-
ate with water via their polar ends and with oil and other ad-
mon coupling agents are low molecular weight alcohols, gly-
ditive molecules via their nonpolar ends. This is shown in
cols, and triols, which become part of the non-oil portion of
part A of Fig. 5. The result is water miscibility in oil, or wa-
the package. This decreases the need for the large amount of
ter-in-oil emulsion. The mechanism of oil-in-water emulsion
water necessary to solubilize additives thereby improving
is similar, except that the additive molecules associate in the
emulsification. It is important to note that although these
reverse manner. This situation is shown in part B of Fig. 5.
components are organic in nature, they impart little or no lu-
As a general rule, nonionic emulsifiers are used in metal- bricity to the final fluid.
working fluids based on naphthenic stocks, and fatty acid
carboxylates are used in those based on paraffinic stocks. Structures of some of these additives are given in Fig. 12.
Polyalkylene glycols (hydroxyalkyl ethers) are sometimes Also, see Fig. 11. Common examples of these additives in-
avoided because their enhanced solubility in water does not clude:
allow clean separation for disposal. As mentioned ecirlier, al- • fatty alcohols, such as tridecyl alcohol
kali metal salts (soaps) of carboxylic and sulfonic acids are • glycols, such as ethylene glycol, diethylene glycol, and
among the most commonly used emulsifiers. However, metal propylene glycol
ion exchange with calcium and magnesium, whose salts are • glycol ethers, such as propylene glycol monomethyl ether
present in hard water, degrade emulsions by removing these and hexylene glycol monomethyl ether
soaps as insoluble calcium and magnesium salts. Non-ionic • fatty acids, such as caprylic acid, isononanoic acid, and
emulsifiers lead to emulsions that are less sensitive to hard neodecanoic acid
water. • nonionic surfactants, ethoxylated alcohol, nonylphenol
ethoxylates, and polyethylene glycol esters
NON-IONIC
Film-forming Agents
This type of additives includes friction modifiers (also called
-P ^CHjCHjOH
R—Cs R0{CH,CH,0),CH,CH20H R—N, film-strength additives, oiliness additives), antiwear and ex-
CH2CH2OH
Dialkanolamjde Polyethoxylated Alcohol
treme pressure agents (also called boundary additives, load-
Fatty Diethanolamine
(Hydroxyalkyl Ether) bearing additives), and corrosion inhibitors.
,p CHjOH 0(CH2CH2O)xCH2CH2OH
R—C^ • I
0(CH2CH20),CH2CH20H CHOH
CHjOH CH2OCH3
Polyglycol Ester of a Fatty

CH20-C-0leyl CHjOH / /
Carboxylic Acid H3C—CHI HjC
Glycerol Monooleste Alkylphenol Ethoxylate

CH2OH
\ OH OH
(GMO)
Ethylene Glycol Propylene Glycol Ethylene Glycol Monomethyl
ANIONIC Ether
00 OCH3 OH
H,C. CH,
R—ct©0 I I /
"^"^cPwa® O NHECHjCHjOH],
.0. ,0 OH,
Sodium
Carboxylate
Trlethanolamlne Salt of a Fatty Acid ^^^^^ Alkyll^nzenesulfonate
H,C^ \ ^ C ^
H H,
\
CH, t? OH
R = Fatty Hydrocarbon Group Hexylene Glycol Monomethyl Ether Isononanoic Acid
FIG. 11—Commonly used emulsifiers. FIG. 12—Commonly used coupling agents.

Lubrication is necessary to facilitate the counter move- reactivity of the additives towards metal and involves limited
ment of two sliding surfaces. This function, which is usually bond breakage and bond formation. This situation occurs in
performed by the base fluid, can be enhanced by the use of the case of fatty alcohols and fatty acids that react with the
high viscosity oils, friction modifiers, or extreme pressure metal surface to form metal alkoxides and metal carboxy-
(EP) and antiwear (AW) agents. Since water is a poor lubri- lates, respectively.
cant, the lubricity in water-based fluids is achieved by the use One c o m m o n feature of this class of additives is the pres-
of friction modifiers, also called the lubricity agents, and or ence of a fatty hydrocarbon chain (long linear chain). In ad-
EP agents. These additives improve lubrication ability of the dition to fatty alcohols and acids, this class includes fatty es-
metalworking fluids by forming m o n o m o l e c u l a r physical ters, natural and synthetic; fatty amides; fatty amines; and
and chemiccJ films at the tool-work piece interface, which fatty alcohol derived alkyl acid phosphates. Those used most
minimize metcJ-to-metal contact. often include animal and vegetable oils (commonly called
Film-forming agents are extremely surface active because triglycerides), alkyl and polyol esters of fatty acids, ethylene
of a high polar-nonpolar ratio. The polar-nonpolar ratio in oxide/propylene oxide polymers, TEFLON®, alkanolamides,
additives is discussed in detail in Chapter 9 on Additives and and mono, di, and tri-ethanolamine salts of carboxylic acids.
Additive Chemistry. These additives typically contain hydro- The structures of these additives are shown in Fig. 14.
carbon groups of 10-18 carbon chain size and very polar A greater degree of protection is needed in applications,
functional groups. Therefore, they, have the tendency to sep- such as metal removal operations, which generate high tem-
arate on surfaces, where they interact by a physical or a peratures. This is because physically a n d chemically ad-
chemical m e c h a n i s m . Modes of interaction of additive sorbed additive films are easy to remove. That is where ex-
molecules with surfaces [23] are depicted in Fig. 13. treme pressure/antiwear agents become important. These
Physical adsorption, or physisorption, is a weaker associa- additives chemically react with metal surfaces to form a more
tion of the additive with metal than chemical adsorption, or tenacious protective film. The process involves extensive
chemisorption, which in turn is weaker than chemicsd reac- bond breakage and bond formation via complete breakdown
tion. During adsorption, a n additive molecule generally of the additive. These additives are primarily organic com-
keeps its structural integrity and involves no bond breakage pounds of chlorine, sulfur, and phosphorus.
or bond formation. This is t5rpical of additives, such as natu- The extent of EP protection in the equipment depends
ral fats and oils, which have a low reactivity towards metals. upon the conjunction temperature of the two metal surfaces
However, when the temperature reaches beyond a certain in contact [2]. Figure 15 shows a direct correlation between
threshold temperature, these additives desorb and the fluid the conjunction temperature and the degree of EP protection
loses its friction-reducing properties. The result is wear dam- needed. Conjunction temperature is the temperature of the
age. Chemical adsorption, on the other hand, requires some two surfaces in contact and determines the type of additives
needed for protection. It is important for the activation tem-
perature of the EP additives to match the conjunction tem-
perature in order to provide the necessary protection. The ef-
fective t e m p e r a t u r e ranges of different tj^pes of additives
Additive (Molecule Metal Surface when used in metalworking applications [16] are provided in
Table 6. Equipment that operates at low speeds and high
loads generally requires more EP protection than equipment
that operates at high speeds and low loads. This is because
the former t5rpe of operation involves more metal-to-metal
contact, which generates higher temperatures as a conse-
quence of increased friction.
Physisorption As mentioned before, extreme pressure agents are primar-
ily organic compounds of chlorine, sulfur, and phosphorus,
although sometimes boron and sulfur-nitrogen compounds
are also used. Chlorine c o m p o u n d s include chlorinated
olefins and paraffins, and chlorinated fatty acids and esters.
Sulfur c o m p o u n d s include alkyl polysulfides, sulfurized
Chemisorption olefins, and sulfurized fatty acids and esters of both natural
and synthetic origin. Overbased sodium and calcium sul-
fonates, called PEP (passive extreme pressure) agents, and
molybdenum disulfide (M0S2) are two other commonly used
sulfur-containing EP additives. Phosphorus derivatives in-
clude phosphites and aliphatic and aromatic alkyl phospho-
o o o o o o ric acids (phosphate esters) and their salts. Some EP agents
contain both sulfur and chlorine and others, such as dialkyl
o o o o o o dithiophosphoric acid derivatives, contain both sulfur and

phosphorus. Dithiocarbamates, on the other hand, contain
both sulfur and nitrogen. However, sulfur derived fluids suf-
Chemical Reaction fer from being odorous and supporting biological growth.
FIG. 13—Modes of additive—surface interactions Chlorine derived fluids, on the other hand, are unsuitable for
use in working a l u m i n u m . Representative structures for
,C^—O—CH, some of the compounds that are used as EP agents are pre-
> sented in Fig. 16.
R—c;
< . In all cases, active elements chlorine, sulfur, and phospho-
\ ;c—o—cHa OR'
rus react with metal to form metal halide, meted sulfide, metal
y Alkyl Carboxylate
phosphite, metal phosphate, and metal phosphide protective
or Vegetable Oil films. These films are effective only below the eutectic point
R'« Methyl or Higher Alltyl G r o u p or the decomposition temperature of these salts. Chlorine
R ^ Fatty Hydrocarbon Chain compounds can lead to metal corrosion by hydrogen chloride,
which results from their hydrolysis. Hence, this must be taken
into account prior to their use in cutting oils. In view of their
II H, H, II
R C O C C O C R effective range, sulfur compounds are used in heavy-duty and
HO-J-CHjCHj—o4-4-CH2CH—oj—H extra heavy-duty cutting operations. Metal sulfide films ap-
R C O
/\
CH2 H2C O C R p e a r to have a higher load-carrying capacity and shear
O O
Ethylene Oxide - Propylene Oxide Polymer strength t h a n carboxylic acid soaps and metal phosphates.
Film formation by these additives occurs by a two-step
Pentaerythritol Carboxylate
mechEinism: adsorption on the metal surface and thermal de-
composition and reaction with the metal surface because of
J'" frictional heat. The resulting metal Scilt films have low coeffi-
O HNECHjCHjOHh
NECHjCHjOHJz cients of friction and also demonstrate anti-weld properties,
0 ©
both of which minimize tool wear. Metal chloride films have
Dialkanolamide Triethanolamine Salt of a CarboxylJc Acid a transition temperature of ~ 600°C and metal sulfide films
have a transition temperature of ~ 1000°C. This makes or-
FIG. 14—Commonly used friction modifiers. ganic sulfides better extreme pressure additives than organic
chlorides, because sulfide films can endure higher tempera-
tures before becoming soft and getting removed. Chlorinated
fats, chlorinated esters, a n d chlorinated paraffins are the
400- common organic chlorides used in formulating metalwork-
ing fluids. Sulfurized fats, sulfurized oils, sulfurized paraf-
fins, dissolved sulfur, and sulfochlorinated products are the
O
S_-35C common organic sulfides used. The sulfur in these additives
£ is of two types: active and reactive. Active sulfur is the dis-
3 solved or easily releasable form of sulfur, which has the ten-
dency to corrode yellow metals—a low temperature reaction.
(U 30C
Q. Because of this, the presence of active sulfur in the metcJ-
E working fluid formulation is of concern. On the other hand,
0)
I- reactive sulfur is the bound form of sulfur, for example as a
C 250
_o
msm sulfide or disulfide, and is released or reacts with metal only
at high temperatures.
^
o Because of the reactivity of sulfurized hydrocarbons to-
c
,3 wards copper, bronze, and other non-ferrous metals, and the
'B20C IJI.hBdd tendency of chloropareiffins to corrode metal via hydrolysis
o
O or thermolysis, the need for new extreme pressure agents ex-
150 ists. New extreme pressure technology based on overbased
alkylbenzenesulfonates a n d carboxylates, which does not
suffer from these drawbacks, has recently become available.
Such additives, called passive EP agents, are believed to func-
tion by forming a metal carbonate film at the tool-work piece
Temperature [2]
interface. The high effectiveness of these additives in cutting,
FIG. 15—Extreme Pressure (EP) protection versus conjunc- tapping, a n d threading operations suggests a n alternative
tion temperature. mechanism. That is, the high pressures at the tool-metal in-
terface convert amorphous calcium carbonate, present in ba-
sic sulfonates and carboxylates, into crystalline salts that fa-
TABLE 6—Effective temperature range of lubricity agents and cilitate metal removal. The films formed are of low shear
EP/AW agents. strengths and high melting points. These additives do not
Effective contain phosphorus, reactive sulfur, or chlorine but are syn-
Additive Type Temperature Range
ergistic with sulfur-containing E P additives. In addition, they
Carboxylic acids, esters, and metal salts (soaps) < 200°C are less corrosive, easier to dispose of after use, cause little or
Chloropraffins and other chlorinated derivatives 180^50°C
Organophosphorus compounds, such as 200-700°C no foam, and are easily removed from the work piece surface.
phosphoric acids and their derivatives They can be used both for ferrous and nonferrous metals,
Organosulfur compounds, such as polysulfides 600-1000°C which is an added benefit.
Dispersants Corrosion Inhibitors

These additives are mainly used to suspend inorganic solids, These additives are of two types: film-formers axid acid (cor-
such as graphite and molybdenum disulfide, in specialty lu- rosive component) neutralizers. Film-formers protect against
bricants and include high molecular weight alkenylsuccin- corrosion by forming physical films on metal surfaces. Acid
imides, alkylsalicylates, and alkylbenzenesulfonates. The neutralizers control corrosion by neutralizing acidic species
structures of these additives are shown in Fig. 17. either present in a lubricant or produced during use. The se-
lection of these additives depends upon the fluid type and the
Anti-misting Agents metal to be protected. For straight oils, overbased metal sul-
Some metalworking operations generate mist, which is not fonates are used to protect against iron corrosion (ASTM D
only of concern because of worker safety, but it also leaves an 665 and D 4627).
undesirable oily residue on parts and equipment. Anti-mist-
ing agents are polymeric thickeners that are used to mini-
mize mist generation in mineral oil derived fluids. These ad-
ditives control mist formation by modifying droplet size and P1B-X^^.._
NCHjCHzNHCHjCHjtvr
/
include ethylene-propylene copolymers, polyacrylates and
polymethacrylates, polyacrylamides, polybutenes and poly-
isobutenes, polystyrenes, and styrene-butadiene copolymers. Polyisobutenylsuccinimide Metal Salicylate
Alkalinity Agents .SOjJxM

M = Ca, Ba, Na
These additives are used to impart reserve alkalinity (ASTM > X = 1 or2
D 974 and D 4739) and include alkanolamines, complex
amines, and metal hydroxides and carbonates. These not Alkylbenzenesulfonate
only stabilize emulsions through a buffering action, but they
also control corrosion by neutralizing corrosive acids. FIG. 17—Commonly used dispersants.
R CH=CH CH2—COOR"
R (S), R Sx
Alkyl polysulfide R — C H r — CH CHzCOOR'
R = C4 and higher; n = 2-4

Sulfurized Cairboxylic Acids and Esters
R' = H; Acid R' = All<yl; Ester
M (ROJJR:
\
Metal Dithiocarfoamate Dlalkyl Hydrogen

M = Zn (zinc), Sb (antimony)
Phosphite
(RO),P(OH)y- RNH2 (R0)2 P

.^' Zn
\.
Amine Phosphates
X, y = 1 o r 2
Zinc Dlalkyl Dithiophosphate
IVI = Na or Ca
SO,
M . M (CO3) *" ~^ '*"' sodium and 2 for calcium
n =2 for sodium and 1 for calcium
Basic Alkylbenzenesulfonate
FIG. 16—Structures of common EP agents.

Additives used to control iron corrosion in metalworking to use two different biocides in an alternating fashion to
fluids include fatty amines, neutral and basic barium and guard against microbes developing immunity [10].
calcium alkylaromatic sulfonates, and metal and amine salts Commonly used biocides include formaldehyde-release
of carboxylic acids, boric acid, and organic acid phosphates. agents and others. Others can be further divided into hetero-
Sulfonates are either alkylbenzene derived or alkylnaphtha- cyclics and organohalogen compounds. The structures of
lene derived. Both the fatty acids and the high molecular some of the biocides are shown in Fig. 19. l,3-Di(hydroxy-
weight oxidates (oxidized hydrocarbons) are used to manu- methyl)-5,5-dimethyl-2,4-dioxoimidazole, 2-hydroxymethyl-
facture soaps. Alkanolamides, imidazolines, and sarcosines, aminoethanol, hexahydro-l,3,5-tris (2- hydroxyethyl)-s-tri-
often used as rust inhibitors, are also alkaline derivatives of azine, and oxazolidine are examples of formaldehyde-release
carboxylic acids. Of these, amines and overbased sulfonates, agents. These additives control bacterisJ growth by releasing
which are basic, perform by acid neutralizing mechanism. formaldehyde, an antibacterial agent. Formaldehyde results
Others perform via film formation. For yellow metal protec- from the hydrolysis of these additives in water-based fluids.
tion (ASTM D 130), benzotriazoles and dimercaptothiadia- Heterocyclics include isothiazolone, benzisothiazolinones,
zole (DMTD) derivatives are used. Structures of these in- morpholine, sodium pyrithione (sodium omadine), benzo-
hibitors are provided in Fig. 18. triazole, and dimercaptothiadiazole. Organohalogen com-
pounds include 2,4,5-trichlorophenol, bis (2-chloroethyl)
Antimicrobial Agents ether-tetramethylenediamine copolymer, and 2,2-dibromo-3-
These additives, also known as biocides, are control specific. nitrilopropionamide. A variety of other compounds that are
outside these general classes are also used to control micro-
A fluid can therefore have a combination of these: one acts as
bial infestation. These include o-phenylphenol, carbamates,
an antibacterial and the other as an antifungal and yeast con-
dithiocarbamates, glutaraldehyde, and nitroalcohols.
trol agent. Microbial attack is undesired because it causes
buildup of acidic materials, corrosion of machinery and Most of these compounds destroy bacteria directly.
tools, destruction of additives, objectionable odors, and it Sodium omadine is an effective antifungal agent. Materials,
produces materials that destabilize emulsions. Fungal attack such as 2,2-dibromo-3-nitrilopropionamide, are useful for
can lead to slimy material that can coat the machinery and controlling bacteria and fungi, including yeast. These addi-
tools as well as clog pumps and filters. This makes monitor- tives, by virtue of protecting against infestation from all
ing for microbes a necessity. Monitoring is carried out three, minimize worker exposure and prolong emulsion
through commercial culture techniques. Standard practice is batch life. Boron containing formulations usually do not ex-
Ca
R
Polyethoxylated Phenol Neutral Calcium Sulfonate
O
II SO,
R—CH —C—OH
Ca. xCaCOs
CH—-C—OH -LR 2
II
O
Alkenylsuccinic Acid Basic Calcium Sulfonate
O
II
RO—P—OH . R'NHj-
^CHjCHjOH
R—N, OR AII<ylammoniun
CH2CH2OH Phosphates
O
II
Dlethanolamine RO—P—OH . R'NH,"
I
OH
RS.^/*»\,^SR
\\ //
N—N
Dimercaptothiadiazole Alkylbenzotriazole
Derivative
FIG. 18—Common corrosion inhibitors

perience bacterial growth. While choosing an antimicrobial certain triglycerides, water-insoluble polyglycols, ethylene
agent, one must consider its toxicity, its effect on emulsion glycol-propylene glycol copoljaners, and polyacrylates.
stability, and regulations considering its discharge into waste Silicone type inhibitors can adosrb on the metal surface
streams. and, in a subsequent operation, reduce the ability of paint or
coating to adhere to the metaJ part. Their use is also unde-
Foam Inhibitors (Antifoam Agents, Defoamers) sired because of the environmental and waste treatment con-
These additives are used to control foam (ASTM D 892 and D cerns, plating effect or "fisheyes," and effects on cleaning and
3601, IP312) in metalworking fluids. Foam in lubricants oc- finishing. They are h a r d to remove by washing, which may be
curs because of air or gas entrainment and impairs their flow necessary for finishing the part via painting, varnishing, and
and lubricating ability. Air entrainment is c o m m o n during enameling. The structures of some of the foam inhibitors are
spraying and p u m p i n g of lubricants. F o a m is particularly shown in Fig. 20.
c o m m o n in water-based fluids because they usually contain
surfactant type water-soluble additives. F o a m is undesired Oxidation Inhibitors
because it interferes in lubrication, inhibits cooling, and cre- These additives are used in lubricants to minimize deteriora-
ates a problem if it overflows sumps and tanks. Foam in- tion of the organic component due to oxidative attack. If not
hibitors are readily dispersible additives, which are added to controlled, oxidation will lead to acidic products that tend to
the fluid in a low concentration, that is in parts per million or form sludge and corrode metal surfaces. For a more detailed
parts per billion. They perform by reducing the surface ten- discussion on oxidation, consult Chapter 30 of this treatise.
sion of bubbles (ASTM D 1590), thereby resulting in their co- Because many metalworking operations involve high tem-
alescence. Common types include amide and ester waxes, sil- peratures a n d metal debris, the rate of oxidation is even
icones and modified silicones, long-chain saturated alcohols. faster. This makes the need for these additives even more
FORMALDEHYDE-RELEASE AGENTS
eH,CH,OH
I
Hj H2
HOHjCHjC^ CH2CH2OH
2-{Hydroxymet)iylamino)ethanol Hexahydro-1,3,5-tris (2-hydroxyethyl)- s-triazine
CH3
H3C-C-NCH2OH
° ^ N ^ O
CHjOH
•:?;>
1,3-dJ (hydroxymethyl)-5,5- Oxazolidine
dimethyl-2,4-dioxoimidazole
OTHERS
HC NH. NH
\\ ;
HC-C,
isothiazolone BenzoisothiazoUnone BenzotFiazole
a: />-SH N
0
^S _
Sodium pyrithione
Sodium omadine
0 H
H^N-V*"^
Br Br
N
3
2,4,5-Trichlorophenol 2,2-Dibronio-3-nitrilopropionafnide
FIG. 19—Structures of some biocides.

CH, CH, CH,

I ^ I I ^
-O-Si—O Si—O Si
I I
CH3 CH3 '/< ^
™CH3
CH3
Dimethylsiloxane Polymer
Arylamine 2,6-Di-t-butyl-4-niethylphenol
HO(CH2CH20)xCH2CH20[CH2CH(CH3)0]yCH2CH(CH3)OH
.CHzCOOH
Ethylene Oxide - Propylene Oxide Copolymer N.
CH2COOH
^CHzCOOH
FIG. 20—Common foam Inhibitors.
N,
'CH2COOH
Ethylenediaminetetraacetic Acid
p a r a m o u n t . Alkylated aromatic amines, alkylphenols, and
FIG. 21—Oxidation Inhibitors for metalworking fluids.
quinolines are the c o m m o n oxidation inhibitors. Sulfur com-
pounds that are extensively used in metalworking fluids to
provide extreme pressure protection have the added advan-
tage of acting in this capacity.
Lubricant Formulations
Metal ions, such as those resulting from the attack of acidic
species on metal are known oxidation promoters (see Chap- E a c h metalworking operation places a different d e m a n d
ter 30 on Oxidation). Metal passivators, or chelators, are used on the lubricant. A lubricant must therefore possess specific
to control oxidation by complexing with the metal ions and properties to perform effectively. The properties that fulfill
making them innocuous. Chelators include triazoles, thia- the c o m m o n needs of most operations include cooling, lubri-
zoles, and organic diamines, such as ethylenediamine- cation, w e a r control, a n d protection against corrosion.
tetraacetic acid (EDTA) and nitrilotriacetic acid. Structures Metcdworking fluids, like other lubricants, are obtained by
of c o m m o n l y used oxidation inhibitors are provided in blending base fluid and additives. These fluids must meet
Fig. 2 1 . performance specifications, which for these fluids are pri-
marily established by OEMs and end-users. Table 7 provides
Dyes the additive composition of metal removal fluids and Table 8
These additives are used to impart color to the lubricant cind provides the additive composition of metal forming fluids
include a n t h r a q u i n o n e s , azo c o m p o u n d s , a n d triphenyl- and miscellaneous others. In Tables 9 and 10, additives are
listed in the form of formulations. Table 9 presents formula-
methane.
tions based on the base fluid and Table 10 presents formula-
Odor Control Agents tions based on the fluid function.
These agents are used to control undesirable odors present in

lubricants or produced during use. Odor control agents in- TABLE 7—General composition of metal removal fluids.
clude sjrnthetic sassafras, pine oil, terpenes such as teipinol
and d-limonene, and methyl salicylate. Metal Removal Fluid Composition"
Straight cutting oil Mineral oil; friction reducer (fatty acids,
Inorganic/Organic Solids their metal salts and esters); extreme
pressure agent (chlorinated isobutylene,
These include graphite, M0S2, metal powders, metal oxides, dibenzyl sulfide, organic phosphates).
metal halides, mica, a n d tetrafluoroethylene polymer. Water-soluble Water; corrosion inhibitor (sodium or
Tetrafluoroethylene polymer, or TEFLON®, is one of the few cutting oil potassium nitrite; mono-, di-, or
organic materials that are used to formulate metalworking tri-ethanolamine); emulsifier (non-ionic
surfactants; natural and synthetic fatty
fluids. These solid additives are suspended in oil or water- acid soaps; polyalkylene glycols).
based lubricants by the use of high molecular weight disper- Grinding oil Water; mineral oil; friction modifier;
sants, referred to as carriers. During use, the solid separates extreme pressure/antiwear agent;
at the tool-work piece interface to form a low-shear film that anti-misting additive.
provides lubrication, in a m a n n e r similar to that of the film- Lapping oil Mineral oil; dispersant; lapping agent.
Honing oil Mineral oil; friction reducer (fatty acids and
forming agents. These additives are generally not used in (precision triglycerides); extreme pressure agent
metal removal lubricants, although some passive EP agents grinding) (chlorinated isobutylene, dibenzyl sulfide,
that are used are colloidal dispersions. However, the use of organic phosphates).
inorganic solids is more c o m m o n in formulating fluids for Punching lubricants Mineral oil; friction reducer (fatty oils,
certain metal forming operations, such as extrusion and forg- (emulsifiable and graphite, mos2, mica, or talc); extreme
nonemulsifiable pressure agent (organophosphorus,
ing. Suspension process generally involves mechanically agi- minereil, and solid organosulfur, and organohalgen
tating finely divided powders in oil or water, in the presence dispersion type) compounds).
of an emulsifier or a dispersant.
"Not all formulations contain all the listed additives.
TABLE 8—General composition of metal forming and other fluids.

Lubricant Composition"
Metal forming fluids
Hot rolling oil (emulsion type) Water; mineral oil (primarily naphthenic); emulsifier; coupling agent; corrosion inhibitor
(alkanolamides); antimicrobial agent (triazines); friction reducer (fatty acid derivatives); anti-misting
additive (polyisobutylenes); and extreme pressure agent (organophosphorus compounds).
Cold rolling oil (straight oil type) Mineral oil (kerosine cut); friction reducer (dodecanol, fatty acids and esters); and extreme pressure agent
(organophosphorus, organosulfur, and organohalgen compounds).
Cold rolling oil (emulsifiable Water; mineral or fatty oil; friction reducer (fatty alcohols, acids and esters); emulsifier; coupling agent;
type) corrosion inhibitor (alkanolamides, sulfonates); foam inhibitor (ethoxylated fatty alcohols);
antimicrobial agent (triazines); and extreme pressure agent (organophosphorus, organosulfur, and
organohalgen compounds).
Cold rolling oil (aqueous solution Water; friction reducer/EP agent ( o r g a n o p h o s p h o r u s c o m p o u n d s , polyalkylene glycols); corrosion
or synthetic type) inhibitor (fatty amines).
Wire drawing lubricants (straight Mineral oil; friction reducer (animal or vegetable oils); lubricant carriers* (phosphoric acid, oxalic acid,
oils and emulsion types) lime); extreme pressure agent (organic chlorides)
Tube drawing fluids (straight oils Mineral oil; friction reducer (animal or vegetable oil); lubricant carrier (phosphates, oxalates, lime);
and emulsion types) extreme pressure agent (organic chlorides);
Deep drawing fluids (straight oils Mineral oil; friction reducer (animal or vegetable oil); corrosion inhibitor; sdhesion improver
and emulsion types) (polymethacrylates); extreme pressure agent (organophosphorus, organosulfur, a n d organohalgen
compounds).
Extrusion lubricants (powder, Mineral oil; friction reducer (alksdi metal soaps of fatty acids, fatty animal and vegetable oils); lubricant
grease, solid, and straight oil carrier (phosphoric acid, oxalic acid, lime); extreme pressure agent (organophosphorus, organosulfur,
types) and organohalgen compounds).
Cold forging lubricants Mineral oil; lubricant carrier (zinc phosphate); a n d extreme pressure agent (organosulfur a n d
organohalgen compounds).
Metal treating fluids
Quenching oils (straight oil type) Mineral Oil; oxidation inhibitor (alkylphenol); quenching p r o m o t e r (high molecular weight hydro-
carbons).
Quenching oils (washable) Mineral oil; emulsifier; oxidation inhibitor; quenching promoter (high molecular weight hydrocarbons).
Quenching oils (emulsifiable Mineral oil; emulsifier; oxidation inhibitor; quenching promoter (high molecular weight hydrocarbons);
type) antimicrobial agent; corrosion inhibitor.
Metal protecting fluids
Rust preventive oils straight oil Mineral oil; corrosion inhibitor
type)
Rust preventive oils (emulsifiable Mineral oil; emulsifier; water; plasticizer (ethyl cellulose or cellulose acetate); micronized waxes;
type) corrosion inhibitor (alkali and alkaline earth natural metal sulfonates; fatty carboxylates; naphthenates;
and extensively oxidized hydrocarbons, both neutral and overbased, amino alcohols and triazoles)
Slidewav lubricants Mineral oil; friction modifier (fatty acid derivatives); antiwesir agent; oxidation inhibitor
"Not all formulations contain all the listed additives.

''These additives, appHed through surface bonding, increase surface roughness, which improves adhesion of the lubricant/EP additives.
TABLE 9—Fluid based formulations.

Fluid Type Approximate Fluid Composition
Straight oil Mineral oil (60%), ususdly solvent-refined blends to achieve ISQ 10, 15, 22, 32, 46, 68 grades; lubricity agent
(15.3%)—natural fats, synthetic esters; EP additives (20%), chlorinated paraffins, overbased sulfonates,
phosphorus, sulfur, sulfurized fats, and sulfurized olefins; corrosion inhibitor (4.7%).
Soluble oil Mineral oil of 40°C viscosity of 15-20 cSt (53.9%); emulsifler/corrosion inhibitor (30.3%)—anionic - sulfonates,
alkanolamine salts—amphoteric - a m i n o acid soaps—nonionic - ethoxylates, alcohols, amines; other
additives (10.3%)—foam inhibitor, bactericide/fungicide, extreme pressure agent/s; water (5.5%).
This additive package is diluted with water in 1:10 to 1:50 ratio to yield the finished fluid, which appears
opaque.
Semisynthetic fluid Mineral oil (14.7%); emulsifier/corrosion inhibitor (50%)—anionic - sulfonates, alkanolamine soaps, boron
amides; nonionic - ethoxylates, alcohols, amines; other additives (10.3%)—foam inhibitor, oiliness agent,
extreme pressure agent/s; water (25%).
This additive package is diluted with water in 1:20 to 1:60 ratio to give the finished fluid that appears almost
clear.
Synthetic fluid Corrosion inhibitor (39.7%)—alkanolamines, water soluble soaps, b o r o n soaps/salts, fatty acids/esters;
wetting/lubricity agents (7.2%)—polyglycols and esters; other additives (3.1%)—bactericide/fungicide, foam
inhibitor, extreme pressure agent; water (50%).
This additive package is diluted with water in 1:10 to 1:100 ratio to give the finished fluid that appears
completely clear.
TABLE 10—Âpplication based formulation.

Lubricant Approximate Composition
Mineral forming fluid Extreme pressure agent (20.0-35%)-chlorinated wax a n d sulfurized fat mixture; corrosion inhibitor
(1.0-2.0%)-alkanolamine; lubricity agent/friction modifier (10.0-20.0%)-soap or lard oil
Soluble-oil forming fluid Extreme pressure agent (25.0-30.0%)-chlorinated wax a n d sulfurized fat mixture; corrosion inhibitor
(4.0-6.0%)-alkanolamine; lubricity agent/friction modifier (10.0-20.0%)-soap o r lard oil; foam
inhibitor (0.5-1.0%)-polyacrylate; buffer (4.0-6.0%)-diethanolamine o r triethanolamine; biocide
(1.0-2.0%)-triazine; emulsifier (4.0-6.0%)-soap.
Straight removal fluid Extreme pressure agent (10.0-20.0%)-chlorinated wax o r sulfurized olefins; corrosion inhibitor
(0.5-1.0%)-alkanolamine or triazole; friction modifier (5.0-10.0%)-carboxylic acid derivative.
Soluble-oil removal fluid Extreme pressure agent (10.0-15.0%)-chlorinated wax or sulfurized olefins; corrosion inhibitor/buffer
(4.0-6.0%)-alkanolamine; lubricity agent/friction modifier (5.0-10.0%)-carboxylic acid derivative;
foam inhibitor (1.0-2.0%)-polymethacrylate; biocide (2.0-3.0%)-triazine; emulsifier (5.0-10.0%)-soap.
Semi-synthetic removal fluid Extreme pressure agent (4.0-6.0%)-chlorinated wax or sulfurized olefins; corrosion inhibitor/buffer
(5.0-10.0%)-alkanolamine; lubricity agent/friction modifier (5.0-8.0%)-carboxylic acid derivative;
foam inhibitor (1.0-2.0%)-polymethacrylate; biocide (2.0-3.0%)-triazine; emulsifier (5.0-10.0%)-soap
or petroleum sulfonate.
Synthetic removal fluid Extreme pressure agent (2.0-3.0%)-sulfurized olefins or zinc dialkyl dithiophosphate; corrosion
inhibitor/buffer (5.0-10.0%)-alkanolamine; lubricity agent/friction modifier (4.0-6.0%)-carboxylic
acid derivative; foam inhibitor (1.0-2.0%)-polymethacrylate; biocide (2.0-3.0%)-triazine; emulsifier
(5.0-10.0%)-soap or petroleum sulfonate.
Mineral protecting fluid Corrosion inhibitor (2.0-3.0%)-neutral metal sulfonate mixture.
Synthetic protecting fluid Corrosion inhibitor (0.5-1.0%)-amine carboxylate and amine borate mixture; lubricity agent/friction
modifier (0.5-1.0%)-phosphate ester; buffer (5.0-10.0%)-alkanolamine; biocide (1.0-5.0%)-triazine.
Mineral treating fluid Oxidation inhibitor (0.1-0.5%)-phenol and arylamine mixture; speed improver (1.0-10.0%)-calcium
sulfonate.
Synthetic treating fluid Corrosion inhibitor (1.0-2.5%)-alkanolamine; foam inhibitor (0.5-1.0%)-polyacrylate; buffer
(5.0-10.0%)-alkanolamine; biocide (2.0-3.0%)-triazine.
TABLE 11—List of tests for metalworking fluids. standards contain these tests, as summarized in Table 13. De-
Oil-Base Fluids Water-Based Fluids tails of these tests are available in books on ASTM, IP, and
Corrosion Tests Corrosion Tests DIN Standards [13,14,24]. It is important to point out that
Ferrous metals (ASTM D 665) Ferrous Metals (ASTM the tests across standards do not always match. They may dif-
D 4627, IP 287, and IP 125 fer because of disparity in hardware, test method, or the way
Cu and Cu Alloys (ASTM D 130) Cu and Cu alloys (ASTM D 130) they are performed.
EP-Load Carrying Tests EP-Load Carrying Tests
Falex EP wear-Pin-on V-block- Falex E P wear-Pin-on-V-block-
(ASTM D 2670) and D 3233) (ASTM D2670 and D 3233)
4-Ball Wear (ASTM D 4172) 4-Ball Wear (ASTM D 4172)
USED LUBRICANT RECYCLING
4-Ball EP Weld (ASTM D 2783) 4-Ball EP Weld (ASTM D 2783)
Metal Removal Meted Removal Toxicity, safety, and environmented compatibility of chemi-
cals are becoming a growing concern. Toxicity determines the
Falex No. 8 Tapping Torque Falex No. 8 Tapping Torque
Lubrizol CNC tapping torque Lubrizol CNC tapping torque ability of materials to h a r m life. While h a r m to h u m a n s is a
Lubrizol CNC drill wear/life Lubrizol CNC drill wear/life major concern, the effect of chemicals on the environment as
Lubrizol CNC milling/surface Lubrizol CNC milling/surface a whole cannot be ignored. Unused lubricants are generally
finish finish considered less toxic t h a n used lubricants. Exposure to used
Lubrizol pipe threading test Lubrizol pipe threading test
oils primarily occurs through skin absorption. Over the short-
Other Tests Emulsion Stability
term, the toxic c o m p o n e n t s present in t h e used oil can lead to
GM Quenchometer (ASTM Emulsion stability skin irritation; over the long-term, they can act as carcino-
D 3520) characteristics-(ASTM
D 1401, IP 263) gens. The Occupational Safety and Health Administration
Cooling curve analysis (ASTM Moderate Timken aquarium test (OSHA) requires all lubricant manufacturers to provide ma-
D 6200) Lubrizol centrifuge procedure terial safety data sheets (MSDSs) on their products. While
Other Tests each MSDS contains a variety of information, its primary pur-
Cooling curve analysis (ASTM pose is to provide physical and health hazard data on prod-
D 6482 and D 6549) ucts, so as to facilitate safe handling. H u m a n exposure can be
minimized by avoiding contact with the lubricant by using
protective equipment, such as gloves, oil-impervious clothing
METALWORKING FLUID TESTS a n d boots, and by adopting explosion and fire prevention
measures. Environmental protection requires that neither
Test methods to evaluate the performance of these fluids are new nor used lubricant be released to air, water, or land. This
not well standardized. Some are standardized tests, such as can be achieved only if proper procedures pertaining to stor-
ASTM, IP, and DIN Tests, while others are additive supplier age and handling of lubricants, lubrication, equipment main-
or the end-user required tests. The standardized tests t h a t are tenance, and disposal of used lubricants are in place. Because
either presently used or can be used to judge the suitability of lubricant disposal is costly and is subject to a n u m b e r of fed-
metalworking fluids are listed in Table 11, and the p a r a m e - eral, state, and local regulations, minimizing the volume of
ters they evaluate are briefly described in Table 12. Many the used or the leaked lubricant is highly desired.
TABLE 12—Metalworking fluid tests.

Test and Procedure Purpose
Corrosion
Copper (ASTM D 130) 3 h at 100°C Measures fluid's non-ferrous compatibility.
Turbine oil rust (ASTM D 665) Measures the ability of inhibited mineral oils to aid in preventing the rusting of ferrous
A-Distilled water metals in the presence of water.
B-Synthetic sea water
Aqueous cutting fluid (IP 125) Measures corrosion protection of aqueous cutting fluids.
Filter paper chip breakpoint (IP287) Evjiluates rust inhibition properties of aqueous cutting fluids.
Aluminum cup stain 20 min at 350°C Cup appearsince indicates non-ferrous corrosion properties.
Humidity cabinet rust (ASTM D 1748) Measures ability of preservative oils to protect metal parts from rusting under conditions
of high humidity.
Salt spray (MIL-B-117-64) Steel part corrosion protection measured after exposure to 5% salt spray for 24 h.
Cleveland condensing humidity cabinet Measures anti-rust properties of metal preservative fluids on steel panels. Considered more
(ASTM D 2247) severe than ASTM D1748 humidity test.
Extreme pressure
4-Ball wear (ASTM D 2266)
40 kg, 1200 rpm, 75°C,1 h average Evaluates anti-wear and anti-weld properties of lubricants.
coefficient of friction; maximum scar
diameter (mm)
Timken (ASTM D 2782) Measures abrasion resistance and load carrying capacity of lubricants.
OK Load (lb)
4-Ball EP (ASTM D 2783) Evaluates extreme pressure and anti-weld properties of lubricants.
seizure (kg); Weld (kg); LWI (kg)
Falex EP (ASTM D 3233) Measures load carrying capacity and wear properties of lubricants.
Stability
Foam (ASTM D 892, IP312) Determines foaming characteristics of lubricating oils at specific temperatures.
tendency/stability (ml)
Panel coker Determines relative stability of lubricants in contact with hot metal surfaces.
4 h at 260°C, continuous splash
Demulsibility (ASTM D 1401) (mL Measures separation of oil and water from emulsion over time.
oil/mL water/mL emulsion)
Emulsion stability (IP263) Measures emulsion stability in water.
Aquarium biostability Measures foam, bacteria, fungus, and odor over time in controlled aqueous environment.
Miscellaneous
Color (ASTM D 1500) Visual determination of fluid color based on colorimetric readings.
GM quenchometer (ASTM D 3520) R. C. Determines heat removal speed of a quench oil.
index
Thread tapping (Lubrizol test) Evaluates fluid efficiency by measuring torque required during tapping operation in steel.
Pipe threading (Lubrizol test) Evaluates fluid efficiency by measuring torque required during threading operation on cast
iron or stainless steel.
Stick-slip (Cincinnati milacron test) Measures static and dyneimic coefficients of friction in slideway lubricants.
Bijur filtration Determines compatibility of lubricants with Bijur setup (specific to Bijur filter design)
Falex #8 Evaluates fluid efficiency by measuring torque required during tapping operation in steel.
SLT (Draw Bead Simulator) Evaluates friction generated in a drawing process.
Reichert Measures load-carrying properties of lubricants.
Recycling of the used lubricant is one option. At present, • clay treatment to remove polar oxygenated materials or to
three methods are used for recycling: reprocessing, reclama- improve color
tion, and re-refining [25]. Reprocessing is used to make used • aeration or biocide treatment to get rid of bacterial con-
oil suitable for combustion as burner fuel. The simplest in tamination
terms of treatment, this technique involves the removal of • additive blending to make u p for the depleted additives
particulates, water, and contaminants that can cause scaling Some feed streams need fewer steps than others do. A com-
of the heat transfer surfaces and fouling of the burners and mercial lubricant reclaiming company uses a host of analyti-
of the fuel lines. Particulates and water are removed by the cal techniques to determine the degree of treatment required
use of settling, filtration, and or centrifugation. Sometimes to operate cost-effectively. The listed steps for reprocessing
demulsifiers and heat are employed to facilitate the removal and reclamation are shown in Fig. 22. It is important to point
of contaminants. Reclamation involves a higher degree of out that the quality of the reclaimed lubricant is either the
processing and is primarily used for industrial lubricants, same or lower than that of the lubricant prior to use.
such as hydraulic oils, gear oils, and metalworking fluids. It
Re-refining is the most complex of the three recycling pro-
is more effective if the feed streams are unmixed. Reclama-
cesses and uses petroleum refining techniques, such as vac-
tion involves:
u u m distillation and hydrotreating, both of which require
• settling, centrifuging, and filtering to remove solids specialized equipment. Because of this, only a limited num-
• clay and eJkali treatment to remove acidic contaminants, ber of companies are involved in this process. Re-refining,
followed by washing to remove the resulting soaps primarily used to recycle engine oils, results in clean high
• mild heating or distillation to remove volatile components quality basestocks.
TABLE 13—Compsirative test standards.

Test ASTM Designation ISO Designation IP Designation DIN Designation
Standard test method for pour point D 97-96a 3016-1994 15/95 DIN- ISO
of petroleum products 3016:1982-10
Standard test method for detection of D 130-94 2160-1998 154/95 51 759
copper corrosion from petroleum
products by the copper strip
tarnish test
Standard test method for kinematic D 445-97 3104-1994 71/97 51 550
viscosity of transparent and opaque
liquids (the calculation of dynamic
viscosity)
Standard test method for rust- D 665-98 7120-1987 135/93 51 585 A-HE
preventing characteristics of
inhibited mineral oil in the
presence of water
Standard test method for foaming D 892-98 6247-1998 146/82 51 566 E
characteristics of lubricating oils 312/74 Edition 12/83
Standard test method for acid and D 974-97 6618-1997 139/98
base number by color-indicator
titration
Standard test method for water D 1401-98 6614-1994 51599
separability of petroleum oils and
synthetic fluids
Standard test method for emulsion D 1479 290/84
stability of soluble cutting oils (Discontinued)
Standard test method for ASTM color D 1500-98 2049-1996 196/97
of petroleum products (ASTM color
scale)
Standard test method for rust D 1748-83 366/84 51359
protection by metal preservatives
in the humidity cabinet
Standard test method for wear D 2266-99 239/97 51 350 Part 5
preventive characteristics of
lubricating grease (four-ball method)
Standard practice for csJculating D 2270-93 2909-1981 226/91 DIN-ISO
viscosity index from kinematic 2909:1997-10
viscosity at 40 and 100''C
Standard test method for measurement D 2782-94 51 434 Part 2
of extreme-pressure properties of
lubricating fluids (timken method)
Standard test method for measurement D 2783-88 293/97 51350
of extreme-pressure properties of Part 2
lubricating fluids (four-ball method)
Standard test method for low- D 2983-87 267/84
temperature viscosity of automotive
fluid lubricants measured by
Brookfield viscometer
Standard test method for foam in D 3601-88 312/74 51 395-1
aqueous media (bottle test) Dynamic Test
Standard test method for wear D 4172-94 293/97 51 350 Part 3
preventive characteristics of
lubricating fluid (four-ball method)
Standard test method for iron chip D 4627-92 287/94 51 360 Part 2
Corrosion for water-dilutable 125/82
metalworking fluids
Standard test method for evaluating D 5182-97 334/93 51 354 Part 2
the scuffing (scoring) load capacity
of oils
Standard test method for apparent D 5293-99- 383/94
viscosity of engine oils between
- 5 and -30°C
Settling Filtration Dehydration
Reprocessed Oil
Satds and Water Fine Solids
Clay/Alkali
Settling Fillratlon Dehydration Treatment Water Washing
^~^ /• \ /•
\
\ J
V
-Acidic Contaminants
^
Solids and Water
I
Fine Solids
\
Water
Heating/Distillation
/• \
-^ Volatiles (Solvents, Fuel, Water) Additive Blending
Clay Treatment
Reclaimed Lubricant
FIG. 22—Flow schemes for lubricant reprocessing and reclamation.
REFERENCES [14] DIN Handbuch—Mineralole

GmbH, Berlin, 1998.
und Brennstoffe, Beuth Verlag
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MNL37-EB/Jun. 2003
Petroleum Waxes
G. All Mansoori, ^ H. Lindsay Barnes,^
WAXES ARE USUALLY SOLID AT ROOM TEMPERATURE because they try as a gelling agent for organic solvents and as a raw mate-
contain linear paraffinic hydrocarbons with carbon chains of rial used in lipstick formulations for t h e cosmetic market.
various lengths. Waxes can vary in consistency from easily C a m a u b a wax is recognized generally a s safe by the United
kneadable t o brittle. They exhibit relatively low viscosity at States Food and Drug Administration.
t e m p e r a t u r e s slightly above their melting point. The a p - Candelilla wax is harvested from the shrubs Eurphorbiea
pearance of waxes can vary from translucent to opaque, but antisiphilitica, E. cerifera, and Pedilanthus pavonis in Mexico
they are not glassy. The consistency (i.e., hardness) and solu- and southwest Texas. The candelilla wax is recovered after
bility of waxes depends on the temperature at which they are the entire mature plant is uprooted and immersed in acidi-
observed. fied boiling water. During the immersion, the candelilla wax
The use of waxes dates back more than 5000 years. As early floats to the surface and is skimmed off. The primary market
as 4200 B.C. the Egyptians extracted a waxy substance from for candelilla wax is cosmetics where it is a component in lip-
the honeycomb of bees and used it to saturate linen wrap- stick formulations. The chemical composition of c a m a u b a
pings of m u m m i e s [1]. The sculptured portrait of the de- and candelilla wax is listed in Table 2.
ceased decorating a coffin cover w a s often modeled in Synthetic waxes are derived from either the Fischer-Trop-
beeswax and painted with pigmented beeswax. Another use sch process [7] or by ethylene based polymerization pro-
of wax was in the preparation of erasable writing tablets. Fas- cesses [8]. The Fischer-Tropsch (F-T) process originated in
tening together several tablets with fiber produced forerun- Germany in the 1920s and is illustrated schematically in E q
ners of the m o d e m book [2]. 1. The F-T process was developed to synthesize hydrocarbons
Waxes are classified by the matter from which they are de- and oxygenated compounds from a mixture of hydrogen and
rived: insect, vegetable, synthetic, and mineral [3]. Beeswax carbon monoxide. During World War II, the F-T process was
is a n example of insect wax. The chemical composition of used by Germany to produce fuels from coal-derived gas. The
beeswax is u n i q u e a n d its characteristics vary with t h e first commercial plant in South Africa started in 1955 at
species of the honeybee. Apis mellifera is the most common Sasolburg, using coal as a feedstock. The so-called Sasol pro-
cultured bee in the world and will provide a chemical gener- cess is illustrated in Fig. 1 [9]. This plant produces waxes, fu-
alization of composition of wax for this species [4]. Beeswax els, pipeline gases (i.e., ethylene, methane), and other prod-
is secreted in eight glands on the underside of the worker bee. ucts using a fixed bed catalyst F-T process. During the F-T
Bees are believed to secrete one p o u n d of wax for every eight process, carbon monoxide, which is generated from coal
pounds of honey they produce. Since secreted beeswax read- gasification, is reacted u n d e r fixed-bed conditions using
ily absorbs color, the final color of the beeswax is influenced high-pressure at approximately 220°C in the presence of a n
by the source of the pollen. A typical composition analysis of iron catalyst to p r o d u c e synthetic hydrocarbon waxes, as
beeswax is provided in Table 1. Beeswax is extracted by melt- shown in Eq 1. Typical reaction products that may be derived
ing or boiling the honeycomb in water and has applications from the F-T process are listed in Table 3.
in pharmaceuticals and cosmetics, and is the primary com-
ponent of religious candles. 2nH2 + nCO -> C„ Hzn + nH20 (1)
Vegetable waxes are extracted from the leaves, bark, and Poly(ethylene) waxes may be produced by the industrial
berries (seeds) of plants and trees. Almost all multi-cellular polymerization of ethylene using high or low pressure ethy-
plants are covered by a layer of wax [5]. Only a few species lene polymerization technology [10], or as thermal decompo-
grown in semiarid climates produce enough wax to be com- sition products of the polyethylene polymers. The molecular
mercially viable for recovery. C a m a u b a and csmdelilla wax weights Emd melting points of the synthetic waxes as com-
are two of the most c o m m o n vegetable waxes that are compared with the Fischer-Tropsch waxes are listed in Table 4.
mercially marketed [6]. C a m a u b a wax is removed from the
The market stability of pricing a n d availability of insect
dried leaves (fronds) of palm trees grown in the northeast re-
and vegetable waxes is affected by climate conditions a n d
gion of Brazil. C a m a u b a is utilized in the polish paste indus-
natural disasters. With the advent of the petroleum industry,
the waxes from mineral and synthetic sources surpassed the
' Department of Chemical Engineering, University of Illinois at annual production of the combined total of the other two wax
Chicago, 810 S. Clinton Street, Chicago, IL 60607-7000. categories. Waxes from insect and vegetable sources are mix-
^ CITGO Petroleum Corporation, Highway 108 South, P.O. Box
1578, Lake Charles, LA 70602. tures of long chain fatty acids, esters of aliphatic alcohols,
^ 63 Rocklege Rd., Hartsdale, NY 10530. and hydrocarbons. Waxes from mineral origins are chemi-
525
TABLE 1—Compositional analysis of beeswax. TABLE 3—Products derived from t h e Fischer-Tropsch process.
Component Amount in wt. % Approx. Typical
Product Yield (wt. %)
Monoesters, CisHjiCOOCsoHsi; C25H51COOC30H61 55-65
Diesters, triesters, hydroxy diesters 8-12 Paraffins (i.e., methane, ethane, propane, 7.2
Free fatty acids, C23COOH-C31COOH 9.5-10.5 and butane)
Free fatty alcohols, C34OH-C36OH 1-2 Olefins (i.e., methylene, ethylene, propylene, 5.6
Hydroxy-monoesters, Ci4H29CH(OH)COOC26H6i 8-10 and butylene)
Hydrocarbons", C25H52-C31H64 12-15 Gasoline (Cs-Cn) 18.0
Moisture and mineral impurities 1-2 Diesel (C12-C18) 14.0
"Hydrocarbons most commonly found in beeswax include nonacosane Ci9 to C23 7.0
(C29H60) and nentriacontane (C31H64). Medium Wax (C24-C35) 20.0
Hard Wax (>C35) 25.0
Water soluble non-acid chemicals 3.0
Water soluble acids 0.2
TABLE 2—Chemical composition of carnauba and candelilla wax.

Component Carnauba (wt. %) Candelilla (wt. %)
TABLE 4—Comparison of Fischer-Tropsch waxes with other
Monoesters 83-88% 28-30% synthetic waxes.
Fatty alcohols 2-3 2-3 Type of Wax iWolecular Weight Melting Points, °C
Free fatty acids 3-4 7-9
Hydrocarbons" 1.5-3.0 49-57 Fischer-Tropsch wax 500-1200 85-110
Resins 4-6 4-6 Low Pressure polyethylene 900-3000 90-125
Moisture and inorganic residue 0.5-1 2-3 wax
High Pressure polyethylene 500-4000 85-130
"Hydrocarbons commonly found in carnauba and candelilla wax are prin- wax
cipally hentriacontane (C31H64) and tritriacontane (C33H68). Pyrolysis" waxes 1000-3000 90-130
"Pyrolysis waxes are derived from thermo-cracking of polyethylene.
POWER
cally inert and are primarily composed of straight chain
COAL PLANT (paraffinic) hydrocarbons.
SIEAM Petroleum wax may vary compositionally over a wide
1 range of molecular weight, up to hydrocarbon chain lengths
OXYGEN
GASmCAHOM 4— PLANT AIR of approximately C50-C60. It is typically a solid at room
temperature and is derived from relatively high boiling
AE GON N,
petroleum fractions during the refining process. Petroleum
'' waxes are a class of mineral waxes that are naturally occur-
nrr^f
RAW CAS ring in various fractions of crude petroleum. They have a
FDBinCAIION
OSOTE
CO, + H,S-* PflTAR NAPHTHA wide range of applications that include: coating of drinking
PURE GAS cups; an adhesives additive; production of candles and rub-
FT ber; as components of hot melts, inks, and coatings for paper;
PROCESS and they can be used in asphalt, caulks, and binders. This
AI.COHOLS KErroms
chapter will provide a review of petroleum waxes including
LA.
F T WATER WATER FHACnOHAIION
history, production, types, chemical composition, molecular
structure, and property testing.
SEPARATION
WORK-UP
GASES
NAI>^HA on. WAX
CRYOGENIC
rt:o,
DISCUSSION
WATER SEPARATION
praancATioN
CH« Cj/Ci Classification of Crude Oils and Chemical
EIHYL0IE PHACnONAnON
Structure of Ingredients
REFORMING OUCOMEBISAHON ••OILS
PLANT
Petroleum crude oil, commonly referred to as crude oil, is a
complex mixture of hundreds of compounds including
solids, liquids, and gases that are separated by the refining
STEAM O2 process. Solid components at room temperature include
asphalt / bitumen and inorganics. Liquids of increasing vis-
CHj CjHj cosity vary from gasoline, kerosene, diesel oil, and light and
heavy lubricating stock oils. Also included are the major com-
FIG. 1—Generalized Sasol Plant for hydrocarbon synthesis ponents of natural gas, which include methane, ethane,
by the Fischer-Tropsch Process. propane, and butane [11].
An elemental einalysis of crude oil shows that it consists of
primarily two elements: hydrogen (11-14%) and carbon
CHAPTER 19: PETROLEUM WAXES 527
TABLE 5 --Crude oil content.

Crude Type Solvent Neutral Oil Base Oil Wax Content Sulfur and Nitrogen Asphalt API Gravity" ASTM Test Method
Paraffinic base Yes Yes <10% Low No >40 E-1519
Naphthenic base No Yes No Low No <33 D-2864
Intermediate base No Yes <6% Low Yes 33-40 D-8
Asphaltic base No Yes 0% High Yes <10 D-1079
"American Petroleum Institute gravity is an arbitrary scale expressing the density of liquid petroleum products. The measuring scale is calibrated in terms of
degree API ("API) and can be calculated in terms of the formula: "API = 141.5/(SG'-[60''F]) — 131.5 where SG'' stands for liquid specific gravity with respect to wa-
ter. The higher the value of API gravity, the more fluid the liquid.
(83-87%). Crude oil hydrocarbons contain long hydrocarbon TABLE 6—ASTM test methods used for sampling, separation, and
chains (saturated and unsaturated), branch structures, and classification of various oil samples and the procedures used.
ring structures, with each having specific physical and chem- Test Method Procedure and Application
ical properties. Small quantities of other compounds con- D 4057 Practice for manual sampling of petroleum and
taining sulfur, oxygen, nitrogen, carbon, and hydrogen are petroleum products
frequently present in crude oils. D 270 Sampling of petroleum and petroleum products
D 4007 Centrifuge method for determination of water and
Crude oils are generally classified based on their predomi- sediment in crude oil
nant hydrocarbon structure type, as shown in Table 5. The D 86 Distillation of petroleum products
t5rpes are referred to as paraffinic, naphthenic, intermediate D 2007 Clay-gel absorption chromatography for oil samples
(mixture of paraffinic and naphthenic crude), and asphaltic of initial boiling point of at least 260°C (500°F) into
base crude [12]. the hydrocarbon types of polar compounds, aro-
matics and saturates, and recovery of representa-
Paraffinic hydroccirbon fractions are saturated linear or tive fractions of these types
branched alkanes. Naphthenic fractions contain five and six D 2425 Mass spectrometry for classification of hydrocarbon
carbon cyclic alkane (alicyclic) structures. Naphthenes cire types in middle-distillate
monocyclic in the lower-boiling fractions (i.e., gasoline) and D 2549 Elution chromatography for separation of represen-
polycyclic in the higher-boiling fractions (i.e., lubricating oils) tative aromatics and non-aromatics fractions of
high-boiUng oils, between 232 and 538°C (450 and
[13]. The asphaltic crudes contain unsaturated aromatic 1000°F)
structures containing rings of five and six m e m b e r carbon D 2786 High ionizing voltage mass spectrometry for hydro-
atoms. Aromatics are defined as those classes of organic com- carbon types analysis of gas-oil saturate fractions
pounds that behave chemically like benzene. They are cyclic, D 2887 Gas chromatography for boiling range distribution
unsaturated organic compounds that C£m sustain an induced of petroleum fractions
D 3239 High ionizing voltage mass spectrometry for aro-
electronic ring current due to delocalization of electrons matic types analysis of gas-oil aromatic fractions
around the ring. Aromatic base oils contain 20-25% aromatic D 3279 Titration for determination of the weight percent of
compounds. A constituent of asphaltic crudes is asphaltene. asphaltenes as defined by insolubility in normal
Asphaltenes are defined as the high molecular weight non- heptane solvent
hydrocarbon fraction of crude oil precipitated by a designated
paraffinic naphtha solvent at a specified temperature and sol-
vent-oil ratio [14]. Like the naphthenic crude, the aromatic talline wax. Those formed from naphtenes are known as mi-
rings are monocyclic in the lower boiling fractions and poly- crocrystalline wax. A hydrocarbon in pure state has definite
cyclic in the higher boiling fractions. Various ASTM test boiling and freezing (or melting) points, which can be mea-
methods listed in Table 6 are used for sampling, separation, sured in the laboratory [16]. Knowing the intermolecular en-
and characterization of petroleum fractions. ergy parameters or critical properties cuid acentric factor
Petroleum waxes are derived from both paraffinic and in- and/or refractive index of hydrocarbons, one can predict their
termediate crude oils and are composed of three basic carbon boiling point using vapor pressure correlations or equations
structures (i.e., linear, branched, and ring) that are charac- of state as discussed in Section I of this report. However, such
teristic of the crude oil. methods are not capable of predicting pure hydrocarbon
freezing points. There are other methods that can be used to
predict hydrocarbon and wax freezing (melting) point, which
Production, Transportation, and Refining of Waxy include but are not limited to variational statistical mechani-
Petroleum Crudes] cal theory [17] and cell-lattice theories [18].
The majority of crude oils produced around the world contain
substantial a m o u n t s of paraffin weix. These c o m p o u n d s , Waxy Crude Oil
sparingly soluble in solution components of the crude oils, A waxy crude usually consists of: (a) a variety of light and in-
crystallize at lower temperatures and are the major contribu- termediate hydrocarbons (paraffins, aromatics, naphtenic,
tors to petroleum Wcix deposits [15]. The wax present in etc.); (b) wax as defined above; and (c) a variety of other
petroleum crudes primarily consists of paraffin hydrocarbons heavy organic (non-hydrocarbon) compounds, even though
(C18-C36), known as paraffin wax, and naphtenic hydrocar- at very low concentrations they include resins, asphaltenes,
bons (C30-C60). Hydrocarbon components of WEIX can exist diamondoids, organometcillics, etc. When the temperature of
in various states of matter (gas, liquid, or solid) depending on a waxy crude oil is lowered to its cloud point, first the heav-
their temperature and pressure. When these hydrocarbons ier fractions of its weix content start to freeze out. Upon low-
freeze, they form crystals, which are known as macrocrys- ering of the temperature of a crude oil to its pour point al-
most all the fractions of its wax content will freeze out. A
waxy crude is characterized by its cloud point and pour
point, which are measured according to ASTM Test Methods
D 2500 and D 97, respectively, as they are discussed later in
this report.
A clean waxy crude is defined as a crude oil in which there
exists only hydrocarbons and wax as its only heavy organic
constituent. As the clean waxy crude flows through a cold
pipe or conduit (with a wall temperature below the cloud
point of the crude) wax crystals may be formed on the wall,
which could then grow until possibly the whole inner wall is
covered with the encapsulating oil inside the weix layers. As
the wax thickness increases, pressure drop across the pipe
needs to be increased to maintain a constant flow rate. As a
result, the power requirement for the crude transport will in-
crease. The cirterial blockage problems of clean waxy crude
can be efficiently controlled by insulation and heating of the
y^'.-'
pipe to a temperature above its cloud point. Most of the ex-
isting wax deposition problems of the clean waxy crudes are
due to the lack of proper insulation and heating systems. As FIG. 2—Pipeline petroleum transport plugging due to
a result, application of chemical anti-foulants and frequent wax and other heavy organics depositions (Courtesy of
use of pigging operations have become necessary [15]. Regu- Phillips Petroleum Company).
lar paraffinic or waxy crudes are widespread. The major com-
plex systems problems related to the production, processing,
and transportation of these medium-gravity fluids is not just To predict the deposition as a function of time, principles of en-
crystallization of their wax content at low temperatures, but ergy and mass conservation, the laws of diffusion, and the prin-
the formation of deposits that do not disappear upon heating, ciples of phase transitions need to be considered [21,22]. In or-
and will not be completely removed by pigging. der to prevent or remediate arterial blockage/fouling and
Regular waxy crudes are not clean and, in addition to wax, facilitate the production of regular waxy crudes, many issues
they contain other heavy organics such as asphaltene, resin, must be underteiken: (a) detailed fluid properties characteriza-
etc. [15]. Asphaltenes do not generjJly crystallize upon cooling tion, (b) production scheme alternatives, (c) retrograde con-
and, for the most part, they may not have definite freezing densation and deposition behavior prediction, (d) onsets of de-
points. Depending on their natures, these other heavy organics position studies, (e) equipment and facility options, (f) design
will have different interactions with wax, which could either and use of chemical anti-foulants and/or pour-point depres-
prevent WEIX crystal formation or enhance it. Existence of sants and blending alternatives, (g) performance specification
branched paraffins, aromatics, naphtenes, and resins in and maintenance planning, and (h) transportation, storage,
petroleum, however, contribute less to these deposits, but mod- and blending studies [23,24].
ify their crystallization behavior. However, asphaltene pres-
ence in the crude oil could prevent or enhance wax deposition Petroleum Refining
depending in the microscopic nature of asphaltene [19,20]. Crude oil is first desalted if salty, deasphalted if asphaltenic,
The precipitation of wax from petroleum fluids during pro- and dewaxed if highly waxy, before it is distilled in an atmo-
duction and transportation may give rise to a veiriety of prob- spheric distillation unit to separate light ends (gases), naph-
lems [17]. One of the main problems observed is deposition of tha, gasoline, jet, kerosene, gas oil distillate, and residuum
solid material on well and pipe walls as demonstrated in Fig. (resid) (see Fig. 3). The residuum (resid) remaining after the
2. This happens if (a) the temperature of the wall is below the atmospheric distillation is then further fractionated in a vac-
cloud point of the oil, (b) a negative radial temperature gradi- uum distillation unit into fractions that are distinguishable
ent is present in the flow, (c) the wall friction is high enough by viscosity for further processing into lubricating oil base
for wax crystals to stick to the wall, and (d) asphaltene present stocks. Wax is concentrated in the distillate stream and the
in the crude oil has already deposited and has increased the residuum fraction is used to produce the base oils for lubri-
friction of the wall (changed of wettability) and acting as mor- cant formulation. Both the distillate and residual lube frac-
tar for the sticking together of wax crystals. Wax crystalliza- tions (stock) contain undesirable constituents such as aro-
tion may cause three problems: (a) higher viscosity, which matics that must be removed by extraction to jdeld base oils
leads to pressure losses, (b) high yield stress for restartability that are thermally stable with a sufficiently high viscosity in-
of flow, and (c) fouling of petroleum flow arteries [15]. dex'' product. The distillate fraction is extracted with a sol-
To predict wax deposition tendency of a crude oil it is im-
portant to know its composition for paraffin wax and the other * Viscosity Index is defined as V.I. = (/XL ~ hiodKlJ'i. ~ MH)- wiiere /AL
components present in, or added to, the crude oil; their com- is the viscosity at 100°F of the zero-V.I. oil, /U-H is tiie viscosity at
position distributions; and the pressure ctnd temperature of the 100°F of the 100 V.I. oil, and /itx is the viscosity at 100°F of the un-
known (test) oil. See ASTM D 567 and D 2270 for further detail. A
system. Thermodynamics and statistical mechanics of phase measure of the magnitude of viscosity changes in lubricating oils
transitions in polydisperse mixtures can be utilized to develop with changes in temperature. The higher the viscosity index number,
predictive models for wax deposition in petroleum fluids [17]. the more resistant the oil is to change in viscosity.
vent (such as furfural) that has a greater solubihty (selective point (i.e., the temperature where the oil ceases to be fluid) is
solvent) for the components having a low viscosity index. The reduced.
residuum fraction is extracted with propane to remove bitu-
m e n (asphalt) and resinous material. The desirable oil and
Solvent Dewaxing Process
wax component is solubilized for further processing.
The nonsoluble portion of the distillate extraction and the The solvent dewaxing process can be divided into three dis-
soluble portion of the residuum fraction are referred to as the tinct sections: (a) crystallization of the wax components by di-
raffinate phase and b o t h contain the m o r e paraffinic oil. lution and chilling, (b) filtration of the wax from the solution
Wax, which typically exhibits a high viscosity index, remains of dewaxed oil and solvent, and (c) recovery of the solvent
in the raffinate phase for further processing. Because the raf- from the dewaxed oil and wax products [25]. To overcome the
finate produced from the extraction process contains wax, high pour point, a solvent dewaxing process has been devel-
which crystallizes at relatively high temperatures (>15°F = oped to remove the wax from lubricating oil basestocks, as
-9.4°C), the fluidity of the base oil that exhibits a high pour shown in Fig. 4. The most widely used solvent dewaxing pro-
s' X Dewaxed
iDeasphaltingp
Asphalt
FIG. 3—Schematic illustration of various possible locations of wax production in

petroleum refining.
OflyWax
Product Shipped
Receiving
ik ik
Blended
Product
Blending &
Oily Wax f .Ciystallization Sulvent Packaging
Storage
Mditives I
Decoloiid]^
&
FntratiDn Deodortdng
Wax
&
Snlinnt Solvrait
Recnwer; StmagB
Stop Tlbxnr Fnnti Oil PrnductllAx
FIG. 4—Solvent dewaxing process for tine removal of wax from lubri-
cating oil slacltwax basestocks.
go- deweixing process. The major process variables include: 1)

go H solvent composition, 2) feedstock composition, 3) solvent di-
70 lution procedure, 4) filtration temperature, 5) filtration pro-
«o cedure, and 6) solvent recovery method.
50 — 1. Ketone based solvents Etre excellent solvents for oils at low
40- temperatures necessary to remove the wax by filtering. Di-
30
i 20 —
10-
luting the raffinate with too much ketone-based solvent can
cause the oil to separate into a distinct layer. Oil phase sep-
aration will adversely affect the yield of wax and result in
0 OaPbaaie the w£ix portion having a n undesirable higher oil content.
S«panition
-10—1 The likelihood of oil phase separation can be determined
-20 experimentally by maintaining a constant solvent dilution
-30 ratio and changing the percentage of ketone content.
-40—1 2. If the raffinate feedstock contains a high proportion of
-50 \ \ \ \ \ I paralBnic content, it will have a high viscosity or viscosity
30 40 50 60 70 80 90 100 index. An oil phase sepeiration can occur when a ketone-
% MEK Content in Dewax Solvent based dilution solvent is mixed with the raffinate.
FIG. 5—Illustration of the effect of the ratio of MEK to the 3. The amount of dilution with the solvent can affect the oil
petroleum fraction being dewaxed on the resulting cloud point content of the wax. Using a solvent dilution greater thcin 2
of the mixture. parts solvent to 1 part raffinate will result in a reduction of
the oil content of the wax.
4. The cooling temperature used to crystallize the wax during
the filtration process can affect the oil content of the wjix
and the desired physical properties such as melting point
cesses are based o n solvent mixtures of methyl ethyl ketone
and hardness. If the dilution solvent is too cold or low cool-
and toluene, methyl ethyl ketone and methyl isobutyl ketone,
ing temperatures are used, the crystal size of the wax formed
or methyl isobutyl ketone itself. Figure 5 illustrates the effect
on the surface of the rotary filter will be small and will re-
of the ratio of MEK to the petroleum fraction being dewaxed
tain more oil. As the dewEixing temperature is reduced,
on the resulting cloud point of the mixture. In the dewaxing
softer and lower melting point wax fractions will increase
process, the raffinate (feedstock) is diluted with solvent and
the overall production yield. As illustrated in Table 7, as a
heated 15-20°F ( - 8 - 1 1 °C), above the cloud point of the raffi-
nate/solvent mixture (or slurry) and chilled at controlled rates
in double-pipe scraped-surface heat exchangers and chillers.
The slurry is chilled to 5-20°F ( ~ 3 - l l ° C ) below the desired
pour point of the oil. When the wEix/solvent solution is cooled,
wax crystals precipitate from the solution, which are then
removed by filtration using a rotary vacuum filter. The crys-
tallized wax forms as a layer (cake) on the surface of the rotary
vacuum filter. The wax cake (filtrate) is washed with a spray
of a cold solvent to remove any residual oil before being dis-
charged from the primary filters. At this point, the wax
contains 10-40% oil and is referred to as "slack wax" if it is de-
rived from the distillate lube fraction, or "petrolatum" if it is
derived from the residual lube fraction. Figure 6 illustrates the
effect of solvent dilution ratio on the a m o u n t of residual oil
content in the slack wax.
To produce waxes with lower oil contents (<5%), an addi-
tional dewaxing process is performed. The wax cake from the
primary filter is diluted with additioneil solvent and filtered in
a second (repulp) rotary vacuum filter using the same oper-
ating conditions as the primary filters to obtain the desired
FIG. 6—Illustration of the effect of solvent dilution ratio on
wax oil content.
the amount of residual oil content in the slack wax.
The solvent is recovered from the dewzixed oil filtrate by
flash vaporization and distillation. The solvent is recycled for
future use in the dewaxing process. ResiducJ solvent in the
TABLE 7—Effect of dewax temperature on wax.
wax is recovered by flash vaporization and is recycled for fu-
Wax Needle
ture process use. Dewax Wax Wax Melt.Point Penetration
Temperature Yield (ASTM D 127) @ yy-F (25°c)
("F) (°C) (%) (°F) CC) (ASTM D 1321)
Dewaxing Process Variables
60 15.6 62 141 60.6 11
Wax production yield, oil content of the wax, and the pour 55 12.8 67 139 59.4 13
point of base oil are directly affected by variables of the 50 10.0 72 137 58.3 16
lower dewEixing temperature is used, wax yield increases tween 1 and 3 % . Petrolatums are derived from the residual
and the melting point and softness change. lubricant fractions with oil contents between 10 and 30%
5. The dewaxing process is performed to maximize the re-
covery of the wax with the desired oil content and physical Compositional a n d Molecular Characteristics of
properties such as melting point a n d hardness. This re- Petroleum Wax
quires maintaining a uniform thickness (less than 2.5 cm)
Paraffin waxes consist predominately of a mixture of straight
of the wax cake on the rotary filter by controlling the pro-
chain saturated hydrocarbon molecules (normal-alkanes)
cess temperatures and rotational speed of the filter. Apply- with the chemical formula CnH2n+2 with n > 16 [27,28]. In
ing wash solvents (for reducing oil content) uniformly pre- order to demonstrate the physical properties of straight chain
vents cracking of the wax cake. Diluting with adequate saturated h y d r o c a r b o n molecules. Table 8 is reported as
repulp solvent is necessary to provide a sufficiently fluid taken from Ref 28. In this table the molecular weights, melt-
raffinate. ing points, latent heats of fusion, densities (at 20°C), specific
heats in solid and liquid states, and boiling points of the nor-
The Wax Finishing Process mal cdkanes from Ci to Cioo, all at atmospheric conditions,
are reported. According to this table, the first four alkanes of
The last step in producing petroleum waxes is the finishing the series, (from methane, CH4, u p to butane, C4H10) are
process. This process involves the removal of odor and ques- gaseous at room temperature and atmospheric pressure. The
tionable color. In addition, the finishing process may involve alkanes between C5 and C17 are liquids a n d alkanes with
steps to reduce the polycyclic hydrocarbons to a level that more than 17 carbon atoms are waxy solids at room temper-
meets the Food and Drug Administration regulations for food ature. The melting points and heats of fusion of alkanes in-
contact.^ crease with their n u m b e r of Ccirbon atoms. In addition to the
Wax color removal m a y b e performed by flowing wax n-alkanes, paraffin waxes may contain varying amounts of
through a static bed of activated clay or bauxite. There is a iso- and cyclo-alkanes (i.e., branched chains and aliphatic
production loss in the amount of wax after completing the rings). Typiccdly, peiraffin weixes contain carbon atom chains
clay or bauxite contact process. This loss is attributed to ab- of Cis to C44. Their macrocrystalline structure is illustrated in
sorption of the wax on the clay or bauxite medium and the Fig. 7. Their plate-like crystal structures are illustrated by an
production loss is greater for darker colored weixes. Newer atomic force microscope image given in Fig. 8. Their molec-
finishing process technology is based o n hydrofinishing ular weights are usually less than 450 and their kinematic vis-
(fixed bed cataljîc process using hydrogen) and doesn't re- cosity at 100°C (212°F) will usually be less than six centis-
quire any filtering medium. Hydrofinishing has the advan- tokes. Being derived from distillate fractions, paraffin waxes
tage of processing waxes with negligible product loss [26]. have distinct boiling point curves that consist of a minimum
If the wEtx exhibits a questionable odor (such as extraction and maximum value.
or deweixing solvent odor), the wax may be steam stripped
Microcrystcilline waxes contain higher proportions of iso-
(distilled) to remove traces of processing solvent. Hydrofin-
and cyclo-alkanes (naphthenic) t h a n paraffin wEixes. Micro-
ishing may also be used to produce odor free wjixes. After the
rystalUine waxes exhibit molecular weights between 500 and
wax has completed the finishing process step, it can be
700 with carbon atom chains ranging typically from C23 to
shipped to consumers; either in solid form (i.e., 22 kg car-
C85 in length. Their microcrystalline structure is illustrated
tons) or as a molten liquid (in specialized tanks with electri-
in Fig. 9. Microcrystalline waxes (microwaxes) exhibit kine-
cal heaters or steam coils).
matic viscosities greater t h a n 10 centistokes a t 100°C
(212°F). Because microcrystalline waxes are derived from
Types of Petroleiun Waxes residual fractions, they do not have a distinct boiling range.
Physical properties of microcrystalline waxes vary with the
There are two general types of petroleum waxes that are pro- t5ê of crude oil and processing conditions used to produce
duced during the dewaxing process. WEIX that is obtained the wax. Tj^pically, microcrystalline, naphthenic waxes ex-
from the distillate lubricating oil fractions is k n o w n as hibit needle-like microstructures.
macrocrystalline wax (paraffin wax), and wax derived from Intermediate wax properties are intermediate between
the residual distillate lubricating oil fraction is referred to as those exhibited by paraffin and microcrystalline waxes. They
microcrystalline wax (microwax). This n o m e n c l a t u r e is generally exhibit viscosities between 6 and 10 centistokes at
based on the crystal structure of the wax as seen through a 100°C (212°F) a n d a melting point between 155-165°F
microscope (microstructure). A peiraffin wax can be distin- (~68-74°C). Intermediate waxes are derived from the highest
guished from a microwax by its larger crystal structure. boiling distillate lubricating oil fraction and like paraffin
Paraffin waxes usually exhibit plate-like crystal structures WEixes, they exhibit a distinct boiling point range.
while microwEixes exhibit needle-like crystal structures.
Petrolatums are soft, unctuous products having a melting
The composition, nomenclature, and physical properties of point between 100-149°F (~38-65°C). The term "unctuous"
petroleum are related to the refinery process used in their means "smooth and greasy" in texture. Petrolatums are gener-
production. Slack wax is a refinery term for distillate-derived cJly produced from the same residual oil fraction as micro-
waxes that have oil contents ranging from 3-40% by weight crystcJline waxes and can be prepared by controlled blending
oil. Scale wax is a distillate wax that has an oil content be- of microcrystalline wax with mineral oil. Petrolatums generally
exhibit oil contents greater than 10% and are meirketed with
colors that vary from dcirk brown to white. Table 9 lists the gen-
' FDA regulations for waxes, 21 CFR 172.886 and 21 CFR 178.3710. eral physical properties of the different petroleum waxes.
TABLE 8—Physical properties of n-Alkanes [28].

Specific Heat (/mol K)
Latent Heat
No. of Melting Ft of Fusion Density at lO'C Solid at Liquid at Boiling Pt
Alkanes C Atoms Mol. Wt (K) (kJ/kg) (kg/m3) 298 K 353 K (K)
Methane 1 16 90.68 58 0.658 (g) 116.6
Ethane 2 30 90.38 95 0.124 (g) 184.6
Propane 3 44 85.47 80 1.834(g) 231.1
Butane 4 58 134.79 105 2.455 (g) 272.7
Pentane 5 72 143.45 117 621 (1) 0167.2 309.0
Hexane 6 86 177.83 152 655 (1) 195.4 341.9
Heptane 7 100 182.55 141 679 (1) 225.0 371.6
Octane 8 114 216.37 181 699 (1) 254.2 398.8
Nonane 9 128 219.65 170 714 (1) 284.5 424.0
Decane 10 142 243.50 202 726 (1) 314.5 447.3
Undecane 11 156 247.55 177 737 (1) 345.0 469.1
Dodecane 12 170 263.55 216 745 (1) 376.0 489.5
Tridecane 13 184 267.75 196 753 (1) 406.9 508.6
Tetradecane 14 198 278.95 227 759 (1) 438.5 526.7
Pentadecane 15 212 283.05 207 765 (1) 470.0 543.8
Hexadecane 16 226 291.25 236 770 (1) 501.5 560.0
Heptadecane 17 240 295.05 214 775 (s) 534.3 575.2
Octadecane 18 254 301.25 244 779 (s) 485.4 564.4 589.5
Nonadecane 19 268 305.15 222 782 (s) 514.6* 618* 603.1
Eicosane 20 282 309.75 248 785 (s) 544.3 658* 617.0
Heneicosane 21 296 313.35 213 788 (s) 570.7* 698* 629.7
Docosane 22 310 317.15 252 791 (s) 598.1* 739.0 641.8
Tricosane 23 324 320.65 234 793 (s) 625.0* 772.0 653.4
Tetracosane 24 338 323.75 255 796 (s) 651.4* 805.0 664.5
Pentacosane 25 352 326.65 238 798 (s) 670.4* 815.9 675.1
Hexacosane 26 366 329.45 250 800 (s) 677.8 870.0 685.4
Heptacosane 27 380 331.95 235 802 (s) 728.1* 928* 695.3
Octacosane 28 394 334.35 254 803 (s) 752.8* 937.0 704.8
Nonacosane 29 408 336.35 239 805 (s) 777.2* 1001* 714.0
Triacontane 30 422 338.55 252 806 (s) 801.2* 1037* 722.9
Hentriacontane 31 436 341.05 242 808 (s) 824.5* 1073* 731.2
Dotriacontane 32 450 342.85 266 809 (s) 867.4 1095 740.2
Tri triacontane 33 464 344.55 256 810 (s) 871.0* 1113 748.2
Tetratriacontane 34 478 346.25 268 811 (s) 887.4 1149 755.2
Pentatriacontane 35 492 347.85 257 812 (s) 916.0 1210* 763.2
Hexatriacontane 36 506 349.35 269 814 (s) 937.5* 1206 770.2
Heptatriacontane 37 520 350.85 259 815 (s) 959.1* 1276* 777.2
Octatriacontane 38 534 352.15 271 815 (s) 980.4* 1305* 784.2
Nonatriacontane 39 548 353.45 271* 816 (s) 1001* 1341* 791.2
Tetracontane 40 562 354.65 272 817 (s) 1022* 1411 795.2
Dotetracontane 42 590 357.32 273 817 (s) 1062* 1435 804.2
Tritetracontane 43 604 358.65 273* 819* (s) 1085* 1465* 813.2
Tetrateracontane 44 618 359.55 274 820* (s) 1102* 1495* 818.2
Hextetracontane 46 646 361.45 276 822* (s) 1140* 1553* 829.2
Octatetracontane 48 674 363.45 276 823 (s) 1177 1595 838.2
Pentacontane 50 702 365.15 276 825* (s) 1213* 1665* 848.2
Hexacontane 60 842 372.15 279 831* (s) 1380* 1916* 888.2
Heptacontane 70 982 378.65 281* 836* (s) 1526* 2131* 919.2
Hectane 100 1402 388.40 285* 846* (s) 1869* 2598* 935.2
(*)Predicted value.
(a) X 200 X 1000 (b)

FIG. 7—A scanning electron microscopic illustration of a macrocrystalline structure wax
(a = 200X;b = 1000X).
FIG. 8—An atomic force microscope image of the spiral growth of paraffin crys-
tal (measuring approximately 15 microns across). Inset shows orthorhombic ar-
rangement (0.49 nm x 0.84 nm) of chain ends of one of the crystal terraces (cour-
tesy of Professor M.J. Miles).
(a) X200 X 1000 (b)

FIG. 9—A scanning electron microscopic illustration of a microstructural characteriza-
tion of a refined paraffin wax (a. = 200 X; b = 1000 X).
TABLE 9 --Physical properties of petroleum waxes.

Property Paraffin Wax Intermediate Microcrystalline Petrolatum
Melt. Point (°F) 110-155 150-165 140-195 110-180
Molecular Wt. 320^50 450-550 450-700 450-700
Crystal Structure Plates Needles Needles Needles
Color White White—Yellow White—Dark Brown White—Dark Brown
Crystal Structure occurs when the wax crystal structure rotates from a hexag-
onal to o r t h o r h o m b i c form as the wax solidifies from a
ParafBn waxes exhibit several crystalline structures depend- molten state. Paraffins with carbon atom chains above C37 do
ing on their carbon chain length. Odd n u m b e r carbon chains not exhibit a transition point due to the wax solidifying di-
between C19 and C29 exhibit an orthorhombic type crystal rectly into a n o r t h o r h o m b i c crystal structure. Microcrys-
structure. Even numbered carbon chains between Cjg and talline and intermediate type waxes do not exhibit any tran-
C26 exhibit a triclinic structure. Even n u m b e r e d carbon sition point because they contain higher a m o u n t s of
chains between Cjg and C36 exhibit a monoclinic structure. branched alkanes.
All paraffins with carbon chains between C20 and C36 have a Because of the steric effects caused by the arrangement of
distinct transition point (change in crystal form) lower than atoms in the molecule there is a difference between alkanes
the temperature at which they solidify. The transition point with odd and even numbers of carbon atoms. The even-num-
bered homologs have higher latent heat than the odd-num- in the solid state at about 2-5°K below the melting point. The
bered homologs. Humphries [29] showed that alkanes with an difference between the transition temperature and melting
even number of carbon atoms (between 20 and 32) and alka- temperature becomes smaller with increasing molecular
nes with odd number of carbon atoms (higher than 7) exhibit weight and finally disappears for alkanes with more than 36
a lattice transition in the solid state. The even-numbered car- carbon atoms [25,28] as demonstrated in Fig. 10. The heat as-
bon atom alkanes exhibit this transition closer to their melt- sociated with this solid-solid transition is subtracted from the
ing point than the odd-numbered alkanes, as demonstrated in lattice heat of melting. Figures 11 and 12 show variations of
Fig. 10. The boiling point of normal-alkanes for the tempera- the latent heat of melting, melting point, and density of nor-
ture range on the figure are sJso shown in Fig. 10. mal alkanes versus increasing number of carbon atoms in
The lattice transition in alkanes is accompanied by the re- their structure. According to these figures, while the melting
lease of heat of transition. Generally, lattice transition occurs point and density versus the number of carbon atoms have
500
I ' I
25 30 35 40
Number of carbon atoms
FIG. 10—Variation of meiting point (MP), transition temperature (TrT), and boiling point
(BP) of normal alltanes with their number of carbon atoms [28].
1 .
3
_^-<TyOO-C/-
QRRF"^^^
"O
. r,
"
^
cS non )»00
•g250 -
o> O o9?fm
AAI&OO"
I 9NM
rtAl i t " 1
Si wX* *
sw-
•S200 -
_i
150 -
100 -
f
6
20 40 60 80 100
FIG. 11—Variation of the latent heat of melting of normal alkanes with the number of car-
bon atoms in alkanes and exhibition of the steric effect [28].
400 1000 it is necessary to be able to predict thermodynamic proper-

ties of wax. In this section we present five equations of state,
a which are used for prediction of molar volumes, vapor pres-
sures, and supercritical solubilities of alkanes [32].
u
800 •11 The simplest and one of the most widely known equations
3 of state is that of van der Waals. However, this equation of
•§> state is not accurate enough to predict thermodynamic prop-
erties of most fluids. Inspired by the van der Waals model, in-
600 vestigators have proposed several equations of state through
I
the years. Almost every equation of state has been claimed to
400
Table 10—Chemical composition and
thermophysical properties of Suntech PI 16
Paraffin Wax [30].
200 Hydrocarbon Weight -%
n-C-20 2.0
n-C-21 5.5
n-C-22 14.0
^0 n-C-23 23.0
0 20 40 60 80 .100 n-C-24 22.0
n-C-25 14.0
Number of carbon atoms n-C-26 6.5
FIG. 12—Variation of tlie melting point and density (@ 20°C) n-C-27 3.0
of normal alkanes with the number of carbon atoms in alkanes n-C-28 2.5
n-C-29 2.0
[28]. 1.7
n-C-30
n-C-31 1.5
n-C-32 1.3
Melting range 316-329K
smooth variations, the latent heat of meUing goes through Heat of fusion 266 kJ/kg
Liquid specific heat 2.51kJ/kgK
fluctuations. Because of the steric effects (the solid-solid Solid specific heat 2.95 kJ/kgK
phase transitions mentioned above) the latent heats of melt- Liquid thermal conductivity 0.24 W/mK
ing of two consecutive alkanes do not always increase with in- Solid thermal conductivity 0.24 W/mK
creasing number of carbon atoms, as demonstrated in Fig. 11. Liquid density 760 kg/m^
Each even-numbered alkane (with eight carbon atoms or Solid density 818kg/m^
Liquid viscosity 1.90kg/ms
more) exhibit a lower latent heat than the odd numbered Molecular weight 332 g/mol
alkane having one carbon atom less than it. This fluctuation
of the latent heat of melting vanishes as the number of carbon
atoms approaches 40, and after that the latent heat increases
smoothly with increase of the number of carbon atoms.
As an example, the composition and thermophysical data
of a paraffin wax sample (Suntech PI 16) [30], which contains
almost 100% normal alkanes, is reported in Table 10. Ac-
cording to this table, the hydrocarbons with 20-32 carbon
atoms constitute 99% of the mixture and the ones with more
than 32 carbon atoms constitute the remaining 1%. Paraffin
waxes are generally polydisperse compounds for which poly-
disperse solution (continuous mixture) theories may be used
for characterization [31]. Figure 13 is the graphic represen-
tation of the composition data of Suntech PI 16 paraffin wax
reported in Table 10.
Wax can be crystallized out of a solution by lowering its
temperature. Varying the temperature gradient causes a tran-
sition between the growth of wax plates and growth of a tree-
like structure with regular branches as it is shown on Fig. 14.
Also shown on Fig. 14 is the banded growth of wax due to ad-
dition of a crystallization inhibitor.
20 21.22 23 24 25 26 27 28 29 30 31 32
Equations of State
FIG. 13—The distribution of n-alkanes in Suntech P116
In order to characterize the petroleum wax and perform var- paraffin wax as a function of the number of carbon-atoms
ious operations on weix mixtures, such as wax fractionation, [28].
PR, and SRK are three-constant-parameter equations. All the

A-. . " . • - V • • •: ' > fr^,
above-mentioned five equations of state can be written in the
' -'i*.- T i ; • • • • : - - . . ••
following generalized form [32]:
v-V yb
2 = T%v + Tjc)(w + Ac)
(2)
'ivX where a=naaR^ Tj^-^'^ / Pc and 6 = c = rij, ^ i? T,. / P^.

Parameters {1^, ^b, y, V> and ^ ^re component-independent
constants, while a a n d j3 are component-dependent con-
stants, and their numerical values for various equations of
states are given in Table 11. In extending the equations of
state to mixtures, parameters a, b, and c are replaced with Um,
b„, and Cm with the following expressions (mixing rules):
RK. PR, SRK, RM-1: a„ = 5 2 :>'«>'/^y
i i
(4)
bm = 1352y«3'Ay + X>''^« ) r ^rri = '^yAi
For the RM equation there is another alternative in extend-

ing it to mixtures by replacing Tc and Pc with Tcm and Pcm as
given below:
(b) . • ». ..
FIG. 14—(a) An atomic force microscope image of wax RM-2: T,m = {^yiyiTl^pMy^yiyiT,i,pX
"trees" growth in a lowering temperature solidification of wax
from solution. Varying the temperature gradient causes a tran-
sition between the growth of wax plates and growth of a
tree-like structure with regular branches; (b) An atomic force
microscope image of banded growth of wax due to addition of
crystallization inhibitors (courtesy of Prof. J.L. Hutter).
Rfn = YI,yiyiR%
i J
These equations of state can be used to calculate properties
be superior in some respects to the earlier ones. The Redhch-
of Wcix, its components, i.e., vapor pressure, and molar volumes
Kwong (RK) equation that is a modification of the van der
of liquid at saturated-, sub-cooled and supercriticEd-conditions
Waals equation, was a considerable improvement over other
as well as the solubility of wax in supercritical solvents.
equations of relatively simple forms at the time of its intro-
To perform phase equilibrium and other saturated prop-
duction. In the Soave-Redlich-Kwong (SRK) equation, the
erty calculations for WEIX in liquid and vapor states, we need
temperature-dependent term of a/T"-^ of the RK equation is
to perform equality of pressures and fugacity calculations
replaced by a function denoted by a that depends on the
[32]. The fugacity coefficient of a component of the wax in a
acentric factor of the compound and temperature. The Peng-
mixture (<^r)?derived from the generalized Eq 1 is in the fol-
Robinson (PR) equation is another cubic equation of state in-
volving acentric factor. Riazi and Mansoori [33] modified the TABLE 11—Parameters of the generalized equation of state.
parameter h of the RK equation by introducing a function, Eq. of State —»
denoted by '?, that depends o n the refractive index of the com- Parameters 4- RK MMM RM PR SRK
pound. They showed that the resulting equation is quite ac- y 0 1.3191 0 0 0
curate in the prediction of hydrocarbon densities. Mohsen- iq 1 1 1 1 -H V2 0
A 0 0 0 1 -V2 0
Nia et al. [34] proposed that the 3M equation in which the 0.5 0 0
e 0.5 0.5
repulsive part of the RK equation is modified based on the Oa 0.42748 0.487480 0.42748 0.45724 0.42748
statistical mechanics improved the thermodynamic predic- ftfa 0.08664 0.064462 0.08664 0.07780 0.08664
tions appreciably. This equation is shown to be more accu- a 1 1 1 «PR CSRK
rate for heavy hydrocarbon phase behavior calculation than /3 1 1 PRM 1 1
most of the other equations of state. RK and 3M equations apR = [1 + (0.37464 + 1.524226M - 0.26992m^)(l - T?')]^
CSRK = [1 + (0.48508 + 1.55171a) - 0.15613«2)(1 - T°-^)T
are two-constant-parameter equations of state, while the RM, (fe«)-' = 1+ [0.02[1 - 0.92 exp(-l,000 \T, - I|)] - 0.035 (T, - 1)]{R*-1)
CHAPTER 19: PETROLEUM WAXES 5 3 7
lowing form [32]: erence system, SG = specific gravity, Th = normal boiling

point, in degrees Rankine, a = \ - Th I T°, ASG = specific
dinbmVdtii gravity correction and f = correction factor.
In <AF = (1 + y) ln(i; - bm/v)
The critical volume (in cubic feet per pound mole) is given
by the following expressions [37]
-InZ-
CnRT'^^^"^ {v + TprnXv + XCm) dtli
K = y ° [ ( l + 2fv)l(l - 2fv)r (8)
(6)
Uffj 1 1 d(rp-a„) 1 d{nc„) where
ir, - \)c„RT^'^^^ Cm drii
fv = ^SGv [0.466590/ri'2
+ (-0.182421 + 3.0172/r^'^)ASGv]
ASGv = exp [4(SG°2 - SG^)] - 1
where for RK, PR, SRK, RM-1:
V? = [(0.419869 - 0.505839a - 1.5643a3 - 9481.70a'4)]-»
1 dinÛm) ^^ d{nbm) a(nc,n) L The critical pressure (in psia) is given by the following ex-
pression [37]:
for 3M: P, = P° (r,/7^)(V?/yj[(l + 2fp)/(l - 2fp)f (9)
1 din^dm) -V ^(nb„,) where

= 2 > V.77.V —
n anj an; fp = ASGp [(2.53262 - 4 6 . 1 9 5 5 / 7 ^ - 0.00127885 n)
+ (-11.4277 + 252.140ITl'^ + 0.00230535 Tb)ASGp]
M^l^yih - YLyiythj + ^« bu
ASGp = exp [0.5(SG° - SG)] - 1
and for RM-2: P° = (3.83354 + 1.19629ai'2 + 34.8888a

+ 36.1952a2 + 104.193a^)2
J_ d{n a^) ^ ^ RTO-SI^Y V T^ IP - - T T vT IP
J- -J ii^xvj cfn\ -^/^^jj]^ CI}'^ CI} ^ cm / , Yi^ cii'^ ci and where V = molar volume, in f?^/lbmole, P = pressure, in
' \ / / psia and subscripts V and P refer to the volume and pressure.
d{nbm) d(ncm) / o, 9/3 V v v T- /D ^ The acentric factor can b e estimated with the use of the
- — = (-li + n - ^ j \ l l yffi TclPciij generalized Edalat et al. vapor pressure equation [38]:
drii dm
In PR = (ar + br^'^ + cr^ + dr^)l{\ - T) (10)
where
To calculate liquid molar volume and vapor pressure us- T=l-T/Tc, (11)
ing equations of state, t h e data of critical temperature a n d W= (-logP«)7-^=o.7 - 1
pressure, acentric factor, a n d molar refraction are needed.
The experimental critical properties of n-alkanes u p to C24 and
are available in the literature [35,36], while those of n-alka- a{ca) = - 6 . 1 5 5 9 - 4 . 0 8 5 5 & ;
nes higher t h a n C24 c a n b e estimated using correlations. fo(w) = 1.5737 - 1.0540(0 - 4.4365^:10^^^(0))
The critical temperature (in degrees Rankine) can be writ- c(w) = - 0 . 8 7 4 7 - 7.8874W
ten as [37]: d{(,}) = (-0.4893 - 0.9912W + 3.15510^)''
r , = r ° [ ( l + 2fr)/(l - 2 / r ) ] ' (7) The above equation is quite accurate for calculation of va-
por pressure provided the acentric factor and critical proper-
where ties of a fluid a r e available. The molar refractions of wax
compounds needed in the RM equation of state are available
JT = ASGr [-0.362456/7^'^ in Ref. 36.
+ (0.0398285 - 0.948125/4'2)ASG7-] The accuracy of molar volumes of saturated liquid wax
components, molar volumes in sub-cooled and supercritical
ASGr = exp [5(SG° - SG)] - 1
conditions a n d vapor pressures calculated using various
Tt = Tb (0.533272 -t- 0.191017 X 10"^ Tb + 0.77968 equations of state are reported in Tables 12-14, respectively.
According to these tables the three-constant RM equation of
X 10"^ Ti -0.284376 X l O " ' " Tl + 0.959468 X 10^^ T^ " ) state is quite satisfactory for molar volume prediction while
SG" = 0.843593 - 0.128624a - 3.3615a^ - 13749.5a'^ the SRK is accurate for vapor pressure prediction of wax.
In Fig. 15 the solubility of n-tritriacontane (n-CaaHgg) in su-
and where subscript T refers to t e m p e r a t u r e , subscript c percritical carbon dioxide is depicted along with the predic-
refers to the critical conditions, superscript o refers to the ref- tions obtained from various equations of state. According to
TABLE 12—The average deviations of various equations of state in predicting saturated liquid molar volumes of pure
compounds compared with those csilculated using the hankinson and thomson (1979) correlation.
AAD%
Compound Tr Range RK 3M RM PR SRK
CO2 0.71-1.00 19.5 8.8 19.5 4.7 14.7

CH4 0.48-0.99 4.5 13.9 4.5 8.6 4.5
C2H6 0.33-0.99 10.3 11.8 6.4 6.0 9.2
C3H8 0.35-0.98 11.2 10.8 3.9 5.3 9.2
H-CAHIO 0.36-0.96 13.3 9.0 3.0 3.6 10.3
M-C5H12 0.47-0.99 16.8 7.5 2.4 3.4 12.5
n-C(,}ii4 0.39-0.99 19.9 6.9 2.2 2.2 14.8
n-CjHif, 0.41-0.99 22.3 7.4 1.4 2.7 16.0
n-CsHis 0.41-0.99 24.7 6.9 1.2 4.2 17.7
M-C9H20 0.42-0.98 26.8 7.8 0.8 5.1 18.7
n-CioH22 0.43-0.98 29.9 10.5 0.7 7.0 20.8
n-CiiH24 0.55-0.78 31.1 10.5 0.3 7.4 21.3
n-Ci2H26 0.54-0.89 35.3 14.7 0.4 10.1 24.3
"-C13H28 0.56-0.80 37.6 16.5 0.2 11.4 25.8
n-Ci4H3o 0.54-0.85 42.8 21.4 1.2 15.0 29.9
W-C15H32 0.58-0.82 45.8 24.1 1.2 16.7 31.8
"-C16H34 0.56-0.81 49.7 26.9 1.8 19.7 35.1
M-Ci7H36 0.59-0.83 56.2 32.9 3.9 24.3 40.3
H-C18H38 0.55-0.84 59.5 35.5 4.0 26.9 43.1
M-C19H40 0.56-0.85 63.5 39.0 4.4 29.6 46.1
ra-C2oH42 0.57-0.85 67.9 42.9 4.8 32.2 49.0
M-C22H46 0.55-0.81 57.6 31.8 4.5 25.1 40.6
ra-C24H5o 0.56-0.82 66.2 39.2 2.9 31.1 47.2
n-C28H58 0.58-0.84 62.9 36.4 11.2 27.7 43.1
Overall 36.5 19.7 3.6 13.8 26.1
TABLE 13—The average deviations of various equation of state in predicting molar volumes of liquids in sub-cooled and
supercritical conditions compared with experimental data.
AAD% Experimental Data
Compound Tr Range Pr Range RK 3M RM PR SRK No. of Data Pts. Ref
CO2 0.7-2.2 1.0-13.6 5.0 4.8 5.0 2.9 6.1 447 a

CH4 0.5-2.6 0.0-15.2 2.0 11.1 2.0 7.4 2.4 459 b
C2H6 0.3-2.3 0.0-14.3 3.8 11.2 1.7 5.6 4.1 474 c
C3H8 0.2-1.9 0.0-16.5 5.9 9.6 1.8 4.2 5.9 533 d
M-C4H10 0.3-1.7 0.0-18.5 8.4 8.4 1.6 3.8 7.9 638 e
W-C5H12 0.4-0.7 0.0-71.3 11.2 7.6 0.8 2.5 9.4 880 f
n-C6Hi4 0.4-0.7 0.0-332 14.7 5.8 2.0 2.5 12.6 510 f
n-C7Hi6 0.6-1.1 1.8-183 14.5 5.6 2.3 3.3 13.5 70 f.g
n-C9H2o 0.5-1.0 2.2-218 18.8 3.1 2.2 5.1 17.1 66 S
W-C11H24 0.5-0.9 2.6-259 25.1 3.1 2.6 10.4 23.1 70 S
M-C13H28 0.4-0.9 3.0-303 32.3 7.9 3.2 16.7 30.1 70 s
n-CnH36 0.4-0.8 4.1^10 48.5 19.8 7.2 31.0 45.9 60 s
W-C20H42 0.4-0.8 5.0-500 59.9 28.6 9.9 41.1 57.1 50 s
M-C30H62 0.4-0.8 6.8-682 62.7 28.9 6.8 43.5 59.8 50 s
Overall 22.3 11.1 3.5 12.8 21.0 4377
" Angus et al., 1976.
''Goodwin, 1974.
' Goodwin and Roder, 1976.
'^ Goodwin and Haynes, 1982.
' Haynes and Goodwin, 1976.
f Frenkel et al., 1997a.
i^Doolittle, 1964.
TABLE 14—The average deviations of various equations of state in predicting vapor pressures of pure compounds
compared with the experimenteJ data.
AAD% Experimental Data
Compound Tf Range RK 3M RM PR SRK No. of Data Pts. Ref
CO2 0.71-1.00 19.1 4.0 19.1 0.8 0.5 47 a
CH4 0.48-0.99 17.2 50.0 17.2 0.7 2.9 84 b,c
C2H6 0.33-0.99 11.5 36.3 11.9 3.0 2.6 114 b,d
C3H8 0.35-0.98 19.8 39.5 8.3 3.0 1.9 101 b,e
n-C4Hio 0.36-0.96 43.2 32.4 7.0 5.6 1.9 130 b,f
n-CsHn 0.47-0.99 63.4 19.2 9.9 0.8 1.5 91 b,h
n-C6Hi4 0.39-0.99 >100 15.8 16.5 3.1 1.9 88 b,h
n-CyHie 0.41-0.99 >100 11.0 20.7 2.4 1.2 80 b,h
n-CgHis 0.41-0.99 >100 18.5 28.9 2.7 1.2 87 b,h
n-C9H2o 0.42-0.98 >100 33.2 33.3 2.1 1.5 82 c,h
f3-CioH22 0.43-0.98 >100 51.4 37.4 3.1 1.2 86 b,g,h
n-CiiH24 0.55-0.78 >100 81.7 37.7 6.6 4.4 27 b
n-Ci2H26 0.54-0.89 >100 89.9 31.7 2.9 0.4 40 b,g,h
n-Ci3H28 0.56-0.80 >100 >100 28.8 3.3 0.5 27 b
n-Ci4H3o 0.54-0.85 >100 >100 30.3 5.8 2.5 42 b,g,h
W-C15H32 0.58-0.82 >100 >100 23.4 4.0 0.6 27 b
«-Cl6H34 0.56-0.81 >100 >100 29.3 5.6 0.9 45 b,g,h
n-Ci7H36 0.59-0.83 >100 >100 23.9 6.2 1.6 43 b
n-CisHss 0.55-0.84 >100 >100 30.2 9.2 3.0 44 b,g
?2-Ci9H40 0.56-0.85 >100 >100 30.4 10.4 3.6 42 b,g
n-C2oH42 0.57-0.85 >100 >100 33.0 8.8 2.4 42 b,g
ra-C22H46 0.55-0.81 >100 >100 69.1 18.6 1.2 21 b,g
n-C24H5o 0.56-0.82 >100 >100 79.4 24.7 1.5 22 b,g
n-C28H58 0.58-0.84 >100 >100 57.9 33.9 1.7 23 b,g
M-C29H60 0.54-0.84 >100 >100 82.5 42.5 2.7 12 b
n-C3oH62 0.54-0.84 >100 >100 75.8 44.5 2.7 12 b
M-C32H66 0.55-0.85 >100 >100 61.5 48.9 3.2 12 b
n-C33H68 0.55-0.85 >100 >100 56.9 51.8 3.9 12 b
Overall -2100 -650 35.4 12.7 2.0 1483
" Angus et al.. 1979.
'' Frenkel et al. , 1997a.
•= Goodwin, 1974.
'' Goodwin and Roder, 1976.
" Goodwin and Haynes, 1982.
' H a y n e s and Goodwin, 1976.
^ Morgan and Kobayashi, 1994.
'• Salerno et al. , 1986.
this figure, the 3M and RM equations aire capable of predict- ning the experiment by supplying heat with the main heaters,
ing supercritical solubilities accurately. In all these cases the while heating the temperature difference (AT) between the
unlike-interaction parameter,fcy,is best fitted to experimen- sample and reference pans is sensed using a thermopile (set
tal data. Table 15 shows the interaction parameters of vari- of thermocouples) which produces a small (0-5/xV) off-set-
ous equations of state for a number of systems at various ting voltage. The auxiliary heater is then used to heat the
temperatures along with the AAD%. According to this table, sample pan to keep the off-balance voltage close to zero. The
the 3M equation of state gives the least value of AAD%. instrument displays the differential power (AP) between the
two pans as a function of temperature. The area under the
peak of differential power (AP) versus temperature (T) pro-
Differential Scanning Calorimetry vides an experimental measure of the energy or total enthalpy
When a solid is heated, it may absorb heat resulting in a tem- change (AH) of the entire process [39,40].
perature increase or a structural change (phase transition) As described in ASTM Test Method D 4419, the melting
such as a solid to liquid or a transition from one crystalline point can readily be determined by DSC analysis, as can heat
form to another. These transitions may be endothermic (ab- of fusion, which is also an important characterization pa-
sorb heat) or exothermic (emit heat) depending on the ther- rameter for waxes. Heat of fusion is defined as the increase in
mal process that is occurring. These thermal processes may enthalpy accompanying the conversion of one mole, or a unit
be quantitatively measured by differential scanning mass, of a solid to a liquid at its melting point at constant
calorimetry (DSC). pressure and temperature [43]. The heat of fusion (AATf) is ob-
DSC analysis is performed by heating two small sample tained from the melting transition peak illustrated in Fig. 16,
pans, one containing the material being analyzed and the by measuring the total area under the peak that is propor-
other empty and used as a reference. The analysis concept is tional to the heat flow per mass of material. Heat flow is the
that the two sample pans are maintained at a very small tem- heat emitted per second, therefore the area under the peak is
perature difference (± 0.01°C). Each pan is heated with two given in units of (heat • temperature • time"*) for the mass of
heaters; a main heater and an auxiliary heater. After begin- the sample used. As a result the area per unit mass (APUM)
o
-5 /—tr-s-S^*-" °
-6 j
^-7 1
0-9
/
-11 /
-12 RK
•
Pr
•4
-5 /--rrQjQ.oo o
-6
Ss
-n PR
-12 • • f „M-~-.
-13
Pr
2 Pr
FIG. 15—Solubility of n-tritriacontane (n-CssHes) in supercritical carbon dioxide at 308

K as predicted by various equations of state and compared with the experimental solubil-
ity data [32].
of the sample will be trace shown by Fig. 17 demonstrates the decrease in crys-
Heat X Temperature Q J- tallinity as the melting point of the wax increases. The ther-
APUM (12) mal analysis procedure for this work was started at - 50°C for
Ttime X Mass ^ ~0M
o p t i m u m crystallization of the wax. The wax sample was
Typically, the actual units of \Hf&re (joules • Kelvin • sec- heated at a controlled rate to +150°C. The point at which
o n d s " ' • g r a m s " ' ) . Typically, the APUM is divided by the there is a deflection in the base line is the temperature that
heating rate (K/s) of the DCS experiment used to collect the the wax begins to melt. The point at which the peak scan re-
data. This will simplify the expression to yield the specific turned to the base line is the temperature the wax sample is
heat of melting: completely melted. The peak area represents the amount of
energy used to melt the wax sample and is calculated as de-
Q.T scribed above. In addition, an estimate on the expected melt-
APUM e.M Q_ (13) ing point can be distinguished. The experienced technologist
Heating Rate X M could tell by looking at the shape of a DSC trace if the wax is
e a paraffin, intermediate, or microwax. Paraffin waxes typi-
Since the mass of the sample that was analyzed is known, it cally exhibit sharp peaks as shown in Fig. 16a, DSC peak
is then multiplied by the heat emitted/gram of sample to 5deld shapes for intermediate waxes are less sheirp as shown in Fig.
the amount of heat given off (Q) during the melting process. \6b, and microwaxes exhibit even less sharp peaks, typically
like the peak shown in Fig. 16c.
%XM =M (14)
M It should be noted that there is a characteristic small tran-
Figure 16 illustrates the DSC traces for three different sition peak in the DSC trace for a macrocrystalline paraffinic
petroleum waxes; one for each wax type - paraffin (Fig. 16a), wax as illustrated in Fig. 16fl. The transition that is indicated
intermediate (Fig. 16^), and microwax (Fig. 16c). The DSC is a solid-solid phase change (orthorhombic to hexagonal
TABLE 15 —Interaction parameter (ki2) of some systems.
kyi AAD%
T P
System [K] [bar] RK 3M RM-2 PR SRK RM-1 RK 3M RM-2 PR
C2H6 - M-C28H58 308.2 56-240 -0.4638 -0.2099 0.0807 -0.0553 -0.0189 -0.1283 46.2 27.0 14.4 38,
C2H6 - n-C29H6o 308.2 65-240 -0.4146 -0.1618 0.1215 -0.0131 0.0260 -0.0701 53.1 29.9 23.9 48.
C2H6 - M-C30H62 308.2 66-200 -0.4777 -0.2066 0.1025 -0.0571 -0.0206 -0.1121 25.0 22.8 57.2 22.
313.2 66-136 -0.4738 -0.2137 0.0901 -0.0517 -0.0139 -0.1233 13.9 30.8 29.7 18.
C2H6 - K-C32H66 308.2 66-240 -0.5124 -0.2259 0.1020 -0.0707 -0.0297 -0.1214 46. 43.0 56.2 41.
313.2 66-200 -0.5011 -0.2264 0.1050 -0.0658 -0.0263 -0.1131 24.4 34.5 40.2 20.
318.2 80-240 -0.5248 -0.2438 0.0966 -0.0762 -0.0347 -0.1142 45.2 17.7 22.8 32.
319.2 80-136 -0.4872 -0.2241 0.1087 -0.0565 -0.0157 -0.1219 23.6 37.4 39.3 28.
C2H6 - ra-C33H68 308.2 65-240 -0.4632 -0.1933 0.1100 -0.0286 0.0137 -0.0779 50.2 34.4 50.7 43.
313.2 65-202 -0.4459 -0.1845 0.1433 -0.0240 0.0193 -0.0580 39.6 21.5 28.9 25.
318.2 65-240 -0.4506 -0.1918 0.1433 -0.0203 0.0228 -0.0530 45.7 24.2 28.0 42.
CO2 - n-C28H58 307.2 123-181 -0.3458 -0.0936 0.2487 0.0110 0.0507 0.0211 51.0 7.5 34.4 45.
308.2 80-240 -0.3161 -0.0901 0.2477 0.0296 0.0708 0.0194 52.3 18.3 35.0 49.
313.2 90-275 -0.2910 -0.0835 0.2532 0.0365 0.0765 0.0286 46.7 25.0 44.5 39.
318.2 100-250 -0.2915 -0.0867 0.2504 0.0359 0.0746 0.0232 64.7 13.4 31.0 47.
318.6 119-284 -0.3067 -0.0859 0.2531 0.0347 0.0736 0.0278 53.7 8.2 33.2 45.
323.4 125-327 -0.2973 -0.0869 0.2552 0.0385 0.0764 0.0314 62.5 5.8 28,9 53.
325.2 121-284 -0.2946 -0.0867 0.2540 0.0321 0.0690 0.0287 64.2 7.3 22,6 45.
C 0 2 - M-C29H60 308.2 100-240 -0.2751 -0.0530 0.2782 0.0645 0.1075 0.0670 71.8 21.5 12,9 67.
318.2 100-240 -0.1961 -0.0540 0.2789 0.0818 0.1451 0.0672 81.2 22.2 6,9 76.
CO2 - «-C3oH62 308.2 90-250 -0.3254 -0.1141 0.2481 0.0327 0.0779 0.0084 69.6 17.1 28,8 66.
318.2 105-250 -0.3125 -0.1197 0.2439 0.0273 0.0700 -0.0005 67.5 8.3 28.7 57.
CO2 - n-C32H66 308.2 120-240 -0.4140 -0.1500 0.2448 -0.0162 0.0316 -0.0139 59.5 8,1 24.1 54.
318.2 140-240 -0.3913 -0.1462 0.2483 -0.0035 0.0426 -0.0092 67.3 6.7 22.3 55.
328.2 140-240 -0.3777 -0.1345 0.2596 0.0044 0.0477 0.0104 57.5 9.2 27.1 40.
CO2 - n-CjsHfts 308.2 120-240 -0.3461 -0.1051 0.2825 0.0262 0.0754 0.0496 68.4 25.0 11,3 64.
318.2 140-240 -0.3384 -0.1043 0.2832 0.0280 0.0872 0.0494 65.0 22.9 4,8 61.
328.2 140-240 -0.3057 -0.0990 0.2878 0.0428 0.0876 0.0557 67.4 18.5 3,5 60.
Overall 60.0 20.3 28,3 46.
" Kalaga and Trebble, 1997.
' Moradinia and Teja, 1986.
" Suleiman and Eckert, 1995
•' Moradinia and Teja, 1988.
" McHugh et al., 1984
^Reverchon et a ., 1993.
^ Chandler et al., 1996.
S5.0
2\S»C
sao 55.syc
SISJ
7SJ>
fata 1316.99
TOO ^ 2IB.99
sg s ^*'
&o-
1 *"-
35,B-
JM
Z5JI
"T— I
-2SJ) IOOLO 12M 1500
soo TSJ»
Tenq>a-îire(<0
XI ^xsrc
TS3yC
4M-
«
PCA 6ssn
Am I13&63
rtH 17172
H e i ^ 43Jf7
^
S, 4 M -
* -
s
1-: ..
3W1-
1 1 1 1 1
-1S.0 25,0 5IU 7U lOOJ) 125,0 151
TemperatnTO (°Q Teiiii)eratiire('C)
FIG. 16—The heat of fusion (AHr) calculation from the DSC melting transition peak by
measuring the total area under the peak, (a) paraffin, (b) intermediate, (c) microwax.
respectively. Referring again to Fig. 16a (paraffin wax), the

endotherm is started at — 50°C for optimum crystallization
of the wax. The wax sample is heated at a controlled rate to
-l-150°C. The point at which there is a deflection in the base
line is the temperature that the wax begins to melt. The
point at which the peaik scan returned to the base line is the
temperature the wax sample is completely melted. The peak
area represents the a m o u n t of energy used to melt the wax
sample as discussed above. Figure 17 illustrates that as the
melting point of paraffin wax increases, the heat of fusion
decreases because of the higher content of less crystalline
branched alkane structures. Microcrystalline waxes have a
lower heat of fusion than paraffin wax that is directly re-
lated to the greater amount of branched alkanes (less crys-
1 r 1 r
-50.0 -25.0 ao 25.0 50.0 75.0 talline microstructure). Listed in Table 16 are the typical
lOaO 125.0 150.0
heats of fusion data for both paraffin and microcrystalline
Temperature (°Q waxes.
FIG. 17—The heat of fusion (AH) calculation from the DSC
melting transition peak by measuring the total area under the Effect of Additives
peak of several paraffins demonstrating the decrease in crys-
tallinity as the melting point of the wax increases. In the petroleum wax industry, it is often necessary to use ad-
ditives to improve the processability of wax or wax mixtures
by modifying their physical properties. This may be accom-
crystal structure). As the wax crystal continues to absorb en-
plished by the addition of additives that may include stearic
ergy, a larger peak is recorded and then actucil melting occurs
acid, polyethylene, ethylene-vinyl acetate copol5'mer or a Fis-
with a return to the base line as the temperature continues to
cher-Tropsch wax. For example, stearic acid may be added to
increase.
a paraffin weix to increase firmness, reduce melting point, aid
In addition, there is a bimodality indicated in the DSC
in mold release, prevent candles from losing their shape in
trace peak shapes for intermediate (Fig. 16b) and microciys-
warm weather, etc. Polyethylene is another additive that may
talline (Fig. 16c) waxes. Bi-modal shape is related to the
be used. Polyethylene m a y b e added to a paraffin wax to
breadth of the wax composition. Bimodal peak shape is not
harden the wax structure, modify burning rate, and improve
related to transition. The apparent bimodality indicates that
strength and gloss. In addition to physical property modifi-
the wax has not been made as a narrow distillation cut. The
cation, additives also could alter the microstructure of waxes
melting point of wax is in the DSC area that the curve begins
as demonstrated by Fig. 14.
to return to the base line (downward slope) as the tempera-
ture increases. The squat DSC peak shape of the microwax
shown in Fig. 16c indicates that it is less crystalline and has Test Procedures for P e t r o l e u m Wax
a broader melting. The apparent bimodality of the microwax
Characterization
is related to the different melting fractions that appear in this
particular wax. There are three properties used to characterize petroleum
Determination of the heat of fusion of a wax is of practical waxes: (1) physical properties, (2) chemical properties, and
significance for a n u m b e r of reasons. For example, the (3) functional properties.
changes of shape of a DSC trace to that of known waxes may
indicate that a wax has been contaminated or altered. This Physical Property Determination
may be confirmed by comparing the heat of fusion of a pre- Melting Point - Test Methods ASTM D-87,D 3944, and D127—
viously purchased paraffin wax with the suspect wax. For ex- Melting point is a wax property that is of interest to the con-
ample, a historical value for heat of fusion of a wax may be sumer and can be an indication of the performance proper-
200 J/g and a newly purchased paraffin wax may have a heat ties of the wax being tested. The melting point of a wax is
of fusion of 180 J/g. This variation confirms that the two defined as the temperature at which the melted petroleum
waxes exhibit different properties. wax first shows a m i n i m u m rate of temperature change when
Another application of the heat of fusion could be for the allowed to cool under prescribed conditions.
comparison of properties of nominally similar waxes offered Test Method D 87 is one of the most commonly utilized
by two different suppliers. The higher the heat of fusion, the tests for melting point determination for petroleum waxes.
more crystalline the wax is. For some applications, like can- Paraffin waxes are often marketed based on melting point
dles, high crystallinity is desirable to aid in the mold release data produced by D 87. This test method is performed by
properties due to shrinkage upon cooling. Low crystalline placing a specimen of molten wax in a test tube equipped
waxes do not shrink as m u c h as high crystalline products. with a thermometer as illustrated in Fig. 18a. The test tube is
ASTM Test Method D 4419 has been developed to char-
acterize petroleum waxes and measurement of their transi-
tion t e m p e r a t u r e s by Differential Scanning Calorimetry TABLE 16—Typical heats of fusion (J/g).
(DSC). Figures 16a, 16b, and 16c are DSC endothermic Fully Refined Paraffin wax 180-210
scans of a paraffin, intermediate, and microcrystalline wax. Microcrystalline wax 140-190
Dimensions in inches (millimeters)
PuraRn WiuE 'MtanaxfabMaa Wax.
t
I
I
Tnutskkai Point-^ \ p
(b) Time-* . Tim*-* (c)

FIG. 18—(a) Apparatus for ASTM Test Method D 87. Cooling curve for: (b) a paraffin wax,
(c) for intermediate wax, microwax, petrolatum, or waxes containing a higfi percentage
(>50%) of branched alkanes
then placed in an air bath that is immersed in a water bath Method D 3944, which is a "solidification point" method (Fig.
and held at 16-28°C (~61-82°F). Temperature readings are 19a), can be used for melting point determination. The solid-
taken periodically until the wax solidifies u n d e r specified ification point of a petroleum wax is: the temperature in the
conditions. During solidification, the rate of temperature de- cooling curve of the wax where the slope of the curve first
creases and produces a plateau in the cooling curve, which is changes significantly as the wax sample changes from a liq-
obtained by plotting the temperature versus elapsed time as, uid to a solid state. This is illustrated in Fig. I9b, which is a
illustrated in Fig. I8b. The temperature where the plateau oc- typical cooling curve for solidification point measurement of
curs is defined as the melting point. (Note: The thermometer a petroleum wax.
used for this work shall conform to ASTM Specification E-1.) Test Method D 3944 is performed by heating 50 mg of sam-
Test Method D 87 is not applicable for microcrystalline ple in a test tube above the solidification temperature. Once
wax, intermediate wax, petrolatum, or waxes containing a the wax is melted. Fig. 20a, a thermocouple (connected to a
high percentage (>50%) of branched alkanes, because a tem- recorder) is placed in the sample, as illustrated in Fig. 20b,
perature plateau will not occur with such type of waxes as il- and allowed to cool to ambient temperature. As the sample
lustrated in Fig. 18c and because these type of waxes have a cools, a plot of temperature versus time (Fig. 18a) is ob-
much broader melting distribution (characterized by DSC) tained. This test method is based on the same methodology
t h a n paraffin waxes. For non-paraffin type waxes. Test as D 87 with the exception that automated test equipment is
Iticxmo couple
Lead-
Ifi-Iluorocarbon
Boldsr Adapter Aluminum Heating
r~^~^
Bloek
exSO nun Test Tiibe , 50x50x50 nm
(2x2x2 in).
0.020 i n (H)
Metal Sheathed Au£otrans£otner
Tbexnocouple Probe
IFE-Sluorocarbon TO 110
Disk Centering AC
Guide Outlet
llOV
50 mg 30-Hatt
Wax Sample' Cartridge Heater
(a)
Temperature Heat turned off
solidification
Point First significant change in slope
(b)
FIG. 19—(a) Apparatus for determination of melting (solidification) point (cooling curve)
of non-paraffin type waxes used in ASTM Test Method D 3944; (d) A typical cooling curve
for melting (solidification) point measurement of non-paraffin type waxes.
Test Method D 127 is performed by depositing a sample on

two thermometer bulbs by dipping chilled thermometers into
the sample. The thermometers are then placed into test tubes
and heated in a water bath until the specimens melt and the
first drop of wax falls from the thermometers. The average of
the temperatures at which these drops fall is recorded as the
drop melting point. Other ASTM test methods for melting
and freezing point determination eire listed in Table 17.
Pour Point - Test Method D 97—The pour point of a fluid is
that temperature where the fluid ceases to flow and it may be
determined by Test Method D 97 (Test Methods ISO 3016).
This test method is conducted by preheating the sample un-
til it is sufficiently fluid to pour into a test jar. At this point
the sample is cooled at a specified rate and examined at in-
tervals of 3°C for flow characteristics. The lowest tempera-
ture at which the movement of the test specimen is observed
DmKnsionsmmches(mS&r, is recorded as the pour point. Test Method D 97 is intended
(a)
for use on any petroleum product.
Congealing Point - Test Methods D 938 and D 3944—
Another important physical property for wax characteriza-
tion is congealing temperature (set point), which is defined
To Sccorder
as that temperature at which molten petroleum wax, when al-
lowed to cool under prescribed conditions, ceases to flow or
that temperature where molten wax begins to solidify. Test
Methods D 938 and D 3944 (see above discussion for Test
Method D 3944) are used for determining the congealing
temperature. (ISO 2207 may also be used.) These tests are
^ more applicable for waxes with broader melting ranges, such
6 jt SO vm
as microwaxes, petrolatums, and wax blends containing ad-
T e s t Tubs ditives. The congealing a n d solidification point is always
0 . 0 2 0 I n c h O.D.
Metal Sheathed
Thermocouple
lower than the recorded drop melting point.
1 / 8 " Thick
Test Method D 938 is performed by dipping the bulb of a
I?£-n.iwr»c«"bcm
Diak Cant«-tnc
thermometer to cause a droplet of wax to adhere on the ther-
Quid* m o m e t e r bulb. The t h e r m o m e t e r is then placed in a pre-
t
warmed air jacket and cooled at a fixed rate while the ther-
mometer is rotated in a horizontal position until the wax
sample ceases to flow (congeals). When congealing occurs,
the wax may be at the solid state or it may be at the semisolid
35 X 52 ran.
Vial—
state, depending on the composition of the sample.
(b)
Cloud Point - Test Method D-2500—The cloud point of a
FIG. 20—(a) Apparatus for determination of melting point petroleum product is the temperature at which a cloud of
of paraffin wax. The same methodology as Test Method D 87 solid crystcJs appears in a liquid when it is cooled under pre-
with the exception that automated test equipment shown in scribed conditions. The cloud point is an index of the lowest
Fig. 20b is used; (b) Once the wax is melted (Fig. 20a), a ther-
mocouple (connected to a recorder) is placed in the sample,
as illustrated here, and allowed to cool to ambient tempera-
TABLE 17—Other test methods for melting and freezing
ture. point determination.
Method Test Procedure
used. (ISO 3841 or BS 4695 are also used for cooling curve Capillary/liquid bath ASTM E 1
determination.) DIN 53181
Test Method D 127 may also be used to determine the Capillary/metal block DIN 53736
"drop melting point" of a wax. The drop melting point is de- Kofler hot bar ASTM D 3451
Differential thermal analysis & differential ASTM E 473
fined as that temperature where the Wcix becomes sufficiently ASTM E 537
scanning calorimetry
fluid to drop from the thermometer being used for making Freezing temperature BS 4633
the determination under prescribed test conditions. BS 4695
Test Method D 127 is commonly used for non-paraffin type DIN 51421
DIN 53175
waxes and paraffin wax blends. These include paraffin/mi- ISO 1392
crocrystalline wax blends and paraffin/additive blends that JIS K 00-65
may contain polyethylene, ethylene-vinyl acetate copolymer, NFT60-114
or a Fischer-Tropsch wax. Test Method D 127 is used to de- NFT20-051
termine the melting characteristics of petrolatums and other Pour point ASTM D 97
ISO 3016
high viscosity petroleum waxes.
temperature of its utility for certain applications. The cloud the formation of two liquid phases. If this occurs, the method
point is determined by cooling a petroleum sample in a cloud is not applicable to the material being tested.
point test apparatus illustrated in Fig. 2 1 . At a specified rate Solvent Solubility - Test Method D 3235—Test Method D
a n d periodic examination, the t e m p e r a t u r e at which a 3235 is a solvent extraction method used to determine the to-
"cloud" is first observed at the b o t t o m of the test j a r is tal amount of wax components that are soluble in the extrac-
recorded as the cloud point. This test method covers only tion solvent. The test is performed in the same manner as
petroleum products that are transparent in layers 40 m m Test Method D 721 except that a different solvent composi-
thick and with a cloud point below 49°C. tion is used.
Oil Content - Test Method ASTM D 721—Test Method D Viscosity - Test Methods D 445, D 2669, and D 3236—
721 describes the determination of oil in petroleum weixes Molten wax viscosity is important for determining the proper
having a congealing point of 30°C (86°F) or higher as deter- melt flow properties for applying waxes by end use machin-
mined in accordance with Test Method D 938, and contain- ery under low shear conditions. Test Method D 445 for the
ing not more than 15% of oil. The test is conducted by dis- m e a s u r e m e n t of kinematic viscosity of t r a n s p a r e n t and
solving the weix in a solvent (methyl ethyl ketone—MEK) opaque liquids is used for petroleum waxes with viscosities
and chilling to a low temperature to precipitate the wax. less than 25 centistokes at 99°C.
The wax is filtered from the solvent and the solvent soluble Test Methods D 2669 and D 3236 are used for waxes that
residue is evaporated to determine the oil content. The oil have been c o m p o u n d e d with wax additives resulting in a
content of paraffin waxes is indicative of the degree of re- high viscosity, u p to 2000 poise at 175°C (347°F). Fluid vis-
fining or processing that has been performed. Fully refined cosity is determined by placing a representative sample of the
wax generally does not have an oil content exceeding 0.5%. molten wax into a thermally controlled sample chamber. Ap-
Paraffin waxes having oil contents exceeding the 0.5 limit parent viscosity is determined u n d e r thermal equilibrium
are marketed as scale ( < 3 % oil) and slack paraffin waxes conditions using a precision rotating spindle type viscometer
(<40% oil). Microwaxes a n d petrolatums have a higher as illustrated in Fig. 22. Data for several temperatures can be
affinity for oil than the paraffin waxes and are marketed plotted on appropriate semi-logarithmic graph paper and ap-
with oil contents as high as 20%. parent viscosity at intermediate temperatures can be esti-
With some t5fpes of waxes with oil contents greater than mated. Although precision has not been studied. Test Method
5%, there may be an incompatibility with MEK resulting in D 3236 may be adaptable to measure fluids with viscosities
4*^-Mk»Uk
3U-3iJ0lIlu
aiiLO- aiAU).
CORK '
OOOUWr LEVEL-
JMnr
I
9
MM-
MC •
-rP ini
All dimensions in millimeters

FIG. 21—Apparatus for Standard Test Method D 2500 to measure the cloud point of
petroleum products.
VISCOMETER
TMEKMOMmn
auui IN HomzoNDU.
PLMC WITH C i N I U
OF SPINOLC
aoncM or luiwii
«M> HTTOKOrtUMO
MCK
x_x ^ : ^ "
FiG. 23—Needie pen-

etration apparatus of
Standard Test Method D
1321 used for measure-
FIG. 22—Viscosity measurement apparatus, side view, used in ASTIM ment of hardness of
petroleum waxes.
Test Method D 2669.
greater than present 2000 Poise limit and temperatures above which a standard needle penetrates into the wax under de-
175°C (347°F). Equipment described in this procedure per- fined conditions using a penetrometer such as the one illus-
mits testing of materials having viscosities as high as 160 000 trated schematically in Fig. 23.
Poise and provides temperatures up to 260°C (500°F). To measure the hardness of a wax, Test Method D 1321, the
Hardness - Test Method D1321—The hardness of a wax is a Needle Penetration Method is commonly used. This method
measure of its consistency. Waxes can show variation in is based on a standardized needle penetrating into the wax
hardness and the differences are more pronounced at higher surface at a specific temperature. The smaller the numerical
temperatures. For example, two waxes may have the same value obtained from this test, the harder the wax is. The hard-
hardness as measured at one temperature, but are dissimilar ness of the wax can be indicative of undesirable blocking ten-
at a different temperature. Hardness is determined by pene- dency for wax-coated paper. (Note: Test Method D 1321 is
tration and is defined as the depth in tenths of a millimeter to similar to Test Method D 937, which is a cone penetrometer
Sample
Reference
Resistance Resistance
Thermometer Thermometer
Heater Heater
Nitrogen AT-Signal
(a)
First-Order Transition:
Apex
Second Order-Transition:
Apex - Tjj^
Onset
End
(b) T.-^,,*..,. -r-
FIG. 24—(a) Differential scanning calorimetry (DSC) experimental set up; (b) Schematic
of petroleum wax DSC curve (heating cycle) sample determined to have soiid-liquid and
solid-solid transitions. This figure is similar to Fig. 16a.
method for petrolatum, which may also be used for softer gram. DSC can differentiate the tj^je of petroleum wax being
waxes. The cone penetration value is more of a measure of evaluated by its melting and crystallization property. Figure
firmness or consistency rather than hardness.) 2Ab (which is similar to Fig. 16a) is the schematic of a
Transition Temperatures by Differential Scanning Calorime- petroleum wax DSC curve exhibiting solid-liquid and solid-
try (DSC)-Test Method D4419—Test Method D 4419 is a rapid solid transitions (Heating Cycle) and the calculation of such
and convenient method for determining the temperature lim- temperatures. Paraffin waxes being derived from the distilla-
its governing the change a wax undergoes from solid to liquid tion process have sharp peak shapes, while microcrystalline
or as a solid-solid transition. This test method measures the waxes being derived from residual fractions have broader
transition temperatures of petroleum waxes, including mi- peak shapes. This is shown in Fig. 16 (Note: Refer to Stan-
crocrystalline waxes, by differential scanning calorimetry dard Terminology E 473 for additional information).
(DSC) as shown in Fig. 24a. The normal operating tempera-
ture range extends from 15-150°C. DSC is a technique that Chemical Property Determination
measures the difference in energy inputs into a substance Petroleum waxes being composed of hydrocarbons Eire rela-
and a reference material using a controUed-temperature pro- tively inert but they can undergo compositional chemical
changes when exposed to elevated temperatures in the pres- wax and placing approximately 10 g of thin shavings on odor-
ence of oxygen due to oxidation. Waxes can degrade in the free paper or glassine. Individual test specimens are then eval-
presence of heat and oxygen. The degradation process in- uated for odor by each panel member and assigned a number
volves breaking a bond between a carbon and a hydrogen according to the odor scale shown in Table 18 that best fits the
atom to make a free radical. The free radicals quickly form intensity of the odor. As an alternative procedure, the wax
peroxides initially and further react to form acids. The shavings are placed in bottles with each panel member mak-
changes in composition can possibly be detected by testing ing an odor determination between 10 and 60 min after the
for color a n d odor. Antioxidants are added to p e t r o l e u m shavings are placed into the bottles. The average of the panel
waxes to chemically stabilize them from the heat degradation ranking is reported as the odor rating of the sample.
process [41]. Composition by Gas Chromatography-Test Method D 5442—
Color - Test Methods D 156 and D 1500—The color of Test Method D 5442 is applicable to petroleum derived waxes,
petroleum waxes can indicate the degree of refinement or including blends of waxes. This test method covers the quan-
possible contamination. Color is not always a reliable pa- titative determination of the carbon n u m b e r distribution of
rameter for determining quality and should be used judi- petroleum wEixes in the range of n-C17 through n-C44 by gas
ciously as a specification. There are two methods for deter- chromatography using internal standardization. In addition,
mining the color of petroleum waxes: Test Methods D 156 the content of normal and non-normal hydrocarbons for each
and D 1500, and both are subjective and measure the empir- carbon n u m b e r is also determined. Material with a carbon
ical value based on visual observation of the wax in the number above n-C44 is determined by difference from 100
molten state. mass % and reported as C 45 +. (Note: Standard Practice E 260
Test Method D 156 is the Saybolt Chronometer Method for provides further information on gas chromatography and
quantifying the color of petroleum products such as a Standard Practice E 355 provides information relating to gas
petroleum wax. Saybolt color is an empirical definition of the chromatography terms and relationships.)
color of a clear petroleum liquid based on a scale of —16 Test Method D 5442 is not applicable to oxygenated waxes,
(darkest) to +30 (lightest). The number is derived by finding such as synthetic polyethylene glycols (i.e., Carbowax), or
the height of a column that visually matches the appropriate natural products such as beeswax or c a r n a u b a . This test
one of three glass standards and referring to Table 1 of Test method is not directly applicable to waxes with oil content
Method D 156. This is done using a Saybolt chronometer (see greater t h a n 10% as determined by Test Method D 721.
Fig. 25), which consists of a sample and standard tubes, op-
tical system, light source, and ASTM color standards. Functional Property Determination
While Test Method D 156 is used to determine the degree The following methods are for the evaluation of wax base
of whiteness of a wax, Test Method D 1500 is used to measure coatings intended for paper and paperboard. The methods
the color of waxes that have a tint darker than off-white. Test were developed in concert with the Technical Association of
Method D 1500 is conducted using a standard light source, Pulp and Paper Industries.
with liquid sample placed into a standard glass container Specular Gloss - Test Method D 1834—Specular gloss is
(sample jar) (see Fig. 26) and compared with colored glass defined as the degree to which a surface simulates a mirror
disks ranging in value from 0.5-8.0 with 0.5 increments. in its capacity to reflect incident light. Test Method D 1834
Carbonizable Substances - Test Method D 612—Test Method is a method designed to determine the capacity of a wax
D 612 is applicable to paraffin waxes for pharmaceutical use coated surface to simulate a mirror in its ability to reflect an
as defined in the United States National Formulary. Molten incident light beam using a glossmeter such as that illus-
wax is treated with sulfuric acid and the acidic layer is com- trated in Fig. 28. Surface gloss is desirable for some waxed
pared visually with a colorimetric reference standard to de- paper applications. For determining the gloss of book pa-
termine if it passes the conformance criteria for refined wax per, reference should be made to Test Method D 1223. For
using the color comparator shown in Fig. 27. very high gloss paper refer to Wink et al. [42].
Peroxide Number - Test Method D 1832—Waxes are heat Gloss Retention - Test Method D 2895—This test is intended
sensitive and they are susceptible to the action of the oxida- to correlate with the conditions that are likely to occur in the
tion process. The detection of peroxides is the first indication storage and handling of wax-coated paper and paperboard.
that a wax has begun to deteriorate in terms of oxidation sta- Test Method D 2895 is intended primarily to measure the
bility. Petroleum waxes should not have any measurable per- gloss retention, which is defined as the percent of original
oxide values. Deterioration of petroleum wax results in the gloss retained by a test specimen after aging under specified
formation of peroxides a n d other oxygen-carrying com- conditions. It is calculated as the final gloss divided by the
pounds that will oxidize potassium iodide. Peroxide content initial gloss multiplied by 100. The initial gloss of waxed pa-
is reflected by the peroxide n u m b e r that is defined as the mil- per or p a p e r b o a r d is m e a s u r e d in accordance with Test
liequivalents of constituents per 1000 g of wax that will oxi- Method D 1834, then remeasured after aging the sample in
dize potassium iodide. an oven at 40°C (104°F) for 1 and 7 days. The 1-day test is
Odor - Test Method D 1833—In some end-use applications, conducted to observe trends while the 7-day test is the stan-
such as food packaging, the intensity of the odor is an impor- dard test duration.
tant characteristic. Odors can be an indication of the degree Surface Wax - Test Methods D 2423, D 3521, and D 3522—
of refining, contamination, or oxidation. Test Method D 1833 Wax coatings are applied to provide a better moisture bar-
describes how to rate the odor intensity based on a subjective rier, appearance, and abrasion resistance. These perfor-
evaluation using a multiple-member test panel. This test is mance features are influenced by the amount of wax present
conducted by preparing odor test specimens from petroleum on the surface. Test Method D 2423 is used to determine the
HMDU
NOTC-HiUHLE It FMTOltD T O V
0 Suae
0 oouw
0 couM oovn
m j 0 mm «uiw
(i) nacMw
© (iMm UTHADML «•» (LTCntlfK
0 «T mm MUUM seM»ovia
0 suun oi*x
0 WTAININt iHM
0 UtlX
X) t n i m *
LS « 0 WATT soil. MMTHI
SCOTIOH "A-A"
Saybolt Chromometer Tube Heater Adapter

FIG. 25—ASTM Standard Test Method D156 Saybolt Chromometer and artificial daylight
lamp.
amount of wax present on the surface of the substrate, but Test Method D 3 521 also determines the a m o u n t of wax that
not the absorbed wax. Test methods that determine the apis present on the surface of corrugated paperboard. This
plied wax by solvent extraction (such as Test Method D 3344) method is applicable to a board on which wax has been ap-
do not differentiate between the wax present at the surface plied by curtain coating, roll coating, or other methods. The
and to that which penetrated the substrate. substrate board may or may not contain impregnating (satu-
ration) wax within its structure. If it is known that the speci-
men has coating wax only, with no internal saturating wax,
then Test Method D 3344 may determine the total coating wax
applied. Determination of the total amount of wax present by
ASTM D 3521 involves delamination of the coated facing to
obtain a ripple-free sheet, then scraping off the wax using a ra-
zor blade and calculating the amount of wax removed.
Test Method D 3522 is used to determine the amount of
wax that has been applied to the individual layers of the cor-
rugated paperboard and the a m o u n t of the impregnating
(saturation) wax in the same facing. This is accomplished by
peeling the coated facing from the medium and then splitting
it into two layers; one bearing the coating on waxed fibers
only and the other containing waxed fibers only. The layers
are extracted separately, collecting both fibers and wax. This
will permit the calculation of the applied surface coating and
the amount of impregnating wax.
TABLE 18—Odor intensity scale.

Numerical Rating Odor Description
FIG. 26—Standard None
glass sample jar used Slight
in Test Method D 1500 Moderate
to measure the color of Strong
Very strong
waxes.
e-i'*Mo/es
Section A-A.
Plan T l 3 STOPPER
SiaTlSNECK
I Hi
m "5«
-i
ISLi
i
I h !
i li
$>!$ I40±2MM
!l< '
A A Appnox.
CAPACITY
-i-n-j. T I
TO STOPPER
late TO {SA ml
145H5.0
MM 0.0.
Elevation End Elevation WALL"
I.ZOIMM
AVER
TEST TUBE
FIG. 27—Color comparator used in Standard Test Method D 612 for measurement of car-
bonizable substances in paraffin waxes for pharmaceutical use.
disruption occurs across 50% of the waxed p a p e r surface

Vacuum
Specimen Holder when the test strips are separated. The temperature at which
' l^L
'^-— f^\\
Porou* Plate
>.Specimen
the first film disruption occurs on the waxed paper when the
test strips are separated is the wax picking point. Test
Method D 1465 is used to d e t e r m i n e the t e m p e r a t u r e at
which two strips of wax-coated p a p e r will adhere to each
ViU.:.v.M>'.'-.-..!.-.vA-.X!-'.J-; L other. Surface disruption of wax coatings at relatively low
J J t j J J ^
a m b i e n t t e m p e r a t u r e s is a performance problem for low
melting point waxes. If the surface of a waxed p a p e r is
blocked together, then surface gloss and barrier properties
will be altered. Two strips of wax-coated paper are placed on
a calibrated t e m p e r a t u r e gradient plate for 17 h and re-
moved, cooled, and peeled apart to determine the block point
temperature. Figure 29 illustrates a Type A and a Type B
blocking plate used for these measurements.
Coefficient of Kinetic Friction - Test Method D 2534—A
coated surface under load is pulled at a uniform rate over a
second coated surface. This is d o n e experimentally by
preparing a "sled" with a weight and then pulling it over the
surface to be tested using a horizontal plane and pulley as-
sembly. The force required to move the load is measured, and
the coefficient of kinetic friction (/j-k) is calculated as follows:
fH, = A/B (15)

Where A = the average scale reading from the electronic
load cell-type tension tester for 150 m m (6 in) of uniform slid-
ing and B = sled weight (g). The value obtained is related to
the slip property of the wax coating. High slip property val-
ues may not be desirable for many commercial articles that
have been coated with petroleum wax.
Abrasion Resistance - Test Method D 3234—This test
method is designed to help predict the resistance in change of
gloss that coatings may be subject to during the normal han-
dling of coated paper and paperboard products. Abrasion re-
sistance is the resistance to change in gloss when that coat-
ing has been subjected to an abrading action by an external
rf J ^JJ ^^*/J
object. Test Method D 3234 is conducted by dropping 60 g of
FIG. 28—Diagram of relative positions of essential elements sand on a very small area of a coating under fixed conditions.
of Glossmeter used in Standard Test Method D 1834. The abrasion resistance test apparatus is illustrated in Fig.
30. Gloss is measured with a 20° specular glossmeter illus-
trated in Fig. 28 before and after the abrading action by the
falling sand.
Hot Tack - Test Method D 3706—Hot tack is defined as the
Total Wax Content - Test Method D 3344—Many of the func- cohesive strength during the cooling stage before solidifica-
tional properties of a wax-treated paperboEird are dependent on tion of a heat seal bond formed by a wax-polymer blend. Flex-
the amount of wax that is present. Test Method D 3344 deter- ible packaging materials are formed into finished packages by
mines the total amount of wax in a sample of wax-treated cor- joining surfaces with heat sealed bonds. The bonding process
rugated paperboard by extraction. It is applicable to specimens is performed o n high-speed packaging lines and the applica-
that have been waxed by either impregnation (saturation) option pressure used to hold the surfaces together is released be-
erations or coating operations, or combinations of the two. fore the bond has completely solidified. The wax-polymer
Weight of Wax Applied During Coating - Test Method D blend must have enough hot tack while still in a molten stage
3708—Test Method D 3708 is used to determine the weight of to hold the sealed areas together until the blend has cooled.
a hot melt coating applied to corrugated board by curtain In Test Method D 3706, flexible packaging specimens are
coating. This method is intended for use as a routine process heat-sealed together over a series of temperatures and dwell
control in the plant. The a m o u n t of wax applied is deter- times. Immediately after each seal is formed and before it has
mined by attaching a folded sheet of paper to production cor- started to cool, a force tending to separate the specimens is
rugated board, running the combination through the curtain applied by a calibrated spring. If the hot tack of the blend is
coater, and subsequently determining the applied weight of strong enough, the seal remains closed until it has solidified;
wax on the sheet of paper. if not, the seal separates. Thus each spring force and test con-
Blocking Point - Test Method D 1465—The blocking point of dition either passes or fails. The pattern of pass/fail results is
a wax is defined as the lowest temperature at which a film plotted to the blend characteristics.
$1 nun K 30S KHX K S I S MDI
Itey ttDck mtil Medkt 2S mm » 2B RHR (1" s 1"). ( r « i s r K »*i
7C2 MR iVty Iwit. 13 MM ^ l / r i h
(AM. T«m4l lor 13 mm d / T }
Type A Blocking Plates
Into (Mb tWRi tmiiiimd
Type B Blocking Plate

FIG. 29—The two types of blocking plates used In Standard Test Method D-1465 to mea-
sure the blocking point of wax.
500 ml
Separatory Funnel
60 g of Sand
Stopcock
Size I H
Stem Cut Off from

Separator/ Funnel
U.S. Standard Sieve

No. 12
^ " ^ 2 B mm (I") I.D.
Specimen
For tscating Exact Position for For Dropping 60 g of Sand

Mailing Glossmeter Readings
FIG. 30—Apparatus for measuring abrasion resistance of wax coat-

ings in Standard Test lUlethod D 3234.
Acknowledgments D 721 Test Method for Oil Content of Petroleum Waxes

D 937 Test Method for Cone Penetration of Petrolatum
The authors thank Dr. George Totten for his helpful advice D 938 Test Method for Congealing Point of Petroleum
and guidance in the preparation of this chapter and Dr. Sony Wcixes, including Petrolatum
Oyekan, Dr. Chen-Hwa Chiu, Dr. Sang J. Park, and Mr. D 1168 Test Method for Hydrocarbon Waxes Used for
Adrian D'Sousa for their technical assistance. Electrical Insulation
D 1298 Test Method for Density, Relative (Specific Grav-
ity) or API Gravity of Crude Petroleum and Liquid
ASTM STANDARDS Petroleum Products by Hydrometer Method
D 1223 Test Method for Specular Gloss of Paper and Pa-
No. Title perboard
D 87 Test Method for Melting Point of Petroleum Wax D 1321 Test Method for Needle Penetration of Petroleum
D 97 Test Method for Pour Point of Petroleum Products Waxes
D 127 Test Method for Drop Melting Point of Petroleum D 1465 Test Method for Blocking and Picking Points of
Wax Including Petrolatum Petroleum Wax
D 156 Test Method for Color, Saybolt, of Petroleum D 1500 Test Method for Color, ASTM, of Petroleum Prod-
Products ucts (ASTM Color Scale)
D 287 Test Method for Gravity, API, of Crude Petroleum D 1832 Test Method for Peroxide Number of Petroleum
and Petroleum Products (Hydrometer Method) Wax
D 445 Test Method for Kinematic Viscosity of Transpar- D 1833 Test Method for Odor of Petroleum Wax
ent and Opaque Liquids D 1834 Test Method for 20° Specular Gloss of Wax Paper
D 612 Test Method for Carbonizable Substances in D 2423 Test Method for Surface Wax on Waxed Coated
Paraffin Wax Paper
D 2500 Test Method for Cloud Point of Petroleum ISO 1392 Determination of crystallizing point—
Products General method
D 2534 Test Method for Coefficient of Kinetic Friction ISO 2207 Petroleum waxes—Determination of
for Wax Coating congealing point
D 2669 Test Method for Apparent Viscosity of Petroleum ISO 3016 Petroleum products—Determination of
Waxes Compounded with Additives (Hot Melts) pour point
D 2895 Test Method for Gloss Retention of Waxed Paper ISO 3841 Method for determination of melting
and Paperboard after Storage at 40° C (104° F) point of petroleum wax (cooling curve)
D 3234 Test Method for Abrasion Resistance of JIS K 00-64 Testing methods for melting points of
Petroleum Wax Coatings chemical products
D 3235 Test Method for Solvent Extractables in JIS K 00-65 Test methods for freezing point of chem-
Petroleum Waxes ical products
D 3236 Test Method for Apparent Viscosity of Hot Melt NFT60-114 Petroleum products—Melting point of
Adhesives and Coatings Materials paraffins
D 3 344 Test Method for Total Wax Content of Corrugated NFT20-051 Chemical products for industrial use.
Paperbocird Determination of melting point. Method
D 3451 Standard Practices for Testing Polymeric Pow- for the determination of crystallizing
ders and Powder Coatings point (freezing point).
D 3521 Test Method for Surface Wax Coating on Corru-
gated Board
D 3522 Test Method for Applied Wax Coating and Im- REFERENCES
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D 3 706 Test Method for Hot Tack of Wax-Polymer Blends lishing Co., Inc., NY, 1972.
by Flat Spring Test 2] Warth, A. H., Chemistry and Technology of Waxes, Reinhold Pub-
D 3708 Test Method for Weight of Wax Applied During lishing Corp., NY, 1956.
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5] Warth, A. H., Chemistry and Technology of Waxes, Reinhold Pub-
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E 355 Practice for Gas Chromatography Terms a n d 8] Erchak, Jr., M., "Process for the Oxidation of High Molecular
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Analysis 9] Haggin, J., "Fischer-Tropsch: New Life for Old Technology,"
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E 537 Test Method for Assessing the Thermal Stability
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35, No. 2, 1984, pp. 130-134.
1] Brooks, B. T., Boord, C. E., Kurtz, S. S., and Schmerling, L., The
OTHER STANDARDS Chemistry of Petroleum Hydrocarbons, Vol. 1, Reinhold Publish-
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2] Gruse, W. A., Chemical Technology of Petroleum, 2°'' ed., Mc-
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Graw-Hill Company, NY, 1942.
BS 4633 & 4634 Method for the determination of crystal- 3] Mazee, W. M., "Petroleum Waxes," Modem Petroleum Technol-
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1965, pp. 228-243.
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[19] Park, S. J. and Mansoori, G. A., "Aggregation and Deposition of of Alkanes by Equations of State," Chemical Engineering Com-
Heavy Organics in Petroleum Crudes," International Journal of munications, Vol. 173, 1999. pp. 23-42.
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Park, S. J., and Manafi, H., "Asphaltene Flocculation and Col- 1993, pp. 108-111.
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Engineering, Vol. 32, 2001, pp. 217-230. Cubic Equation of State for Hydrocarbons and Other Com-
[21] Svendsen, J. A., "Mathematical Modeling of Wax Deposition in pounds," SPE Paper No. 26667, Proceedings of the 1993 Annual
Oil Pipeline Systems," AIChE Journal, Vol. 39, No. 8, 1993, pp. SPE Meeting, Society of Petroleum Engineers, Richardson, TX,
1377-1388. 1993.
[22] Brown, T. S., Nielsen, V. G., and Erickson, D. D., "Measurement [35] Nikitin E. D., Pavlov, P. A., and Bessanova, N. V., "Critical Con-
and Prediction of the Kinetics of Paraffin Deposition," Journal stants of n-Alkanes with from 17 to 24 Carbon Atoms," Journal
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[23] Noll, L., "Treating Paraffin Deposits in Producing Oil Wells," [36] Frenkel, M., Gadalla, N. M., Hall, K. R., Hong, X., and Marsh, K.
Topical Report NIPPER-551 (DE92001010), Bartelsville Project N., TRC Thermodynamic Tables-Hydrocarbon; Non-Hydrocar-
Office, U.S. Department of Energy, Bartelsville, OK, 1992. bon, R. C. Wilhoit, Ed., Thermodynamic Research Center, The
[24] Sanchez, J. H. P. and Mansoori, G. A., "In Situ Remediation of Texas A & M University System, College Station, TX, 1997.
Heavy Organic Deposits Using Aromatic Solvents," Paper # [37] Twu, C. H., "An Internally Consistent Correlation for Predicting
38966, Proceedings of the 68th Annual SPE Western Regional the Critical Properties and Molecular Weights of Petroleum and
Meeting, Bakersfield, CA, May 1998. Coal-Tar Liquids," Fluid Phase Equlibrium, Vol. 16, 1984, pp.
[25] Paraffin Products: Properties, Technology, Applications, G. Y. 137-150.
Mozes, Ed., Elsevier, NY, 1982. [38] Edalat, M., Mansoori, G. A., and Bozar-Jomehri, R. B., "Vapor
[26] Murad, K. M., Lai, M., Agarwal, R. K., and Bhattachaiyya, K. K., Pressure of Hydrocarbons, Generalized Equation," Encyclope-
"Improve Quality of Wax by Hydrofinishing," Petroleum Hydro- dia of Chemical Processing and Design - 61, Marcel Dekker, Inc.,
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[27] Ferris, S. W., "Characterization of Petroleum Waxes Tappi," [39] Letoffe, J. M., Claudy, P., Garcin, M., and Voile, J. L., "Evalua-
TAPPI Special Technical Association Publication No. 2, 1963, tion of Crystallized Fractions of Crude Oils by Differential Scan-
pp. 1-19. ning Calorimetry, Correlation With Gas Chromatography,"
[28] Himran, S., Suwono, A., smd Mansoori, G. A., "Characterization of Fuel, Vol. 74, No. 1, 1995, pp. 92-5.
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ergy Storage Medium," £nergySoMrce5, Vol. 16,1994, pp. 117-128. Fette Seifen Anstrichm, Vol. 82, No. 2, 1980, pp. 76-81.
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component Mixtures: Continuous Mixture Gibbs Free Energy ternational, Warrendale, PA, 2000, p. 205.
MNL37-EB/Jun. 2003
Lubricating Greases
Thomas M. Verdura, ^ Glen Brunette, ^ and Rajesh Shah~
T H E ESSENTIAL FUNCTION OF ANY LUBRICANT is to prolong the life tremely small, uniformly dispersed, and capable of forming a
and increase the efficiency of mechanical devices by reducing relatively stable, gel-like structure with the liquid lubricant.
friction and wear. Secondary functions include heat dissipa- Greases are distinct from lubricating pastes that can ap-
tion, corrosion protection, power transmission, and contam- pear grease-like. Pastes are mostly solids; generally about
inant removal. Generally, fluid lubricants are difficult to re- 70-95% solids, but sometimes merely wetted solids. The solid
tain at t h e point of application a n d m u s t be replenished thickener concentrations of greases range from about 3-30%,
frequently. If, however, a fluid lubricant is thickened, its re- tjrpically about 10%. Also, for pastes, affinity between the
tention is improved, a n d lubrication intervals c a n b e ex- solid and liquid phases is not essential; neither is it necessary
tended. A lubricating grease is simply a lubricating fluid that a stable, gel-like structure be formed. The manufactur-
which has been gelled with a thickening agent so that the lu- ing methods also differ. Pastes are simply solid-liquid mix-
bricant can be retained more readily in the required area. tures formed using low-shear mixing. Grease manufacturing
This is not to say that the thickener does not play a part in the requires considerably m o r e processing, usually including
lubrication. Depending on the type of thickener being used synthesizing the thickener in the fluid. A strict time, temper-
and the lubricating regime, some thickeners will contribute ature, a n d mixing profile must be followed to properly syn-
in the lubrication. thesize the thickener. Next, thorough mixing and blending in
Lubricating greases have a n u m b e r of advantages over lu- the desired additives at the proper time and temperature has
bricating fluids. Some of these are: to be done prior to the final finishing a n d processing. In-
cluded in the finishing a n d process steps is homogenization,
• Dripping and spattering are nearly eliminated
where t h e grease is passed through a mill to disperse the
• Less frequent applications are required
thickener and additives, or deaerating, to remove entrained
• Greases are easier to handle
air or both where needed.
• Less expensive seals can be used
• Greases can form a seal in many cases and keep out con-
taminants
• They adhere better to surfaces COMPOSITION
• They reduce noise and vibration
• Some grease remains even when relubrication is neglected Greases are composed of a lubricating fluid, a thickener, and
usually performance enhancing additives. A complete discus-
Grease was previously defined as a gelled lubricating fluid.
sion of the many variations of grease formulations and man-
Although this simplistic definition conveys the general con-
ufacturing process would require far more space than allot-
cept of a grease, a more extensive discussion is required to
ted for this work. Extensive discussion on grease chemistry
provide a fuller understanding of just what constitutes a lu-
and manufacturing process has been published [1-4]. There-
bricating grease. A lubricating grease is a semi-fluid to solid
fore, only a n overview of the most common grease types and
product of a dispersion of a thickener in a liquid lubricant.
methods has been presented.
Additives, either liquid or solid, Eire usually included to im-
prove grease properties or performance. The lubricating fluids t h a t c a n b e thickened to form
By definition, grease is a lubricant. It is also essentially a greases vary widely in composition and properties and are a n
two-phase system—a liquid-phase lubricant into which a extremely important component of the grease. Lubricating
solid-phase finely divided thickener is uniformly dispersed. fluids can account for as m u c h as 95% of a grease. By iar, the
The liquid is immobilized by the thickener dispersion that largest volume of greases in use today consists of those made
must remain relatively stable with respect to time and usage. with petroleum oils thickened with soaps. Many types of
At operating temperatures, thickeners are insoluble or, at petroleum oils are used, including naphthenic, paraffinic, hy-
most, only slightly soluble in the liquid lubricant. There must drocracked, and hydrogenated. The viscosity of the oil used
be some affinity between the solid thickener and the liquid lu- also varies. Oil blends with a viscosity between an ISO 100
bricant in order to form a stable, gel-like structure. The thick- and 220 are most common, however, for specialized greases,
ener can be constituted of fibers (such as various metallic the oil viscosity can be lighter or much heavier. In addition to
soaps), or plates or spheres (such as certain non-soap thick- petroleum oils, other lubricating fluids such as vegetable oils,
eners). The essential requirements are that the particles be ex- silicones, synthetic hydrocarbons, and others can be used. Of
the synthetic fluids used in grease manufacturing the most
common type is poly(alpha)olefin (PAO). Because it is more
expensive, its usage is small compared t o petroleum oil.
Greases made with PAO as the lubricating fluid can provide
' Retired, General Motors NAO Research and Development, War- good performance over a wide-temperature range.
ren, MI.
^ CITGO Petroleum Corporation, Oklahoma City, OK. Many products have been used as thickeners for grease.
^ Koehler Instrument Company Inc., Bohemia, NY. Soaps were the first thickeners used and still have the widest
557
S Lithium soaps The most common basic components used to neutralize

the fatty acids are hydroxides of lithium, calcium, and
sodium. The resulting greases are named according to the ba-
0 Calcium soaps sic component and the acidic component used to form the
soap, e.g., calcium stearate grease, lithium 12-hydroxy-
H Aluminum soaps stearate grease, etc.
H Sodium and other Grease Selection

soaps
gô m Clay & other non-soaps When selecting a grease for a particular application, one
should first determine the type and viscosity of the lubricat-
B Polyurea ing fluid required because the fluid has a major influence in
grease lubrication. The properties of greases are determined
FIG. 1—Worldwide grease production by thickener type by the characteristics of the thickener system, by the viscos-
(1999 NLGI Survey). ity and type of the fluid component, and by the performance
additives used. Similar criteria as is used for selecting indus-
trials oils can be used when determining the type and viscos-
application (see Fig. 1). Some of the other thickeners that
ity of the lubricating fluid needed in a grease for a particular
have been employed include polymers, clays, silica gel, and
application. In general, heavily loaded and slow speed appli-
pigments.
cations require higher oil viscosity Eind lightly loaded high
Soaps are present in greases in the form of fibers. The
speed applications require lower oil viscosity. E a c h thickener
structure and size of these fibers, i.e., thickness and length,
system has its own unique characteristics. Additional discus-
depend on the metallic moiety and the conditions u n d e r
sion of the properties of the various soap type greases will be
which they are formed. In general, soap fibers can vary from
provided in subsequent paragraphs.
about l-100^lm in length with about a 10 t o l length-to-di-
ameter ratio. Large, coarse fibers do not absorb fluids as well
as fine, closely knit fibers. Thus, a higher percentage of thick-
ener is required for coarse fiber soaps to make greases hav- GENERAL CHARACTERISTICS
ing the same consistency as those made with fine fiber soaps.
Non-soap thickeners are generally smaller, even colloidal, Describing the general characteristics of a grease based on
and have either a spheroidal or plate like structure. the thickener type is difficult because the base oil compo-
Soap thickeners are formed by neutralization reaction of nents and the performance additives used effect the charac-
an acid and base to form a salt and water as a byproduct. teristics of the grease as m u c h or more than the thickener
When the acid is a fatty acid, its salt is called a soap, and the type. Therefore, assigning characteristics to a grease based
reaction is Ccilled saponification. If the acidic component has on thickener t5ê has limited value, however, some charac-
a narrow range of moleculcir weight, as in fatty acids, a sim- teristics inherent to the thickener tjfpe are discussed below.
ple soap is made, e.g., lithium stearate. Reacting the metallic The reader should be aware that some of the weaknesses of a
base with two dissimilar acids of widely different molecular thickener type can be improved and some of the strengths of
weight will form a complex soap, e.g., calcium stearate ac- a thickener type can be degraded with the inclusion of per-
etate. Mixed-base greases consist of a mixture of two or more formance additives.
different thickener systems, such as sodium-calcium or alu-
m i n u m complex-clay.
Aluminum Soap Greases
The natural fatty materials used for soap formation can be
of animed or vegetable origin. Beef tallow and its derivatives Aluminum soap greases are usually made with preformed
are the major source of animal fatty materials. The reaction soap unlike most other thickeners that Eire made in situ. Alu-
product with beef tallow derivatives Eind lithium hydroxide is m i n u m distearate is the m o s t c o m m o n conventional alu-
lithium stearate soap. Castor oil derivatives are the m a i n m i n u m soap used to make grease. It is dissolved in hot oil in
source of vegetable oil fatty materials. Because the acids de- a mixing grease kettle, and the hot mixture is poured into
rived from castor oil have a hydroxyl group (OH) on the 12''' pans to gel and cool. The cooling rate affects the final consis-
carbon of the acid molecule, the reaction product with castor tency. The final product is a smooth, transparent grease with
oil derivatives and lithium hydroxide is lithium 12-hydroxy- a tendency to thin when worked but with excellent water re-
stearate soap. Although the resulting soap is named accord- sistance. Aluminum soap greases are used as thread and way
ing to the acid most prevalent, the natural occurring fatty lubricants. The poor work stability of aluminum-soap
acids are actually mixtures of similar acids (in the form of a greases is used to advantage in electrically conducting con-
glyceride) with slightly different molecular weights. The type veyers of electroplating systems; the grease thins down dur-
of fatty materials used affects the properties of the soap and ing use, allowing good electrical contact in the track rollers
the grease. Greases made from castor oil derivatives Eire more while still providing good lubrication.
work stable and have higher dropping points than greases
made from beef tallow derivatives due to the hydrogen bond-
ing at the hydroxyl group. The use of mixtures or blends of Calcium Soap Greases
fatty materials can obtain improved cost, oil separation, The Ccirliest known greases were made with calcium soaps.
worked stability, or other properties. Greases thickened with hydrated calcium soaps (usually cal-
CHAPTER 20: LUBRICATING GREASES 559
cium stearate) are water resistant, work stable, and inexpen- thermal limitations of the oils and additives they contain.
sive. The name hydrated calcium comes from the fact that a Aluminum complex greases have excellent water tolerance
small amount of water (about 0.1% wt.) is required to stabi- characteristics as well as high-temperature resistance, conse-
lize the grease. The water associates with the calcium soap quently, they are widely used in steel mills and other wet ap-
and provides the molecular cohesion needed for efficient plications. The soap used for aluminum complex grease is
thickening. These calcium greases are also known as conven- usually eJuminum benzoyl stearoyl hydroxide. This soap can
tioneJ calcium, calcium cup, or lime soap greases. The great- be formed by reacting aluminum isopropylate with stearic
est shortcoming of a hydrated calcium soap grease is its low acid, benzoic acid, and water. To limit or avoid the isopropyl
dropping point, typically about 95°C (200°F). This limits con- alcohol byproduct, other aluminum compounds can be used.
ventioneJ calcium soaps to use in only low temperature ap- Compatibility with other greases can be a problem with alu-
plications. minum complex greases.
Anhydrous calcium soaps (usually calcium 12-hydroxy-
stearate) are not as temperature limited because they do not
need water to hold the soap together due to the stabilizing ef- Calcium Complex Soap Greases
fect of the hydroxyl group (OH). With a dropping point of Calcium complex greases Eire usually made by reacting acetic
about 150°C (300°F), they are somewhat more temperature acid and a fatty acid with lime. The resulting grease has in-
resistant. Anhydrous calcium greases have the same advan- herent EP (extreme pressure) properties and provides good
tages as hydrated calcium greases, but are slightly more ex- friction and wear performance. Thickening efficiency is not
pensive cind do not run the risk of drying out and softening. very good with this soap, therefore, a relative high soap con-
They can be used as multi-purpose greases within their tem- centration is required. As a result, the low-temperature per-
perature limitations. Historically, the greatest usage for Ein- formance is not as good as other complex soap greases, and
hydrous calcium grease has been in a low temperature grease they tend to harden in long-term storage or under pressure in
made with a low-viscosity base oil designed to meet earlier lubrication systems. Used within its limitations, calcium
versions of the military specification MIL-G-10924 for appli- complex greases are cost effective but are not compatible
cations where operation over a wide range of climatic condi- with most other grease types.
tions is essential.
Lithimn Complex Soap Greases

Sodium Soap Greases
Lithium complex grease performance is generally like that of
Sodium (soda) soap greases have higher dropping points lithium greases except dropping points are about 50°C
[about 175''C (350°F)] than calcium greases and form a very higher. Lithium complex is a misnomer used to describe high
fibrous grease. They Eire not water resistant and emulsify in dropping point lithium greases. Because, lithium is mono-va-
the presence of water, yet, they have inherent rust protection lent (mccining it can only react with one acid per ion) it can-
properties. The soap can be made by reacting sodium hy- not form a traditional complex soap where two or more acids
droxide cind tallow, therefore, is a very inexpensive thickener. are reacted with one basic ion. However, there are severed
In earlier times, when calcium and sodium greases made up components that can be used to enhance the molecular in-
most of the market, these greases were the most temperature teractions of the soap molecules and increase the dropping
resistant. They are still used in moderately high temperature point enough to call the resulting grease a "lithium complex."
applications, such as electric motor bearings. Sodium soap The most common method is by forming a lithium salt of a
greases are not normally compatible with other greases. dibasic acid (usually azelaic or sebacic) in situ with lithium
12-hydroxystearate soap. Lithium complex greases provide
good low-temperature performance and excellent high-tem-
Lithium Soap Greases perature life performance in tapered roller bearings. It is the
Lithium greases were the first so-called multipurpose most populcir of the complex greases and has wide-spread
greases. They provide both good water resistance, similar to application.
calcium soap greases, and even higher-temperature proper-
ties than sodium soap greases. The soap is usually manufac-
tured in a portion of the lubricating oil using lithium hy- Polyurea Greases
droxide and a fatty material of either animal or vegetable Polyurea greases are similar to the complex soap greases with
origin. Lithium 12-hydroxystearate greases have dropping respect to high-temperature performance; dropping points
points of about 190°C (375°F). They also have good work sta- are about 245°C (475°F). The reactants (isocyanates and
bility; that is, they do not soften much when worked. Lithium amines) are hazardous but the resulting thickener is consid-
greases have good over-all performance and are cost effec- ered quite safe. Polyurea greases can be made by various
tive. In North America more lithium grease is made them all methods resulting in various strengths and weakness. Most
other tjês combined. have good oxidation resistance, water resistance, pumpabil-
ity, and high temperature performemce. Wesiknesses gener-
ally associated with poljoirea greases include poor shear sta-
Aluminum Complex Soap Greases bility, poor storage stability, and incompatibility with other
Complex soap greases are noted for their high-dropping greases, however, some of these weaknesses have been over-
points [230°C (450°F) and higher], although most are come with more recent formulations [5]. Although used in all
not recommended for use up to the dropping point due to types of bearings, they have proved especially useful for the
lubrication of sealed-for-life, ball bearings used in electric TABLE 1—Guide to requirements for grease categories
motor bearings where superior oxidation resistance and (ASTM D 4950).
high-temperature life is essential. Test Description LA LB GA GB GC
D-217 Penetration / / / • /
0-566" Dropping Point / / • / /
Organo-Clay Greases D-1264 Water Washout • /
D-1742 Oil Separation / / /
Clay thickened greases are made with a modified clay design D-1743 Rust Protection / • /
to have some affinity for the lubricating oil. The process can D-2266 4 Ball Wear • / / /
be as easy as mixing the modified clay thickener with the lu- D-2596 4 Ball EP / /
bricating oil and providing enough shear to disperse the D-3527 High Temperature; Life / •
D-4170 Fretting Wear /
thickener. They have been referred to as non-melting greases D-4289 Elastomer Compatibility / / • /
because they tend to decompose before reaching their drop- D-4290 Leakage / /
ping point. They usually have poor work stability properties D-4693 Low Temperature Torque / / • /
as compared to soap greases. Because many of the common '^D-2265 may be substituted.
additives used in grease will soften clay thickened greases,
they are more difficult to inhibit with extreme pressure addi-
tives. Although water resistant, they can be susceptible to se-
vere degradation from other contaminants, such as brine.
TEST METHODS AND THEIR
Low-temperature performance could be considered satisfac-
SIGNIFICANCE
tory, but many clay greases are formulated with high-viscos-
ity base oils for high-temperature applications; such greases Greases are used for particular lubrication applications be-
will have poor low-temperature properties. Clay greases are cause of their intrinsic properties. Users and producers alike
not normally compatible with other greases. need a common means to describe the properties required
for grease performance for particular applications. Test
methods are devised to describe the requisite properties.
When the usefulness of some test becomes known through-
CLASSIFICATION AND SPECIFICATIONS out the industry, it is developed, through cooperative effort,
into an industry standard such as an ASTM standard. The
Over the past six decades, efforts to develop a grease classifi- standard tests used to determine the properties of petroleum
cation system were frustrated by seemingly insurmountable oils Eire commonly applied to grease base stocks, as well. Few
difficulties. Until recently, the American grease industry had among these are kinematic viscosity (D 445), flash and fire
not developed grease specifications for industry-wide ap- points (D 92), pour point (D 97), and aniline point (D 611),
plications. However, in 1989, after about 15 years of devel- etc. The significance of these tests are discussed elsewhere
opment, ASTM D4950, Standard Classification and Spe- throughout this book.
cification for Automotive Service Grease, was published. There are no standard tests for the evaluation of grease
Development of this standard was a cooperative effort by thickeners, per se, because most thickeners (soaps) are
ASTM International, NLGI (National Lubricating Grease In- formed in situ and are not used independently of the grease.
stitute), and SAE (Society of Automotive Engineers). It is the Consequently, there is little need for standard tests to evalu-
first and only cooperatively-developed grease specification ate neat thickeners. However, work is currently in progress,
accepted by American industry. Development of this stan- including an ASTM Round Robin using the Penn State Mi-
dard was made possible only because several grease perfor- crooxidation test, to study oxidation characteristics of
mance tests were developed specifically for automotive ap- greases, which helps lend limited insight to the evaluation of
plications. These performance tests (D 3527, D 4170, D 4289, the thicker system.
D 4290, and D 4693) are discussed subsequently. ASTM and IP (Institute of Petroleum) have developed and
D 4950 classifies automotive service greases into two chas- standardized a number of tests to describe the properties and
sis grease and three wheel bearing grease categories based on performance characteristics of lubricating greases. Because
the performance needs of several service conditions. A guide these tests are conducted in laboratories under well-defined
to the requirements of these categories is given in Table 1. conditions, they are used primarily as screening tests. Some
The NLGI has established a licensing procedure for greases of the grease tests do indicate how a grease might perform in
qualifying for ASTM D 4950, categories GC and LB. In con- service, but direct correlation between laboratory and field
junction with licensing, three certification symbols can be performance is often unattainable because the tests never
used only with the highest-performance categories of chassis precisely duplicate service conditions.
and wheel bearing greases. NLGI specifically prohibits the
use of the symbols with lesser-performance grease categories.
Consistency
Industry response to the licensing system has grown over
the last decade and containers of grease bearing the certifi- Consistency can be defined as the degree to which a plastic
cation symbols are commonly available in the aftermarket, material, such as a lubricating grease, resists deformation
and their availability is expected to expand. Beginning with under an applied force. It is a measure of the firmness or
the 1992 model year, most U.S. automakers began recom- rigidity of the thickener structure of the grease. The standard
mending the use of NLGI Service Greases GC, LB, and GC- method for measuring grease consistency is the penetration
LB for scheduled maintenance of chassis and wheel bearings test. Consistency is reported in terms of ASTM cone penetra-
of passenger cars and light-duty trucks. tion, NLGI Consistency Number, or apparent viscosity. Cone
penetrations and NLGI number are discussed in the follow- Instead, the penetration is determined on three faces of a
ing paragraphs. Apparent viscosity is included in the Shear freshly-cut, 50-mm (2-in.) cube of grease.
Stability section. Undisturbed Penetration—Undisturbed penetration is that
measured on a grease sample in a container as received, with-
Cone Penetration out any disturbance. This measurement was formerly a re-
ASTM D 217 (IPSO) Test Methods for Cone Penetration of Lu- quirement in D 217, but because of the uncertainty of re-
bricating Grease is the universal standard for the determina- peatable sample handling, it now is included merely as an
tion of the penetration of a normal grease sample. (In this information item. Such measurements can be used for con-
context, normal greases are those that are neither too soft nor sistency control in grease manufacture, and to assess the de-
too hard to be measured by this method.) In this method, a gree to which a grease develops false body or set with pro-
double-tapered cone of prescribed construction sinks under longed storage.
its own weight into a sample of grease at 25°C (77°F) for 5 s. NLGI Consistency Numbers—On the basis of worked pene-
The depth of penetration, measured in tenths of a millimeter, trations, the NLGI has standardized a numerical scale as a
is the penetration value. (It is common practice to omit the means of classifying greases in accordance with their worked
units when reporting or specifying penetration vEilues.) Firm consistency. This scale is shown in Table 2 in order of in-
greases have low-penetration values, whereas soft greases creasing hardness. The majority of greases used in automo-
have high-penetration values. tive and industrial applications fall in the range of NLGI No.
Full-scale penetration tests require about 500 g (1 lb) of 1 to NLGI No. 3.
sample. The penetration number for smaller samples of
grease can be determined by using ASTM D 1403 (IP310),
Test Methods for Cone Penetration of Lubrication Grease Us- Consistency Stability
ing One-Quarter and One-Half Scale Cone Equipment. The The consistency of a grease may change with its history.
one-quarter and one-half scale tests require about 5 and 50 g Some greases may harden with age; others may change due
samples, respectively. As might be expected, the reduced- to wide fluctuations in temperature. Evaluation of these
scale tests are not as precise as the full-scale tests. Reduced- changes needs to be on an individual basis. That is, the test
scale penetration values are not normally used as such; in- grease needs to be subjected to controlled aging or tempera-
stead, equations are given to convert the reduced-scale ture fluctuations, with penetration measurements taken peri-
penetrations to equivalent full-scale values. Recent advances odically.
in instrumentation, such as automatic and digital Penetrom- The consistency of greases may also change in service due
eters, have helped improve the precision of this test method. to changes in the size and dispersion of thickener particles re-
The following paragraphs describe the several types of pene- sulting from mechanical shearing. The ability of a grease to
tration measurements. resist changes in consistency during mechanical working is
Unworked Penetration—This value is obtained when a pen- referred to as consistency stability, shear stability, work sta-
etration measurement is made on a grease transferred from bility, or mechanical stability. Two test methods have been
the original container to the standard grease worker cup, standardized to evaluate the stability of a grease resulting
with only a minimum amount of disturbance. This result is from two degrees of low-shear working.
not always reliable, because the amount of disturbance can-
Prolonged Worked Penetration & Low Temperature
not be controlled or repeated exactly. This measurement may
Penetration
be significant to indicate consistency variances in transfer-
ring grease from container to equipment. ASTM D 217 (IP50), described previously, is used before and
after prolonged working in a grease worker to determine the
Worked Penetration—Worked penetration is the standard
change in grease consistency. Because shear rates are low,
penetration measurement for a grease. It is measured after a
evaluation of shear stability by prolonged working is time
grease has been worked for 60 double strokes in the standard
consuming (working 100000 strokes takes nearly 28 h). Me-
grease worker. This method is more reliable than unworked
chanical grease workers with cut off timers help make this a
penetration, because the disturbance of the grease is stan-
little more manageable task, however, this test is not exten-
dardized by the prescribed working process. A significant dif-
sively used anymore.
ference between unworked and worked penetration can indi-
cate poor shear stability—and indicate a need for further
evaluation by prolonged working or roll test (see the Shear
Stability section).
TABLE 2—NLGI consistency classification.
Prolonged Worked Penetration—This value is obtained after NLGI ASTM Worked
a sample has been worked for a prolonged period in the Consistency No. Penetration at 25°C
grease worker, i.e., 10000, 50000, 100000, etc., double 000 445-475
strokes. After prolonged working, the sample and worker are 00 400-430
brought back to penetration test temperature 25°C (77°F) in 0 355-385
1.5 h. It is then worked for 60 double strokes and the pene- 1 310-340
tration is measured. This test is significant because it can in- 2 265-295
3 220-250
dicate the degree of shear stability of a grease. 4 175-205
Block Penetration—If a grease is firm enough to hold its 5 130-160
6 085-115
shape, it is not transferred to a worker cup container for test.
Roll Stability The trident probe test gives information not obtained with
Results can be obtained more quickly with the roll stability the dropping point test. The dropping point test (to be de-
test, which operates at somewhat higher shear conditions. scribed subsequently) determines the temperature at which
Roll stability is determined by ASTM D 1831, Test Method for the first drop of material drops from the orifice of the stan-
Roll Stability of Lubricating Grease. It is used in conjunction dard cup. That first drop may be "melted" grease or leeiked
with the reduced-scale penetration test [D1403 (IP310)]. fluid. For example, if a grease becomes so fluid that it drops
from the cup, the trident probe test will show a low viscosity
After a worked penetration has been measured on a grease
at the same temperature. In another case at the same tem-
sample, 50g of the worked grease is transferred into a hori-
perature, where it is only oil that drops from the cup, the tri-
zontally-mounted cylinder containing a 5-kg (11-lb) steel
dent probe will show a higher viscosity than the first case, in-
roller. The cylinder is rotated at 165 r p m for 2 h. The inner
dicating that the grease is still firm.
roller rolls over the grease, working it during the test. After
the test, the penetration of the grease is once again measured The results of this test provide a n indication of the flow
by D 1403, and the change between before and after penetra- properties of a grease between room a n d elevated tempera-
tions gives a n indication of shear stability. Recent trend (last tures. Although the test does not give actual flow rates, as in
few years) has been to run the roll stability tests at elevated a pipeline, it provides a means for obtaining some indication
temperatures, often even above 100°C, instead of the conven- of this property. This test is used more for grease develop-
tional room temperature tests, to help evaluate the roll sta- ment, rather than for specifications.
bility of greases at a higher temperature.
Apparent Viscosity
Roll stability tests are widely used in specifications. Test re-
sults are significant insofar as they can show a directional Grease is by nature a non-Newtonian material. It is charac-
change in consistency that could occur during service. No ac- terized by the fact that flow is not initiated until stress is
curate correlation between roll-test results and actual service applied. Increases in shear stress or pressure produce dis-
performance has been established. proportionate increases in flow. The term apparent viscosity
is used to describe the observed viscosity of greases; it is
In both shear stability tests, the change in consistency is re-
measured in Poises in D 1092, Test for AppEirent Viscosity of
ported as either the absolute change in penetration values or
Lubricating Greases. Since apparent viscosity varies with
the percent change as outlined in ASTM D 1831. If absolute
both temperature and shear rate, the specific temperature
values are to be reported, the quarter-scale values are first
and shear rate must be reported along with the measured
converted to full-scale values.
viscosity.
In this test, a sample of grease is forced through a capillary
Flow Properties tube by a floating piston actuated by a hydraulic system us-
ing a two-speed gear p u m p . From the predetermined flow
The consistency of a grease is a critical p a r a m e t e r which rate cind the force developed in the system, the apparent vis-
helps define the ability of a grease to perform under given op- cosity is CcJculated using the classic Poiseuille equation. A se-
erating conditions. Consistency, as measured by penetration, ries of eight capillaries and two p u m p speeds provide 16
is affected by temperature. But the penetration test is not shear rates for the determination of apparent viscosities. The
suitable for determining the minor, yet sometimes signifi- results are expressed in a log-log graph of apparent viscosity
cant, changes in consistency as the grease approaches tem- as a function of shear rate at a constant temperature, or ap-
peratures at which phase changes in the thickener occur. parent viscosity at a constant shear rate as a function of tem-
Penetration is basically a flow measurement; in addition, perature.
there are other flow-measurement tests that can be utilized to
This apparatus also has been used to measure the pressure
evaluate this property at other conditions.
drops of greases u n d e r steady-flow conditions at constant
temperature. Such information can be used to estimate the
Flow Properties at High Temperatures pressure drop or required pipe diameters in distribution sys-
ASTM Test Method D 3232, Measurement of Flow Properties tems. Also, apparent viscosity data are useful for evaluating
of Lubricating Greases at High Temperatures, can be used to the ease of handling or pumping at specified temperatures of
evaluate flow properties of lubricating greases under high- dispensing systems; it is often used to evaluate pumpability
t e m p e r a t u r e , low-shear conditions. Using this method, a at low temperatures. (The NLGI can provide a group of
grease sample is packed into a n annular channel in an alu- charts that relate pressure drop, apparent viscosity, shear
m i n u m block. The packed block is placed on a hot plate ca- rate, and pipe-flow data.) Apparent viscosity also is used to
pable of attciining temperatures in excess of 315°C (600°F) at provide an indication of the directional value of starting and
a heating rate of 5 ± r C (10±2°F)/min. A special trident running torques of grease-lubricated mechanisms. Specifica-
probe spindle, attached to a Brookfield-RVF viscometer, is tions may include limiting values of apparent viscosity for
lowered into the grease sample, and the hot plate is turned greases to be used at low temperature.
on. Simultaneously, the spindle is rotated at a constant 20 Currently an ASTM Round Robin is being conducted to
rpm, and torque measurements are read from the viscometer rewrite the U.S. Steel Grease Mobility test method under the
every minute. Readings are continued until the reading drops aegis of ASTM. The Low Temperature grease mobility test
below 0.5 on the viscometer scale or until the maximum sam- method utilizes only one capillary tube, maintained at vari-
ple temperature of interest is attained. With these data and ous temperatures. The amount of grease collected in a spe-
a n appropriate conversion equation, a plot of apparent vis- cific time (gms/minute) is measured and used as an indica-
cosity versus temperature is prepared. tion of the mobility of the grease. The test is easier to conduct
t h a n ASTM D 1092, and uses axi apparatus similEir to the ap- different low-temperature characteristics. It is used for
parent viscosity test method. specification purposes, a n d it is one of the automotive
grease performance tests required by D 4950. It is not
Low-Temperature Torque (Ball Bearings) known to correlate with other types of service. It should be
Greases designed for low-temperature applications must not noted that greases having such characteristics that permit
stiffen or offer excessive resistance to rotation. However, torque evaluations by either D 1478 or D 4693 will not give
greases harden emd become more viscous as the temperature the same values in the two test methods (even when con-
is lowered. Sometimes the grease can become so rigid in the verted to the same torque units) because the apparatus and
bearing t h a t excessive torque is required for rotation. In test bearings are different.
extreme cases, the grease can solidify to the point of bearing D 4693 determines the extent to which a grease retards the
lock-up. Two standard test methods are available to measure rotation of a specially-manufactured, tapered roller bearing
bearing torque at low temperatures. Both operate on the assembly. The test unit is a model device that closely dupli-
same principle—the restraining force or torque is measured cates an automotive wheel bearing assembly. Additionally, it
while grease-lubricated test bearings are r u n at low speed. employs a spring-loading m e c h a n i s m to improve test re-
The tests differ in the size and types of bearings, the intended peatability; and it is not intended to simulate any service-load
applications, and types of greases (i.e., in viscosity character- condition. Although the test assembly cind torque-measuring
istics). transducer are necessarily inside the cold-test chamber, the
ASTM D 1478, Test Method for Low-Temperature Torque drive mechanism can be either inside or outside.
for Ball Bearing Greases, measures the starting and running In this test, a sample of test grease is stirred and worked,
torque of lubricating greases packed in small ball bearings at and a specified a m o u n t is packed into the two test bearings.
temperatures as low as —54°C (—65°F). In this procedure, The test assembly is heated to mitigate the effects of grease
fully packed bearings are installed on a spindle that can be history; it is then cooled at a specified rate to —40°C (—40°F).
rotated at 1 rpm. The assembly is inserted in a cold box. The A drive m e c h a n i s m rotates the spindle at 1 rpm, a n d the
outer race is connected by a cord assembly to a spring scale, torque required to prevent rotation of the h u b is measured by
which measures the restraining force. When the m o t o r is a strain gage load cell at precisely 60 s after start of rotation.
started, the initial, peak restraining force is recorded. After The results are recorded on a strip chart or using a data ac-
running for 10 min, the restraining force is recorded again. quisition system that can be displayed and stored via com-
The force values are multiplied by the length of the lever arm, puter. (Starting torque was found to be less repeatable, as
and the products are reported as the starting and running well as a redundant measurement, and is not determined in
torque in gram-centimeters (g-cm). [Because the cgs (cen- this test.)
timeter-gram-second) metric unit, g-cm, is nearly universally
used in grease specifications, it is the standard unit of torque
measurement for this test; some newer specifications require Heat Resistance
the SI torque unit, N-m (Newton-meter).] In the past several Heat affects greases in several ways. As the temperature in-
years, advances in data acquisition techniques have helped in creases, greases soften and flow more readily (see description
making these test methods easier to r u n and have improved of D 3232); oxidation rate increases (see description of D
precision and reliability. 942); oil evaporation increases (see descriptions of D 972 and
Because this method was developed using greases with ex- D 2595); the thickener melts or loses its ability to retain oil
tremely low-torque cheiracteristics at - 5 4 ° C (-65°F) it may (see descriptions of D 566 and D 2595). Sometimes these phe-
not be applicable to other greases, speeds, or temperatures. If n o m e n a are all involved simultaneously (see descriptions of
a machine has significantly more power available than is ac- D 3336, D 3337, and D 3527).
tually required, torque is not an important consideration. On
the other hand, it can be very i m p o r t a n t in low-powered Dropping Point
equipment. This test is significant because it provides a The dropping point of a grease is the temperature at which it
means of comparing the low-temperature torque effects of passes from a semi-solid to a liquid. Although a thickener can
widely different greases. It is useful in the selection of greases have a definite melting point, the resulting grease does not.
for low-powered mechanisms, such as instrument bearings Rather, the thickener loses its ability to function as a grease
used in aerospace applications. The suitability of this method thickener as the temperature is increased. As the temperature
for other applications requiring different loads, speeds, and is raised, the grease softens to the extent that it loses its self-
temperatures should be determined on an individual basis. supporting characteristic, the structure collapses, and the
Usually, test conditions are substantially different from those grease flows under its own weight. When this phenomenon
found in service, so test results may not correlate with actUcJ takes place in a standard cup under standard conditions, it is
service performance. called the dropping point.
Two similar procedures are used to determine the drop-
Low-Temperature Torque (Tapered Roller Bearings) ping point of grease. In both methods, a prescribed layer of
For applications using larger bearings or greater loads, grease is coated on the inner surface of a small cup whose
D 4693 Test Method for Low-temperature Torque of Grease- sides slope toward a hole in the bottom. With ASTM D 566
Lubricated Wheel Bearings, is better suited than D 1478. (IP132), Test Method for Dropping Point of Lubricating
D 4693 can be used to predict the performance of greases Grease, the sample is heated at a prescribed rate until a liq-
in automotive wheel bearings operating at low tempera- uid drop falls from the cup. In ASTM D 2265, Test Method for
tures. It will differentiate among greases having distinctly Dropping Point of Lubricating Grease Over Wide Tempera-
ture Range, the sample is introduced into a preheated envi- Evaporation Loss Over Wide Temperature Range
ronment so that the heating rate is controlled more uni- D 2595, Test Method for Evaporation Loss of Lubricating
formly. In both tests, the difference in temperature between Greases over Wide Temperature Range, augments D 972,
the grease in the cup and the environment are taken into ac- which is limited to 150°C (300°F), and was developed because
count when calculating the dropping point of the grease. of higher service temperatures. D 2595 can be used to deter-
Some greases containing non-soap thickeners may not sepa- mine the loss of volatile materials from a grease over a tem-
rate oil or melt. perature range of 93-316°C (200-600°F). This test uses the
Cooperative testing indicates that dropping points by same sample cup as D 972, but the rest of the apparatus is
Methods D 566 and D 2265 generally agree up to about 260°C markedly different. It uses an aluminum block heater, instead
(500°F). In cases where results differ, there is no known sig- of an oil bath, to achieve much higher temperatures. The other
nificance. test conditions, i.e., air flow rate and test duration, remain the
The dropping point is useful (1) in establishing bench same. Laboratories equipped with D 2595 do not need D 972;
marks for quedity control, (2) as an aid in identifying the type the results will be similar, but not necessarily identical.
of thickener used in a grease, and (3) as an indication of the Within their respective temperature constraints, both tests
maximum temperature to which a grease can be exposed can be used to compare evaporation losses of greases in-
without complete liquefaction or excessive oil separation. tended for similar service. All other factors being equal,
(For simple soap greases, the maximum usable temperature greases having the least evaporative losses will probably per-
is about 20-30°C lower than the dropping point. For complex form longer in high-temperature service. Results of these
soap grease, the maximum usable temperature is limited by evaporation tests may not be representative of volatilization
the base oil characteristics, and under dynamic conditions that can occur in service.
seldom exceeds 175°C. Some complex soap greases will tol-
erate intermittent operation at higher temperatures, and al- Oil Separation (Static Bleed Test)
though they may liquefy somewhat, their structure will re-
form as the temperature is reduced.) Nearly all greases will separate some oil during storage, but
they differ markedly in the amounts that are liberated. If a
Greases normally do not perform satisfactorily at temper- grease separates too much oil, the grease could harden to the
atures near or above the dropping point; other factors are in- extent that lubrication will be affected. Opinions differ on
volved. High-temperature performance can depend on the whether or not lubrication depends on oil bleeding; greases
application method and frequency, whether a softened that do not separate some oil during operation can be noisy
grease is retained at the point of application by proper seals, in service. However, excessive liberation of free oil during
and whether the high temperature is continuous or intermit- storage is to be avoided. Oil can be released from a grease at
tent. High temperature stability and evaporation properties varying rates depending on the gel structure, the nature and
of the grease also can affect performance. viscosity of the lubricating fluid, and the applied pressure
Dropping point is most useful as a quality-control tool. Un- and temperature.
less correlation has been established, dropping point has no ASTM D 1742, Test Method for Oil Separation from Lubri-
direct bearing on service performance. Performance at high cating Greases During Storage, is used to determine the ten-
temperature would be better evaluated with one of the per- dency of lubricating greases to separate oil when stored at
formance-type tests or by actual experience. 25°C (77°F) at an applied air pressure of 1.72kN/m^ (0.25psi).
It gives an indication of the oil retention characteristics of lu-
Evaporation Loss bricating greases stored in both normally-filled and partially-
Exposure of a grease to high temperatures can cause evapo- filled containers. This test is not suitable for use with greases
ration of some of the liquid lubricant, thus causing the re- softer than NLGI No. 1 consistency because of a tendency for
maining grease to become drier and stiffer or leading to other the grease to seep through the screen.
undesirable changes in the grease structure. Greases con- The test is useful because the results correlate directly
taining low-viscosity oils for good low-temperature perfor- with oil separation, which occurs in 16-kg (35-lb) containers
mance may be susceptible to evaporation losses at higher of grease stored at room temperature. Storage in other con-
temperatures. Evaporation also can cause problems where tainers gives similar results. This test should not be used to
vapors may be hazardous or combustible, or interfere with predict the oil separation of grease under dynamic service
operations. In most applications, even high-temperature ap- conditions. (See Standards Under Development, Cone Test,
plications, evaporation is not a serious problem because of for a description of an elevated-temperature, static bleed
effective sealing. However, when it is necessary to evaluate test.)
evaporation loss, two ASTM test methods are available.
Oil Separation (Centrifuge Test)
Evaporation Loss of Greases and Oils ASTM D 4425 describes a procedure for determining the ten-
D 972, Test Method for Evaporation Loss of Lubricating dency of lubricating grease to separate oil when subjected to
Greases and Oils, determines mass evaporative losses from high centrifugal forces. The results can be related to grease
greases or oils at any temperature in the range of 100-150°C performance in shaft couplings, universal joints, and rolling
(210-300°F). A weighed sample of lubricant is placed in an element thrust bearings subjected to large or prolonged cen-
evaporation cell in an oil bath at the desired test temperature. trifugal forces. Results correlate well with actual service per-
Heated air at a specified flow rate is passed over the sample formance.
surface for 22 h, after which, the loss in sample mass is de- In this test, pairs of centrifuge tubes are charged with test
termined. grease and placed in a high-speed centrifuge. The grease sam-
pies are subjected to a centrifugal force equivalent to a rela- then pressurized to 758kPa/cm^ (llOpsi) with oxygen. The
tive centrifugal acceleration, G value, of 36000 at 50°C. (The bomb is heated in a bath at 99°C (210°F) to accelerate oxida-
units for the G value are awkward and not used, but they have tion. The amount of oxygen absorbed by the grease is
acceleration dimensions of length/time'^.) The normal test recorded in terms of pressure drop over a period of 100 h and,
duration is 24 h, but it can be extended to 48 or 96 h. At these in some cases, 500 or 1000 h. The pressure drop is a net re-
specified time intervals, the centrifuge is stopped, and the sult of the consumption of oxygen by oxidation of the grease
amount of separated oil is measured and the volume percent and the gain in pressure due to any gases or volatile by-prod-
calculated. The resistance-to-separation index, called the ucts released from the grease.
K36 value, is reported as the volume percent of separated Care must be exercised in the interpretation of data derived
oil/total test hours (both actual values are reported as a frac- from the oxidation bomb test. Additives incorporated into the
tion; the fraction is not to be reduced). grease can produce misleading results because they can also
react with oxygen. As an example, sodium nitrite is some-
Leakage from Wheel Bearings times added to grease to serve as a rust inhibitor. In the oxi-
There are two tests to evaluate leakage of grease from wheel dation bomb test, this material consumes oxygen to form
bearings at high temperatures. The older test, D 1263, Test sodium nitrate. In this instance, the drop in pressure is not
Method for Leakage Tendencies of Automotive Wheel Bear- indicative of the amount of oxidation of the grease alone.
ing Greases, utilizes a modified automotive front hub assem- Also, greases containing excess carbonate can release CEirbon
bly (1940s vintage design and bearings). The two bearings are dioxide gas whose vapor pressure will tend to offset the pres-
packed with a specified amount of test grease, and an addi- sure decrease due to oxygen absorption.
tional 85g is distributed in the hub. The assembly is run at The bomb oxidation test was originally designed to predict
660 rpm for 6 h at 104°C (220°F). After the test, the amount shelf storage life of greases in prepacked bearings. Whatever
of grease that leaked into the hubcap and collector is its original intent, experience has shown little correlation
weighed. The bearings are washed and examined for varnish, with the stability of grease films in bearings or on other parts.
gum, and lacquer-like materieJ. It predicts neither the stability of greases stored in containers
ASTM Test D 1263 provides a means to differentiate among for long periods nor those used under dynamic conditions.
grease products with distinctly different leakage characteris- Its primary usefulness is for quality control to indicate batch-
tics. In addition, skilled operators can observe significant to-batch uniformity. It can be used to estimate relative oxi-
changes in other grease characteristics that may have oc- dation resistance of greases of the same type, but it should
curred during the test. However, these observations are sub- not be used to compare greases of different types.
ject to differences in personal judgment and cannot be used Although widely used for specification purposes, it is im-
for quantitative ratings. The test does not distinguish between portant to note that D 942 has been severely criticized for its
wheel bearing greases having similar or borderline leakage. potential for misleading results and for having no relation to
oxidation in service. There are no standard, dynamic oxida-
Accelerated Leakage from Wheel Bearings tion tests. For dynamic tests that are influenced to a greater
ASTM D 4290, Test Method for Determining Leakage Ten- or lesser extent by the oxidation resistance of the grease, see
dencies of Automotive Wheel Bearing Grease Under Acceler- descriptions of D 3336, D 3337, and D 3527.
ated Conditions, uses the same principle of operation as does
D 1263. It is, however, a more modem test that uses a model PDSC Oxidation Test
front wheel-hub-spindle assembly employing current pro- A number of grease test methods have recently been devel-
duction, tapered roller bearings. The test apparatus is identi- oped by the ASTM grease committee, one of them being the
cal to that used in D 3527 (however, the test conditions are PDSC (pressure differential scanning calorimetry) technique
markedly different). In D 4290, the test temperature, 160°C for evaluating oxidation stability. In this test, a few mg of
(320°F), is significantly higher, and the duration, 20 h, is grease is placed in a sample pan in a bomb, which is pressur-
much longer than that of D 1263. ized to 3.5MPa (500psi) with oxygen and regulated at that
D 4290 was developed to evaluate wheel bearing leakage of pressure until an exothermic reaction occurs. From a plot of
greases intended for use in vehicles equipped with disk heat as a function of test time, the oxidation induction time
brakes, which involve much higher operating temperatures. (called extrapolated onset time) is determined. This method
It is used in grease specifications for such applications, and of evaluating oxidation stability has two significant advan-
it is one of the performance tests required by D 4950. This tages over D 942: 1) It is considerably faster, generally less
test is not known to correlate with any other type of service. than an hour, vs. 100 h or more, and 2) unlike D942, this
method is not subject to false values from greases that give off
carbon dioxide or other gases during heating. The disadvan-
Oxidation Stability tages are that the apparatus is expensive, and like D942 the re-
Bomb Oxidation Test sults are not known to correlate with service performance.
The Standard Test Method for Oxidation Stability of Lubri- Another test being developed is the thin film microoxida-
cating Greases by the Oxygen Bomb Method, D 942 (IP142), tion test, which has been shown in literature to provide a
determines the resistance of lubricating greases to oxidation good indication of the oxidation stability of a grease sample.
when stored statically in an oxygen atmosphere in a sealed
system at an elevated temperature. In this test, five glass Greases in Ball Bearings at Elevated Temperatures
dishes are filled with 4g of grease, each, for a total of 20g. ASTM D 3336, Test Method for Performance Characteristics
These dishes are then racked and sealed in a bomb, which is of Lubricating Greases in Ball Bearings at Elevated Temper-
atures, is used to evaluate the performance characteristics of Extreme Pressure and Wear
lubricating greases in ball bearings operating u n d e r light
loads at high speeds cind elevated temperatures for extended A lubricant functions by separating bearing surfaces. If the
periods. Correlation with actual field service cannot be as- separation was always complete, parts would never wear.
sumed. This method has been criticized for having two test However, the integrity of the lubricant film cannot be main-
spindles qualified that purportedly do not necessarily give the tained u n d e r all conditions, and contact occurs to varying de-
same results. grees. Such contact depends on operating conditions (such as
In this test, the lubricating grease is evaluated in a 20-mm, load and speed), lubricant properties (such as fluid viscosity
SAE No.204, heat resistant, steel ball bearing rotated at and grease consistency), and lubricant chemistry (such as the
10000 r p m under light loads of 22-67N (5-151bf) at a speci- presence of wear inhibitors and extreme pressure additives).
fied elevated temperature u p to 370°C (700°F). The test is r u n Several tests are available for evaluating the antiwear and
on a specified, test-temperature-dependent, operating cycle load-carrying properties of greases.
until lubrication failure or completion of a specified time.
(Unless automatic controls Eire used, a 72-h weekend shut- Extreme Pressure Timken Method
down is required.) With superior greases, tests can last u p to ASTM D 2509, Test Method for Measurement of Extreme
several thousand hours. Multiple tests need to be r u n because Pressure Properties of Lubricating Grease (Timken Method),
the results follow Weibull, rather than normal, distributions. can be used to determine the load carrying capacity of a
grease at high loads. Non-stemdard techniques have been de-
Greases in Small Bearings vised to measure wear at lighter loads, but they are not dis-
The computer and aircraft industries have used miniature cussed.
bearings for many years. As the trend toward miniaturiza- In the Timken test, a tapered roller bearing cup is rotated
tion increased in other industries, a suitable test was needed against a stationary, hardened steel block. Both parts are lu-
to evaluate lubricating greases in small bearings. ASTM D bricated with the test grease prior to starting the test. During
3337, Test Method for Evaluation of Greases in Small Bear- the test, the p a r t s are continuously lubricated with fresh
ings, was developed to serve this purpose. Although this test grease by means of a feed mechanism. Using a lever system
is not the equivalent of long-term service-performance tests, with a ten-fold mechanical advantage, fixed weights apply a
it can be used to predict relative grease life at high temper- force to the block in line contact with the rotating cup. Loads
ature in a reasonable test period. Also, this test can measure are applied step-wise until lubrication failure occurs, as evi-
running torque at both one r p m and 12000 r p m if this prop- denced by inspection for scoring or welding. The "OK Value"
erty is significcmt for the intended application. The method is the m a x i m u m load the lubricant film will withstand with-
will not differentiate among greases of closely related char- out rupturing and causing scoring in the contact zone after a
acteristics. 10-min. run.
ASTM D 3337 determines grease life and torque in a small This test is a rapid method that can be used to differentiate
(6.35mm bore) R-4 ball bearing. In this test the bearing is run between greases having low, medium, or high levels of ex-
at 12000 r p m with a 2.2N (1/2-lbf) radial and a 22N (51bf) ax- treme pressure properties. It is widely used for specification
icJ load. While a test temperature of 250°C (or 500°F) may be purposes; however, the results may not correlate with service
typiccJly specified, the equipment is capable of testing u p to performance.
315°C (600°F) if high-temperature bearings are used.
Extreme Pressure Four-Ball Test
Wheel Bearing Grease Life ASTM D 2596, Test Method for Measurement of Extreme
With the advent of automotive disk brakes in the 1960s, then Pressure Properties of Lubricating Grease (Four-Ball
c u r r e n t test m e t h o d s proved inadequate for evaluating Method), is another test used to determine the load-carrying
greases for this high-temperature application. A specific, cor- properties of lubricating greases. With this procedure two
relating test method was needed, and after several yeeirs of evaluations are made: (1) the Load-Wear Index (formerly
development, one was standardized. ASTM D 3527, Standard called Mean-Hertz Load), and (2) the Weld Point.
Test Method for Life Performance of Automotive Wheel This test was developed to evaluate the extreme pressure
Bearing Greases, evaluates grease life in a tapered roller, and antiweld properties of a lubricant. The tester is operated
wheel bccirings in a model, front wheel assembly r u n at 1000 with one steel bcdl rotated under load against three like bsJls
rpm, under a thrust load of 11 IN, at 160°C, using a cycle of held stationary in the form of a cradle. The grease under test
20 h on and 4 h off. The test apparatus is the same as that of covers the contact area of the four balls. Loads u p to 800 kgf
D 4290, b u t the operating conditions a n d measured peirame- (7845N, 17601bf) can be applied to the balls to achieve unit
ters are quite different. pressures u p to 6.9 X lO^kPa (1 000 000 psi).
Motor torque is monitored, and the test is terminated at a The procedure involves the running of a series of 10-second
calculated, preset torque vEilue. Grease life is indicated by the tests over a range of increasing loads until welding occurs.
n u m b e r of "on" hours (or n u m b e r of cycles) to failure. This is During a test, scars are formed in the surfaces of the three
a severe test; the results are influenced by a combination of stationary balls. The diameter of the scar depends on the
grease properties, such as oxidation stability, shear stability, load, speed, test duration, and lubricant. The scars are mea-
and volatility. As with D 3336, multiple tests need to be r u n sured under a microscope having a calibrated grid. From the
because the results follow Weibull distributions. This test scetr measurements, the Load-Wear Index is calculated. The
method is used for specification purposes and is required by lowest load at which the rotating ball seizes and then welds
D 4950. to the stationary balls is called the weld point; it indicates
that the load carrying capacity of the grease has been ex- A related, but somewhat different, phenomenon often ac-
ceeded. companies fretting wear. False brinelling is localized fretting
The significance of this test is that it is a rapid method that wear that occurs when the rolling elements of a bearing vi-
can be used to differentiate a m o n g greases having low, brate or oscillate with small amplitude while pressed against
medium, or high levels of extreme pressure properties. It is the bearing race. The mechanism proceeds in stages: 1) as-
widely used for specification purposes, b u t the results may perities weld, are torn apart, and the wear debris which is
not correlate with service performance. Because of their poor subsequently formed is oxidized; 2) due to the small-ampli-
lubricity, some lubricating greases containing a silicone or a tude motion, the oxidized detritus cannot readily escape, and
halogenated silicone fluid component are not suitable for being abrasive, the oxidized wear debris accelerates the wear.
testing by this test method. As a result, wear depressions are formed in the bearing race.
These depressions are often polished and appear similar to
Wear Preventive Characteristics of Grease the Brinell depressions obtained with static overloading,
ASTM D 2266, Test Method for Wear Preventive Characteris- hence the term, false brinelling. D 4170 cannot distinguish
tics of Lubricating Grease (Four-Ball Method) is used to de- between false brinelling and fretting wear. If false brinelling
termine the wear-preventive characteristics of greases in slid- does occur, it is included in the determination of fretting
ing steel-on-steel applications. This test does not distinguish wear when bearing race mass losses are measured.
between EP and non-EP greases. This test correlates with the fretting performance of
As in D 2509, a four-ball configuration is used, but there greases in wheel bearings of passenger cars shipped long dis-
are few other similarities as the apparatus and operating con- tances. D 4170 also has been used to predict grease perfor-
ditions are conspicuously different. Wear prevention quali- mance in automobile drivelines. It is used for specification
ties are evaluated from the diameters of the wear scars that purposes and is one of the performance tests required by D
occur on the stationary balls during the test. 4950.
The test is significant because it can be used to determine
the relative wear-preventing properties under the test condi- Oscillating Motion
tions, so it is useful for grease development. D 2266 is widely There is another wear test involving oscillatory motion,
used in grease specifications, but its actual usefulness is sus- namely, ASTM D 3704, Test Method for Wear Preventive
pect because of the following limitations. If test conditions Properties of Lubricating Greases Using the Block on Ring
are changed, the relative ratings may change. Test Machine in Oscillating Motion. Ring and block parts,
1. Wecir characteristics are not predicted for metal combina- similar to those of the Timken Tester (D 2509), are operated
tions other than AISI (American Iron and Steel Institute) u n d e r varying conditions of load, speed, oscillation angle,
E52100 steel unless non-stcindard balls of other materials time, temperature, and specimen surface finish and hardness
are used. to simulate service conditions. This test can distinguish
2. No differentiation can be made between extreme pressure among greases of low, medium, and high wear preventive
and non-extreme pressure greases. properties and can be used for grease development. The user
3. No correlation can be inferred between the results of the should determine whether test results correlate with service
test and field service unless such correlation has been es- performance or results from other bench test machines.
tablished.
Oscillating Wear (SRV) Test
Fretting Wear A high load, high frequency, low amplitude, high speed re-
Fretting wear is a form of attritive wear caused by vibratory versal test, using the SRV (Schwingung, Reibung, Ver-
or oscillatory motion of small amplitude. It is characterized schleiss) a p p a r a t u s simulates high-speed vibrational or
by the removal of finely-divided particles from the rubbing start-stop motions that occur in many mechanisms. Two pro-
surfaces. Air can cause immediate loccil oxidation of the cedures, using a ball-on-disk configuration, have been devel-
wear particles produced by fretting wear, and moisture can oped: [ASTM D 5706 (EP Test) and ASTM D 5707 (Wear)]
hydrate the oxidation product. In the case of ferrous metals, one to measure wear-protection qualities and coefficient of
the oxidized wear debris is abrasive iron oxide (Fe203) hav- friction, and the other to measure the ability of a grease to
ing the appearance of rust, which gives rise to the nearly- carry loads under extreme pressure. (This apparatus can use
synonymous terms, fretting corrosion and friction oxida- other configurations to suit different applications.) Both pro-
tion. cedures have been correlated with grease performance in au-
Fretting is a serious problem in industry. If severe enough, tomotive driveline mechanisms and are used in grease speci-
it can cause destructive vibrations, premature failures, and fications for these applications. These procedures can be
pcirts seizure. No grease can give total protection if fretting used to evaluate lubricants and materials for other applica-
conditions exist, but greases vary significcintly in their ability tions of similar motion.
to mitigate fretting wear. ASTM D 4170, Test Method for
Fretting Wear Protection by Lubricating Grease, evaluates Corrosion
grease performance in a proprietary test machine (Fafnir
Friction Oxidation Tester) which oscillates two grease-lubri- Copper Corrosion
cated, ball thrust bearings, u n d e r specified conditions of Lubricated parts that contain copper alloys, such as copper
load, speed, and angle. Fretting wear is determined by mea- or brass electrical components or bronze gears and bearings,
suring the mass loss of the bearing races (the balls Eind re- m a y be susceptible to the corrosive effects of formulated
tainers are not included). greases. For example, such corrosion can cause high resis-
tance in electrical contacts, or premature bearing failure bricating film. ASTM D 1264, Test for Water Washout Char-
from chemical attack. acteristics of Lubricating Greases, evaluates the resistance of
D 4048, Test Method for Detection of Copper Corrosion a lubricating grease in a bearing to washout by water.
from Lubricating Grease by the Copper Strip Tarnish Test, is This test method uses a standardized bearing, available
the grease analog of the more familiar D 130 used to evaluate from ASTM. It is a 204K Conrad-type, ball bearing equipped
oils. In this test, a prepared copper strip is totally immersed with shields but without seals. The bearing is packed with 4g
in test grease and heated at specified conditions, usually of test grease then rotated at 600 rpm while a jet of water, at
100°C (210°F) for 24 h. At the end of the test period, the strip either 38°C (100°F) or 79°C (175°F), impinges on the bearing
is removed, washed, and compared with the ASTM Copper housing for 1 h. The bearing is then dried, and the percent
Strip Corrosion Standards. grease loss by weight is determined.
Although this method is used in specifications, the user This test method serves only as a relative measure of the re-
must establish correlation between test results cind actual ser- sistance of a grease to water washout. It should not be con-
vice performance. This test does not determine the ability of sidered the equivalent of a service evaluation unless such cor-
a grease to inhibit copper corrosion caused by factors other relation has been established. Test results are affected by
than the grease itself; neither does it determine the stability of grease texture and consistency. Test precision is poor, espe-
grease in the presence of copper. The sole determination is the cially with soft greases. Although widely used, this test can
chemical staining of copper by lubricating grease. give misleading results. Even comparative results between
similar greases may not predict the relative performance of
Rust Prevention the two greases in actual service.
Greases must not be corrosive to metals they contact and
should not develop corrosion tendencies with aging or oxida- Water Spray-Off
tion. A method for assessing rust prevention by greases is ASTM D 4049, Test Method for Resistance of Lubricating
ASTM D 1743, Test Method for Corrosion Preventive Proper- Grease to Water Spray, is used to evaluate the ability of a
ties of Lubricating Greases. grease to adhere to a metal panel when subjected to direct
In this method, a tapered roller bearing is packed with water spray. Test results correlate directly with operations in-
grease, and following a short run-in period, dipped into dis- volving direct water impingement, such as steel mill roll neck
tilled water and stored above the water in 100% relative hu- bearing service and certain automotive body hardware appli-
midity at 52°C (125°C) for 48 h. The bearing is then cleaned cations.
and examined for corrosion. Either a Pass or Fail result is re- In this test, a 0.79 mm (1/32 in.) film of test grease is uni-
ported. formly coated onto a stainless steel panel; then water, at 38°C
The significance of this test is that it indicates those greases (100°F), is sprayed directly on the panel for 5 min. The spray
capable of preventing rust and corrosion in static or storage is controlled by specified spray nozzle, pump, and plumbing.
conditions. This test is widely used in grease specifications. After the spraying period, the panel is dried, weighed, and the
The correlation with service conditions, particularly under percentage of grease spray-off is determined.
static conditions, is considered to be quite good.
Accelerated Corrosion Tests Miscellaneous

Two test methods were recently worked on to evaluate the Contamination
corrosion protection properties of greases under severe con- ASTM D 1404, Test Method for Estimation of Deleterious
ditions. These are: 1) a version of D 1743 using synthetic sea Pcirticles in Lubricating Grease, defines a deleterious particle
water now called ASTM D 5969, and 2) two procedures of the as one which will scratch a polished plastic surface. The test
IP220/DIN51802 dynamic rust test [commonly known as the is applicable to all greases, even those containing fillers. In
EMCOR test (ASTM D 6138)], one using distilled water and fact, it can be used to test fillers, such as graphite, if they are
another using salt water. dispersed into a grease (or petrolatum) that is known to be
free of deleterious particles. It can be used also to test other
semi-solid or viscous-liquid substances.
Effect of Water
With this method, the test material is placed between two
Contamination by water can affect greases and grease per- clean, highly polished acrylic plastic plates held rigidly and
formance in several ways. Corrosion or rust protection, pre- parallel to each other in metal holders. The assembly is
viously discussed, is one. Other effects include change in con- pressed together by squeezing the grease into a thin layer be-
sistency, texture, or adhesiveness. An emulsion can be tween the plastic plates. Any solid particles in the grease
formed, which will probably be an inferior lubricant, or it larger than the distance of separation of the plates and harder
could be washed away. Attempts to standardize means of than the plastic will become embedded in the opposing plas-
evaluating these effects have had mixed success. Two stan- tic surfaces. The apparatus is so constructed that one of the
dard tests do exist, however: the water washout test and the plates can be rotated about 30° with respect to the other
water spray-off test. while the whole assembly is under pressure. This will cause
the embedded particles to form characteristic arc-shaped
Water Washout scratches in one or both plates.
The ability of a grease to resist washout under conditions The relative number of such solid particles is estimated by
where water may splash or impinge directly on a bearing is an counting the total number of arc-shaped scratches on the two
important property in the maintenance of a satisfactory lu- plates.
The test has significcince because it is a rapid means for es- shear stability (either by prolonged working or by the roll
timating the n u m b e r of deleterious particles in a lubricating test, D 1831), oil separation (D 1742), and storage stability
grease. However, a particle that is abrasive to acrylic plastic (cheinge in consistency after prolonged storage, such as one
m a y not be abrasive to steel or other bearing materials. to six m o n t h s ) . Other tests, s u c h as D 3527 (life perfor-
Therefore, the results of this test do not imply performance mance), D 4290 (leakage), water spray-off (D 4049), etc. EJSO
in field service. should be r u n if the application warremts such. Incompati-
bility is indicated if any mixture tests worse t h a n the poorer
Elastomer Compatibility of the neat greases. The repeatability of the test methods
Nearly all grease-lubricated mechanisms have elastomeric must be tciken into consideration when making such deter-
seeds to retain lubricant zmd exclude contaminants. In order minations.
for these seals to function properly, the grease must be com-
patible with the rubber-like elastomer seal. ASTM D 4289, Static Bleed (Cone) Test
Test Method for Compatibility of Lubricating Grease with Federal Test Method (FTM) 791C, Method 321.3, static bleed
Elastomers, is a simple total immersion test designed to eval- test (also known as the cone test), was developed as ASTM
uate the compatibility of grease with elastomer specimens Standard D 6184. In this method, a 10-g sample of grease is
cut from standard sheets. It also can be used as a guide to placed in a 60-mesh wire cone, which is then suspended in a
evaluate compatibility of greases with rubber products not in covered bejiker and placed in a n oven at 100°C (212°F) for 30
standard sheet form. h (some specifications may require different temperatures or
Unlike other standard compatibility tests, which are de- durations). The amount of oil that bleeds from the grease col-
signed to evaluate elastomers in standard fluids, the empha- lects in the bejiker is weighed, and the percentage of sepa-
sis of D 4289 is the evaluation of the greases. Elastomer spec- rated oil is calculated. Some specifications require the cone
imens are cut from s t a n d a r d ASTM sheets (D 3182) a n d and residual grease to be weighed also, and the additional
immersed in test grease for 70 h at either 100 or ISO'C. Com- weight loss is reported as evaporation.
patibility is evaluated by determining the changes in volume
and DurometerA hardness (D 2240). (Volume is determined
by the water displacement method, D 471.) Chemical Analysis
The volume and hardness change values determined in this D 128, Test Methods for Analysis of Lubricating Grease, is
test do not duplicate the changes that occur in rubber seals in the premier standard for grease analysis. This procedure
actual service conditions. However, they can be correlated in gives flow diagrams and details for the analysis of conven-
many instances. For example, the volume-change values cor- tioneJ greases, i.e., those made of soap-thickened petroleum
related very well (r^ = 0.99) with those that occurred in a ve- oils. The constituents that can be determined are soap, un-
hicle test. Because of wide variations in grease and elastomer saponifiable matter (petroleum oil, etc), water, free alkalin-
formulations and service conditions, correlations between ity, free fatty acid, fat, glycerin, a n d insolubles. A supple-
this test and particular applications should be determined on mentary test method is provided for application to greases
an individual basis. that cannot be analyzed by conventional methods because of
This method provides for optional testing with two Refer- the presence of nonpetroleum oils or nonsoap thickeners.
ence Elastomers to evaluate relative compatibility. The re- These test procedures can be used to identify and estimate
sults CcUi be used to judge a service characteristic of lubricat- the a m o u n t of some of the constituents of lubricating
ing greases; in this respect, the test m e t h o d is useful for greases. The methods are applicable to many, but not all,
specification purposes. ASTM D 4950 requires testing with greases. Composition should not be considered as having a
Reference Elastomer CR (polychloroprene) cind Reference direct bearing on service performance unless such correla-
Elastomer NBR-L (acrylonitrile-butadiene). tion has been established.
D 128 references several useful, but nonstandard, methods
Compatibility that can be used for grease analysis. Infrzired Spectroscopic
Mixing of two different grease types often occurs when a (IR) analysis is commonly used for research purposes, qual-
mechanism is service lubricated with a type of grease dif- ity control, and specification purposes. But, a n IR method
ferent from that already in the bearing. If the two greases has not been standardized because the technique frequently
are incompatible, the likelihood is that lubrication will be must be adapted to the specific grease being analyzed.
inadequate and/or the lubrication life will be greatly short- Although D 128 is the general analytical method for
ened. greases, t h e r e are other test m e t h o d s for specific con-
The problem of incompatible grease mixtures has long stituents. These include the following:
been known. Foreknowledge of the chemistry of the greases • D 95—Test Method for Water in Petroleum Products and
is not often reliable in predicting compatibility. Compatibil- Bituminous Materials by Distillation
ity needs to be judged on a case-by-case basis. In light of this • D 129—Test Method for Sulfur in Petroleum Products
need, a standard practice was developed Eind is now our new (General B o m b Method)
ASTM method ASTM D 6185. • D 808—Test Method for Chlorine in New a n d Used
There are several non-standard means worthy of consider- Petroleum Products (Bomb Method)
ation, however. One such practice involves the preparation of • D 1317—Test Method for Chlorine in New and Used Lu-
three binary mixtures in concentrations of 10:90, 50:50, and bricants (Sodium Alcoholate Method)
90:10 mass ratios. These three mixtures and the two neat • D 3340—^Test Method for Lithium and Sodium in Lubri-
greases are then tested for dropping point (D 566 or D 2265), cating Greases by Flame Photometer.
DISCONTINUED STANDARDS nificance. The line call-out code will have the following for-
mat:
Severed standards have been discontinued since the 5th edi-
ISO-L-XSiS2S3S4N
tion of the Manual on Significance of Tests for Petroleum
Products. Unless otherwise noted, the reason for discontinu- where:
ance of the following test methods was lack of interest, i.e.,
the standcirds were no longer being used or supported by the ISO = identification of the standards organization
industry: L = designator for class (lubricants)
• D 1262—Test Method for Lead in New and Used Greases X = designator for family (grease)
(Discontinued 1991) Si = symbol for Lower Operating Temperature
• D 1402—Test Method for Effect of Copper on Oxidation 52 = symbol for Upper Operating Temperature
Stability of Lubricating Greases by the Oxygen Bomb 53 = symbol for Water Contamination
Method (Discontinued 1985) 54 = symbol for EP
• D 1741—Test Method for Functional Life of Ball Bearing N = NLGI consistency number
Greases (Discontinued 1991)
• D 3428—Test Method for Torque Stability, Wear, and Symbols (letters) are used to designate the four operating
Brine Sensitivity Evaluation of Ball Joint Greases (Discon- conditions. The Lower Operating Temperature is defined
tinued 1990). (D 3428 was withdrawn because the ball joint by symbols representing requirements at 0, -10, -20, —30,
used as the test piece was no longer available and a suitable —40, and <—40°C; the Upper Operating Temperatures is de-
substitute was not found.) fined by symbols representing seven temperatures from 60 to
>180°C. Nine symbols are used to define the effects of water,
which include both water contamination and antirust re-
STANDARDS UNDER DEVELOPMENT quirements. Only two symbols are used for the EP or load
carrying requirement.
Ignition Test Limits have been tentatively established for the operating
conditions. But, full implementation of IS06743-9 depends
Because grease fires in steel mills are a common occurrence, on the development of ISO standard test methods. National
there is a need for a standard method for evaluating the igni- standards must be converted to ISO format and approved by
tion and flammability characteristics of greases used in such the ISO community. The national standards proposed to ISO
applications. Techniques for evaluating these cheiracteristics are as follows:
are being developed. The procedure most likely to be evalu-
ated in round robin testing consists of placing a shaped sam-
ple of grease on a metal ramp; a methenamine tablet is in- Lower Operating NFT60-171 (France), a low-
serted in the grease and ignited. If the grease burns, the Temperature temperature penetration test.
characteristics of the fire (time to grease or oil ignition, bum Upper Operating ASTM D 566 and D 3336
time, fire size, self-extinguishing, etc.) are compared with ref- Temperature
erenced descriptions and assigned a rating. Water Effect ASTM D 1264 for Water Contami-
nation and DIN 51802 (Germany)/
IP220 (United Kingdom) for Rust
Protection
ISO STANDARDS EP (load carrying ASTM D 2596
capacity)
In 1987, ISO (International Standards Organization) pub-
lished ISO 6743-9, which is an international classification
system for grease. About 75% of commercial greases can be
described by this standard. This standard classifies lubricat- ASTM STANDARDS*
ing greases according to the operating conditions of the use—
unlike most other ISO product standards, which are classi- No. Title
fied according to specific end-use. The nature of greases D 217 Test Methods for Cone Penetration of Lubricating
allows a specific grease to be used in many applications. This Grease
makes it impractical to classify greases by end-use, and a D 566 Test Method for Dropping Point of Lubricating
properties description is a reasoned alternative. Conse- Grease
quently, users are advised to use ISO 6743-9 to define the req- D 942 Test Method for Oxidation Stability of Lubricating
uisite grease properties, but are they cautioned not to rely Greases by the Oxygen Bomb Method
solely on the standard for grease selection for a particular ap- D 972 Test Method for Evaporation Loss of Lubricating
plication. Rather, users are advised to consult with the grease Greases and Oils
supplier, as well. D 1092 Test Method for Apparent Viscosity of Lubricating
In this classification system, each grease will have one sym- Greases
bol only. This symbol should correspond to the most severe
conditions of temperature, water contamination, and load in
which the grease can be used. Grease products are designated
in a uniform manner, with each character having its own sig- ' Analytical standards not included.
D 1263 Test Method for Leakage Tendencies of Automo- bricating Grease Using the (Falex) Block on Ring
tive Wheel Bearing Greases Test Machine in Oscillating Motion
D 1264 Test Method for Water Washout Characteristics of D 4048 Test Method for Detection of Copper Corrosion
Lubricating Greases from Lubricating Grease by the Copper Strip Teir-
D 1403 Test Methods for Cone Penetration of Lubricating nish Test
Grease Using One-Quarter and One-Half Scale D 4049 Test Method for the Resistance of Lubricating
Cone Equipment Grease to Water Spray
D 1404 Test Method for Estimation of Deleterious Parti- D 4170 Test Method for Fretting Wear Protection by Lu-
cles in Lubricating Grease bricating Greases
D 1478 Test Method for Low-Temperature Torque of Ball D 4289 Test Method for Compatibility of Lubricating
Bearing Greases Grease with Elastomers
D 1742 Test Method for Oil Separation from Lubricating D 4290 Test Method for Determining the Leakage Tenden-
Grease During Storage cies of Automotive Wheel Bearing Grease Under
D 1743 Test Method for Corrosion Preventive Properties Accelerated Conditions
of Lubricating Greases D 4425 Test Method for Oil Separation from Lubricating
D 1831 Test Method for Roll Stability of Lubricating Grease by Centrifuging (Koppers Method)
Grease D 4693 Test Method for Low-Temperature Torque of
D 2265 Test Method for Dropping Point of Lubricating Grease-Lubricated Wheel Bearings
Grease Over Wide Temperature Range D 4950 Classification and Specification for Automotive
D 2266 Test Method for Wear Preventive Characteristics Service Greases
of Lubricating Grease (Four-Ball Method) D 5483 Test Method for Oxidation Induction Time of Lu-
D 2509 Test Method for Measurement of Extreme Pres- bricating Greases by Pressure Differential Scan-
sure Properties of Lubricating Grease (Timken ning Calorimetry
Method) D 5706 Test Method for Determining Extreme Pressure
D 2595 Test Method for Evaporation Loss of Lubricating Properties of Lubricating Greases Using a High-
Greases Over Wide-Temperature Range Frequency, Linear-Oscillation (SRC) Test Machine.
D 2596 Test Method for Measurement of Extreme-Pres- D 5707 Test Method for Measuring Friction and Wear
sure Properties of Lubricating Greases (Four-Ball Properties of Lubricating Grease Using a High-Fre-
Method) quency, Linear-Oscillation (SRV) Test Machine.
D 3232 Test Method for Flow Properties of Lubricating D 5969 Test Method for Corrosion Preventive Properties
Greases at High Temperatures of Lubricating Greases in the Presence of Dilute
D 3336 Test Method for Performance Characteristics of SjTithetic Sea Water Environments
Lubricating Greases in Ball Bearings at Elevated D 6138 Test Method for Determination of Corrosion Pre-
Temperatures vention Properties of Lubricating Greases Under
D 3337 Test Method for Evaluation of Greases in Small Dynamic Wet Conditions (EMCOR Test)
Bearings D 6184 Test Method for Oil Separation from Lubricating
D 3527 Test Method for Life Performance of Automotive Grease (Conical Sieve Method)
Wheel Bearing Grease D 6185 Standard Practice for Evaluating Compatibility of
D 3704 Test Method for Wear Preventive Properties of Lu- Binary Mixtures of Lubricating Greases
OTHER STANDARDS^
Standard No.
ISO DIN IP NF-T 60 FTM791b COST Characteristic/Property
2176 51801 132 102 1421 6793 Determination of Dropping Point
2137 51804/1-2 50 132 311 5346 Determination of Cone
Penetration
1/1 - 1/2 - 1/4 Cone
51805 Determination of Flow Pressure
51802 220 135 40001.2 5757 Corrosion Preventing Properties
2160 51811 112 5309.4 Corrosive Effects on Copper
51803 5 M 07-037 1461 Determination of Ash of
6474 Greases (Incl. Sulfate)
51809/1-2 37/137/139 133/112 Neutralization Number
51813 134 3005.3 6370 Content of Solid Foreign Matters
Effect of Water
51807/2 215 Water Washout Test
51807/1 Static Test
51808 142 3453 5734 Oxidation Stability
51817 121 321/2 7142 Oil Separation
1631
51814 Content of Base Oil and Soap
51815 M 07-38 Content of Li/Na/Ca by Atomic
Absorption Spectroscopy
(continues)
Standard No.
ISO DIN IP NF-T 60 FTM 791 b COST Characteristic/Property
199 Determination of Li/Na by Flame
Photometer
51831 3720/22 Determination of Solids
(Graphite or M0S2)
51832 9270 Determination of Particle Size of
Solid Lubricants
59 Density
183 9566 Evaporation Loss
3733 74 113 1044 Content of Water
2077
Pumpability Properties
51816/1 SheU-DeLimon Rheometer
51816/2 Decompression Characteristics
139 Apparent Viscosity
Roll Stability
Extreme Pressure Properties
51350-4/5 239 6503.2 Shell-Four-Ball Test
326 Timken Test
Mechanical Dynamic Testing
51806 331.2/333.1 SKF-R2F
168 Roller Bearing Performance
266 Churning
(51821/2) FAG-FE 8 (EP Greases)
(51821/1) FAG-FE 9
Wheel Bearing Leakage
186 Low Temperature Torque
Elastomer Compatibility
R868 53505 Hardness Change (Shore A)
1817 53521 3603.3 Volume Change
Tests on Base Oil
3104 51562 71 Viscosity
3016 51597 15 Pour Point
2592 51376 36 Flash Point
2977 51775/51787 2 Aniline Point
51820 E Infrared-Analysis
^ Reprinted with permission from The Lubrizol Corporation, Wickliffe, OH.
Institute (NLGI) Grease Education Advanced Course, Kansas

REFERENCES City, MO, 1998.
[6] "Lubricating Greases," Ch. 9, Manual on Significance of Tests for
[1] Polishuk, A. T., A Brief History of Lubricating Grease, Llewellyn Petroleum Products, 5th ed., G. V. Dyroff, Ed., ASTM Interna-
& McKane, Inc., Wilkes-Barre, PA, 1998. tional, West Conshohocken, PA, 1989.
[2] Boner, C. J., Manufacture and Application of Lubricating Grease, [8] Federal Test Method Standard No. 79IC: Lubricants, Liquid Fu-
Reinhold PubUshing Corp., NY, 1954. els, and Related Products: Methods of Testing, Available from
[3] Boner, C. J., Modem Lubricating Greases, Scientific Publications Global Engineering Documents, Irvine, CA, Sept. 30, 1986.
(G.B.) Ltd, Broseley, Shropshire, England, 1976. [9] "Index of the NLGI Spokesman," Compact Disk, National Lu-
[4] Lubricating Grease Guide, 4 * ed.. National Lubricating Grease bricating Grease Institute, Kansas City, MO, 2000.
Institute, Kansas City, MO, 1996. [10] Annual Book of ASTM Standards, Volumes 05.01, 05.02, 05.03,
[5] Ward, C. E., "Polyurea Greases," National Lubricating Grease ASTM International, West Conshohocken, PA.
MNL37-EB/Jun. 2003
Mineral Oil Heat Transfer Fluids

John Fuhr, ^ Jim Oetinger, ^ George E. Totten,^ and Glenn M. Webster^
BECAUSE OF COST AND POTENTIAL FOULING PROBLEMS, indirect The focus of this chapter will be on mineral oil derived heat
process heating designs are usually preferred over direct, tremsfer fluids. This discussion will include a basic overview
fuel-fired heating or individual electrically heated units [2]. of the heat transfer coefficient as a fluid chciracterization pa-
For indirect process heating, heat transfer is usually rameter followed by a discussion of fluid chemistry and the
accomplished by steam or by using a h e a t transfer fluid impact on properties. An overview of various test procedures
(HTF). Examples of HTFs include: petroleum based mineral used in the selection and maintenance of mineral oil heat
oils, glycols, silicones a n d various S3Tithetic fluids such as transfer fluids will be provided. System maintenance, opera-
alkyleated aromatics, terphenyls, a n d mixtures of bi and tion, and design will be discussed toward the closing.
diphenyls and their oxides. Selected physical properties for a
n u m b e r of illustrative tj^pes of heat transfer fluids are
provided in Table 1. These data show that there are notable
differences in the physical properties of different classes of DISCUSSION
different fluids within a class.
Steam is one of the most economical, since it is generated Heat Transfer Coefficient
easily and it possesses excellent heat transfer properties, due For heat transfer fluid selection, a n u m b e r of fluid-related
to its relatively high heat of vaporization and high thermal factors m u s t be considered including fluid performance,
conductivity. However, steam suffers frora a n u m b e r of dis- thermal stability, and safety. Several physiccd properties of a
advantages such as corrosion and the fact that it must be heat transfer fluid directly affect fluid flow, a n d thus heat
used in high-pressure equipment. It is often most suitable for transfer performance, which are quantitatively illustrated us-
temperatures of <300°F [3]. ing the classic Seider and Tate equation for the fluid-film
In some cases, reactors must not only be used for heating, heat transfer coefficient (h) for fully turbulent flow in a tube
but also for cooling. In these cases, a secondary coolcint may [1,4,20]:
be used such as a n aqueous glycol coolant like those illus-
trated in Table 2 [3]. In these situations, the use of steam and hdA = 0.027 (Jvp/M)°* (.Cpfi/kf-^^ (fc)"-*^ (M/MW)"'^
cooling water in separate loops reduces the available heat
Where: h is the fluid-film heat transfer coefficient, d is the in-
treinsfer cirea and increases the amount of piping required. It
side diameter of the tube, k is thermal conductivity, v is ve-
also increases the thermal stresses arising from the alternat-
locity, p is fluid density, Cp is the specific heat capacity, fi is
ing flow of chilled water and steam. In general, glycol water
the absolute viscosity at the bulk fluid temperature, and /AW is
solutions are most applicable for applications requiring mod-
the absolute fluid viscosity at the wall temperature. Seider
erate heating and/or temperatures to 0°F.
and Tates correlation analysis showed that there was little
Above 500°F, mineral oil and synthetic eiromatic based heat variation between /x and /xw in the region of turbulent flow
transfer fluids are often used because of the cost of using fluids seldom exhibit large temperature coefficients of vis-
steam at the corresponding temperatures. Furthermore, heat cosity and because heat transfer rates are high, there are less
transfer fluids are often the better choice for intermediate high temperature differences. W h e n the exponent of the vis-
temperatures above 300°F, particularly for the single process cosity gradient (;U//AW) was 0.14 for fully turbulent flow, (see
user who cannot justify a steam boiler and also for systems above equation for hd/k), the viscosity gradient was equal
requiring both heating and cooling. Some mineral oil heat to 1. Therefore, the simplified equation for h, the fluid-film
transfer fluids may be used above 600°F although the most heat transfer coefficient is obtained [1].
c o m m o n use range for these fluids is 300-570°F. The ISO
6743-12 fluid classifications for mineral oil based heat trans- h = 0.027 id)'"-^ (v)«« (p)0« (Cp)0" ikf" (/x)-o-47
fer fluids is shown in Table 3. For higher temperatures u p to
The Seider and Tate equation shows that higher heat trans-
700°F, fluids such as modified terphenyls may be used cind
fer is favored by: increasing fluid density, increasing heat ca-
biphenyl emd other fluids such diphenyl oxides may be used
pacity, increasing conductivity, increasing fluid velocity and
u p to 750°F [3].
turbulence, and decreasing fluid viscosity [2]. Rates of heat
transfer are also affected by system heat sources and heat
' Paratherm Corporation, Consholiocken, PA 19428. sinks, geometry, and temperature gradients [2].
^ G.E. Totten & Associates, Inc., LLC, PO Box 30108, Seattle, WA
98103. Heat transfer properties of two fluids can be compared by
^ 63 Rockledge Rd., Hartsdale, NY 10530. assuming they are flowing through the same pipe. Therefore,
573
TABLE 1—Comparison of typical heat transfer fluid properties.

Comparison
Inside Film Coefficients Max" Max" Flash Fire Auto Coefficient Vapor
(BTU/Hr) (ft^) (°F) 2" Bulk Film Point Point Ignition of Thermal Pour Pressure Vise
Type of Sched 40 Pipe @ 87Sec Temp Temp (coc) (coc) Temp Expansion Point @600°F 100°C
Fluid Fluid 400^ 500°F eoo-F °F °F °F °F °F %rF "F psia cSt
Caloria Paraffinic 236 267 302 600 660 406 453 632 0.0483 10 15 5.0
HT43 hydrocarbon
Dowtherm Diphenyl oxide/ 492 547 590 750 800 236 245 1139 0.0642 53 45.34 0.13
A biphenyl blend
Dowtherm Di- a n d triaryl 350 404 449 685 750 266 275 1083 0.0525 -40 22 0.29
G ether
Therminol Modified 332 397 449 650 705 363 414 705 0.046 -25 7.47 3.8
66 terphenyl
Dowtherm Diethyl benzene 449 428 384 600 650 136 140 788 0.105 -100 174 0.07
J
Dowtherm Diphenyl 417 451 465 625 675 249 255 773 0.0569 -30 37.74 0.14
Q
Mobiltherm Paraffinic 304 354 399 550 625 380 375 670 0.0531 25 2.9 4.0
603 mineral oil
Paratherm Napthenic 317 388 464 600 650 345 385 690 0.0304 -45 4.72 3.686
NF® hydrocarbon
Syltherm Polydimethyl- 239 265 279 750 800 320 380 725 0.0813 -76 87 0.46
800 siloxane
Syltherm Polydimethyl- 329 298 242 500 550 116 N/A 662 0.1143 -168 163.4 0.09
XLT siloxane
' Manufacturer's recommended maximum temperatures.
TABLE 2—Comparison of selected secondary coolants.

Pumping Limit Temperature for 10 cP Corrosion Inhibitor Normal Boiling
Coolant ("F)" Viscosity'' (°F) Required" Point (°F)
Aqueous Glycol Solutions
Propylene Glycol: 30% 5(FP) 17 Yes 212
Ethylene Glycol: 30% 6(FP) < 6 (FP) Yes 212
Propylene Glycol: 50% 141 51 Yes 223
Ethylene Glycol: 50% -31 20 Yes 224
Other Coolants
Synthetic Hydrocarbon'' <-120 -52 No 378
Silicone Oil'' <-120 -85 No 347
Alkylated Benzene'' - 1 0 0 (FP) -100 No 358
Water 32 (FP) 32 Yes 212
"Pumping (fluidity) limit is defined as the point where coolant is at the freezing point (FP) or 2000 cP viscosity [3].
^Possible limit to efficient heat exchange, below which turbulent flow is not effectively obtained in economic heat exchangers.
'When in contact with metal equipment.
''Data shown tor typical commercial grades in coolant service.
velocity and tube diameter are equal and the ratio of the two This is illustrated with the following equation for pressure
heat transfer coefficients is dependent only on the ratio of the drop in r o u n d pipe that is expressed in lbs/100 ft of pipe:
fluid densities, specific heat capacities, thermal conductivi-
(62.3292)(p)(V)^
ties, and absolute viscosities raised to the appropriate power AP =
[1].
From this equation and the above expressions for heat 0.01171
transfer coefficient, it is evident that h is a good summary pa- 0.0001906 + (2)
(927.4777)(fi,)(p)(V)\o-381
rameter that incorporates all of the important fluid proper-
ties as they relate to their effect on heat transfer.
where:
di = I.D. of pipe in inches
Pressure Drop p = Fluid density in lb/gal
An i m p o r t a n t p a r a m e t e r used by process designers in the K = Thermal conductivity in BTU/hr-ft2 °F/ft
analysis of heat transfer systems is pressure drop (/IP). The fi = Viscosity in cPs
pressure drop of a system is related to the energy required to V = Fluid velocity in feet per second
move the heat transfer fluid through a stem at a given pres- Cp = Specific heat in BTU/lb °F
sure and it is related to the physical properties of the fluid. NOTE: p, K, u, and Cp at average fluid temperature
CHAPTER 21: MINERAL OIL HEAT TRANSFER FLUIDS 575
Many manufacturers supply computer programs that are pounds are classified as resins, asphaltines, or carbenes, de-
m o r e easily used to perform such calculations. These pending on their solubility [6]:
programs are available upon request, or many fluid and hard- • Resins—pentane or heptane soluble
ware suppliers make such softweire available on the Internet. • Asphaltenes—pentane or heptane soluble
Selected examples of such p r o g r a m s that are currently • Carbenes—^benzene insoluble, carbon disulfide soluble
available at a web site are provided in Table 4. Crude oils eire classified as paraffinic, naphthenic, inter-
mediate (mixed), or asphaltic as shown in Table 5. Paraffinic
fractions are saturated linear or b r a n c h e d alkanes. Naph-
M i n e r a l Oil F l u i d C o m p o s i t i o n
thenic fractions contain cyclic alkane fractions. Also in-
Crude petroleum oil is a complex mixture of petroleum cluded are aromatic (pol5ainsaturated cyclic) chemical struc-
hydrocarbons as well as nitrogen, oxygen, and s u l f u r - tures derived from benzene. Aromatic components exhibit a
containing compounds, which are separated into fractions greater tendency to form sludge and varnish than paraffinic
by refining. Solid components include petroleum coke, as- or naphthenic derivatives [7]. Generic examples of typiceil
phalt bitumen, and inorganics. Liquids of increasing viscos- structures are illustrated in Fig. 1 [8,9]
ity vary from gasoline, kerosene (paraffin oil), diesel oil, en- In addition to paraffinic, n a p h t h e n i c , a n d aromatic
gine crankcase oil, light a n d heavy m a c h i n e oil, a n d derivatives, petroleum oils also contain heterocyclic (cyclic
cylinder oil. Also included are methane, ethane, propane derivatives of nitrogen, sulfur and oxygen), and other polar
and butane, the major components of natural gas, which c o m p o u n d s such as carboxylic acids, usually saturated
are gases at room temperature [6]. Aromatic aspheilt com- aliphatic or cycloaliphatic (naphthenic) acids, and aldehy-
TABLE 3—ISO 6743 classification of fluids for lieat transfer.

More Product Type
Code General Particular Specific and Performance Symbol Typical
Letter Application Application" Application Requirements ISO-L Application Remarks
Q Heat Maximum Open circuit Refined mineral QA Open oil containers The fire risk for the
Transfer Measured oil or synthetic For heating of particular application
Temperature fluid mechanical electrical shall be a consideration.
<250C or with stability components including the system,
To oxidation operating environment
and the fluid itself
Maximum Closed circuit Refined mineral OB -Heat transfer fluid 1) Units with heat
Measured with/or oil or synthetic heating system transfer fluid heating
Temperature without fluid with -Closed-circuit systems should be
<300C forced thermal stability water bath fitted with efficient
circulation expansion tank, vent
and filtrationsystems.
Maximum Closed circuit Refined mineral oil QC 2) For units with heat
Measured with forced or synthetic fluid Exchangers for heating
Temperature circulation with thermal of foodstuffs the heat-
>300 C and stability transfer fluid shall
<320C comply with applicable
national hygiene and
safety regulations.
Maximum Closed circuit Synthetic fluid QD Heat transfer fluid
Measured with forced with particularly heating systems
Temperature circulation high thermal
<320C stability
Maximum Cooling Refined mineral oil QE Unit with hot flow
Measured circuit or synthetic fluid and/or cold flow
Temperature with low viscosity
>-30Cand at low temperatures
<200C and with thermal
stability
"Temperatures indicated in the column are of the bulk of the oil, measured in the discharge line from the heater. They are not the temperatures of the film of
oil contact with the heater, which may reach higher values.
TABLE 4—Sources and web site addresses for computer programs to calculate heat transfer coefficients.
Company Program Name Web Site Address
Dow Chemical Company FLUIDFILE™ http://www.dow.com/heattrans/index.html
Paratherm PARACALC™ http;//www.paratherm.com
Solutia Inc. http://www.therminol.com
Engineering Process Tools http://www.processassociates.com/process/tools.htm
K & K Thermal Connection http://www.tak2000.com
TABLE 5—Crude oil content and suitability.

Solvent Neutral Base Specialty Wax S&N API
Crude Type Base Oil Oil Oil Content Content" Asphalt Gravity''
Pciraffinic base Yes Yes No Yes Low No >40
Naphthenic base No Yes Yes No Low No <33
Mixed base No Yes No Yes Low Yes 33-40
Asphaltic base No Yes No No High Yes
"S is sulfur and N is nitrogen.
''API gravity is scale in degrees adopted by the American Petroleum Institute where: "API = [141.5/specific gravity] — 131.5.
Viscosity Pour derivatives, exhibit a pro-oxidant effect; this effect is

NmmaiclatnTg Index Point accelerated in the presence of copper [10].
n-Panffins Very high ParafHnic base oils contain 45-60% paraffinic compounds.
High
Naphthenic base oils contain 65-75% of naphthenic com-
iso-Paraffins m^ Low pounds and aromatic base oils contain 20-25% aromatic
compounds [8]. Table 7 provides a summary of the effect of
paraffinic, naphthenic, and aromatic content of base oils on
Naphthenes -^ T^Y^
Moderate Low fluid density [6].
Base oil composition affects physical and chemical
properties of the oil. Base oil properties may be estimated
Anunatics Low Low from aromaticity (aromatic carbon content), which is
^ I primarily dependent on the degree of refining [11,12]. The
degree of aromatic compound content of a base oil may be
FIG. 1—Typical organic structures present in determined from the aniline point and is determined by
mineral oil. ASTM D 611. The aniline point is determined by mixing spec-
ified volumes of the base oil, aniline, and heptane and then
the mixture is heated at a controlled rate until it becomes
Dibenzothiophene miscible. The mixture is then cooled at a controlled rate and
the temperature where two phases separate is recorded as the
aniline point. Aromatic hydrocarbons exhibit the lowest
value and paraffinic hydrocarbons the highest value.
1,7-Phenandirone Cycloparaffins and olefins exhibit intermediate aniline
points.
Another parameter that is reflective of base-oil quality is
sulfur content since sulfur-containing polar compounds may
exhibit significant antioxidant activity. Therefore, a determi-
nation of both the aniline point and sulfur content are neces-
Furan sary to determine base oil type, which is reflective of its
resistance to oxidation.
API has developed a classification system for petroleum oil
Pynole base, which can be used as an aid in selecting basestocks that
exhibit improved oxidative stability. These classifications are
[27]:
• Group I—Base oils with a viscosity index of 80-120, and
containing less than 90% saturated hydrocarbons and/or
Thitqihene more than 0.03% elemental sulfur.
• Group II—Base oils with a viscosity index of 80-120, and
FIG. 2—Examples of heterocyclic containing > 90% saturated hydrocarbons and/or ^ 0.03%
derivatives typically present in a elemental sulfur.
petroleum oil. • Group III—Base oils with a viscosity index of s 120, and
containing a 90% saturated hydrocarbons and/or £ 0.03%
des. Selected examples of polar derivatives that may be found sulfur.
in petroleum oils are illustrated in Fig. 2 [6-8]. Traces of phe- • Group IV—Âll polyalphaolefins
nolic and furan derivatives may also be present. A summary • Group V—All other base stocks not included in Groups I,
of the overall effect of these different derivatives on physical II, III, or IV.
and chemical properties is provided in Table 6 [7]. A reduction in the overall composition of aromatic deriva-
Yoshida has shown that the pro-oxidant effect of nitrogen tives and polar compounds of a petroleum base stock may be
heterocyclic compounds is a function of the basicity of the ni- accomplished by high-temperature catalytic hydrogenation.
trogen in the compound. Generally, only the more basic ni- This will produce a base stock with improved color and
trogen heterocyclic compounds, pyridine and quinoline oxidative stability [13,14],
There are various methods for the determination of the the viscosity-gravity constant (VGC) and refractivity to deter-
composition of petroleum oil derived heat transfer fluids. mine oil composition in terms of aromatic carbon (%CA),
These methodologies, many of which have not been devel- naphthenic carbon (%CN), and paraffinic carbon (%CP). The
oped into ASTM or other national standards, have been VGC parameter is derived from kinematic viscosity and den-
reviewed previously. One such review is provided in Ref. 28. sity and is dependent on the saturated/aromatic hydrocarbon
ASTM methods for petroleum oil compositional analyses ratio. The equation to calculate VGC from kinematic
are classified by Drews into: correlative, chromatography, viscosity at 100°C (V') and density at 15°C (G) is:
a n d spectrometric methods [21]. Correlative methods are
those that are derived by statistical analysis of a measured G - 0.108 - 0.1255 Log ( V ' - 0.8)
composition-dependent property. It is important to note that VGC-
0.90 - 0.097 Log (V - 0.8)
correlative carbon-type data are not directly comparable to
data obtained by molecular structural analysis. However, Aromatic (RA) and naphthenic (RN) ring distribution of
correlative analysis data are often an effective means of mon- the so-called "average molecule" is determined using ASTM
itoring the effect of a process change, such as oxidative Test Method D 3238.
stability, with variations in the composition of the oil. Naphthenic content of a petroleum oil can be determined
Examples of ASTM correlative methods are provided in by ASTM D 2159 using the refractivity intercept which is
Table 8. Test Method D 2140 utilizes a correlation between defined as: Refractivity Intercept = n - {d/2) where n is the
TABLE 6—Effect of composition on base stock properties.

Property n-Alltane iso-Alkane Napthene Aromatic Polar Compounds
Viscosity Index Very high High Low Low Low
Pour point (high/low) High Low Low Low Low
Oxidative Stability Good Good Average Average/Poor S is antioxidant;
N and 0 are pro-oxidant
Response to Good Good Good Some poor Poor
Antioxidants
Volatillity Good Good/Average Average Poor Poor
(high = poor)
(low = good)
TABLE 7—Relationship between molecular carbon type and density.

Base Oil Type Paraffinic Carbon Naphthenic Carbon Aromatic Carbon Density (kg/L)
Paraffinic 65-70 25-30 3-8 0.800-0.812
Naphthenic 50-60 30-40 8-13 0.834-0.844
Mixed 48-57 24-33 17-22 0.850-0.872
Aromatic 21-35 20-30 40-50 0.943-1.005
TABLE 8--ASTM test methods for determining petroleum oil composition used for heat transfer fluid formulation.
ASTM No. Standard Test Method for Separation Type
D 1319 Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption Chromatography
D2007 Characteristic Groups in Rubber Extender and Processing Oils and Other Petroleum- Chromatography
Derived Oils by the Clay-Gel Absorption Chromatographic Method
D2140 Carbon-Type Composition of Insulating Oils of Petroleum Origin Correlation
D2425 Hydrocarbon Types in Middle Distillates by Mass Spectrometry Spectrometry
D2501 Calculation of Viscosity-Gravity Constant (VGC) of Petroleum Oils Correlation
D2502 Estimation of Molecular Weight (Relative Molecular Mass) of Petroleum Oils From Correlation
Viscosity Measurements
D2549 Separation of Representative Aromatics and Nonaromatics Fractions of High-Boiling Chromatography
Oils by Elution Chromatography
D2786 Hydrocarbon Types Analysis of Gas-Oil Saturates Fractions by High Ionizing Voltage Spectrometry
Mass Spectrometry
D3238 Calculation of Carbon Distribution and Structural Group Analysis of Petroleum Oils by Chromatography
the n-d-M Method
D3239 Aromatic Types Analysis of Gas-Oil Aromatic Fractions by High Ionizing Voltage Mass Spectrometry
Spectrometry
D3524 Diesel Fuel Diluent in Used Diesel Engine Oils by Gas Chromatography Chromatography
D3525 Gasoline Diluent in Used Gasoline Engine Oils by Gas Chromatography Chromatography
D4291 Trace Ethylene Glycol in Used Engine Oil Chromatography
D4808 Hydrogen Content of Light Distillates, Middle Distillates, Gas Oils, and Residua by Spectrometry
Low-Resolution Nuclear Magnetic Resonance Spectroscopy
D5186 Determination of Aromatic Content and Polynuclear Aromatic Content of Diesel Fuels Chromatography
and Aviation Turbine Fuels by Supercritical Fluid Chromatography
D5291 Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Petroleum Products Spectrometry
and Lubricants
D5292 Aromatic Carbon Contents of Hydrocarbon Oils by High Resolution Nuclear Magnetic Spectrometry
Resonance Spectroscopy
refractive index at 20°C and d is the density at 20°C. The mal/oxidative stability properties. This test method is not di-
naphthene content in percent by volume is determined from rectly applicable to petroleum oils of greater than 0.1 mass %
a plot of refractivity intercept and density as shown in Fig. pentane insolubles. The hydrocarbon types and structural
3. Polycyclic naphthenes, if present, will cause a high value groups measured by this method include:
for total naphthenes to be indicated. Although basic data for • Asphaltenes, or n-pentane insolubles that are defined as in-
this correlation compensate, in part for the presence of di- soluble matter that precipitates from a solution of oil in n-
cyclic naphthenes, results may be high by as m u c h as 1% pentane under specified conditions.
for each 1 volume % dicyclic naphthenes present. Thus, the • Polar compounds that are material retained ion adsorbant
n a p h t h e n e content indicated for stocks with end points clay after percolation of the same in n-pentane eluent un-
greater than 163°C (325°F) should be considered "equivalent der specified conditions.
naphthenes." • Polar aromatics, which is a synonym for polar compounds.
The chemical composition of a petroleum base oil may also • Aromatics that are materials that, o n percolation, pass
be calculated from physical properties such as refractive in- through a column of adsorbant clay in a pentane eluent but
dex {ni°) at 20°C, density at 20°C (df), percentage sulfur (S) adsorb on silica gel u n d e r the conditions specified.
concentration, and average molecular weight (M) by ASTM D • Saturates which are materials that, on percolation in an n-
3238, which describes the "n-d-M Method" (refractive index, pentane eluent, is not adsorbed on either clay or silica gel
density and molecular weight method). under the conditions specified.
Chromatographic methods for determining the composi- In addition to ASTM D 5186, which utilizes supercriticcJ
tion of p e t r o l e u m oil are s u m m a r i z e d in Table 8. These fluid chromatography (SFC), a n u m b e r of additional meth-
methods include gas chromatography and open-column sep- ods have been reported for use with petroleum oils including
arations on silica gel or clay-silica gel columns. Molecular- thin layer chromatography (TLC) and high pressure liquid
type analyses are conducted using open-column separations chromatography (HPLC) [21,22-25].
such as those outlined in ASTM D 2007. ASTM Test Method There are various spectrometric methods for petroleum
D 2007 may be used to classify petroleum oil samples with an compositional analysis, which are summarized in Table 8.
initial boiling point of at least 260°C (500°F) into the hydro- Non-ASTM methods for the use of infra-red (IR) spec-
carbon types of polar compounds, aromatics, and saturates troscopy for quantitative analysis of hydrocarbon t5ês have
and recovery of representative fractions of these types. been reported. Fourier trzmsform (FT) IR methods have also
ASTM D 2007 is conducted by diluting the sample with sol- been reported for the analysis of degradation by-products
vent and then charging it to a glass-percolating column con- present in used oils [21,26]. Nuclear magnetic resonance
taining clay in the upper section and silica gel plus clay in the (NMR) spectroscopy methods have been developed including
lower section. n-Pentane is then charged to the double-col- ASTM D 4808 and D 5292.
u m n until a definite quantity of eluent has been collected. There are three spectrometric test methods for petroleum
The upper (clay) section is removed from the lower section analysis based on mass spectroscopy (MS): ASTM D 2549, D
and washed with n-pentane. A toluene-acetone mixture is 2786, and D 3239. ASTM D 2786 yields information on the
t h e n charged to the clay section for desorption a n d a relative amounts of paraffins, 1-through 6-ring naphthenes
specified volume of eluent is collected. The lower (silical) gel and alkyl naphthenes. ASTM D 3239 determines eighteen
column may be desorbed by recirculation of toluene. After aromatic t3ês and three aromatic thiophene structures [21].
solvent removal, the aromatics are collected by difference. Both methods require the use of Test Method D 2549 for
This is a useful procedure for classifying petroleum oils into prior separation of the paraffinic a n d aromatic fractions.
structural groups that may be related to their inherent ther- ASTM D 2425 may be applicable for petroleum oils in the
lower molecular weight range [21].
1.047
n —' •
\
M i n e r a l Oil F l u i d P r o p e r t i e s
^^ ^ ~>-N It has been shown that heat transfer fluid performEuice is de-
0^
^^ - -
-—•
-^ pendent on the physical properties of the fluid including:
o .o\
'^ thermal conductivity, density, specific heat capacity, and vis-
—' ^
IM
> cosity. It has also been shown that the physical and chemical
N
,\ ^ ^ / > properties of a mineral oil are dependent on its composition
e y
"^
>< y , / -" / a n d degree of refining. However, Table 1 showed that the
y / / ' ^'
j»
% physiced properties of heat transfer fluids of a given type, in-
>
fP ^
i- /' cluding mineral oil-derived fluids, varied with respect to each
\ \A sMN
1 "'•>, /' other. This is illustrated in Table 9 where the physical prop-
ec iO<] erties of two commercially available mineral oil heat transfer
\ /
'•
*• rf)N fluids are compared. One fluid is a hydrotreated pEiraffinic
/
jPN f base and the other is a napthenic base. It is essential that the
engineer obtain the actual data he requires for the fluid being
1.033 ,^ considered. This data is available from the fluid supplier.
0.64 0.66 0.6B 0.70 OTZ 0.74 0.76 07B 0.60 0.B2
0cflsityaf2OC
A s u m m a r y of ASTM test procedures r e c o m m e n d e d in
FIG. 3—Naphthene content by volume percent using the re- ASTM D 5372 for mineral oil-based heat treinsfer fluids is
fractivity intercept. provided in Table 10.
TABLE 9—Comparison of the physical properties of two different commercially

available heat transfer fluids.
ASTM Test
Physical Property Procedure Fluid 1 Fluid 2
Feedstock Base Napthenic Paraffinic
Viscosity (cSt)
300°F 1.96 2.79
400°F 1.16 1.52
500°F 0.74 0.98
Density (lb/gallon)
300°F 6.82 6.51
400°F 6.64 6.22
500°F 6.45 5.92
Specific Heat (BTU/lb-°F)
300°F 0.56 0.56
400°F 0.61 0.61
500°F 0.66 0.66
Thermal Conductivity (BTU/hr-ft^-°F
300°F 0.072 0.071
400°F 0.069 0.069
500°F 0.067 0.066
Vapor Pressure, psia @
300°F 0.0003 0.00039
400''F 0.1470 0.00970
500°F 0.9670 0.13500
Coefficient of Thermal Expansion 0.000304/°F 0.000592/°F
Viscosity (ASTM D 445)

Viscosity is important in determining Reynolds and Prsindtl
TABLE 10—Summaiy of ASTM D 5372 recommended test numbers for heat transfer systems, to estimate fluid turbu-
procedures for mineral oil heat transfer fluids. lence, h e a t transfer coefficients, and heat flow. Viscosity
Recommended Test ASTM Test Procedure measurement by various tests, including ASTM D 445, is dis-
Mineral Oil Fluid Properties cussed in detail in Chapter 32, Flow Properties and Shear Sta-
Flash Point, Closed Cup D93 bility, and will not be discussed here.
Pour Point D97
Viscosity D445
Specific Viscosity D1298
Pumpability
Water Content D95 Pumpability refers to the ease of pumping a fluid in a heat
Safety transfer system. According to ASTM D 5372, if the fluid vis-
Autoignition Temperature E659 cosity is greater than 200 cS, it is difficult to p u m p . If a heat
Flash Point, Open Cup D92
transfer fluid is subjected to temperatures below its mini-
Flash Point, Closed Cup D93
m u m p u m p i n g t e m p e r a t u r e w h e n not in use, the system
Effect on Equipment
should be heat traced to w a r m the fluid start-up. The p u m p
Rubber and Elastomeric Seals D471
Corrosion G4 and system design will determine the viscosity limit required
Efficiency for pumping, and therefore the minimum pumping tempera-
Thermal Conductivity D2717 ture. The construction of a viscosity/temperature curve using
Specific Heat D2766 measured viscosities in the temperature range of interest can
Service Life be used to estimate m i n i m u m pumping temperature.
Thermal Stability Laboratory Tests" It should be noted that the "pumpability" concept of ASTM
Precipitation Number D91
D 5372 is not the same concept as "pumping limit" used by
Insolubles D893
Flash Point, Open Cup D92 Green and Morris [3] and cited in Table 2. The Green and
Flash Point, Closed Cup D93 Morris concept refers to those conditions defined by freezing
Carbon Residue D189 point of the fluid or a viscosity of 2000 cP as conditions where
" D524 a fluid is n o longer p u m p a b l e . In the ASTM approach,
" D4530
"pumpability" refers to that fluid viscosity (200 cS) above
Viscosity D445
Distillation D86 which the fluid would be difficult to pump—which is a con-
" D 1160 sensus value.
" D2887
Neutralization Number D664
Water Content D95
Thermal Stability
"At present no suitable method has been approved for heat transfer fluids. Thermeil stability (cracking) is defined as the resistance of a
Test method D 2160 is of limited value due to limitation in testing small non- heat transfer fluid to permanent physical changes caused by
circulatory samples in glass containers.
exposure to heat (themiEil cracking). Depending on the com-
position of the oil, these changes can become noticeable at
temperatures as low as 250°C while rapid changes in compo- increase in the amount of air contact (foaming air entrain-
sition (thermal cracking or pjrolysis) begin around 350°C. ment, fluid turbulence) will also affect the rate of oxidation.
These changes include evolution of solid carbon particles Oxidative stability is a function of the base stock selected.
(coke) and lower boiling point components (light ends). If For example, paraffinic oils exhibit better oxidative stability
there are substantial a m o u n t s of asphaltenes and polar than naphthenic oils, but they exhibit poorer "solvency"—
residues in the fluid, the coke may adhere to the heater sur- poorer ability to dissolve byproducts [17]. The presence of
faces, causing fouling, which in t u r n reduces heat transfer alkylaromatic derivatives a n d some polar components fur-
rates. The lower boiling point components will cause the ther increases the susceptibility of a petroleum oil to oxida-
overall system pressure to increase and m a y result in vation, and other derivatives such as some sulfur-containing
porous cavitation at the p u m p section. These components compounds may exhibit a stabilizing effect [18].
will also tend to depress the Flash Point of the fluid. Thermal
cracking is often accompanied by color change [19] however, Carbon Residue (ASTM D 189, D 524, and D 4530)
color change is more c o m m o n when oxidation is present. "Carbon residue" is defined as the residue formed by evapo-
While higher viscosity oils are generally more susceptible to ration and thermal degradation of a carbon containing mate-
cracking than lower viscosity, the main cause is due to over- rial, which provides an indication of the fluid's tendency to
heating. Overheating typically results from flame impinge- form carbonaceous deposits.
ment and/or low velocity through the tubes of fired heaters. One test that is used to determine carbonaceous residues is
In forced circulation electric immersion heating systems, sat- Test Method D 189 the Conradson Carbon Residue. In this
isfactory fluid life has been obtained with heat flux of 15-22 test, a sample is added to a crucible and subjected to de-
watts per square in., and in free convection systems (no cir- structive distillation. The residue formed undergoes cracking
culating pumps), 5-12 watts per square in. and coking during the fixed period of severe heating. At the
conclusion of the test, the crucible is cooled and weighed.
Thermal Stability (New ASTM Test Method The Conradson Carbon Residue is the % of residue remain-
Under Development) ing at the conclusion of the test. This test provides a rough
Although it is true that there are few tests that directly assess approximation of the tendency of the heat transfer fluid to
the thermal stability of a heat transfer fluid, there is one test form deposits when heated and the formation of volatile by-
currently being balloted within ASTM, Standard Test Method products is possible.
for Thermal Stability of Organic Heat Transfer Fluids [ 1 ]. This Another test that is used to determine the tendency for a
test is conducted by adding the heat transfer fluid to be ana- heat transfer fluid to form carbonaceous residues is Test
lyzed into a test cell that is purged with nitrogen and tightly Method D 524, the Ramsbottom Carbon Residue test. In this
sealed to remove and preclude the introduction of oxygen and test, the sample is weighed into a special glass bulb and
water from the atmosphere. The fluid is then heated in the test placed in a metal furnace where it is heated quickly to 550°C.
cell for a prescribed time and temperature. The boiling range All volatile material is evaporated out of the bulb, with or
of the fluid after themicJ stressing is then determined by gas without decomposition, while the remaining residue under-
chromatography (using Test Method D 2887) and compared goes cracking and coking reactions. After the test, the bulb is
to the unused fluid. This portion of the thermally stressed cooled and weighed. The residue remaining is reported as %
fluid that has a boiling point outside of the boiling range of of original sample and is called the R a m s b o t t o m Carbon
new, unused fluid is defined as "degradation." Residue.
Guffey has introduced the concept of "overall degradation Test Method D 4530 is a "Micro Method" for determination
rate" [1], where components exhibiting boiling points above of carbon residue. In this test, a weighed sample of the fluid
or below the original boiling point range are assumed to be is heated in a 2 mL glass vial at 500°C under an inert atmo-
degradation products. To determine the overall degradation sphere (nitrogen) in a controlled manner for a specific time.
rate, it is assumed that 99% of the fluid volume is equally dis- The sample undergoes coking reactions and the volatiles that
tributed at the heater-outlet, heater-inlet, and the heater-inlet are formed are swept away by the nitrogen. The carbona-
temperature minus a selected amount such as 50°F (which ceous residue formed is reported as % of original sample as
accounts for the fluid in the system expansion tank). The re- "carbon residue (micro)." This test method is reported to be
maining 1% is assumed to be at the fluid-film temperature. equivalent to the Conradson Carbon Residue (ASTM D 189).
Degradation rates are then taken from the test at various tem-
peratures. This data is then used to calculate the "overall Specific Gravity (ASTM D 1298)
degradation rate" [1]. Hydraulic shock during p u m p i n g has been predicted via the
use of a combination of density and compressibility data.
Oxidative Stability
Oxidation occurs when the hot fluid comes into contact with Metal Content
air (oxygen). Oxidation rates double every 10°C (18°F) in- Transition metals (0.1-50 ppm), capable of a one electron
crease temperature. The principal oxidation byproducts are transfer process, will act as a catalyst for hydrocarbon oxida-
organic acids which can undergo further reaction to form ex- tion. Homolytic peroxide decomposition occurs by:
tremely high molecular weight components that are soluble in
the fluid and increase the viscosity of the fluid [15]. Above RCOOH + M"+ -> RO • + M<"+"+ + H O "
200°C these components will precipitate out on hot surfaces
RCOOH + M<"+'>+ ^ RCOO • + M"+ + H^
and become insoluble. Insoluble byproducts will lead to foul-
ing of heater surfaces, filter plugging, and sticking valves. Any 2 RCOOH M"^/M<-^"^ ^ j^QQ ,+ R o • + H2O
These free radical processes, a n d others not shown, are by the fluid supplier or contract laboratory. The following
strongly affected by temperature. This is illustrated in Table are some simple tests that should be performed in the plant
11 where it is shown that if both water and the metal are pre- weekly or biweekly.
sent, the oil degradation rate was 10-fold (iron) to 30 fold
(copper) that of the uncontaminated oil [16]. There are nu- Listen to the System
merous test procedures that are discussed in detail in Chap- Minered oil heat transfer fluids exhibit various characteristic
ter 26, Elemental Analysis, cind therefore will not be discussed sounds that may indicate potential problems. For example:
further here. snapping, crackling, Eind popping noises indicate that water
may have entered the system. Loud noises in the circulation
Thermal Properties—Thermal Conductivity (ASTM D p u m p may indicate potential cavitation, which is a signifi-
2717) and Specific Heat (ASTM D 2766) cant problem and should be dealt with immediately. Sources
Thermal conductivity a n d specific heat tests are difficult to of excessive vibration of any p a r t of the system should be
carry out, facilities for performing them are few, Eind the pre- identified and eliminated.
cision data is yet to be established. Since thermal conductiv-
ity and heat capacity are temperature dependent, to be of use Visual System Inspection
to the designer, they m u s t be determined at different When the system is operating, smoke ciround piping indicates
temperatures. Values can be estimated for design use from that fluid is oozing through gaskets or valve or p u m p seals.
the general chemical composition. The values for thermjd Eventually, a black carbon crust will form at the leak. Unless
conductivity and specific heat may be available from the fluid there is an external source of ignition, these leaks are not nor-
supplier. mally a safety hazard, but more of a housekeeping issue and
should be corrected as soon as possible. During each inspec-
Autoignition (ASTM E 659) tion, examine the expansion tank, vent and overflow catch-
It is important to note that while heat transfer fluids are rou- container. Steam coming from the vent may indicate water in
tinely used above their flash a n d fire points, they should the system. The presence of a n oil mist may indicate that the
never b e used above their autoignition t e m p e r a t u r e . Au- heat transfer fluid is oxidizing. Both situations require im-
toignition is the temperature at which the fluid will ignite mediate attention. The catch-container should be closely in-
spontaneously in contact with air. It is recommended that the spected. If there is heat trzinsfer fluid in the container, the
fluid supplier be consulted for standard recommended safe cause must be identified. Whether the fluid in the container
practices. The autoignition temperature of a heat transfer is water, oil, solvent or another liquid, it is a safety hazard
fluid is determined according to ASTM D 659. and must be removed. Always keep the catch container clean
and dry.
Effect on Rubber or Elastomeric Seals (ASTM D 471)
Heat exchange equipment typically utilizes mechanical seals Unusual Odors
fabricated from steel or other metal. If elastomeric seals are A burning oil odor is usually indicative of a leak. Identify the
present, it is desirable that they exhibit rubber swelling in the source of the leak and repair, if necessary.
range of 1-5% to prevent leakage because of poor seal con-
tact. Seals may degrade in some fluids. As an oil deteriorates Fluid Appearance
in service, additiontJ tests may be required to assure that With the heater off, start the circulating pump(s) and wait ten
seeds remain compatible with the altered oil. The tempera- or fifteen minutes. Open a low-point valve, edlowing a small
ture ranges of the tests should correspond to temperatures to amount of fluid to drain into a clear glass container. Put the
which seals will be exposed in service and the tests should be container on a bench and let it sit. Color may range from light
conducted for at least 1000 h. yellow to dark brown or black. Darker colors do not neces-
sarily indicate that the fluid has become unusable. A hazy
fluid suggests water contamination or oxidation. If there are
Fluid Maintenance—In-plant Tests
particles on the b o t t o m (or floating in the liquid), fluid
Well-maintained, unabused mineral oil heat transfer sys- "coking" may be indicated or mill scale or other hard con-
tems may be smooth running and trouble-free over many taminants may be present. Either condition should be inves-
yccirs of use. To assure long-term and trouble-free opera- tigated before problems escalate.
tion, it is recommended that periodic maintenance be per-
formed. Some of these tests are simple and may be per-
formed by the user. Other tests may need to be performed Fluid Sampling
Recommended locations from which to remove a fluid sam-
ple include a low-point drain near the p u m p or heater or the
TABLE 11—Effect of water and catalysts on oil oxidation. blow-down valve mounted on the Y-strainer. The Y-strainer
Catalyst Water Hours Final Acid Number
is usually located in the return line just upstream of the p u m p
suction. Fluid samples should b e taken when the p u m p has
None No 3500 0.17
been running so that the sample is representative of the fluid
None Yes 3500 0.9
Iron No 3500 0.65 in the system. Ideally, the fluid should be removed from the
Iron Yes 400 8.1 system between 180 and 280°F and put directly into the sam-
Copper No 3000 0.89 ple container. If the fluid sampled is too hot, it will not only
Copper Yes 100 11.2 smoke, but the acid n u m b e r may indicate artificially high
acid levels due to oxidation during the sampling process. The . . fion
sample container must be sealed tightly as quickly as possi- o
ble after filling to minimize contact with air (oxygen). Sam- (1) 550
High Boilers-
ples taJcen from the expansion tank, or from a "dead leg," are 3
•I-*
not representative of fluid in the system. 2 500
a)
CL
The fluid supplier should supply a suitable sample con-
tainer. Contract laboratories typically require approximately E 450
one quart (750 mL) of sample to properly conduct the 10)-
c 400
analysis. o
4-*
m
350
Fluid Maintenance—Laboratory Tests m _ Low < Fresh Fluid
n Boilers - • - Thennally Degraded Fluid
•o 300
Laboratory analysis of the fluid should be performed at set in- a>
tervals to ensure that abnormal degradation is not occurring. JO 250
3
Abnormal degradation can result from contamination that E
catalyzes the breakdown, oxidation, or overheating. The con- CO 200 _i_
10 20 30 40 50 60 70 80 90 100
dition of the fluid can be accurately established by three basic
tests, which determine the amount of thermal cracking and/or Amount Distilled (%)
oxidation that has occurred. Additional tests may be required FIG. 5—Gas chromatographic distillation (GCD) com-
to identify specific contaminants such as water and solids. parison of a new and used mineral oil based heat trans-
fer fluid.
Acid Number (ASTM D 664 and D 974)
Acid number (AN) measures the acidity produced when the Distillation (ASTM D 1160, and D 2887)
fluid is oxidized. Unless the expansion tank is maintained un-
The distillation test compares the boiling temperatures of
der inert gas blanket, some increases in AN are unavoidable
standard fractions of new fluid with those for a used fluid.
over time. The higher the operating temperature, the more
This is illustrated graphically in Fig. 5 [19]. When a heat
critical the AN becomes since the ensuing fluid degradation
transfer fluid undergoes thermal or oxidative degradation
is temperature dependant. In general an increase of 0.5
(overheated) it generates lower boiling and/or higher boiling
should be viewed as a warning sign, with immediate fluid re-
components, which in turn causes a change in the boiling
placement at an increase of 1.0. The increase in AN with in-
temperatures of the various fractions. The percentage shift in
creasing time is illustrated in Fig. 4 [19].
temperatures versus new fluid collectively determines how
Test Method D 664 is conducted by dissolving a sample of much degradation had occurred. Typically, a shift of 10% in-
the HTF to be analyzed into a solution of toluene and iso- dicates that the fluid has been severely damaged.
propanol containing a small amount of water and titrated po-
In Test Method D 1160, 100 ml of fluid sample is distilled
tentiometrically with alcoholic potassium hydroxide and a
in a single stage equivalent apparatus under vacuum. The
saturated calomel reference electrode. The meter readings
temperature readings and volumes of condensate are
are plotted manually or automatically against the respective
recorded along with the volume of residue and any vapor
volumes of KOH titrant and endpoints are taken only at well-
losses. The data is converted to atmospheric equivalent tem-
defined inflections of the resulting curve. This titration may
peratures in a table.
be performed colorimetrically according to Test Method D
974. Alternatively, infrared analyses may be used, which pro- Test Method D 2887 is a gas chromatographic procedure that
vides a more reliable method of detecting oxidation. simulates distillation. It is conducted by injecting a quantity of
the fluid sample on to a nonpolar packed or open (capillary) gas
chromatographic column. The hydrocarbon components are
eluted in order of increasing boiling point. The column tem-
1.4 perature is raised at a reproducible linear rate and the area un-
#—«n der the chromatogram is recorded throughout the analysis.
5> 1.2
X • Oxidized Fluid Boiling points are assigned from a calibration curve obtained
§1.0
under the same conditions of a known mixture of hydrocar-
o> • / bons covering the boiling range expected for the sample.
e -
Viscosity (ASTM D 445)
3 0.6 While viscosity is not the most critical test for fluid
•D
• maintenance, it does provide useful information and also
B 0.4 -
confirmation of other test results. Viscosity is of import in
|0 0.2 -
• determination of Reynolds and Prandtl numbers for heat
transfer systems, to estimate fluid turbulence, heat transfer
0 ...U .... 1. n 1
coefficients and heat flow. In general, viscosity increases as
Increasing Fluid On-Stream Time —>• the result of oxidation and decreases due to thermal cracking.
FIG. 4—Illustration of the increasing solids content Changes in viscosity may also be the result of contamination
present in a mineral oil based heat transfer fluid with by a different fluid. Fluid viscosity is compared with that of
increasing time after the onset of degradation. new fluid in Table 12. Viscosity measurement by various
TABLE 12—Comparison of a new and used mineral oil fluid. Safety

Physical Property ASTM Procedure Fresh Fluid Used Fluid
Mineral oil heat transfer fluids are hydrocarbons, and there-
Flash Point, Open Cup D92 450 392
(°F)
fore are combustible with the associated safety risks. How-
Viscosity (cS) D445 25.0 94.5 ever, mineral oil based heat transfer systems have been in
AN (mg KOH/g) D664 0.05 2.12 safe operation for over 100 years.
Solids Content, (%) 0.0 7.6
Iron (ppm) 0.0 700 System Leakage
GCD Low Boilers, (%) D2887 4.7
Unlike hydraulic systems, mineral oil heat transfer systems
are not generally pressurized. The leaks that do occur are
found mostly in threaded fittings, joints, valves, and pumps—
TABLE 13—Correlation of base stock aromatic content and color
generation during oxidation. the fluid will slowly weep rather than gush or spray. Leaking
heat transfer fluid will tjrpically smoke rather than bum—even
ASTM Color
N S Wt. % After Heating at temperatures in excess of their flash and fire points. How-
Fluid (ppm) (ppm) aromatics in Air ever, hot mineral oil fluid vapors can also be highly flammable
A 27 6200 26" >8 if allowed to accumulate in a poorly ventilated area.
B 1 92 4 5.5
C <0.2 1 1 2.5 Insulation Fires
All organic heat transfer fluids are capable of spontaneous
combustion when leaks occur into porous insulation (such as
tests, including Test Method D 445, is discussed in detail in fiberglass or calcium silicate). The exact mechanism of the
Chapter 32, Flow Properties and Shear Stability and will not autoignition has not been established. One possibility is that
be discussed further here. partial oxidative decomposition occurs in the insulation
(similar to the way heat is generated in a pile of oily rags or
Open Cup and Closed Cup Flash Points (ASTM D 92 wood chips). The heat produced adds to the system heat and
and D 93) ultimately exceeds the autoignition temperature of the fluid.
Because the majority of systems operate safely above the An alternate mechanism is that the autoignition temperature
Flash Point of the fluid, periodic determination is usually un- of the fluid decreases as it degrades in the insulation. In ei-
necessary. A reduction in flash point does indicate the pres- ther case, if air enters the insulation at this point and con-
ence of low boiling components, which result from thermal tacts the degraded fluid, spontaneous combustion will occur.
cracking. A rapid decrease in flash point may indicate that se-
vere overheating has occurred. The presence of volatile com- Automatic Shutdown Controls
ponents can be determined by ASTM D 92, Cleveland Open Although rare, fires have occurred in heaters when fluid cir-
Cup Flash Point and/or ASTM D 93 Pensky-Martens Closed culation is interrupted (due to pump failure or blockage) and
Cup Flash Point Test. As determined by these methods, the the high temperature shutdown fails. In this situation, the
flash point is the lowest temperature, corrected to baromet- fluid temperature rapidly increases above the autoignition
ric pressure of 101.3kPa (760 mm Hg), where the application temperature while the increasing thermal stress eventually
of an ignition source causes the vapors of the fluid being causes either the heater tube or housing to fail. All systems
tested to ignite, either in an open cup (D 92) or closed cup (D should incorporate automatic shutdown controls for high
93). These test procedures are described in detail in Chapter fluid outlet temperature and loss or reduction of fluid flow
25, Volatility. through heater.
Water Content (ASTM D 95 and D 1744)
Design and Construction
Heat trsinsfer systems operating at temperatures of 120°C or
greater must, for reasons of safety, be dry, because destruc- Like any other industrial system, the proper design and in-
tive high pressures are generated when water enters the high stallation of heat transfer fluid systems is critical to their
temperature sections of the system. If water is not removed, smooth functioning and extended operating life. In this sec-
the vapor will cause pump cavitation and possible fluid dis- tion, an overview of recommended practices to minimize the
charge through the expansion tank vent potential of system fires will be provided.
Test Method D 95 is a classic distillation procedure for wa-
ter content. It is conducted by heating the fluid under reflux Component Selection
with a water immiscible solvent that codistills with water in In designing and constructing a thermal oil system, attention
the fluid. Condensed water and solvent are continuously sep- must be paid to the selection of appropriate components. If
arated in a trap, the water settles in the graduated section of care is not taken, poor operation, system failure, and fires
the trap. The amount of water is reported as % by volume of can result. In this section, an overview of various system de-
the original sample. However, distillation is only suitable for sign considerations for mineral oil heat transfer fluids will be
relative high levels of water content. In most well-maintained provided.
heat transfer systems, the actual water content is lower than
that necessary for distillation. A more suitable procedure for Piping
determination of water content is Test Method D 1744, a Karl Schedule 40 seamless carbon steel piping is recommended.
Fischer method where the sample is titrated to an electro- Schedule 80 piping is recommended for threaded installa-
metric end point [19]. tions up to 1 in. Threaded fittings are not recommended for
piping greater than 2 in. Pipe should be free of mill scale, Y-strainers
wedding flux, quench oils, and lacquers. The use of copper One-quarter to Ys in. opening is recommended. A 60 mesh el-
should be minimized. ement should be instcJled for start-up only.
Flanges and Fittings
Flow Protection
Flanges and fittings must be 300 lb forged steel, Yu in. raised
Many systems utilize a pressure differential switch to provide
face. Studs and nuts should be continuous threaded, alloy
a method of shutting the system down when fluid flows drop
steel with heavy hex nuts.
below set limits. Some systems are equipped with flowmeters
Valves should be 300 lb cast or forged steel, or nodular in addition to the pressure differential switches. However,
(ductile) iron with steel or stainless steel trim. For o p t i m u m since flowmeters can fail in the open position, they are typi-
service, bellows may be considered. The use of cast iron in cally not recommended for use as a flow switch.
thermal oil systems is not recommended.
Suggested gasket and packing materials include: Installation
• Flange gaskets—Spiral wound graphite filled or filled PTFE During installation or construction, four areas should be ad-
(maximum temperature 450°F) dressed:
• Valve stem packing—Rings of die formed graphite foil • system cleanliness
• Pump packing—End (nonextrusion) rings of braided car- • component orientation
bon yeim • system tightness
• Mechanical Seals—Carbon versus silicon or tungsten car- • allowance for thermal expansion and contraction
bide for continuous service. Silicon Ccirbide versus tung-
sten carbide for intermittent service. System Cleanliness
Elastomers Care must be taken to assure that the system is clean and dry.
Both the "hard" and "soft" contamination must be removed
Fluoroelastomer r e c o m m e n d e d to 450°F, perfluoroelas-
as the system is being assembled. Hard contamination such
tomers recommended to 600°F. Compatibility of other elas-
as mill scale, weld spatter/slag, and dirt can cause premature
tomers should be evaluated using tests such as ASTM D 471.
failure of p u m p and vzJve seals. A startup strainer should be
Insulation monitored continuously during initial system circulation.
Soft contamination such as quench oil, welding flux, and
Heat loss should not exceed 80 btu/ft at operating tempera-
protective lacquer coatings can potentially dissolve in the
ture. Nonporous (closed cell foam glass type) insulation is
fluid. Although this would be expected to exhibit only a min-
recommended. Porous insulation(such as glass fiber and cal-
imal effect in most cases, such contaminants may be carried
cium silicate) can be used on straight piping runs where leak-
through the heater where they may degrade at much lower
age is unlikely. In such installations, nonporous insulation
temperatures than the fluid itself, and can cause fouling of
should be installed around leak prone areas such as valve and
heater surfaces.
instrument taps and extended 18 in. m i n i m u m on either side.
Weep holes should be drilled in the b o t t o m of insulation
Component Orientation
around veJves. If possible, flanges should be left uninsulated.
Metal covers with weep holes can be installed for personnel Expzinsion tanks should be located far enough away and piped
protection. so that the temperature is n o greater than 1 SOT for vented sys-
tems. Design the expansion tank for twice the expansion vol-
Pumps u m e of the system where the tcink is % full cold and M full when
P u m p s should be cast carbon steel. Positive displacement the system is at operating temperature. Valves should be
p u m p s should be of the "gear within a gear" design. Canned m o u n t e d system sideward so that leakage from the stem or
or magnetic drive p u m p s are typically not required since from bonnet gasketing drips away from the piping.
fugitive emissions regulations do not apply for mineral oils.
System Tightness
It is recommended that the alignment be rechecked after the
system is operating at temperature. Flex hose should be in- The system should be chcirged with an inert gas once con-
stalled on the inlet and outlet. struction is completed. Not only will corrosion be prevented,
but the system can be pressure-tested using simple soap-bub-
Pressure Gauges ble detection methods at potential leak points.
Pressure gauges should be rated to 100 psi, 650°F (343°C) at
a temperature range of 300-600°F; Thermometers should be
calibrated according to ASTM E l to provide accurate read- ASTM STANDARDS
ings in this range [6].
No. Title
Expansion Joints D 91 Test Method for Precipitation Number of Lubricat-
For expansion joints, it is recommended that the HTF system ing Oils
be designed for an expansion growth of 4 in. per 100 ft, min- D 92 Test Method for Flash and Fire Points by Cleveland
i m u m . Both loops and joint expansion devices are accept- Open Cup
able. Either m u s t be high-temperature rated and must be D 93 Test Method for Flash Point by Pensky-Martens
considered part of the piping system. Closed Cup Tester
D 97 Test Method for Pour Point of Petroleum Products D 3524 Diesel Fuel Diluent in Used Diesel Engine Oils by
D 130 Test Method for Detection of Copper Corrosion Gas Chromatography
from Petroleum Products by the Copper Strip Tar- D 3525 Gasoline Diluent in Used Gasoline Engine Oils by
nish Test Gas Chromatography
D 189 Test Method for Conradson Carbon Residue of D 4291 Trace Ethylene Glycol in Used Engine Oil
Petroleum Products D 4530 Test Method for Determination of Carbon Residue
D 445 Kinematic Viscosity of T r a n s p a r e n t a n d Opaque (Micro Method)
Liquids (The Calculation of Dynamic Viscosity) D 4808 Hydrogen Content of Light Distillates, Middle Dis-
D 471 Test Method for Rubber Property-Effect of Liquids tillates, Gas Oils, and Residua by Low-Resolution
D 524 Test Method for Ramsbottom Carbon Residue of Nuclear Magnetic Resonance Spectroscopy
Petroleum Products D 5186 Determination of Aromatic Content and Polynuclear
D 611 Test Method for Aniline Point and Mixed Aniline Aromatic Content of Diesel Fuels and Aviation Tur-
Point of Petroleum Products a n d H y d r o c a r b o n bine Fuels by Supercritical Fluid Chromatography
Solvents D 5291 Instrumental Determination of Carbon, Hydrogen,
D 664 Test Method for Acid N u m b e r of Petroleum Prod- and Nitrogen in Petroleum Products and Lubricants
ucts by Potentiometric Titration D 5292 Aromatic Ccirbon Contents of Hydrocarbon Oils by
D 877 Test Method for Dielectric Breakdown Voltage of High Resolution Nuclear Magnetic Resonance
Insulating Liquids Using Disk Electrodes Spectroscopy
D 893 Test Method for Insolubles in Lubricating Oils D 5372 Guide for Evaluation of Hydrocarbon Heat Trans-
D 1160 Test Method for Distillation of Petroleum Products fer Fluids
at Reduced Pressure D 6546 Stcindard Test Methods for a n d Suggested Limits
D 1169 Test Method for Specific Resistance (Resistivity) of for Determining Compatibility of Elastomer Seals
Electrical Insulating Liquids for Industrial Hydraulic Fluid Applications
D 1298 Test Method for Density, Relative Density (Specific D 6743 Test Method for Thermal Stability of Organic Heat
Gravity), or API Gravity of Crude Petroleum and TrEinsfer Fluids
Liquid Petroleum Products by Hydrometer Method E 659 Test Method for Autoignition Temperature of liquid
D 1319 Hydrocarbon Types in Liquid Petroleum Products Chemicals
by Fluorescent Indicator Adsorption G4 Method for Conducting Corrosion Coupon Tests in
D 1500 Test Method for ASTM Color of Petroleum Products Plant Equipment
(ASTM Color Scale)
D 1744 Test Method for Determination of Water in Liquid
Petroleum Products by ICarl Fischer Reagent OTHER STANDARDS
D 1747 Test Method for Refractive Index of Viscous
Materials ISO 6743-12: 1989 (E) International Standard, "Lubricants;
D 2007 Characteristic Groups in Rubber Extender and Pro- Industrial Oils and Related Products (Class L)"-Classi£ica-
cessing Oils and Other Petroleum-Derived Oils by tion-Part 12: Family Q (Heat Transfer Fluids)
the Clay-Gel Absorption Chromatographic Method
D 2140 Carbon-Type Composition of Insulating Oils of
Petroleum Origin REFERENCES
D 2425 Hydrocarbon Types in Middle Distillates by Mass
Spectrometry [1] Guffey, G. E., "Sizing Up Heat Transfer Fluids and Heaters,"
D 2501 Calculation of Viscosity-Gravity Constant (VGC) of Chemical Engineenng, Vol. 104, No. 10, 1997, pp. 126-131.
Petroleum Oils [2] Green, R. L., Larsen, A. H., and Pauls, A. C, "The Heat Transfer
D 2502 Estimation of Molecular Weight (Relative Mole- Fluid Spectrum," Chemical Engineering, Vol. 96, No. 2, 1989, pp.
cular Mass) of Petroleum Oils F r o m Viscosity 90-98.
[3] Green, R. L. and Morris, R. C, "Heat Transfer Fluids-Too Easy
Measurements
to Overlook," Chemical Engineering, Vol. 102, No. 4, 1995, pp.
D 2549 Separation of Representative Aromatics a n d 88-92.
N o n a r o m a t i c s Fractions of High-Boiling Oils by [4] Seider, E. N. and Tate, G. E., "Heat Transfer and Pressure
Elution Chromatography Drop," Industrial Engineering and Chemistry, Vol. 28, 1936, pp.
D 2717 Test Method for Thermal Conductivity of Liquids 1429-1436; b. Kern, D. Q., "Chapter 6-Counterflow: Double Pipe
D 2766 Test Method for Specific Heat of Liquids and Solids Exchangers," Process Heat Transfer, McGraw Hill Inc., NY,
D 2786 Hydrocarbon T5rpes Analysis of Gas-Oil Saturates 1950, p. 103.
Fractions by High Ionizing Voltage Mass Spec- [5] ASTM E 1, "Specification for ASTM Thermometers," Annual
trometry Book of ASTM Standards, Vol. 14.03.
D 2887 Test Method for Boiling Range Distribution of [6] Anon. "Product Review: Oil Refining and Lubricant Base
Petroleum Fractions by Gas Chromatography Stocks," Industrial Lubricatoin and Tribology, 1997, Vol. 49, No.
4, pp. 181-188.
D 3238 Test Method for Calculation of Carbon Distribution [7] Singh, H., "Characterization of Lube Oil Base Stock—Approach
and Structured Group Analysis of Petroleum Oils by and Significance," Advances Production & Application of Lubri-
the n-d-m Method cant Base Stocks, Proceedings, International Symposium, H.
D 3239 Aromatic Types Anedysis of Gas-Oil Aromatic Frac- Singh, P. Rao, and T. S. R. Tata, Eds., McGraw-Hill, New Delhi,
tions by High Ionizing Voltage Mass Spectrometry 1994, pp. 303-310.
[8] Hoo, G. H. and Lewis, E., "Base Oil Effects on Additives Used to Base Oil," Symposium on Worldwide Prospectives on the Manu-
Formulate Lubricants," Adv. Prod. Appl. Lube Base Stocks, Pro- facture, Characterization, and Application of Lubricant Base Oils,
ceedings, International Symposium, H. Singh, P. Rao, and T. S. Division of Petroleum Chemistry, Inc., 213 National Meeting of
R. Tata, Eds., McGraw-Hill, New Delhi, 1994, pp. 326-333. the American Chem. Society, 1997, pp. 227-228.
[9] Prince, R. J., "Base Oils from Petroleum," Chemistry and Tech- [19] Fuchs, H. C. G., "Understand Thermal Ansdysis Techniques,"
nology Lubricants, R. M. Mortimer a n d S. T. Orszulik, Eds., Chemical Engineering Progress, Vol. 93, No. 12, 1997, pp. 39-44.
Blackie, Glasgow, 1992, pp. 1-31. [20] Kern, D. Q., Process Heat Transfer, McGraw-Hill Book Com-
[10] Yoshida, T., Watanabe, H., and Igarashi, J., "Pro-Oxidant Prop- pany, NY, 1950, pp. 99, 103.
erties of Basic Nitrogen Components in Base Oil," Proceedings of [21] "Chapter 3-Viscous Oils," Manual on Hydrocarbon Analysis, 6'*^
the 11''' International Colloquium of Industrial and Automotive Edition, A. W. Drews, Ed., 1998, ASTM International, West Con-
Luhrication-Vol. 1, W. J. Bartz, Ed., Technische Academie shohocken, PA, p p . 25-30.
Esslingen, Esslingen, 1998, pp. 433-444. [22] B a r m a n , B. N., "Hydrocarbon-Type Analysis of Base Oils
[11] Adhvatyu, A. and Singh, I. D., "FT-NMR and FT-IR Applications and Other Heavy Distillates by Thin Layer Chromatography
in Lubricant Distillation and Base Stock Characterization," Tri- with Flame-Ionization Deection and by the Clay-Gel Method,"
botest Journal, Vol. 3, No. 1, 1996, pp. 89-95. Journal of Chromatograpic Science, Vol. 34, No. 5, 1996,
[12] Singh, H. and Singh, I. D., "Use of Aromaticity to Estimate Base pp. 219-225.
Oil Properties," Advances Production & Application of Lubricant [23] Sassiat, P., Machtalere, G., Hui, F., Kolodziejczyk, H., and Ros-
Base Stocks, Proceedings International Symposium, H. Singh, set, R., "Liquid Chromatographic Determination of Base Oil
P. Rao, and T. S. R. Tata, Eds., McGraw-Hill, New Delhi, 1994, Composition and Content in Lubricating Oils Containing Dis-
pp. 288-294. persants of the Polybuteneylsuccinimide Type," Analytical
[13] Al-Bamwan, M., "Base Stocks Properties/Characteristics, Chimica Acta, Vol. 306, No. 1, 1995, pp. 73-79.
Additive Response and Their Interrelationship," Advances Pro- [24] Kagdiyal, V., Joseph, M., Sastry, M. I. S., Satapathy, S., Basu,
duction & Application of Lubricant Base Stocks, Proceedings In- B., Jain, S. K., et al., "Estimation of Polycyclic Aromatic Hy-
ternational Symposium, Proceedings, International Symposium, drocarbons of Base Oils by HPLC and by UV Spectroscopic
H. Singh, P. Rao, and T. S. R. Tata, Eds., McGraw-Hill, New Technique: A Comparison," Proceedings of the Advances Pro-
Delhi, 1994, pp. 303-310. duction & Application of Lubricant Base Stocks, Proceedings
[14] Al-Sammerrai, D., "Study of Thermal Stabilities of Some Heat International Symposium, H. Singh and T. S. R. Prasada Rao,
Transfer Oils," Journal of Thermal Analysis, 1985, Vol. 30, No. 4, Eds., Tata McGraw-Hill, New Delhi, India, 1994, pp. 295-302.
pp. 163-110. [25] Jain, M. C , Bansal, V., Jain, S. K., Srivastava, S. P., and Bhat-
[15] Jones, C , "Properties of Hydraulic Fluids," Mechanical World nagar, A. K., "The Role of Thermal and High Temperature Gas
Engineering, January 1964, pp. 3-5. Chromatographic Techniques in the Characterization of Base
[16] Farris, J. A., "Extending Hydraulic Fluid Life by Water and Silt Oils Blends," Proceedings Adv. Prod. Lube Base Stocks, H. Singh
Removal," Field Service Report 52, Industrial Hydraulics Divi- and T. S. R. Prasada Rao, Eds., Tata McGraw-Hill, New Delhi,
sion, Pall Corporation, Glen Cove, NY. India, 1994, pp. 272-279.
[17] Godfrey, D. a n d Herguth, W. R., "Physical and Chemical Prop- [26] Powell, J. R. and Compton, D. A. C. "Automated FT-IR Spec-
erties of Industricil Mineral Oils Affecting Lubrication-Part 4," trometry for Hydrocarbon-Based Engine Oils," Lube Engineer-
Lubrication Engineering, Vol. 51, No. 12, 1995, pp. 977-979. ing, Vol. 49, No. 3, 1993, pp. 233-239.
[18] Adhvaryu, A., Pandey, D. C , and Singh, L. D., "Effect of Com- [27] Anon., "Characterizing Base Oils," Lubrizol Newsline, Lubrizol
position on the Degradation Behavior on the Decomposition of Corporation, Wickliffe, OH, December 1996, pp. 5.
MNL37-EB/Jun. 2003
Non-Lubricating Process Fluids:

Steel Quenching Technology
Bozidar Liscic, ^ Hans M. Tensi, ^ George E. Totten, ^
THIS CHAPTER WILL FOCUS ON QUENCHING TECHNOLOGY FOR STEEL The most common transformation products that may be
HEAT TREATING APPLICATIONS. Quenching is the process of cool- formed in quench-hardenable steels from austenite in order of
ing metal parts to achieve the desired microstructure, hard- formation with decreasing cooling rate: martensite, bainite,
ness, strength or toughness. Quenching can produce both de- peeirlite (which is a mixture of ferrite and cementite), and
sirable and undesirable residual stresses and distortion in pearlite/ferrite. Each of these microstructures provides a
addition to cracking. Steel, for example, is heated to the unique combination of properties, and especially the relation-
austenitizing t e m p e r a t u r e , that t e m p e r a t u r e where the ship between ferrite and cementite in pearlite—depending on
austenite m i c r o s t r u c t u r e is formed. To obtain o p t i m u m the carbon content and the cooling velocity—strongly influ-
hardness, strength, and toughness, the maximum amount of ences the mechanical properties. These transformation prod-
martensite transformation microstructure is desired. The ucts have been described by J.R. Davis (in order of their for-
primary function of the quenching medium is to control the mation with increasing cooling velocity) [2]:
rate of heat transfer from the surface to optimize the mi-
1. Austenite—A microstructural phase characterized by a
crostructure while minimizing undesirable features such as
face-centered cubic iron (gamma iron) crystallographic
cracking and distortion [1].
structure. It is the desired solid solution microstructure
The selection of a quenching medium is dependent on the produced prior to hardening. An austenite microstruc-
composition of the alloy, the desired final microstructure and ture is illustrated in Fig. lA [2].
the surface to volume ratio of the part. The most c o m m o n 2. Ferrite—Â near carbon-free solid solution of one or more
quenchant media are usually liquids or gasses. Liquid quen- elements in a body-centered, cubic arrangement in which
chants include: mineral oils, water, water that may contain alpha iron is the solvent. Fully ferritic steels are only ob-
salt or caustic additives, and aqueous polymer solutions. The tained when the carbon content is very low. Ferritic grain
most c o m m o n gasses, which may or may not be pressurized, boundaries, as illustrated in Fig. IB [2] is the most obvi-
include nitrogen, helium, and argon. ous microstructural feature
Various aspects of quenching technology will be discussed 3a. Pearlite—A microstructural phase characterized by its
in this chapter. This includes: hardenability, fundamentals of body-centered crystallographic structure which is a
quench processing, description of c o m m o n quench media, metastable lamellcir aggregate of ferrite and cementite (or
cooling curve analysis, and quench bath maintenance. In- with an extremely low cooling rate, a mixture of globular
cluded in this discussion is the current status of international cementite in ferrite) whose microstructure is shown in
standards development for quenchant characterization. This Fig. 1C [2] resulting from the transformation of austenite
discussion will be limited to steel quenching technology. at temperatures above the bainite range.
Quenching of non-ferrous alloys are not discussed here
3b. Cementite—Brittle compound of iron and carbon, which
although the basic surface cooling principles involved are
is known as iron carbide with the approximate chemical
the same.
formula FesC and is characterized by an orthorombic
crystal structure. When it occurs as a phase in steel, the
chemical composition will be affected by the presence of
DISCUSSION m a n g a n e s e a n d other carbide-forming elements. The
highest cementite contents are observed in white cast
Steel Transformation irons (Fig. ID) [2].
Properties such as hardness, strength, ductility, and tough- 4. Bainite—Â metastable aggregate of ferrite and cementite
ness are dependent on the microstructure and grain size. The resulting from the transformation of austenite at temper-
first step in the process is to heat the steel to its austenitizing atures below the pearlite transformation temperature,
but above the start of martensite transformation (Ms).
temperature. The steel is then cooled rapidly to avoid the for-
Upper bainite is an aggregate that contains parallel lath-
mation of ferrite and maximize the formation of martensite,
shape units of ferrite and carbides and produces a feath-
which is a relatively hard transformation product, to achieve
ery appearance in optical microscopy, as shown in Fig.
the desired as-quenched hardness.
IE [2]. It is formed above approximately 350°C (660°F).
Lower bainite exhibits an acicular appearance similar to
' University of Zagreb, Zagreb, Croatia. t e m p e r e d martensite, as shown in Fig. I F [2] a n d is
^ Technical University of Munich, Munich, Germany.
^ G. E. Totten & Associates, Inc., LLC, Seattle, WA. formed below approximately 350°C (660°F).
587
i>6- ^.•>fl
(a),(b) ? •'"•-*-.^ (c)
•:>..>'^
.• -^y-.
•vs?i. ••/* •*•
.v^>
(d),(e) - - (f)
mA i^-M'S
f^-i-ii
(g),(h)
FIG. 1—Illustrations of microstructural transformation products:

a) Equiaxed austenite grains and annealing twins in an austenitic stainless steel. 250X; ASM Materials and Engi-
neering Dictionary, ASM International, Materials Park, OH 44073-0002, Fig. 20, p. 26. b) Low-carbon ferritic sheet steel
etched to reveal ferrite grain boundaries-. 100X; ASM Materials and Engineering Dictionary, ASM International, Mate-
rials Park, OH 44073-0002, Fig. 25, p. 30. c) Pearlite structure in high-carbon steel (Fe-0.5C). The cementite lamellae
are white; the ferrite is dark: 500X; ASM Materials and Engineering Dictionary, ASM International, Materials Park, OH
44073-0002, Fig. 26, p. 30. d) White cast iron contains massive amounts of cementite (white) and pearlite (dark): 500X;
ASM Materials and Engineering Dictionary, ASM International, Materials Park, OH 44073-0002, Fig. 64, p. 66. e) Upper
bainite in 4360 steel; ASM Materials and Engineering Dictionary, ASM International, Materials Park, OH 44073-0002,
Fig. 173, p.156. f) Lower bainite (dark plates) in 4150 steel; Reprinted from Ref. 3, p. 67 by courtesy of Marcel Dekker,
Inc. g) Microstructure of lath martensite; 500X; Reprinted from Ref. 3, p. 68 by courtesy of Marcel Dekker, Inc. h) Mi-
crostructure of plate martensite; light shading is retained austenite; 500X; Reprinted from Ref. 3, p. 69 by courtesy of
Marcel Dekker, Inc. i) Microstructure of tempered martensite; 500X; ASM Materials and Engineering Dictionary, ASM
international. Materials Park, OH 44073-0002, Fig. 365, p. 308.
CHAPTER 22: NON-LUBRICATING PROCESS FLUIDS: STEEL QUENCHING TECHNOLOGY 589
5. Martensite—A generic term for microstructures formed CCT Diagrams

by a diffusionless phase transformation in which the par-
Alternatively, seimples of a given steel may be continuously
ent and product phases have a specific crystallographic
cooled at different specified rates and the p r o p o r t i o n of
relationship. Martensite in steel is characterized by its
tremsformation products formed after cooling to various tem-
body-centered tetragonal crysteJlographic structure. The
peratures intermediate between the austenitizing tempera-
a m o u n t transformation from austenite to martensite de- ture and the Ms determined to construct a CCT diagram,
pends on the cooling rate and on the lowest temperature such as the one shown for an unalloyed carbon steel (AISI
attained since there is a distinct t e m p e r a t u r e where 1045) in Fig. 2B. CCT curves provide data on the tempera-
martensitic transformation begins (Ms) and ends (Mf). tures for each phase trzmsformation, the amount of transfor-
Three microstructural forms of martensite are: lath (Fig. mation product obtained for a given cooling rate with time,
IG [3]), plate (Fig. I H [3]) a n d t e m p e r e d (Fig. 11[3]) and the cooling rate necessary to obtain mEirtensite. The crit-
martensite. ical cooling rate is dictated by the time required to avoid for-
The formation of these products and the proportions of mation of pearlite for the particular steel being quenched. As
each are dependent on the austenitization time (because of a general rule, a q u e n c h a n t m u s t produce a cooling rate
increasing solution of elements in austenite with increasing equivalent to, or faster than, that indicated by the "nose" of
time), the time and temperature cooling history of the par- the pearlite transformation curve in order to maximize
ticulcir alloy, and composition of the alloy. The transforma- mEirtensite transformation product. CCT diagrams can only
tion products formed are typicEilly illustrated with the use of be read along the curves of different cooling rates.
transformation diagrams, which show the temperature-time
Caution: Although it is becoming increasingly common to
dependence of the microstructure formation process for the
see cooling curves (temperature-time profiles) for different
alloy being studied. Two of the most commonly used trans- cooling media (quenchants) such as oil, water, air, and oth-
formation diagrams are TTT (time-temperature-transforma- ers superimposed on either TTT or CCT diagrams, this is not
tion) a n d CCT (continuous cooling transformation) dia- a rigorously correct practice and various errors are intro-
grams. duced into such analysis due to the inherently different ki-
netics of cooling used to obtain the TTT or CCT diagrams ver-
TTT Diagrams sus the quenchants being represented. A continuous cooling
TTT diagrams, which are also called isothermal transforma- curve can be superimposed on a CCT, but not on a TTT
tion (IT) diagrams, are developed by heating small samples of diagram.
steel to the t e m p e r a t u r e where austenite transformation
structure is completely formed i.e., austenitizing tempera-
Hardenability
ture, and then rapidly cooling to a temperature intermediate
between the austenitizing and the Ms temperature, and then Hardenahility has been defined as the ability of a ferrous ma-
holding for a fixed period of time until the transformation is terial to develop hardness to a given depth after being austen-
complete, at which point the trcinsformation products are de- itized and quenched. This general definition comprises two
termined. This is done repeatedly until a TTT diagram is con- subdefinitions, the first of which is the ability to achieve a
structed such as that shown for a n unalloyed steel (AISI certain hardness [4]. The ability to achieve a certain hcirdness
1045) in Fig. 2A. TTT diagrams can only be read along the level is associated with the highest attainable hardness,
isotherms. which depends on the carbon content of the steel and more
Austenite Temperature = 880 °C
800 A3 ill
m
III Austenite Temperature = 880 °Q,
700 A l T] LUpea rlite - StartI
li Pea lite- End
T Fe •rite -Sta
5 - BOO
2 500
Bajnite - £>ta 1
1
2 m
Q. Bainite End
fc m ^ I v i d r i i
1-
eoo
site^
1 II 1
700
n
7
Seconds
17(7' B]pi0' 10^
1 II
10*
T l » h 15 30 ffb 7 S f B 75 30
Minutes 7 d t SB 1Sl* Minutes T S ifB8 1BSt
(a) -Time- Hours -Time- l-lours (b)
FIG. 2—a) Time-Temperature-Transformation (TTT) diagram of an unalloyed steel containing 0.5% carbon; b) Continuous-
Cooling-Transformation diagram of an unalloyed steel containing 0.6% carbon.
specifically on the amount of carbon dissolved in the austen-

ite after austenitizing. ^600
This is illustrated by considering the problem of hardening
of high-strength, high-carbon steels. The higher the concen-
tration of dissolved c a r b o n in the austenitic phase, the E
greater the increase in mechanical strength after rapid cool- S.400
ing and transformation of the austenite in the metastable E
martensite phase. Martensitic steels typically exhibit increas-
<D "^N^
\-
ing hardness and strength with increasing carbon content, as C \M,
shown in Fig. 3, but they also exhibit relatively low ductility. o
However, with increasing carbon concentration, martensitic ro 200
transformation from austenite becomes more difficult, re- CO
sulting in a greater tendency for retained austenite and cor-

respondingly lower strength.
I 0 0.5 1.0 1.5
The second subdefinition of hardenability refers to the Carbon Content (wt. %)
hardness distribution within a cross section from the surface
to the core under specified quenching conditions. It depends FIG. 4—Influence of the carbon content in steels on
the temperature of the start of martensite formation
on the carbon content, which is interstitially dissolved in
(Ms) and the end of martensite formation (Mf).
austenite and the a m o u n t of alloying elements substitution-
ally dissolved in the austenite during austenitization. There-
fore, as Fig. 3 shows, carbon concentrations in excess of 0.6%
Equivalent bar diameter. In.
do not yield correspondingly greater strength [7]. Also, in-
creasing carbon content influences the Mf temperature rela- 1 2 3 4 5 6 7
tive to Ms during rapid cooling as shown in Fig. 4 [8]. In this 175 1
figure, it is evident that for steels with carbon content above Round Dars-
E
0.6%, the transformation of austenite to martensite will be
E 150
incomplete if the cooling process is stopped at 0°C or higher. m
in
Squ are bi jrs — w
The depth of hardening depends on the following factors: <o c
• Size cmd shape of the cross section = 125
o
• Heirdenability of the materiEd
• Quenching conditions
The cross section shape exhibits a significant influence on
_o
E.
t 100 1
Plates
heat extraction during quenching and therefore, on the hard-
0) *0)
-»
ening depth. Heat extraction is dependent on the surface area I 75 <u
exposed to the quenchant. Bars of rectangular shape achieve e

(0
't 50 TJ
o
3 *-^
T3 u
O
25 •D
O
150
2
f 0
25 50 75 100 125 150 175
Equivalent bar diarneter, mm
100
FIG. 5—Correlation between rectangular cross sections and
D)
C their equivalent round bar and plate sections.
£
w less depth of hardening than round bars of the same cross
•^ 50 section size. Figure 5 can be used to convert square and rect-
>- 0.2 0.4 0.6 0.8 angular cross sections to equivalent circular cross section
Carbon Content (wt. %) sizes [6].
I The effect of steel composition on hardenability may be
30 25 20 calculated in t e r m s of the "ideal critical diameter" or Di,
Nickel Content (wt. %) which is defined as the largest b a r diameter t h a t can be
quenched to p r o d u c e 50% martensite at the center after
FIG. 3—Influence of the carbon content in steel on quenching in an "ideal" quench, i.e., under "infinite" quench-
the yield strength {ao.e) after quench hardening. The
ing severity. The ideal quench is one that reduces surface
yield strength values were obtained from compres-
sion tests; the additional variation of nicltel content temperature of a n austenitized steel to the bath temperature
causes a negligible solid-solution-hardening and was instctntaneously. Under these conditions, the cooling rate at
selected to obtain a constant Ms temperature for the the center of the bar depends only on the thermal diffusivity
start of martensitic transformation. of the steel.
The ideal critical diameter may be calculated from: Determination of spatial grain size, that is, measurement of
the size of the three-dimensional grains in the specimen vol-
Di = Di Base (carbon concentration and grain size) ume, is beyond the scope of these test methods.
X fmn X f s i ^ f c r ^ fiVIo X /V X f c u X /"NI X f^ The test methods described in E 112 are techniques
performed manually using either a standard series of graded
Where fx is a multiplicative factor for the particular substitu- cheirt images for the comparison method or simple templates
tionally dissolved alloying element. The base Dj Base value and for the manual counting methods. Utilization of semi-
one set of alloying factors are provided in Table 1 [6] (Note: automatic digitizing tablets or automatic image analyzers to
This is not an exhaustive listing of alloying factors but these measure grain size is described in Test Method E 1382.
are commonly encountered and they permit calculations to
illustrate the effect of steel chemistry variation on harden- The ASTM grain size number (G), referred to in Table 1, is
ability.) a grain size designation bearing a relationship to average in-
tercept distance at 100 diameters magnification according to
Grain size refers to the dimensions of grains or crystals in the equation:
a polycrystalline metal exclusive of twinned regions and sub-
grains when present. Grain size is usually estimated or mea- G = 10.00 - 21og2L
sured on the cross section of an aggregate of grains. Common
units are: (1) average diameter, (2) average area, (3) number Where L = the average intercept distance at 100 diameters
of grains per linear unit, (4) number of grains per unit area, magnification. The smaller the ASTM grain size, the larger
and (5) number of grains per unit volume. the diameter of the grains.
The effects of quenching conditions on the depth of hard-
Grain size may be determined according to Test Method E
ening are not only dependent on the quenchant being used
112. The test methods covered in Test Method E 112 describe
and its physical and chemical properties, but also on process
the measurement of average grain size and include the com-
parameters such as bath temperature and agitation.
parison procedure, the planimetric (or Jeffries) procedure,
and the intercept procedures. Standard comparison charts
are provided. These test methods apply chiefly to single phase Hardenability Measurement
grain structures but they can be applied to determine the av-
erage size of a particular type of grain structure in a multi- There are numerous methods to estimate steel hardenability.
phase or multiconstituent specimen. However, perhaps the two most common are: Jominy curve
In addition, the test methods provided in E 112 are used to determination and Grossmann hardenability. These two pro-
determine the average grain size of specimens with a uni- cedures will be discussed here.
modal distribution of grain areas, diameters, or intercept
lengths. These distributions £ire approximately log normal. Jominy Bar End-Quench Test
These test methods do not cover methods to characterize the The most familiar and commonly used procedure for mea-
nature of these distributions. Characterization of grain size suring steel hardenability is the Jominy bar end-quench test.
in specimens with duplex grain size distributions is described This test has been standardized and is described in ASTM A
in Test Method E 1181. Measurement of individual, very 255, SAE J406, DIN 50191, and ISO 642. For this test, a 100
coarse grains in a fine-grained matrix is described in Test mm (4 in.) long by 25 mm (1 in.) diameter round bar is
Method E 930. These test methods deal only with determina- austenitized to the proper temperature, dropped into a fix-
tion of planar grain size, that is, characterization of the two- ture, and one end rapidly quenched with 24°C (75°F) water
dimensional grain sections revealed by the sectioning plane. from a 13 mm (0.5 in.) orifice under specified conditions, as
TABLE 1—Hardenability factors for carbon content, grain size and selected alloying elements in steel.
Carbon Grain Size No. Alloying Element
Carbon
Content (%) 6 7 8 Mn Si Ni Cr Mo
0.05 0.0814 0.0750 0.0697 1.167 1.035 1.018 1.1080 1.15
0.10 0.1153 0.1065 0.0995 1.333 1.070 1.036 1.2160 1.30
0.15 0.1413 0.1315 0.1212 1.500 1.105 1.055 1.3240 1.45
0.20 0.1623 0.1509 0.1400 1.667 1.140 1.073 1.4320 1.60
0.25 0.1820 0.1678 0.1560 1.833 1.175 1.091 1.54 1.75
0.30 0.1991 0.1849 0.1700 2.000 1.210 1.109 1.6480 1.90
0.35 0.2154 0.2000 0.1842 2.167 1.245 1.128 1.7560 2.05
0.40 0.2300 0.2130 0.1976 2.333 1.280 1.146 1.8640 2.20
0.45 0.2440 0.2259 0.2090 2.500 1.315 1.164 1.9720 2.35
0.50 0.2580 0.2380 0.2200 2.667 1.350 1.182 2.0800 2.50
0.55 0.273 0.251 0.231 2.833 1.385 1.201 2.1880 2.65
0.60 0.284 0.262 0.241 3.000 1.420 1.219 2.2960 2.80
0.65 0.295 0.273 0.251 3.167 1.455 1.237 2.4040 2.95
0.70 0.306 0.283 0.260 3.333 1.490 1.255 2.5120 3.10
0.75 0.316 0.293 0.270 3.500 1.525 1.273 2.62 3.25
0.80 0.326 0.303 0.278 3.667 1.560 1.291 2.7280 3.40
0.85 0.336 0.312 0.287 3.833 1.595 1.309 2.8360 3.55
0.90 0.346 0.321 0.296 4.000 1.630 1.321 2.9440 3.70
0.95 4.167 1.665 1.345 3.0520
1.00 4.333 1.700 1.364 3.1600
illustrated in Fig. 6 [3]. The austenitizing temperature is se-

lected according to the specific steel alloy being studied, how-
ever, most steels are heated in the range of 870-900°C
270 70 18 5-6
4B9-\Z4'-32.3"1<y
y.6 V,. y.« 'V,,
r,i}cooling rates
(1600-1650OF). Distance from quenched end., in.
-rr- 1 - ^
In the Jominy end-quench test, a cylindrical specimen is
heated to the desired austenitizing temperature and well-
defined time, which is material composition dependent, and
then it is quenched on one end with water. The cooling ve-
1 "a
\U
locity decreases with increasing distance from the quenched
end. After quenching, parallel flats are ground on opposite 60
sides of the bar and hardness measurements are made at 1/16
in. (1.6 mm) intervals along the bar, as illustrated in Fig. 7
[6]. The hardness as a function of distance from the
quenched end is measured and plotted and, together with
50 •
measurement of the relative areas of the martensite, bainite,

and pearlite that is formed, it is possible to compare the hard-
enability of different steels using Jominy curves. As the slope S 40
of the Jominy curve increases, the abiUty to harden the steel I
(hardenabihty) decreases. Conversely, decreasing slopes (or
increasing flatness) of the Jominy curve indicates increasing 230
hardenabihty (ease of hardening). •o
The Jominy end-quench is used to define the hardenabihty 0
of carbon steels with different alloying elements like ^ M '
chromium (Cr), manganese (Mn), molybdenum (Mo) and
has different critical coohng velocities. Jominy curves for dif-
ferent alloy steels are provided in Fig. 8 [9]. These curves il- to
lustrate that the unalloyed, 0.4% carbon steel exhibits a rela-
tively small distance for martensite (high hardness)
formation. The 1% Cr and 0.2% Mn steel, however, can be
1.0 2.0 3.0 in.
» ' ' « ' ' -^—I I t I—
hardened up to a distance of 40 mm. Figure 8 illustrates that 25
steel hardenabihty is dependent on the steel chemistry, that 50 75 mm
unalloyed steels exhibit poor hardenabihty, and that Jominy
curves provide an excellent indicator of relative steel harden- Distance from quenched end
abihty. FIG. 7—Measuring hardness on the Jominy test specimen
The Jominy test provides valid data for steels having an and plotting hardenability curves.
ideal diameter from about 25-150 mm (1-6 in.). This test can
be used for Di values less than 25 mm (1 in.), but Vickers or
microhardness tests must be used to obtain readings that are to making hardness measurements are important factors that
closer to the quenched end of the bar and closer together influence test results. Therefore, all tests should be con-
than generally possible using the standard Rockwell "C" ducted in compliance with the standard being followed [4].
hardness test method [4].
Grossmann Hardenability
The austenitizing time and temperature, extent of special
carbide solution in the austenite and extent of oxidation or Grossmann's method of measuring hardenability uses a
surface decarburization during austenitizing, care and con- number of cylindrical steel bars of different diameters hard-
sistency of surface flat preparation, and bar positioning prior ened in a given quenching medium [6]. Aftier sectioning each
bar at mid-length and examining it metallographically, the
bar that has 50% martensite at its center is selected, and the
diameter of this bar is designated as the critical diameter D^^f
Other bars with diameters smaller than Dent will have more
martensite and correspondingly higher hardness values and
„ ... iwith increasing bars with diameters larger than D^ît will attain 50% marten-
Pearlite fdistance ofttie
I Cemenlite Lamella site only up to a certain depth as shovro in Fig. 9 [4]. The D^^^
value is valid only for the quenching medium and conditioiTs
used to determine this value.
Probi
To determine the hardenability of a steel independently of
the quenching medium, Grossmann introduced the term
Water- 200 400 600 800 ideal critical diameter, Di, which as discussed previously, is
Nozzle—i Hardness (H,) the diameter of a given steel bar that would produce 50%
martensite at the center when quenched in a bath of quench-
FIG. 6—Schematic illustration of the Jominy end-quench test ing intensity H = oo. Here H = co indicates a hypothetical
and microstructural variation with increasing distance from the quenching intensity that reduces the temperature of heated
quenched end. steel to the bath temperature in zero time.
To identify a quenching medium and its condition, Gross- TABLE 2—Effect of agitation on quench severity as indicated by
m a n n introduced the Quenching Intensity (Severity) factor Grossmann quench severity factors (H-factors).
"H". Table 2 provides a summary of Grossmann H-Factors Grossmann H Factor
for different quench media and different quenching condi- Agitation Oil Water Caustic Soda or Brine
tions [1]. Ahhough this data has been pubhshed in numerous None 0.25-0.3 0.9-1.0 2
reference texts for many years, it is of relatively limited quan- Mild 0.30-0.35 1.0-1.1 2-2.2
titative value. One of the most obvious reasons is that quen- Moderate 0.35-0.4 1.2-1.3
chant agitation is not adequately defined and is often un- Good 0.4-0.5 1.4-1.5
Strong 0.5-0.8 1.6-2.0
known, yet it exhibits enormous effects on quench severity.
Violent 0.8-1.1 4 5
The Grossmann value "H" is based on the Biot (Bi) num-
ber, which interrelates the interfacial heat transfer coeffi-
cient (a) thermal conductivity (A) and the radius (R) of the
round bar being hardened:
Bi = a/\-R = H-D
H = al{2- X)
Since the Biot number is dimensionless, this expression means

that the Grossmann value, H, is inversely proportional to the
b a r diameter. This method of numerically analyzing the
quenching process presumes that heat transfer is a steady
state, linear (Newtonian) cooling process. However, this is sel-
dom the case and almost never the case in vaporizable quen-
chants such as oil, water, and aqueous polymers. Therefore, a
significant error exists in the basic assumption of the method.
Another difficulty is the determination of the //-value for a
cross section size other than one experimentally measured.
In fact, //-values depend on cross section size. Values of H do
not account for specific quenching characteristics such as
composition, oil viscosity, or temperature of the quenching
bath. Tables of //-values do not specify the agitation rate of
the quenchant either uniformly or precisely (see Table 2).
Therefore, although //-values are commonly used, more cur-
rent and improved procedures ought to be used when possi-
ble. For example, cooling curve analyses a n d the various
methods of cooling curve interpretation that have been re-
ported [1,5] are all significant improvements over the use of
0 10 20 30 40 50
Grossmann Hardenability factors.
Distance from the Quenched Front Side (mm)
FIG. 8—Jominy curve comparison of the hardenability of one Q u e n c h i n g F i m d a m e n t a l s a n d C o o l i n g Curve
unalloyed and a number of other different alloy steels. All alloy Analysis
concentrations are weight %.
Steel Wetting Kinetics
Hardening of steels (so cedled Martensitic- or Bainitic- Hard-
GO ening) requires preheating (austenitizing) of the steel to tem-
peratures in the range of 750-1100°C, from which the steel is
i 40
M quenched (cooled) in a defined way to obtain the desired me-
chanical properties such as hardness a n d yield strength.
r-i- Most liquid vaporizable quenchants used for this process ex-
i/i -HRC .,s50%M hibit boiling temperatures between 100 and 300°C at atmo-
a> Cfll
spheric pressure. When parts are quenched in these fluids,
"I 20 -?c•^t^ the wetting of the surface is usually time dependant, which
o
I influences the cooling process and the achievable hardness.
1 G. J. Leidenfrost described the wetting process about 250
years ago [10]. The Leidenfrost Temperature is defined as the
'm» surface temperature where the vapor film collapses and the
surface is wetted by the liquid. Literature describes tempera-
ture-values for this event for water at atmospheric pressure
between 150 and 300°C [11-14]. It is apparent that the Lei-
FIG. 9—Determination of critical diameter Dcrit according to denfrost Temperature is influenced by a variety of factors,
Grossmann. part of which cannot be quantified precisely even today.
For a nonsteady state cooling process, the surface temper- surface, which will depress the heat flux from the specimen
ature at all parts of the workpiece is not equal to the Leiden- into the fluid.
frost Temperature. When the vapor blanket (or film boiling)
collapses, wetting begins by nucleate boiling due to the influ- Factors Influencing Film Boiling
ence of lateral heat conduction (relative to the surface) [15]. To quantitatively define the change of the wetting behavior,
This is due to the simultaneous presence of various heat for example, to ascertain the cooling process or to develop or
transfer conditions during vapor blanket cooling (or film aneJyze quenching fluids, the measurement of the electrical
boiling [FB]), nucleate boiling [NB], and convective heat conductance between the submerged sample and a counter
transfer [CONV] with significantly varying heat transfer co- electrode is helpful [13]. During the film boiling phase, the
efficients apB (100 to 250 W/irn^K)); aNB (10 to 20 kW/{m^K)y, hot metal is largely insulated by the vapor film surrounding
and ttcoNv (ca. 700 W/(m'^K)). Figure 10 schematically illus- the metal and conductance between the metal a n d the
trates the different cooling phases on a metcJ surface during counter electrode is low. When the vapor blanket (film boil-
an immersion cooling process with the so-called "wetting ing) ruptures on the metal surface, localized wetting begins
front," w, (separating the "film boiling phase" and the "nu- and conductance increases. The increase in conductance of
cleate boiling phase") and the change of the heat transfer co- the wetted metal is proportional to the amount of the metal
efficients, a, along the surface coordinate, z, (mantle line). In surface wetted by the quenchant. When the metal surface is
most cases during immersion cooling, the wetting front as- completely wetted, conductance is at its highest value.
cends the cooling surface with a significant velocity, v, Figure 13a schematically illustrates a normal electrical
whereas during film cooling the wetting front descends in the conductance, (G) increase corresponding to the percentage
fluid direction [13,16]. of the wetted surface (compare Fig. 11A or 1 IB). Three other
An example of wetting heated cylindrical and prismatic possibilities of wetting are also shown. Figure I3b shows a
specimens which are submerged in water is shown in Fig. rapid rewetting process (or "explosive" wetting) similar to
1 l a and fo [13,17]. Because of the different wetting phases on that shown in Fig. 12. Figure 13c illustrates rapid wetting fol-
the metal surface (and the enormous differences of their val- lowed by insulation by bubbles adhering to the metal surface
ues of apB,ttNB,and acoNv). the time dependant temperature and Fig. I3d illustrates rapid wetting with repeated new for-
distribution within the metal specimens will also be influ- mation of film boiling, a process which occurs with many
enced by the velocity and geometry of the wetting front (for aqueous polymer quenchant solutions. In all four diagrams,
example, circle or parabolic-like) as well as geometry of the the temperature, Tc, is shown, which is measured in the cen-
quenched part. ter of the probes. The time, ts, characterizes the time (and the
Figure 12 illustrates different types of wetting behavior un- corresponding temperature value from the Tc (t) slope, the
der different conditions [17]. By changing a quenching pa- temperature Ts) when wetting begins. This shows that tem-
rameter, for example the chemical composition of the fluid, perature measurements in the center of probes provide poor
the period of wetting (tw) can be reduced over more than one information about the real quenching process that is insuffi-
order of magnitude. The time interval, t^^, when the wetting cient to adequately characterize the hardening process. This
front appears—usually at the lower end of the specimen—ûp is also illustrated in Fig. 14 [19] by T(t) slopes, measured in
to the time the wetting front has moved across the entire the center and the surface of cylindrical probes, quenched in
specimen surface; sometimes two wetting fronts appear as il- water with t^v + 0, and in an aqueous poljTner solution with
lustrated in Fig. l i d . In addition to explosive-like wetting a short ty^ time.
(fw ~ 0), a foam may appear in the fluid neeir the specimen To obtain a better definition of the wetting kinematic, the
starting time, ts, of wetting, the finishing time, tf, of wetting
and the difference between tf and ts as the wetting time fi^
should be used. The effect of vEiriation of these parameters on
Immersion cooling the quenching process is summarized in Table 3.
Film boiling
Wetting front»
Impact of the Wetting Process o n Cooling

Nucleate boiling Behavior
Convective beat An illustration of the influence of a wetting process occurring
transfer
Heal transfer over a long time (a so-called "non-NEWTONIAN wetting") on
coefficient at the temperature - time cooling curves, measured near the
Film cooling surface at different distances from the lower end of the
Film of liquid probe, is illustrated in Fig. 15 [17]. The wetting front requires
Convection boiling
about 18 s to arrive at a height of Z = 80 m m taken from the
discontinuities of the curve "0" (ca. Is) and curve "80" (ca.
19s). If there is an explosion-like wetting of the probe (a so
called "NEWTONIAN wetting"), these five t e m p e r a t u r e
Fluid drops slopes cire congruent. If the temperature was measured (like
usucJ) in the center of the probe, the large differences in wet-
Wetting front ir
ting behavior would not be observed.
FIG. 10—Wetting behavior and cliange of heat transfer coef- The temperature distribution within the probe during
ficient a along the surface [13,16]. quenching (indicated by isotherms at different times after
(a) 4.0 s 7.0 s 10 s
(b) 3.8 s 5.7 s 6.9 s

3^2 s 4,92 s
(c) 4.3 s 8.3 s 12,3 5,97 s 7,38 s (d)

FIG. 11—Process of transition between tlie three cooling phases—film boiling (FB), nucleate boiling (NB) and con-
vective cooling (CONV) during immersion cooling of CrNi -steel specimens with a cylindrical geometry 25 mm dia x 100
mm), a. Wetting process of a cylindrical CrNi-steel specimen being quenched from 850°C into water at 30°C with an ag-
itation rate of 0.3 m/s b. prismatic geometry (15 x 15 x 45 mm) in water of 60°C without forced convection; Immersion
temperature of 860°C, c. CrNi-steel probe (25 mm dia. x 100 mm) in oil at 60°C without agitation, d. hollow cylinder (60
od X 30 id X 60 mm long) quenched into oil at 60° and no agitation. Note: there are two wetting fronts.
beginning the quenching process), having a "non-NEWTO- Cooling Curve Data Acquistion and Analysis
NIAN wetting" is shown in Fig. 16a. where there is a great
difference relative to that of the "NEWTONIAN wetting" Data Acquistion and Analysis
(Fig. 166). In the second case, the temperature gradient, T, The need to acquire sufficient data to adequately define a
is radial whereas in the case 'a it is axial. Of course the cooling curve for subsequent analysis has long been recog-
hardness distribution in the probes must be extremely dif- nized. Special data acquisition devices, including hardware
ferent. In the case of "a," a strong axial hardness distribu- such as oscillographs, were used for work reported by Jominy
tion (accompanied by a very low radial hardness distribu- [20], French [21], and others [21,22]. However, this equip-
tion); in the case of "b," a very strong radial hardness ment is difficult to calibrate, which has inhibited widespread
gradient is observed. use of cooling curve analysis. Currently, sufficient data ac-
quisition rates can be achieved with personal computers 1000

equipped with analog-to-digital (A/D) converter boards. (a) (b) r",
Although computer hardware is available, there are no ! ; a 3
published guidelines for selecting the proper data acquisition
O 750 * c_ i «
2
o
rate, which varies with probe alloy, size, and quench severity. JO \
1
Perhaps the best method for selecting the required acquisi- £ 2 \
S 500 1 "* \
tion rate is to determine it experimentally. This can be done
by repeatedly quenching a probe in cold (25°C, or 77°F) wa-
ter, one of the more severe quenchants, and collecting data at
(0
ki.
ID
Q.
AK /Water
/3
E
9
250 polymer ^
X. 1-3 ^
10 20 30 40 0 10 15 20
Time in s Time in s
FIG. 14—Comparison of cooling curves measured at differ-
ent positions in a cylindrical CrNi-steel probe (25 dia. x 100
mm) during slow wetting (water) and sudden wetting (aqueous
polymer solution) at (a) center and (b) close to the probe sur-
face at three indicated heights (1,2, and 3).
TABLE 3"—Effect of fluid and metal property variation

on quench severity.
Effect on Property Variation
6.35 s 7.65 s (t == Increasing, 4- =Decreasing)
FIG. 12—Transition from film boiling (FB) to nucle- Fluid Property ts.tf Atw a
Type of quenchant ti ti
ate boiling (NB) during immersion of cylindrical silver
specimen (15 mm dia x 45 mm) quenched from 850°C
Addition of additives
Increasing agitation (v)
n
Ti Ti ti
into a 10% aqueous polymer quenchant solution at i i t
Increasing bath
25°C without agitation [18] In comparison with the Temperature (Tt)
tw-values of Fig. 13 a and b, the wetting time is ex-
T T i
Metal Property
tremely short [18]. Increasing thermal
Diffusivity (a) T t t
Increasing cross
section Size T T i
Increasing surface
iIk (a) Roughness i i
G t
Increasing surface
i^
0) Oxidation i i i
1 ".Parameters: ts'. time when wetting starts; tf. time when wetting is finished;
m Atw- time interval of wetting [s]; a: heat transfer coefficient.
<o
o.
E
0) ^ ^
timet ts = tf timet various acquisition rates. For example, a 13 mm X 100 mm

(1/2 in. X 4 in.) cylindrical Inconel 600 probe with a tjqje K
thermocouple inserted at the geometric center was quenched
into 25°C (77°F) water with data acquisition rates of 1, 2.5,
and 5 Hz. (A "hertz" value is equivalent to a data point per
second.) The corresponding cooling time and rate curves are
shown in Fig. 17 [5]. These results show that for this particu-
lar probe, a data acquisition rate of at least 5 Hz was required
to obtain a smooth cooling rate curve in the maximum cool-
ing rate region. Smooth curves are required to minimize er-
timet rors in determining the maximum cooling rate in this critical
region of the quenching process.
FIG. 13—a-d): Temperature decrease, Tc, and in-
In data acquisition, the proper A/D converter card must be
creasing electrical conductance, G, (proportional to
the wetted surface) during quenching in different selected to match the thermocouple being used. The thermo-
quenchants; a) slow wetting, b) rapid (explosive-like) couple output is nonlinear with respect to temperature. If
wetting; c) rapid wetting followed by isolation of bub- software for data analysis is being written for this use, this
bles adhering to the metal surface; d) rapid wetting nonlinearity must be taken into account. One method is to
with repeated formation of film boiling after this pro- create a data file that will convert thermocouple electromo-
cess (see also Figs. 14 and 15) [13,18]. tive force (emf) values to the appropriate temperature.
Tjîcal data acquisition errors were found to be ±0.5°C

(±0.9°F) within the temperature range of 0-900°C
(32-1650°F). Another source of error is the algorithm used to
calculate cooling rates. In general, however, it was found that
the error obtained was primarily a result of an error in the
data.
Most data have some background noise; consequently,
most data acquisition techniques employ data averaging or
smoothing to minimize the noise. One method is a five-point
"running" average [24]:
r„ = {-%5Tn^2) + (%r„_i) + (%rj
+ (%rn+i)-e/35j„+2)
where T is the temperature at the n,n - \,n + l,n - 2, and
n + 2 groups of points being averaged. A running average
means that after T^ is calculated, the average of the next (n +
1) point is then averaged. This process is continued until all
of the data points have been averaged.
Another feature of the A/D converter card that must be con-
15 20 sidered is ice-junction compensation. Because thermocou-
Quenching time ples are only able to measure temperature differences, to ob-
tain accurate temperature measurements, it is important to
FIG. 15—^Temperature drop on the surface of a cylindrical calibrate to a reference temperature, typically ice water.
steel probe (25 mm dia x 100 mm) at various distances zfrom
the lower end [16].
Cooling Time and Rate Parameters
In recent years, several rate- and time-dependent parameters
have been suggested to quantify the severity of various quen-
chant media. Some of these parameters include the cooling
rates at 705 and 205°C (1300 and 400°F), maximum cooling
rate, and time to the cooling rate at 730-260°C (1350-500°F)
[48]. It is generally desirable to maximize the cooling rate at
705°C (1300°F) to avoid the pearlite transformation region. It
is desirable to minimize the cooling rate at 205°C (400°F),
which is in the region of the Ms transformation temperature
for many steels, to minimize cracking. It is also desirable to
/=5s
minimize the time to cool from 730-260°C (1350-500°F) in
order to optimize the potential hardness by avoiding pearlite
formation.
Tensi and Steffen [25] have prepared a set of critical cool-
ing parameters for cooling curve characterization as shown
in Fig. 18:
-825'C • Full-film boiling (vapor blanket cooling) to nucleate boil-
ing transition time, temperature, and rate,i?DHmin- These
parameters characterize the transition from A- to B-stage
-775"C cooling.
t=5s /=10s /=11s /=15s
• Maximize the rate of cooling, i?max. and the temperature
FIG. 16—a and b) Time-dependant temperature distribution where this occurs, TRmax- GenereJly, it would be desirable
during cooling of cylindrical steel probes (25 mm dia x 100 to maximize i?max and minimize ?Rmax-
mm) in the case of slow non-Newtonian wetting and explo- • Rate of cooling at temperatures such as 200°C (i?2oo) and
sive Newtonian wetting. 300°C, (i?3oo)- In order to minimize cracking and distor-
tion, it is desirable to minimize cooling rates in this region.
• Although the dimensions for cooling rate most typically
Zhu [23] analyzed computer data acquisition for cooling used throughout the heat treating industry are [°C/s], this
curve analysis and reported the following sources of error: is physically incorrect. The correct units for cooling rates
• Thermocouple voltage to temperature conversion are [K/s].
• A/D signed conversion One problem with this approach is the potential misinter-
• Preamplifying circuit and signal transmission circuits pretation of low cooling rates in the Ms transformation re-
• Electronic component instability gion. Traditionally, it has been thought that minimizing the
• Error caused by signal interference cooling rates in the Ms transformation region is essential for
Dana collected at 1 HZ
60 Time (sec.)
20 40 60 80 100 120 140 Cooling rate (C/sec.,
Data collected at 2.5 HZ

800
•
i
_^^ «
^ 600 - •
•
w •
3 •
13 -•
w 400 *
Q.
EV
«
1- -•
•
200 w
n 1 11 t • 1 »
10 2G 30 40 50 60 Time (sec.)
0 20 40 60 80 100 120 140 Cooling rate rc/sec.j
Daita collected at 5 HZ
60 Time (sec.)
0 20 40 60 80 100 120 140 Cooling rate fCsec.)
FIG. 17—Effect of data acquisition rate on cooling rate curve smoothness.

minimizing cracking and distortion. This is desirable, but not Hardening Capability (Power)
necessarily a sufficient, condition for reduction of quench
Segerberg [27] has developed an empirical approach for de-
cracking. Zhelokhovtseva [26] has shown that uniformity of
termining of hardening power (HP) of quench oils without
cooling in the Ms region is also critical parameter. It seems
agitation. Segerberg's hardening power approach utilized
reasonable, therefore, that minimal and uniform cooling
cooling curves obtained with the Wolfson probe shown in
rates to minimize stresses that occur due to thermal gradi-
Fig. 19 (see ASTM D 6200). After the cooling curve was de-
ents are probably the necessary and sufficient conditions for
termined according to ASTM D 6200 (or ISO 9950), statisti-
optimizing quenchants in the Ms temperature region.
cal correlation of hardness and cooling rate data provided the
following regression equation:
HP = 3 . 5 4 C R F -1- 12.30 CRM - 168
Where: CR^ is the cooling rate at 550°C (990°F) which is the

at, or at least near, the nose of the pearlitic transformation
for many steels and CRM is the cooling rate at 330°C (595°F),
which is near the Ms temperature for many steels [5].
Segerberg [27] used this procedure to predict the as-
quenched hardness achievable with a commercial quench
system, by strategically placing a series of instrumented steel
probes throughout a typical quench load. The hardening
power at these various positions was calculated from the
above regression equation. Using the correlation curve for
the steel of interest (e.g., the curve for the AISI 1045 steel
shown in Fig. 20, it is possible to predict the hardness for
steel bar with a 16 mm Dia. (0.6 in.) cross section. A similar
procedure can be used for other alloys and different cross
section sizes.
Shock Film Boiling

Time
Full-film boiling, nucleate boiling, and convective cooling
FIG. 18—Critical cooling curve parameters. heat transfer modes have been studied by various authors
-30mm 30mm- M—6mm

9.5mm
13mm (12.5mm after

- f finish grinding)
Not to be 1.5mm tight push
center drilled fit "nominar
Probe details
Support tube Mineral Insulated thermocouple

Material - Inconel alloy 600 Type'K-CNiCr/NIAI)
Tl£^t fit on probe end iwith Sheath materlaNlncone) alloy 600
30° angle weld allowance Diametei=1.5mm; Route length- End support
Probe body Finish Dimensions as (a) 190mm min; Talls-25mm
Details Infig.3(a^ grind Hot iunction~lnsulated; cold seal= -tube
epoxy resin Material» Stainless steel
12.5 ± 0 . 0 1 mm
Termination
Standard tttermocouple
typeV(NlCf/NlAI)
General assembly
FIG. 19—^Wolfson Inconel 600 probe.
Acoustical Measurements
i I
A schematic of the experimental device is shown in Fig. 21
60 • [38]. The working firequency of the acoustical detector is 0-20
kc, which is further divided into 200 channels. The width of
each channel is 100 c/s. E a c h heat transfer mode shock-
boiling, full-film boiling, a n d nucleate boiling is observed
acoustically at characteristic frequencies. These are summa-
50 rized in Table 4.
Note: ASTM E 131 defines frequency as "the number of cy-
DC cles (c) per unit time." ASTM E 349 states "When the inde-
pendent variable is time, t h e unit of frequency is the hertz.
Symbol: Hz (1 H z = P ' ) . (This unit is also called "cycle per
second c/s".) The term "kc" means kilicycles and as used in
-o 40 the above discussion, 0-20 kc means 0-20 000 cycles.
(0 Sound amplitude is proportional to the intensity of the
X
boiling process. High frequencies can be used to detect the
initiation of shock boiling. The time difference corresponds
to the duration of t h e full-film boiling. Knowing t h e r m o -
30 physical properties of the standard sample and duration of
» - full-film boiling, the second critical heat flux density can be
determined [35,36]. From the duration of the fuU-film boiling
HP == 3.54 CRp + 12.30 CR|y| - 168 and nucleate boiling phases a n d the second critical heat flux
density it is possible to characterize quenching capacity.
20 — • A 20 m m silver probe has been utilized, which had a sol-
0 200 400 600 800 1000 dered 0.1 m m chromel-alumel thermocouple inserted t o in
Hardening power (HP) the center of the probe, as shown in Fig. 22. The thermocou-
ple was in a 1.5 m m metal case filled with insulating materisJ.
FIG. 20—Quenchant classification by hardening power. The thickness of the case wall is 0.1 m m .
The piezoceramic sensor for acoustic noise detection was
[31-34]. A m u c h less studied and understood heat transfer

process is shock-film boiling. Shock-film boiling refers t o the
initial formation of the vapor film around the hot metal upon
initial immersion. In most experiments, this cooling process
is not detected unless surface temperature-time measure-
ments Eire made or if alternative experimental methods cire
used to detect this unstable b u t important heat transfer mode.
The cooling capacity of quenchants during full-film boil-
ing, nucleate boiling, a n d in one-phase convection is charac-
terized by critical heat flux density a n d by the heat transfer
coefficient (or specific heat flux) [28-29]. Nonstationary heat
processes: shock boiling, full-film boiling, transition boiling,
nucleate boiling, a n d convection heat transfer have been
readily detected by conventional cooling curve analysis
[28,30]. Except for shock-film boiling, all of these cooling
processes may occur simultaneously o n the hot metal surface
[30,31].
Determination of the first a n d second critical heat flux den-
sities are necessary to properly explain these cooling modes,
FIG. 21—Schematic illustration of acoustical noise analysis
[35,36]. Heat trzinsfer in these boiling regimes is character- measurement device: 1. Furnace, 2. Quenchant, 3. Probe, 4.
ized by two values. One is the first critical heat flux density Thermocouple, 5. Transducer, 6. Amplifier, 7. Acoustic ana-
(?cri), which typically occurs within approximately 0.1 s after lyzer, 8. Glass fiber system, 9. Computer,10. Printer, 11. Time
initial immersion of the h o t metal (shock-film boiling). The analyzer.
next step is full-film boiling. The second critical heat flux
ilcri) is the m i n i m u m heat flux at which the transition from
full-film boiling to nucleate boiling will occur. BCruzhilin has TABLE 4—Characteristic acoustic frequencies for
shown that the ratio of qci2 I ^cri is a constant [37]. Kobasko various heat transfer modes.
et. al. have determined that this constant is 0.204-0.207 for Heat Transfer Mode Frequency Mode (kc)
water [35], If the constamt is known, the difficult to observe Shock-film boiling 9-20
qcri c a n b e calculated from t h e m o r e easily observed a n d Full-film boiling 0.05-1.5
measured g'cr2- Nucleate boiling 0.5-4.0
located at equal distances between probe and wall of the con-

tainer with the liquid to be investigated as shown in Fig. 21.
1.S mm The quenchant was placed in a container of 150 mm diame-
ter and height of 270 mm. The signal from piezoceramic
sensor is transmitted to amplifier (6) and then to analyzer
(7)—see Fig. 21—of acoustic signals connected to a digital
voltmeter and computer.
With this apparatus, in addition to acoustic analysis, cool-
ing curve temperature-time analyses are also conducted.
With this data, the duration of the full-film boiling, second
critical heat flux density, heat transfer coefficient, and the
duration of non-stationary nucleate boiling are determined.
These values are sufficient for the characterization of
quenching capacity. The results obtained by this method
are presented on Fig. 23. The silver probe was cooled from
FIG. 22—Illustration of cast 800°C in 20% aqueous solution of a poly(alkylene glycol)
spherical silver probe. quenchant. The start of full-film boiling and transition to the
nucleate boiling can be detected by conventional time-tem-
perature cooling curve analysis. However, acoustical analysis
9,IW
lot, 4r
i5o: lOS
A136
100
sn
I A jxi.m
2 iot,i
FIG. 23—Comparison of quenching properties of aqueous PAG polymer quenchant (concen-
tration 20% at 20(C). A5 and A136 correspond to 0.5 and 13.6 kc.
was required to observe the transition from shock- film boil-

ing via full-film boiling to nucleate boiling.
Quench Oils
Quenching oils are analogous to other petroleum-derived
products including engine oils, spindle oils, and industrial lu-
bricating oils such as gear lubricants [39]. Although
petroleum oils are usually refined for specific applications,
they remain complex mixtures with a variety of possible com-
O positions, which may vary even when produced by a single
o
refinery. The compositional complexity of quench oils affects
3 their quenching performance. Segerberg [40] compared a se-
« ries of mineral-oil-based quenchants, which were tested by
a cooling curve analysis according to ISO 9950 (ASTM D 6200)
E
and obtained a wide variety of cooling rates, as shown in Fig.
24. Formulated oils can produce an even wider range of cool-
ing rates.
Quenching oils that contain substantial quantities of naph-
thenic derivatives usually exhibit inferior cooling character-
istics, greater deposit-forming tendency, and lower flash
points than paraffinic oils. Tensi [41] has shown that the
quench severity of a particular quench oil is directly related
to its ability to wet a metal surface. The wettability of a
quench oil is quantified by measuring "rewetting" times, as
shown in Fig. 25.
Cooling R a t e . ' C Quench Oil Classification

FIG. 24—Potential variation of the severity of differ- For commercial acceptance, a quench oil must exhibit a
ent quench oils. number of important properties including:
• Acceptable flash and fire points,
• Low sludge formation
• Nonstaining of parts,
• Appropriate heat removal properties.
• Oxidation Resistance
10 30 50 70 90
Distance from end (mm)
FIG. 25—Wetting time and surface hardness of 1045 steel as a function of distance from
the end of the specimen.
Most quench oils are derived from refined petroleum-base 6743 provides a classification code for veirious quench media
stocks. Higher naphthenic fractions usually result in lower including quench oils, which is shown in Table 5.
flash points and greater sludge formation. Sludge formation The three major quench oil classifications are [ 4 2 ^ 5 ] :
reduces heat transfer efficiency, which may result in inade-
• Conventional (nonaccelerated) oils, or cold oils,
quately hardened parts. Increased sludging cJso reduces oil
flow t h r o u g h heat exchangers used to cool the oil during • Accelerated oils,
quenching. • Marquenching oils, or hot oils.
Ideally, a quench oil should not stain parts. High-quality Various characterization criteria for these oils are summa-
paraffinic oils impart a light gray color to quenched parts. rized in Table 6 [46]. The differences in cooling curve profiles
Sulfur-containing derivatives in the oil cause unacceptable for typical m e m b e r s of these oils classifications are illus-
black stains. Some quench rate enhancing additives may also trated in Fig. 26 [46].
cause staining. However, the color of a quench oil is not in- Conventional quenching oils are typically mineral oils,
dicative of its staining tendency. which m a y contain antioxidants to reduce oxidation a n d
Since quench oils are flammable, there is always the po- thermal degradation. Most of these oils have viscosities in the
tential to catch fire in use. The flash point of an oil is used as range of 100-110 SUS (Saybolt Universal Seconds) at 40°C
an indicator of its tendency to ignite. Maximizing the flash (100°F), although some have viscosities u p to 200 SUS at
point minimizes the fire hazard. Increasing the naphthenic 40°C (100°F).
content of an oil usually decreases the flash point. Accelerated quenching oils are usually formulated from a
Quench oils are selected on the basis of their ability to me- mineral oil and contain one or more additives to increase
diate heat transfer during the quench. Oils are classified on cooling rates during the high temperature portion of the cool-
the basis of quenching speed and temperature of use. ISO ing process. This is accomplished by using an additive that
TABLE 5—ISO 6743 Quenchant classification system.

Product Type
General Particular More Specific and/or Symbol
Code Letter Application Application Application" Performance Requirements ISO-L Remarks
Heat Treatment Oil for heat Cold Hardening Oil for normal hardening UHA Certain oils may be
Treatment e < 8o°c easily eliminated by
Oil for quick hardening UHB washing with water.
Semi-hot hardening Oil for normal hardening UHC This characteristic
8O°C<0< ISCC Oil for quick hardening UHD is brought about by
the presence of
Hot hardening Oil for normjd hardening UHE emulsifiers in the
130°C<e<200°C Oil for quick hardening UHF oil formulation.
Such oils are then
Very hot hardening Oil for normal hardening UHG known as
200°C<e<310°C Oil for quick hardening UHH "washable." It is up
to the supplier at
Vacuum hardening UHV the request of the
Other cases UHK ^^'^ user, to provide
this characteristic*
Aqueous Fluids Surface hardening Water UAA
for Heat
treatment Aqueous fluid for slow hardening UAB
Aqueous fluid for quick hardening UAC
Mass hardening Water UAA
Aqueous fluid for slow hardening UAD
Aqueous fluid for quick hardening UAE
Other cases UAK
Molten Salts 150°C<e<500°C Molten salts 150°C<6»<500°C USA
for Heat 500X<6><700°C Molten salts 500°C<e<700°C USB
Other cases USK
Gas for heat Air UGA
treatment
Neutral Gas UGB
Reducing Gas UGC
Oxidizing Gas UGD
Fluidized Bed UF
Other cases UK
"8 indicates the iluid temperature at the time of hardening;
''The washing solution used to remove the emulsified oil may be either detergent (soap) and water or water-borne alkaline cleaners. The cleaning conditions
shall be provided by the oil supplier.
TABLE 6—Quench oil physical property characteristics.

Bath Temperature Flash Point Typical Typical GM
Viscosity at 40°C
Type of Oil °C op °C °F Time (s)
(100°F) SUS
Conventional <65 <150 170 340 105 16.0
Accelerated <120 <250 180 355 94 10
Marquenching <200 <400 300 570 700 30
1600
1400
N ^^Conventional
1200 Fused salt V quench oil
G? 500 °F \ 150°F
« \
2 1000 \
2 \
Martempering oil
1 800 500 °F
600
High speed-
quench oil "^.^ ^ > ^ '^Molten
150'F "^.^ N. metal
400 • 'Ô'^ 500 °F
0.7 1.0 1.5 2 3 4 5 7 10 15 20 30 40 60

Time (sec)
FIG. 26—Comparison of cooling curves for various quench media.
facilitates surface wetting, which destabilizes the film boiling sphere that will inhibit oxidation of the meted surface during
process. Examples of additives that may be used to accom- austenitization, prior to quenching. A protective atmosphere
plish this include: calcium naphthenate [47], alkenyl succi- may be an inert gas such as nitrogen or argon or it may be a
nate [47], and sodium sulfonate [48]. Viscosities of these oils gas used for a heat treating furnace. These same atmospheres
may vary from 50-100 SUS at 40° (100°F). Eire also used to protect the quenching oil, especially martem-
For some steels, quenching at an elevated temperature is pering oils, from the oxygen in air during use, thus reducing
necessary to reduce thermal and transformational stresses the rate of sludge formation and increasing lifetime of the
that may lead to cracking and increased distortion. One pro- quenching oil.
cess that may be used to accomplish this is martempering (or
marquenching). In meirtempering, metal is usually quenched Classification by GM Quenchometer Cooling Times
from the austenitization temperature to a temperature just Cooling rates produced by quench oils have been classified
above (see Fig. 27B) the stcirt of martensite transformation on the basis of the General Motors (GM) quenchometer test,
(Ms) just long enough for the temperature to equalize be- also known as the "nickel ball" test [50,51]. Details of this test
tween the surface and the center of the steel. The metal is Eire provided in Test Method ASTM D 3520. This test involves
then removed from the quench bath and air-cooled. The ther- heating a 22 m m (7/8 in.) d i a m e t e r nickel ball to 885°C
mal cycle for both conventional quenching Eind martemper- (1625°F) and then dropping it into a wire basket suspended
ing is illustrated in Fig. 27 [1]. in a beaker containing 200 m L of the quenching oil at
Martempering or hot quenching oils are used at tempera- 21-27°C (70-80°F) [52]. A timer is activated as the glowing
tures between 95-230°C (200 a n d 450°F). They are usually for- nickel bEJl passes a photoelectric sensor. A horseshoe magnet
mulated from solvent-refined mineral oils with a very high is located outside the beaker as close as possible to the nickel
parafBnic fraction to optimize oxidative and thermal stability. ball. As the ball cools, it passes t h r o u g h its Curie point
Stability is enhanced by the addition of antioxidants. Nonac- (354°C, or 670°F), the temperature at which nickel becomes
celerated and accelerated martempering oils are available magnetic. When the ball becomes magnetic, it is attracted to
Typical t e m p e r a t u r e ranges for m a r t e m p e r i n g oils are the magnet, activating a sensor that stops the timer as illus-
shown in Table 7 [46]. Because martempering oils are used at trated in Fig. 28 [46]. The cooling time required to reach the
relatively high temperatures, a protective, nonoxidizing Curie temperature is sometimes referred to as the "heat ex-
atmosphere over the oil is typically used, which allows oper- traction rate" or "quenchometer time." Table 8 provides t } ^ -
ation closer to the flash point of the oil t h a n if open-air conical GM quenchometer times for the different quench oil clas-
ditions are used [49]. A protective atmosphere is any atmo- sifications. [46,53,54]
Although the GM quenchometer test is commonly used for [62]. Of these, the most commonly used quenchants are
evaluating quench oils, the quenchometer times are based on poly(alkylene glycol)—PAG, poly(vinyl pyrrolidone)—PVP,
a relatively limited portion of the total cooling process and and poly(ethyI oxazoline)—PEOX. However, the most com-
therefore are not related to as-quenched hardness or the monly encountered quenchant for induction heat treating ap-
propensity for cracking. In fact, this test only defines a heat plications worldwide are PAG-type quenchants.
removal rate, regardless of variation of cooling pathway, Some water soluble polymers that are used as quenchants
over the high-temperature portion of the cooling curve. undergo a phase separation as the solution temperature is in-
creased; the hydrogen bonds break and the polymer chain
Aqueous Polymer Quenchants coils upon itself and separates into two phases [63]. The tem-
perature where this occurs is the separation temperature or
A number of polymers have been used as polymer quen- cloud point. PAG pol3Tners separate as hydrates and the de-
chants for heat treating applications [55]. These include: gree of hydration is dependent on the temperature of the so-
poly(vinyl alcohol) [56], poly(alkylene glycol) [56], poly (acry- lution, as shown in Fig. 29 [63]. In addition to solution tem-
lamide) [58], cellulosic derivatives [59], polyvinylpyrrolidone perature, the degree of polymer hydration for PAG polymers
[60], poly(sodium aciylate) [61], and poly(ethyl oxazoline) is dependent on the ethylene oxide/propylene ratio in the
Surface Surface
Center Center
Time
(b)
I
o
o.
E
FIG. 27—Types of quenching cycles: (a) conventional quenching and tempering, (b) martempering,
(c) isothermal quenching and tempering, and (d) austempering.
TABLE 7 --Typical use temperatures for martempering oils.
Minimum Use Temperature

Viscosity at Flash Point Open Air Protective Atmosphere
40°C (100°F)
SUS "C °F °C °F °C »F
250-550 220 430 95-150 200-300 95-175 200-350
700-1500 250 480 120-175 250-350 120-205 250-400
2000-2800 290 550 150-205 300-400 150-230 300^50
polymer chain. Generally, increasing propylene oxide con-

tent in the copolymer decreases the separation temperature.
Poly(ethyl oxazoline)—PEOX, a n o t h e r polymer currently
used in the heat treating industry—also exhibits a sepeu-ation
temperature [63].
Cloud point behavior of polymer quenchants can be used
as an inexpensive way to purify contaminated (by salt, or
hard metal ions from h a r d water, for example) quench bath.
Raising the temperature of the aqueous solution above its
separation temperature as shown in Fig. 29, causes it to sep-
arate into two layers. The upper layer, usually the contami-
nated aqueous s u p e r n a t e n t solution, is removed a n d the
lower layer of the purified polymer is then redissolved to the
required concentration [64].
Nonionic polymers are usually used since ionic polymers,
such as poly (sodium acrylate), typically precipitate in the
presence of hard metal ions. The most c o m m o n examples of
nonionic quenchant polymers are PAG, PVP and PEOX [64].
C o o l i n g Curve A n a l y s i s - I n t e r n a t i o n a l S t a n d a r d s
Cooling Curve Analysis Standards
Although numerous sizes, shapes, and metals have been,
Test oil Nickel ball Quench Curie point and continue to be, instrumented for cooling curve analysis,
(heated) most national and international standards have utilized a
nickel alloy such as Inconel 600 or silver as probe materials.
FIG. 28—Schematic illustration of a GM Quen- One of the earliest national standards that utilized a silver
chometer and the principle of operation. probe with a surface thermocouple was JIS K 2242,
schematically illustrated in Fig. 30 [65]. Since this probe is
very sensitive, it can sometimes be very difficult to obtain
reproducible data.
TABLE 8—GM Quenchometer time To obtain greater data stability and to provide a material
classification of quench oils. with heat transfer properties much more similar to steel, a
GM Quenchometer reusable probe based on an Inconel 600 alloy that does not
Classification Time (s) undergo phase transformation was used [66,67]. This probe
Fast Oil 8-10 has the additional advantage of being resistEint to oxidation
Medium Oil 11-14 and was used to develop the widely used Wolfson Heat Treat-
Slow Oil 15-20 ing Centre Engineering Group Specification [66]. It was sub-
Martempering Oil 18-25
sequently used as the probe for ISO 9950 and ASTM Methods
D 6200, D 6482, and D 6549 is shown in Fig. 19.
A n u m b e r of groups have traditionally not accepted the use
of either an Inconel or a stainless steel probe for cooling curve
analysis. They prefer the use of a high thermal conductivity
Separation
temperature Water iri separated material that does not exhibit phase transformations such as
PAG layer, % silver. There are currently at least two national standards that
"C °F utilize a silver probe. One is the French standard AFNOR NFT
80 (175) 70 - 60778 and the other is the Chinese standard ZB E 45003-88.
90 (195) 46 These two probes differ from each other primarily in size. The
French probe is 16 m m . dia. X 48 m m and the Chinese probe
is 10 m m dia. X 30 m m . They are illustrated in Figs. 31 and 32,
respectively [65]. Table 9 provides a comparison of the exper-
imental requirements for relevant standards [65].
Water with To maintain probe CcJibration and to assure interlabora-
contaminants
Heat tory reproducibility, it is essential that the probe be periodi-
100 0(212°?) Separated cally calibrated during use. This process requires the use of a
polymer calibration fluid for which there are specified cooling prop-
quenchant
erties. The JIS K 2242 and the Chinese standard ZB E 45003-
88 utilize a JIS K6753 "standard liquor" which is: di (2-ethyl-
Homogeneous hexyl) phthalate. Although available in > 9 9 % purity, the
auenchant solution
toxicity properties of this fluid m a k e it undesirable for
FIG. 29—Thermal separation of an aqueous solution widespread and routine use. The Wolfson Standard [66], ISO
of a polyalkylene glycol quenchant. 9950, and the AFNOR NFT 60778 utilize a "standard" min-
Insulating lube
il
S i l v e r wire
s
Pipe made of
silver
Heat resistanl
insulator
M6 X pitch 1
Alumel wire
M> X pitch 0 . 5
Dead
M5 X pitch 0 . 5
> <
«o
Insulating tube
FIG. 30—Japanese JIS K 2242 silver probe (All dimensions are in mm).
eral oil whose physical properties are summarized in Table device, which is shown in Figs 33. [65,71] and 34A. This de-
10 [65]. vice is constructed from a transparent material such as Plex-
The ASTM Test Method D 6200 is based on the Wolfson iglas or glass and holds approximately 1.5 L of quenchant.
standeird [65] and ISO 9950, except the specification limits Agitation is provided by a plastic impeller of 50 m m dia. and
are controlled more tightly and were based on various statis- pitch of 42 m m [72]. One of the advantages of this agitation
tically designed experimentation as required by ASTM system is the uniformity of turbulence and flow throughout
[68-70]. the quench zone as shown in Fig. 35 [71]. This means that the
sensitivity to error with respect to precise placement of the
Development of Cooling Curve Analyses Methods probe in the quench zone will be minimal.
with Agitation Test Method ASTM D 6549 is significantly different from D
Many quenchants, a n d nearly all aqueous polymer quen- 6482 in that p u m p agitation is used. This is illustrated in Fig.
chants, cannot be evaluated reproducibly without the use of 34B. This p u m p agitation system is based on earlier work
agitation. Such quenchants always require the use of agita- performed by N.A. Hilder at Aston University [73]. Probe
tion w h e n used industrially in various heat-treating pro- placement in the fluid reservoir during quenching is illus-
cesses. All of the cooling curve methods discussed d o not em- trated in Fig. 36.
ploy agitation and are essentially limited to analysis of
minercd oil derived quenchants. Quench Bath Mamtenance
There are two ASTM stcindards for cooling curve analysis
with agitation. One method is ASTM D 6482 and the other is Sampling
ASTM D 6549. Both test methods utilize the Wolfson probe Flow is never uniform in agitated quench tanks. There is al-
illustrated in Fig. 19. Test Method D 6482 uses an agitation ways variation of flow rate and turbulence from top to bot-
torn and across the tank. This means that there may be 2. Sampling Position—For each system, the sample shall be
significant variations of particulate contaminants including taken from the same position each time that system is
sludge from oil oxidation and metal scale. For uniform sampled. The sample shall be taken at the most practical
sampling, a number of sampling recommendations have point of maximum flow turbulence. The position in the
been developed: tank where the sample is taken shall be recorded.
1. Minimum Sampling Time—The circulation pump shall be 3. Sampling Valves—If a sample is taken from a sampling
in operation for at least 1 h prior to taking a sample from valve, then sufficient quenching oil should be taken and
a quench system. discarded to ensure that the sampling valve and associated
piping has been flushed, before the sample is taken.
4. Sampling From Tanks With No Agitation—If samples are to
be taken from bulk storage tank or a quench tank with no
agitation, then samples shall be taken from the top and
bottom of the bulk system or quench tank. If this is not
possible and the sample can only be taken from the top,
then the Laboratory Report shall state that the results
represent a sample taken from the top of the bulk system
or quench tank and may not be representative of the total
system.
5. Effect of Quenching Oil Addition as Make-Up Due to Drag-
Out—It is important to determine the quantity and fre-
quency of new quenchant additions, as large additions of
new quench oil will have an effect on the test results, in
particular the cooling curve. If a sample was taken just af-
pefêtofv Ofobecamg. ter a large addition of new quench oil, this shall be taken
into consideration when interpreting the cooling curve of
this oil sample.
6. Sampling Containers—Samples shall be collected in new
containers. Under no circumstances sheJl beverage or food
containers be used.
Thermocoupfe0l R e c o m m e n d e d Test Procedures-Quench Oils

(ASTM D 6710)
Physical and Chemical Properties
Kinematic Viscosity, (Test Method D 445)—The performance
of a quench oil is dependent on its viscosity, which varies
with temperature and oil deterioration during continued use.
Increased oil viscosity typically results in decreased heat
transfer rates [74]. Oil viscosity varies with temperature,
which affects heat transfer rates throughout the process.
The flow velocity of a quench oil depends on both viscosity
FIG. 31—French AFNOR silver probe (All dimensions are in and temperature. Some quench oils are used at higher tem-
mm). peratures, such as martempering oils, also known as hot-oils.
• m* • • '•• < l i iJ m 1B.m.4>W»i

' "• "^ 'J!^ " ^ ""^ ••p* 4 « • « • • . « • *fc w w * . nMk •mmt mm* mmtmmm^m mm mm i » . » •!
v'<' < ^ " ^ ^ < V '^••"''•••"r

s\\\\ mmm
30ia.26 MiO.fi
I a
FIG. 32—Chinese silver probe (All dimensions are in mm).
TABLE 9—Comparison of cooling curve standards for unagitated quench oils.

AFNOR GB
Variable ISO 9950 (NFT 60778) JIS (IS 2242) (ZB E 45003) ASTM D 6200
Probe Alloy Inconel 600 Silver Silver Silver Inconel 600
99.999% pure 99.99% pure 99.96% pure
Probe 12.5 m m Dia. X 16 m m Dia X 10 m m Dia X 10 m m Dia X 12.5 m m Dia X
Dimensions 60 m m 48 m m 30 m m 30 m m 60 m m
Standard See Table 10 See Table 10 Dioctyl Dioctyl
Reference Oil phthalate phthalate See Table 10
Vessel 115 ± 5 m m height 138 m m X 300 mL beaker 300 mL beaker 115 ± 5 m m
Dimensions diameter diameter 99 m m diameter
Oil Volume 2000 mL 800 mL 250 mL 250 mL 2000 mL
Oil Temperature 40°C ± 2°C 50°C ± 2°C 80''C,120°C, 80°C ± 2°C 40°C ± 2°C
160°C
Probe 850°C ± 5°C 800°C ± 5 X 810°C ± 5°C 810°C ± 5°C 850''C ± 5°C
Temperature
TABLE 10—Physical properties of the so-called "Wolfson Oil" used as a reference for ASTM D 6200, ISO 9950,
and AFNOR NRT 60778 standards.
Institute of Petroleum Test Minimum Maximum
Physical Characteristics Method/ASTM Method Value Value
Kinematic Viscosity at 40°C, cS" IP 71/D 445 19.0 23.0
Kinematic Viscosity at 100°C, cS" IP 71/D 445 3.9 4.4
Viscosity Index IP 226/D 2270 95 105
Density at 15°C, kg/L IP 160/D 1298 0.855 0.870
Flash Point PMCC, "C IP 34/D 93 190 210
5% Distillation, °C IP 123 330 360
50% Distillation, °C IP 123 400 420
' 1 cS = lO"** m^/s.
Although the viscosity of a martempering oil may not fluc- gravity of a quench oil is an indirect measure of its inherent
tuate substantially at elevated t e m p e r a t u r e s , the oil may oxidative stability.
become almost solid u p o n cooling. Thus, the viscosity- N o t e 3: Specific gravity is of limited value in monitoring the
temperature relationship of a quench oil may be critically quality of a formulated or used quenching oil. The Test
important from the dual standpoint of quench severity and Method D 287 for specific gravity requires the use of both a
flow velocity. hydrometer and an accurate thermometer or a thermohy-
Typically kinematic viscosity determination by Test drometer. Because specific gravity is temperature depen-
Method D 445 is used. Viscosity measurements are made at dent, the temperature of the oil at the time of measurement
40°C (100°F) for conventional or accelerated oils and also at must be determined precisely.
100°C (212°F) for martempering oils.
Flash Point and Fire Point (Test Methods D92, D93, D13I0)— Aged Fluid Properties-Quench Oils
Use of a quench oil at a temperature near its flash point in an Acid Number (Test Methods D 664 and D 974)—Quench oil
unprotected environment, or near its fire point, may result in oxidation results in the formation of carboxylic acids and es-
an oil fire. General guidelines have been developed for use- ters. These b5fproducts are similar to compounds that may be
temperatures of a quench oil relative to its flash point. used as rate accelerating additives. These acids and esters sig-
N o t e 2: There are various manufacturer-dependent guide- nificantly affect the viscosity and viscosity-temperature rela-
lines for relating the suitability for use of a used quench- tionship of the oil, which in turn affect quench severity. Car-
ing oil with respect to its flash point and they shall be boxylic acids may also act as wetting agents and increase the
followed. In the absence of such guidelines, it is recom- quench rate by increasing the wettability of the quench oil on
mended that the use temperature of a quenching oil in an the metal surface [77].
open system with n o protective a t m o s p h e r e shall be Oxidation of the oil may be monitored by tracking changes
60-65°C (108-117°F) lower than the actual open-cup flash in the neutralization number. Because the fresh oil may be ei-
point. In closed systems where a protective atmosphere is ther alkaline or acidic, depending on the additives present,
used, the use temperature of the used quenching oil shall the absolute value of the neutralization number itself is not
be at least 35°C (60°F) lower than its actual open-cup indicative of qucJity. However, changes in the neutralization
flash point. n u m b e r from the initial condition may be used to indicate
Specific Gravity (Test Method D287)—Specific gravity de- the degree of oxidation. Increasing neutralization numbers
pends on the chemical composition of the base stock used to generally indicate increasing amounts of aforementioned by-
formulate a quenching oil. The oxidative stability of the products.
quenching oil is dependent on the chemical composition, The acid n u m b e r (AN) is determined by titrating the acid-
such as naphthenic/paraffinic ratio. Therefore, the specific ity of a sample of known size with a known amount of stan-
absence of such a value, it is recommended that the AN not

exceed 2.00 mg/g for a used quenching oil.
Infra-Red Spectroscopy—Ân alternative method that is being
used increasingly to identify and quantify oil oxidation, even
in the presence of additives, is infra-red (IR) spectroscopy.
Figure 37 provides an illustration of the use of IR spectral
cmcJysis to identify oil oxidation [77]. Mang zmd Jiinemann
monitored the IR stretching vibrations o f C B O a t l 7 1 0
c m ~ \ for carboxylic acids contained in oxidized oil. IR anal-
ysis has been used to detect and qucintify other carbonyl-con-
taining compounds [78]:
Metal carboxylate salts-1600 and 1400 c m " '
Carboxylic Acids-1710 c m " '
Metal sulfates-1100 and 1600 cm '
Esters-1270 and 1735 cm '
Saponification Number (Test Method D 94)—Oil degradation
may produce both acids and ester by-products. The acid num-
ber quantifies the amount of acidic degradation by-products in
the oil, whereas the saponification number is a measure of the
presence of esters or fatty esters in the oil. The saponification
number of an oil is determined (Test Method D 94) by heating
a sample of the oil with a known amount of basic reagent and
measuring the amount of reagent consumed. Because some
quench oils are formulated with components that also have
saponification numbers, it is necessciry to monitor trends over
time than to rely on an absolute value [81]. An increase in the
saponification number indicates an increased propensity to
sludge formation. It has been suggested that if the results of
other tests are satisfactory, that saponification numbers below
3 mg KOH/g oil may be acceptable [75,82].
Contamination-Oil Quenchants
Water Content (Test Methods D 95, D 1744, D 4007)—TYie
presence of water in a quench oil, which may be present due
to condensation or a leaking heat exchanger, presents a po-
tentially serious problem. Water concentrations as low as
0.1% may cause the bath to foam during the quenching pro-
cess, greatly increasing the risk of fire. Overflowing oil from
the foaming bath may result in a more serious fire than if the
flames were contained by the bath, as the oil may contact
nearby furnaces or other ignition sources. If a sufficient
amount of water accumulates in a hot bath, an explosion
caused by steam generation m a y result [53].
Note 5: The problem of water contamination in the quench
bath, with respect to foaming is illustrated in Fig. 38 where it
is shown that 1 mL of water becomes 1700 mL of vapor when
evaporated (near instantaneously).
FIG. 33—Schematic illustration of the Tensi agitation system Note 5: The amount of foaming that does occur is often
(all dimensions are in mm). dependent on the degree of agitation. Some baths may be
agitated to the point where the quenching oil is ncEirly
splashing on the floor. In such baths, the water vapor is
dard base (Test Methods D 664 or D 974). The test is per- released even faster causing a greater potential foEiming
formed by dissolving the oil in a mixture of toluene and iso- problem.
propanol, then titrating it with a standard solution of potas- The presence of water in a quench oil may also produce
sium hydroxide (KOH). The end-point may be determined variable cooling properties depending o n the nature a n d
colorimetrically with a pH-sensitive indicator. The acid n u m - amounts of cooling rate-accelerating additives present in the
ber (AN) is reported in units of milligrams of KOH per g r a m oil. The magnitude and direction of these effects depend on
of sample (mg/g). the particular quench oil and the amount of water present in
Note 4: The quenching oil supplier will provide a maxi- the oil. Water contamination may also result in staining of
m u m TAN value for the quenching oil being used. In the the part being quenched, uneven hardness, and soft spots.
(b)
FIG. 34—Illustration of commercially available quenchant agitation systems: (A) Tensi agitation system, (B) Drayton agitation
system.
A quantitative test for water contamination involves titra-

tion of the oil with Karl Fisher chemical reagent to an elec-
trometric endpoint (Test Method D 1744). This test is recom-
mended for water levels of 50-1000 p p m (less than 0.1%).
Higher levels of water contamination may be quantified by
distillation (Test Method D 95) or centrifugation of the sam-
ple and measurement of the volume of separated water ac-
cording to Test Method D 4007.
Note 6: A c o m m o n qualitative field test for water contam-
ination is the so-called "crackle test," which is conducted
by heating a sample of the quenching oil and listening for
an audible crackling sound [77]. If the oil is contaminated
with water, a crackling sound will be heard before the
quenching oil has reached its smoke-point.
Carbon Residue (Test Method D189)—One of the greatest prob-
lems encountered when using a quenching oil is the formation
and accumulation of sludge. Although the various analyses
procedures including viscosity, neutralization number, and
saponification number may indicate that a quench oil is ade-
FIG. 35—The flow strings illustrate that the flow in the quate for continued use, the amount of sludge build-up in the
quench zone is without bubbles or twist. A. 0.25 m/s and B is tank may demand that the system be drained and cleEtned.
0.6 m/s. Clccining and sludge disposal cire growing problems for the
heat treating industry. Therefore, determination of the sludge- pounds present. The Conradson carbon residue is deter-
forming potential of a quench oil prior to use is important. mined by placing a weighed sample in an iron crucible. The
One method of quantifying sludge-forming potential in- crucible is heated with a Meeker-type gas burner to a suffi-
volves determination of the Conradson carbon residue (Test ciently high temperature to evaporate and bum the oil. The
Method D 189) measures the polymeric material remaining sample is forther heated until the bottom and sides of the
in the oil after heating to elevated temperatures in the ab- crucible are cherry red and is held at this temperature for 30
sence of sufficient oxygen to bum off all of the organic commin. The crucible is then cooled and weighed. The amount of
PLAN VIEW
FIG. 36—Recommended probe placement in the Drayton centrifugal

pump apparatus shown in Fig. 34b (all dimensions are in mm).
ou
c
<D
jQ
<
1600 1700 1800

Wave number, cm - ^
FIG. 37—Infra-red spectral identification of oxidation of a used quenching oil.
oxide scale, which will act as a contaminant in the oil. If

this occurs, the Conradson carbon residue number may be
abnormally high and misleading.
Precipitation Number (Test Method D 91)—Sludge formation
in a quenching oil is caused by oxidation of various compo-
nents, leading to pol3THerization and cross linking reactions.
These cross linked and polymerized by-products are suffi-
ciently high in molecular weight to cause them to be insolu-
ble in the oil. Other sources that contribute to sludge are dirt,
carbon formation, and soot from the use of a furnace atmo-
sphere with a high carbon potential.
Sludge can plug filters and foul heat-exchanger surfaces.
The loss of heat-exchanger efficiency may result in overheat-
ing of the quenchant and possibly a fire [83]. Increasing
sludge formation often indicates increasing oxidation of the
oil. In addition, sludge may adsorb on a part, causing nonuni-
waterquantity form heat transfer during the quenching process.
It is important to maintain particulate contamination to <
FIG. 38—Illustration of the volumetric expansion of 1 micron to optimize quenching performance [84]. Precipita-
1 mL of liquid water to 1700 mL of water vapor. tion numbers as low as 0.2% may produce staining of nor-
mally bright surfaces [46]. However, staining is more com-
monly observed with precipitation numbers of > 0.5%.
Note 9: These sludge levels correspond to acid numbers of
tar remaining in the crucible relative to the original amount > 0.5 mg KOH/g by Test Method D 974.
of the oil defines the Conradson carbon residue value. Sludge formation may be accompanied by increased
Note 7: Test Method D 189 may be affected by some addi- volatile oxidation by-product formation that may cause a si-
tives used to formulate quenching oils. multaneous increase in fire potential. The viscosity of a
Note 8: In some heat treating operations, steel is austeni- quench bath also changes with the formation of sludge, af-
tized in air, which causes the increased formation of metal fecting both heat transfer and quench severity. The amount
of sludge can be quantified by adding n a p h t h a solvent to the tempt to identify some method of correlating a portion of a
oil sample a n d determining the volume of precipitate cooling curve with GM Quenchometer times [69,70]. The re-
(sludge) after centrifuging (Test Method D 91). sults of this work showed that although some correlations
Ash Content (Test Method D 482)—Âlthough mineral oil base- were obtained, they were not particularly good. Bates and
stocks possess very low ash values, many formulated quench Totten have also been unable to find a correlation [84].
oils contain metallic components that contribute to ash. If Cooling Curve Analysis (Test Method D6200 and ISO 9950)—
the ash content in a bath filled with a formulated quenching The most c o m m o n method in use throughout the world to
oil is decreasing, it is likely that an ash-containing additive is evaluate the cooling properties of a quenching oil is cooling
being removed by drag-out or some other process. If the ash curve analysis. Cooling curve analysis provides a cooling time
content is increasing, the additive is either accumulating in versus temperature pathway, which is directly proportional
the bath or metallic contamination is increasing, perhaps in to physical properties such as hardness, obtainable u p o n
the form of scale accumulation. Ash contents are determined quenching of metal. The results obtained by this test may be
by Test Method D 482, which involves heating a quenching used as a guide in heat treating oil selection or comparison of
oil in a muffle furnace at 775°C (1425°F) under conditions quench severities of different heat treating oils, new or used.
that b u m off organic compounds but leave metallic species Cooling curve analysis of a quenching oil according to Test
such as metal oxides or hydroxides. Method D 6200 and ISO 9950 is conducted by placing the
probe assembly illustrated in Fig. 19. into a furnace and heat-
Quenching Properties of Oil
ing to 850°C (1562°F). The heated probe is then immersed in
Magnetic Quenchometer Method (Test Method D 3520)—Cool- a 2000 mL volume of the quenching oil, typically at 40°C, or
ing rates produced by quenching oils are often classified on other preferred use temperature. Lower quenchant volumes,
the basis of Test Method D 3520, the magnetic quenchometer as low as 700 mL, have been used for compeirative analysis.
test illustrated in Fig. 28 [46]. Table 8 provides a summary for The t e m p e r a t u r e inside the probe assembly and cooling
quench oil classification by magnetic quenchometer times times are recorded at selected time intervals to establish a
[46]. Although this is a widely used test, the quenchometer cooling temperature versus time curve. From the tempera-
times do not relate to metallurgical properties. This is be- ture-time curve, the cooling rate is derived.
cause only a single cooling time is determined; therefore, A series of cooling rate curve comparisons illustrating the ef-
there is insufficient information to indicate the actual tem- fect of oil oxidation on a conventional quench oil and an accel-
perature-time cooling pathway that is required to determine erated quenching oil are illustrated in Figs. 40A and 40B, re-
if a specific steel may be successfully hardened. This is illus- spectively. The effect of water contamination on a conventional
trated in Fig. 39 [46] Therefore, this test is of limited value, quenching oil and an accelerated quenching oil are illustrated
with the possible exception as a quench oil classification test. in Figs. 41A and 41B, respectively. The maximum cooling rate
Guisbert and Moore conducted an extensive study in an at- will shift in proportion to the water content of the oil.
The GM Quenchometer time is the

time required (f- f ) to cool
" nicicei tiail from 885-354 Xi
Time (Sec.)
FIG. 39—Illustration of the Inability of a single cooling time value to suc-

cessfully predict the outcome of a steel hardening process where a cooling
temperature-time curve is required.
SOO
4months'
oxidation
ANawel •
Smonttu' BAftarSnwntha
oxidation ' CMarSmonttia
• L
PAttarOmortha
L..I...I
i I i
amonths' SSSSSS
oxidation ^^5tsp--B
_...4....f...f.. ^^.^f^^Z^^^^^
1 momh's
oxidation ^"-""'''''^ D
No ox'tdatton*
Rr^
1 i i Cbolbio curvM datanninad It •
balhtompeisbirBof 4orc
\ i
« 1 1 .J
Oiddation Of I , 20 40 eo 80 100
quendiing oii[ j
CoollnoiataCcya) (b)
. i j L. 4-1
40 60 80 100 120 140
(a) Coolingrate(°C/s)
FIG. 40—Illustration of tlie effect of oil oxidation on tfie cooling rate curve for (A) a conventional quenching oil and (B) an
accelerated quencliing oil.
Accelerated-speed oil
' • 1 " -
...|...j....
No contamination •\—
No water
0.01% water { 0.5% water
1 % water
2% water
• 0.05% water
0.10% water
i 0.20% water -;
J i ^ I i i
Cooling rate (^C/s) (b)
40 60 80 100 120 140
(a) Cooling rate (°C/s)
FIG. 41—Illustration of the effect of water contamination on the cooling rate curve for (A) a conventional quenching oil and
(B) an accelerated quenching oil.
Performance-Related Physical and Chemical Refractive Index, (Test Method 1747)—One of the most com-
Properties-Polymer Quenchants (ASTM D 6666) mon methods of monitoring the concentration of aqueous
polymer quenchants formulated using poly(alkylene glycol)
Appearance—Contamination of aqueous polymer quenchants
copolymers is refractive index. As Fig. 42 [86] shows, there is
by such fluids as hydrauhc or quench oils may result in a
a linear relationship between quenchant concentration and
nonuniform quench with thermal gradients sufficient to
refractive index. The refractive index of the quenchant solu-
cause cracking or increased distortion, or possible staining,
tion is determined using an Abb6 refractometer (Test Method
of the metal being quenched. The simplest (and an excellent)
1747) equipped with a constant temperature bath. Although
test is to examine the visual appearance of an aqueous poly-
the refractive index could potentially be used at any temper-
mer quenchant in a clear glass container such as a bottle [86].
ature with the control limits of the constant temperature
However, if the oil readily separates from the aqueous poly-
bath, typically either 40°C or 100°F is selected.
mer quenchant solution, it may often be removed by skim-
ming. On the other hand, oil may form a milky-white emul- Although refractive index is a relatively simple and rapid
sion that is not readily reclaimed by heat treaters. method for determination of polymer quenchant con-
centration, it is not sensitive to low levels of polymer degra-
Other problems that are easy to visually identify include
dation and it is often significantly affected by solution
carbon and sludge contamination, which often results in
contamination.
cracking problems. Metal scale contamination is often iden-
Note 10: Refractive index is typically unsuitable for aque-
tifiable by its magnetic properties by placing a magnet on the
ous polymer quenchants formulated with polymers with
outside of the bottle next to the scale and determining if the
molecular weights greater than 50000-60 000 because: 1)
scale exhibits any attraction for the magnet. Carbon, sludge,
The total amount of water-soluble polymer in solution is
and scale may be removed from the quenchant by filtration
not sufficiently different from the water diluent to provide
or centrifugation.
adequate sensitivity and 2) because the total concentration
is relatively low, small changes in polymer concentration
may result even from normal use, which imparts signifi-
cant process effects. However, the corresponding variation
in refractive index may not be detectable.
Note 11: Although it is most desirable to use an Abbe re-
fractometer because of its sensitivity, this is only practical
in a laboratory environment. In the heat treating industry,
for tankside monitoring and control, a temperature-com-
1.341 pensated handheld refractometer similar to the one illus-
trated in Fig. 43a and b should be used. The hand-held re-
fractometer is self-compensated for temperatures of 60°
and 100°F. Although there are various models available,
the most common models provide refractive index read-
ings in Brix degrees over a 0-30° range. Typically, the
smallest scale that can be read directly is in divisions of
10.0 15.0
0.2° as shown in Fig. 44. A concentration-refractive index
QUENCHANT CONCENTRATION (%) curve obtained by a hand-held refractometer is shown in
Fig. 45 [86].
FIG. 42—Illustration of the linear relationship between re-
fractive index and concentration of an aqueous solution of a
polymer quenchant.
FIG. 43—Typical hand-held refractometer; (A) application of quenchant solution to refractometer, (B) observation
of refractive index.
Viscosity, (Test Method D 445)—Âqueous polymer quenchant Comparison of Concentration by Refractive Index and Viscos-
viscosity depends on the quenchant concentration and tem- ity—Â useful procedure for monitoring variations in aqueous
perature, as shown in Fig. 46 [86]. It is readily determined us- polymer quenchants, particularly poly(alkylene glycol) quen-
ing a Cannon-Fenske tube (see Fig. 47), stopwatch, and con- chants, is to compare the difference (delta) in the quenchant
stant temperature bath as described in Test Method D 445. concentration values obtained by refractive index (C«) and
N o t e 12: Although viscosity of most water-soluble poly- viscosity {Cv) [87].
mers is significantly affected by contaminants, particuleirly
^ = CR-CV
ionic salts, the viscosity of quenchants formulated from
poly(alkylene glycol)s are not particularly affected by the Differences in A of greater t h a n 6-8 are significant and the
presence of contaminants. However, solution viscosity is source of this difference (contamination or degradation),
strongly affected by degradation. should be determined. Procedures for doing this follow.
Water Content (Test Methods D 95 and D 1744)—Aqueous
polymer quenchants are composed of water, a water soluble
polymer, and a n additive package to provide corrosion inhi-
bition, foam control, etc. Therefore, determination of water
content is necessary to establish the concentration of the
quenchant in a way that is relatively insensitive to poljTner
degradation.
Water content may be determined by Karl Fisher analysis
(Test Method ASTM D 1744). The advantage of Karl Fisher
analysis is that it is a direct m e a s u r e of water content,
whereas refractive index and viscosity are both indirect mea-
surements that are substantially affected by either contami-
nation (refractive index) or degradation (viscosity).
DEGREES pH Determination, (Test Method E 70)—The performance of
an aqueous polymer quench bath may be criticeJly dependent
on its pH. The p H of a quenchant solution may be determined
BRIX by Test Method E 70. There are many excellent commercially
available sources of p H meters and glass electrodes. The
T/C choice of the instrument will be primarily affected by the de-
sired precision of measurement. Electrodes used for pH mea-
surement are designed for specific pH ranges and tempera-
FIG. 44—Illustration of the Brix refractive index scale used ture; therefore the solution p H and temperature shall be
for a hand-held refractometer. considered when the elecrodes are selected for use.
£3MU ^
£»MU
'^.."
'S
^%m-
1 -
<J
i I i-'. • , - { . > : 1 1 I -i 1
\
om 109 zw 3.to im Sio evoo jm s.m Mm mm
,, ^ ,^ . , ,„^ ,:fihifltaett»e„lnfelt'|''Bpix): I
FIG. 45—Typical refractive index (Degrees Brix) versus quenchant concentration
relationship.
-
250
<0 -
a 200
z (75 °F, 23.9°C)yC^
o
o
-
fsS'F,
u 29.4 °C)
(0 150
s;ff -
(6 }°F, 18.3 •oyy
UJ
> (100 °F,37.8°C)
z 100
3 90
5 -
S 80
>: •
^ 70
-.
f 60
-
M
O 50
-
>
40
-
30
10 15 20 25 30 35 40 45
QUENCHANT CONCENTRATION (%)
FIG. 46—Ouenchant viscosity as a function of concentration and temperature for an
aqueous solution of a poiymer quenchant.
Polymer degradation is t5îcally accompanied by the for-

mation of acidic by-products, which will decrease pH. Some
polymer quenchants, particularly when containing sodium
nitrite as a corrosion inhibitor, cannot be used below pH 7.0
without increasing the polymer degradation rate.
Some aqueous polymer quenchants contain amine or
amine/fatty acid mixtures as corrosion inhibitors. If substan-
tial decrease in the concentration of these inhibitors occurs,
a decrease in pH will result. Thus, pH determination may be
a useful indicator of corrosion protection of some quen-
chants.
In some cases, the quench bath may be contaminated by
ammonia, which is used in some heat treatment processes.
Clearly, pH is an excellent indicator of potential ammonia
FIG. 47—Cannon-
contamination. Quench baths may be contaminated by vari-
Fenslce viscometer ous hydraulic and metalworking fluids, which may signifi-
tube. cantly affect the resulting pH of the aqueous polymer quen-
chant.
For example, solution pH values of >10 for quenchants Conductance, Test Method D 2624—One of the most common
used in aluminum heat treating applications may be disas- and most deleterious contaminants of an aqueous polymer
trous in view of potential caustic corrosion processes that quenchant is hard metal ions (Ca"^^, Mg"^^, Mn"^^, and Fe"^^).
may occur. The relatively simple determination of pH of an The presence of hard metal ions will lead to corresponding
aqueous polymer quenchant may provide significant insight increases in cooling rates. To extend the lifetime of the quen-
into potential polymer degradation, corrosion inhibitor de- chant, it is often recommended that either distilled or deion-
pletion, and contamination. ized water be used for initial polymer quenchant dilution or
for make-up water, which must be added periodically due to

normal evaporation processes. Typically, it is recommended Thermal Separation Process
that the conductivity of the water used for this purpose not For PAG Polymer Quenchant
exceed 15 îS/cm [86].
Note 13: ASTM D 653 defines "conductance (specific)" as:
"a measure of the ability of the water to conduct an electric
current at 77°F (25°C). It is related to the total concentra-
tion of ionizable solids in the water. It is inversely propor-
tional to electrical resistance." ASTM D 616 defines "con-
ductivity" as: "the property of a substance's (in this case
water and dissolved ions) ability to transmit electricity. INmAL 20% SOLUTION
(WITH AGITATION)
SOtOTION IMMEDIATELY
AFTER SEPARATION
The inverse of resistivity. Measured by a conductivity me- (WITH AGITATION)
ter, and described in microsiemens/cm or micromhos/cm,
/LtS/cm."
Another source of ionic contamination that will result in
cooling rate increases is salts from molten salt furnaces
(baths), which may contaminate an aqueous polymer by
dragout on the part upon removal from the salt pot and sub-
sequent immersion in the aqueous polymer quenchant. In-
creased ionic contamination may also result if excessive cor-
rosion inhibitor is added to the quench system.
Since metal ions may result in increased cooling rates, REDISSOLUTION OF
SOLUTION AFTER
SOLUTION AFTER LAYER
FORMATION (NO AGITATION)
which may potentially result in cracking of the metal due to LAYER FORMATION (LOWER LAYER IS
CONCENTRATED POLYMER)
increased thermal and transformational stresses, it is impor-
tant to monitor the variation in the ionic content of an aque-
ous polymer quenchant. This is easily done because increas- FIG. 49—Illustration of the reversible thermal sepa-
ing ionic content results in increasing electrical conductance. ration process of an aqueous solution of a polyalky-
Any equipment capable of giving a conductivity reading allene glycol quenchant.
most instantaneously with the application of voltage across
the two electrodes comprising the conductivity cell as de-
scribed in Test Method D 2624 is acceptable. A typical
portable conductivity meter is illustrated in Fig. 48. The pro-
cedure followed is the same as that described in Test Method
D 2624 except that the aqueous polymer quenchant being an-
alyzed is used.
Separation Temperature (Cloud Point)—Some aqueous poly-
mer quenchants exhibit a characteristic temperature above
which the water soluble polymer becomes mostly insoluble
in the aqueous medium [87]. This reversible process, which
is shown in Fig. 49, [87] is sometimes called the separation
temperature or cloud point.
The separation temperature is determined by heating a so-
lution of the aqueous polymer quenchant and noting the tem-
perature where the fluid becomes sufficiently cloudy that the
thermometer is no longer visible. Although some salts may
affect the separation temperature, oxidative degradation of
the polymer is the most common problem. Degradation that
causes the separation temperature to rise 2-4°C (4-7°F) over
the lifetime of the quenchant bath is not unusual. A larger in-
crease or sudden change in separation temperature is cause
for concern.
Corrosion Inhibitor—Because poljrmer quenchants are water
based, they must be formulated with a corrosion inhibitor(s).
Corrosion inhibitors protect the tank, fixtures, and parts be-
ing quenched by either surface passivation or protective film
formation. Depletion of the inhibitor during use is to be ex-
pected, and periodic replenishment of the corrosion inhibitor
is required to maintain adequate protection of the quenching
bath, parts being heat treated, and fixtures.
FIG. 48—Commercially available portable conduc- Many pol5TTier quenchants use sodium nitrite as the corro-
tivity meter. sion inhibitor. The concentration of sodium nitrite may be
determined according to Test Method D 3867, a cadmium re- 200

duction method that may be performed manually or by an
a u t o m a t e d procedure. Alternatively, nitrite anion m a y be
quantitatively determined by ion chromatography according
^ 150;
to Test Method D 4327.
Note 14: The concentration of nitrite in a quenchant may z
also be determined by a relatively simple color test using a LxJ
I—
commercially available test kit. A tablet, furnished with the Z 100
test kit, is dissolved in a specific volume of the solution, SEC trace for a polymer
from an unused aqueous
and the resulting color of the quenchant solution is com- polymer quenchant solution
pared to a standard color chart of known concentrations of
y 50H
sodium nitrite, as shown in Fig. 50. CO SEC trace for a polymer
from a used aqueous
Although sodium nitrite is a commonly used corrosion in- polymer quenchant solution
hibitor used in the formulation of aqueous polymer quen-
chants, there is an increasing trend in the marketplace for so- 40 50 55 60 65 70
called non-nitrite quenchants. Many of non-nitrite inhibitor
systems are based on various amines or amine-fatty acid RETENTION TIME (sec.)
combinations. Due to the specificity of the required analyti-
FIG. 51—Size-exclusion chromatography data for a fresh and
cal procedures for determination of each non-nitrite in- severely degraded poly(alkylene glycol) quenchant.
hibitor package that may be used, it is most common to sub-
mit samples periodically to the quenchant manufacturer for
analysis.
Foam Testing, Test Methods D 892, D 3519, and D 3601—A
commonly encountered problem in production quench tanks
is excessive foaming. Excessive foaming is bad because it phy (GPC), also k n o w n as size exclusion chromatography
may potentially lead to cracking and/or increased distortion. (SEC), provides the most unambiguous results. This chro-
Relative foaming propensity for one fresh quenchant com- matography technique, described in Test Method D 5296,
pEired to another or a used quencheint compared to a fresh separates poljrmers on the basis of their molecular size.
quenchant or two used quenchant samples may be readily de- Note 15: Test Method D 5296 may be modified for use with
termined by various tests including Test Methods D 892 (us- various nonionic polymers such as those based on
ing a gas diffusion tube), D 3519 (blender test), or D 3601 poly(alkylene glycol). However, many water-soluble poly-
(bottle test). mers are not readily soluble in solvents other than water.
Polymer Molecular Weight Analysis, Test Method D 5296—Âs a In this case, a n a q u e o u s GPC p r o c e d u r e , a procedure
test for pol5rmer degradation, gel permeation chromatogra- where water is used as the solvent for GPC analysis, will
need to be developed.
Illustrative chromatograms for a fresh undegraded poly-
mer from a polymer quenchant and a badlydegraded polymer
are superimposed in Fig. 51 [86].
Note 16: Another method of pol5rmer degradation analysis
is to compare, by superimposition, the GPC chromatogram
for the fresh and used polymer for the specific quenchant
of interest as shown in Fig. 51 [86]. The total area under the
pecik for the degraded polymer is normeJized to that of the
area u n d e r the fresh polymer peak. The resulting "area
shift" of the broader-peaked degraded polymer curve is a
quantitative measure of degradation. Although the area
shifts may vary widely, typically values greater than 10%
are usually cause for concern.
Biological Stability
Fluid Biodeterioration Processes—Fluid biodeterioration in-
volves the reaction of water with a substrate, such as the wa-
ter-soluble polymer used to formulate a n aqueous polymer
quenchant, in the presence of b a c t e r i a or fungi to yield
biomass [89]. If this degradation process is not inhibited,
enormous queintities of biomass may be present in the system
in the form of sludge or microbial scum, which are composed
of dead cells, gelatinous slimes, and fungal threads. It has
been reported that a bacterial cell may double in size cind di-
FIG. 50—Portable color test to determine nitrite concentra- vide into two new cells every 15 min until a limiting condition
tion. is encountered [89,90].
In addition to solid by-products, obnoxious gases may be dures m a y not detect microbial species that do not form
formed from the biodeterioration of certain additives acting colonies and, therefore, may not correlate with biodeteriora-
as microbial nutrients, such as nitrites and nitrates, which tion processes.
are converted to ammonia and sulfur or sulfate, which is con- Cooling Curve Analysis—Polymer Quenchants (Test Methods
verted to hydrogen sulfide (H2S), which exhibits a character- D 6482 and D 6549)—Cooling curve analysis provides a cool-
istic "rotten egg" odor [91]. ing time versus temperature pathway that is directly propor-
Biodeterioration processes that occur in the presence of air tional to physical properties, such as hardness obtainable
(oxygen) are enhanced by system agitation and are desig- upon quenching of metal. Aqueous polymer quenchants are
nated as "aerobic" processes. However, biodeterioration pro- typically used with agitation and it is r e c o m m e n d e d that
cesses may also occur without air (oxygen) being present. cooling curve analysis of this class of quenchants be per-
These are called "anaerobic" processes that are inhibited by formed according to Test Method D 6482 (Tensi Method, see
system agitation. Most aqueous polymer q u e n c h a n t s un- agitation device s h o w n in Fig. 34A) or D 6549 (Drayton
dergo biodeterioration by an anaerobic process. Method, see agitation device shown in Fig. 34B). The results
Biodeterioration Monitoring Procedures (Test Methods D 3946, obtained by these tests may be used as a guide in quenchant
E 686, and E 979)—There are four strategies for monitoring selection or compairison of different quenchants or dilutions
microbial contamination: 1. gross, 2. physical, 3. chemical, of the same quenchant, whether new or used.
and 4. microbiological. Gross detection procedures include Cooling curve analysis of an aqueous polymer quenchant
visucd observation of slimes or detection of foul odors. Phys- by Test Methods D 6482 or D 6549 is conducted by placing
ical detection procedures include the observation of haze and the probe assembly illustrated in Fig. 19 into a furnace a n d
visible, nonmetsdlic particulate matter in the fluid. Chemical heating to 850°C (1562°F). The heated p r o b e is then im-
tests that are often used include pH. Sudden decreases in p H mersed into the agitated quenchant solution at a known agi-
indicate a strong potential for microbial contamination [91]. tation rate and desired temperature. The temperature inside
The fourth procedure is to conduct a microbial test. One the probe assembly and cooling times are recorded at se-
test is to directly observe the microbial species on a glass lected time intervals to establish a cooling temperature ver-
slide under a microscope [91]. Currently, there are three stan- sus time curve.
dard bench test procedures that m a y be used for monitoring A series of cooling rate curve compeirisons illustrating the
resistance to microbial growth: D 3946, E 686, and E 979. Al- effect of aqueous polymer quenchant concentration and bath
ternatively, a commercial dip-slide test that is coated with a temperature is illustrated in Figs. 53 and 54, respectively. The
microbial growth media is often used in the heat treat shop. effect of agitation is illustrated in Fig. 55. Cooling curve com-
This is CcJled a "viable titer method," in which the population parison of a fresh and severely degraded polymer quenchant
densities of the microbial species are estimated after incuba- (compared to water) is shown in Fig. 56.
tion for 24-72 h as illustrated in Fig. 52. Viable titer proce- Advanced Cooling Curve Analysis—Âll of the cooling curve
analysis methods described thus far are essentially labora-
tory quenchant cinalysis procedure. Although they are invalu-
Determtnation of total alerob c bacteria
able for this use, they are of relatively limited direct value to
•
• .'•: m the heat treater, who needs to know if he can through-heirden
a part being produced in production and if he will encounter
distortion or even cracking. Therefore, there are various ef-
« forts underway at the present time to advance cooling curve
m anedysis methodology to permit modeling smd simulation of

the production quenching process. In this section, one cool-
•• *•/
• •. • l'wf\. M%
io>
FIG. 52—Dip-slide test for bacteria and fungi detection.
, —-
800 "V.
U
V\ \
— -- ^ • ^
-
•^^Zy^
~ 600
\ \ 0 10%
,15% 15%]
8» :\\ 1 ''
3
? 400
w \
p 1
3
2 400
2(
r '^'
' - ' • , -
5%
''
. ' ^ ,^
0)
a. a.
E 5%
v. V
\ ^ -.^ E ^^.i
^<.
0
10% <-'
•*
/
0 0
15 SO 100 150 200
Time(s) Cooling Rate(°C/s)
FIG. 53—Illustration of the effect of quenchant concentration on cooling curve and

cooling rate curve performance for an aqueous polyalkylene glycol quenchant at
SOX and 0.5 m/s.
1
i ^
"^ 800 •--.
~YN • \ '
1 '^^ — . ..=--^.
*-st,-
o
o \\ \ \ 1 jy 50°C .^^^
- ^ 600
£ , \ \ V40°C 40°C\ / ^;.--
3 -—
', \ 50°C 3 ^'
a>
a.
30OcX\ N \ ---'
E 1 / \^^^^. a ^
fl 200
*"*-<^ i: 1- •
/
/ _^
0 0
S 10 15 20 100 150 200
Time (s) Cooling Rate(°C/s)
FIG. 54—Illustration of tlie effect of bath temperature on cooling curve and cool-
ing rate curve performance of a 15% aqueous solution of a polyalkylene glycol quen-
chant.
"-1
•-»«
800 • > v 800 • — i
\^ L \ " 0.4 m/« ^^^
o O 1 a2m/s . ^
.0 m/s
S_ 600 1 m/i;'i"
0.6 >Yr
[j I 1
a> ( .6 m/ •.}\Lo.2ni/5 £ s
3 I
5
"2 400 S 400
a> •- V
a
(1.4 m/» "'^ s a.
E
E %^;- |2 200
'. '^
k=
/
• /
0 0
10 15 20 50 100 150 200
Time (s) Cooling Rate (°C/s)
FIG. 55—liiustration of the effect of agitation on cooling curve and cooling rate
curve performance for a polymer quenchant.
800-
GPC Trace Of Fresh and

Used Polymer Quenchant
^600-
o
UJ
K
.3
1400
s
tu
200
-WATER
- USED POLYMER QUENCHANT
- FRESH POLYMER QUENCHANT
I I I I I I I I I I I I 1 I I I I I r I I r I I I I I I I I I I IT r - r I I I IT-T > I I I I I I I
0 20 40 60 80 100
TIME (Sec)
FIG. 56—liiustration of cooling curve performance of a severely degraded aqueous polymer quenchant
compared to water and a fresh solution at the same concentration, bath temperature, and agitation.
ing curve analysis methodology that has been successfully the quenching process to determine optimal quenchant and
used in the heat treating shop will be described. In addition quenching conditions for every part being produced.
to illustrating the overall utility of modeling and simulation In addition, for optimal simulation, it is important that the
of production quenching conditions, this example also illus- m e a s u r e m e n t m e t h o d be sufficiently sensitive to reflect
trated advanced techniques for investigating quenching be- changes in each of the important quenching peirameters (spe-
havior. cific character of the quenchant, quenchant bath tempera-
ture, in addition to mode and degree of agitation). This crite-
Temperature Gradient Quenchant Analysis rion is addressed by recording the temperature-time history
Background—Liscic designed a system for practical mea- (cooling curve) at particular points within the probe used for
surement, recording, and evaluation of quenching (cooling) analysis. This requires the measurement of transient temper-
intensity u n d e r w o r k s h o p conditions, which expresses atures within a solid body when high thermal gradients are
quenching intensity by a continuous change in relevant ther- involved, which requires that the following inherent effects
m o d j n a m i c functions during the entire quenching process. be considered:
This approach should be contrasted with the Grossmann H- • Damping Effect—Changes in surface t e m p e r a t u r e are
factor concept, which expresses quenching intensity with a damped in magnitude when sensed inside the body com-
single value and which was shown earlier to be of limited pared to their magnitude at the surface.
value in quantitatively represented quench severity when ag- • Lagging Effect—Changes in the surface temperature are
itation is used. sensed within a finite time after they occur at the surface.
All of the different cooling curve analysis methods dis- The greater the distance of the temperature measurement
cussed thus far utilize relatively small, usually 12.5 m m or 0.5 point from the surface, the greater the damping and lag-
in diameter, round bar probes with a single thermocouple ging effects.
placed at the geometric center. Such probes, while excellent • Response Time—When working with thermocouples, it is
for quality control purposes, are of limited value for use unimportant to consider another effect that is inherent with
der workshop conditions. The reasons include: every thermocouple-response time, which is the time nec-
• Because of its relatively small mass and low heat capacity, essary to reach 63.2% of its total signal output when the
these small probes will cool in about 10-30 s whereas an thermal junction is subjected to a step change in tempera-
actual workpiece of 50 m m (2.0 in) diameter will require ture [93]. The time constant of a sheathed, grounded ther-
500-600 s to cool below 200°C (392°F) in the center of the mocouple of 1.5 m m (0.062 in) outer diameter is 1.5 s. To
workpiece when quenched into an unagitated quench oil. reach 99% of its full signal output when subjected to a step
Therefore, to adequately model actual quench processes change in temperature, the time constant must be multi-
under production conditions, a probe of similar mass and plied by 5, which makes a 7.5 s delay. Thermocouples with
dimensions is necessary. an even greater diameter will exhibit an even greater time
• The actual heat transfer coefficient during quenching of ac- constant and delay in response time.
tual production parts may be simulated using a small cylin- Theoretical Principles—Because of all of the above described
drical probe. However, the heat transfer coefficient during requirements, effects, and limitations, instead of recording
nucleate boiling is heavily dependent on bar diameter [92]. only one cooling curve at the center of a small cylindrical test
The magnitude of this dependence increases with decreas- probe (as in laboratory tests) the heat flux density at the sur-
ing bar diameter below 50 m m (2.0 in). The dependence is face of the quench probe has been selected as the main fea-
less pronounced for bar diameters greater than 50 m m (2.0 ture in measuring, recording, and eveduating quenching in-
in). Therefore, for the same quenching conditions, the heat tensity. This is because changes of the h e a t flux density
transfer coefficient on the surface of a small diameter cylin- during the quenching process best represent the dynamics of
der is quite different than that expected on the surface of heat extraction.
most production parts with diameters > 5 0 m m (2.0 in). The method itself, known in the literature as the Tempera-
Important criteria for a cooling curve analysis system to be ture Gradient Method, is based on the known physical rule
utilized to model quench processes under workshop condi- that heat flux at the surface of a body is directly proportional
tions should be applicable to: 1) a wide variety of quenchant to the temperature gradient at the surface multiplied by the
media including: water, brine, aqueous polymer solutions, thermal conductivity of the material of the body being
salt baths, quench oils, fluidized beds, and gas quenchants; 2) cooled:
a wide variety of quenching conditions including: different
bath temperatures, agitation rates, and fluid pressures; and dT
q = \
3) all quenching techniques including: direct i m m e r s i o n dx
quenching, interrupted quenching, martempering, austem-
pering, and spray quenching. Where: q is the heat flux density (W/m^), i.e., the quantity
The method to be reported here provides for recording of of heat transferred through a surface unit per unit time, A is
thermodynamic functions during each test to enable the user thermal conductivity of the body material (W/mK), and dT/dx
to ancdyze the peirticular quenching process of interest and is the temperature gradient inside the body at the body sur-
quenching conditions, to evaluate quenching intensity, and to face, perpendicular to it (K/m).
compare it with previously performed tests in other facilities Hardware—The essential feature of the method being de-
under different conditions. To do this, the user will establish scribed here is the LISCIC/NANMAC quench probe." It is
a database of quenching intensities of different systems
within the production facility. This database will provide the "* The Llscic-Nanmac probe is manufactured by the NANMAC Cor-
user with input data for subsequent computer simulation of poration, Framingham, MA.
constructed from AISI Type 304 stainless steel, which is 50 /ixm (0.0036 in), is placed between a split-tapered insert and
mm (2.0 in) diameter X 200 mm ( 4.0 in ) length, instru- pressed into the thermowell (body). The thermal junction is
mented with three thermocouples placed at the half-length formed by grinding and polishing across the sensing tip.
cross section as shown in Fig. 57. One thermocouple mea- The mica insulation between the two dissimilar ribbons is
sures the actual surface temperature of the probe {T„), an- so thin that metallic whiskers of one ribbon element
other measures the temperature at a point 1.5 mm (0.06 bridges across the mica to the other ribbon element, and
in.) below the surface (TO, and the third one measures the makes hundreds of microscopic friction welded junctions,
temperature at the center of the cross section. The thermo- which are parallel to one another, thus forming one com-
couples inside the body are standard sheath-tjrpe thermo- posite measuring junction.
couples. The thermocouple at the surface is of special de- The microscopic burrs of the metal from the thermowell
sign (U.S. Patent 2,829185), which allows continuous (housing) bridge the thin layers of mica, thus electrically
measurement of the true surface temperature of a solid grounding the thermal junction to the thermowell at the
body without any damping or lagging effects, in real time, sensing tip. The metal of the thermowell becomes the third
because of its extremely fast response time of about 10 /AS intermediate element, and since the temperature is the same
(10-5 s)
on both sides of the thermal junction, the EMF produced by
There are two important requirements for a thermocouple the secondary junctions on both sides of the main thermal
used for measuring surface temperature: junction cancel each other out, leaving the EMF of the main
1. Its thermal junction should be two-dimensional (instead of thermal junction as the only observed EMF (Law of Interme-
the usually encountered three dimensional geometry) diate Metals in Thermocouples).
2. It should be flush with the surface Any subsequent erosion of the surface of the thermowell
The unique details of the sensing tip of this thermocouple (body) simply forms new junctions while removing the old
are as follows. In the vicinity of the hot measuring junc- junctions, hence its name "Self Renewing Thermocouple."
tion, the round thermocouple wires are flattened into rib- Because of its unique characteristics, this is the best type of
bons of about 38 /xm (0.0015 in) thickness. These ribbon el- thermal junction to be used for heat transfer calculations be-
ements are electrically insulated from each other and from cause it registers all of the phenomena occurring at the sur-
the thermowell by sheets of mica insulation of about 5 /xm face in real time.
(0.0002 in) thickness. This "sandwich" of ribbon elements The temperatures recorded at the surface iT„) and at 1.5
and mica insulations, having a total thickness of about 91 mm below the surface of the quench probe (Ti) permit the
Handle(optional
i (19mmjO.D. stainless tube
•j-(3.2mnn)O.D. s t a i n l e
|—.060"(1.5mm) sheotlied thermocouples
Adaptor
fiberglass
insulated leads
NANMAC Surface T„ # 20 gage X 36."
Standard connector
(100.3 mm) (990.6 mm) attached.
(3-required-one
. 7.90" shown for c l a r i t y ) .
(200.6 mm)
Thermocouple body
Tapered split pin
Mica insulation
Thermocouple w i r e
FIG. 57—The LISCIC/NANMAC quench probe.

calculation of the temperature gradient within this surface Calculated functions, graphically represented in Fig 58
layer at each m o m e n t throughout the quenching process. The and Fig. 59 permit comparison of the actual quenching in-
role of the center thermocouple (Tc) is to indicate the timing tensity among different quenchants, quenching conditions,
for heat extration from the core of the probe and to provide a and techniques. Based on these thermodynamic functions,
continuous measurement of the temperature difference be- each quenching test m a y be evaluated with respect to:
tween the surface and the core, which is essential for the cal- depth of hardening, (when comparing two quenching pro-
culation of thermal stresses. cesses), thermal stresses, a n d possible superposition of
Specific features of the LISCIC/NANMAC quench probe structural transformation stresses that will occur during a
are: particular quenching process and delayed quenching, i.e.,
whether continuous or discontinuous cooling rates are oc-
1. The size of the probe and its mass ensures sufficient heat curring (with consequences on hardness distribution on
capacity and radially symmetric heat flow in the cross sec- the cross section after hardening). These thermodynamic
tioned plane where the thermocouples are located. functions also provide the basis for automatic control of
2. The probe is constructed from austenitic stainless steel quenching intensity during the quenching process.
and does not undergo microstructural change upon heat-
ing or quenching, n o r does it evolve or absorb heat because 2. Module II: HEAT-TRANSF (Calculation of Heat Transfer
of microstructural transformations. Coefficient and Cooling Curves)—The function of this mod-
ule is the calculation of the temperature distribution in the
3. The surface condition of the probe can be maintained for
cross section of round bars. It is based on the numerical
each test by polishing the sensing tip of the surface ther-
method of control volumes where the heat conduction in
mocouple before each measurement.
the radial direction is solved as a one-dimensional prob-
4. Extremely fast response times of the surface thermocouple
lem. The software consists of two m a i n subroutines. The
(10~^ s), and the absence of any damping or lagging effects
first subroutine utilizes the measured surface temperature
allow any transient temperature at the surface to be mea-
as an input parameter to calculate the temperature distri-
sured and recorded exactly and in real time.
bution over the probe's cross section versus time and the
5. The heat transfer coefficient at the probe's surface, be- heat transfer coefficient between the surface and the quen-
cause of its sufficiently large diameter, may be used in chant versus time and versus the surface temperature as il-
computer simulation of actual production parts. lustrated in Fig. 60a and Fig. (sOb.
W h e n the quenching intensity is to be determined, the The second subroutine utilizes the calculated heat trans-
probe is heated to 850°C (1562°F) in a suitable furnace, then fer coefficient for a particular quenching test as input pa-
transferred quickly to the quenching bath and immersed ver- rameter, which permits the simulation of quenching cylin-
tically. The probe is connected to a data acquisition system drical workpieces of varying diameters u n d e r the
including a personal computer. The data acquisition card conditions of each quenching test that are stored in the
contains three A/D converters and amplifiers enabling digital users database of quenching intensities. Physical proper-
recording of all three thermocouple signal outputs. ties of the workpiece can be selected for the desired steel
Software—In addition to cooling curve data, the cooling grade. The cooling curve at any point within the cross sec-
curve analysis p r o g r a m (TGQAS - T e m p e r a t u r e Gradient tion can be calculated as illustrated in Fig. 60c along with
Quenching Analysis System) described here permits ad- corresponding heat transfer coefficient versus time and
vanced computational modeling of production quenching versus the surface temperature.
systems. The TGQAS consists of three modules: 3. Module III: CCT-DIAGR (Prediction of Microstructure and
Hardness after Quenching)—This module is used to predict
1. Module I: zTEMP-GRAD (Temperature Gradient Method)—
the microstructure and hardness after quenching of cylin-
In each test, three cooling curves are obtained: r „ for the
drical workpieces of different diameters. It contains a n
surface of the probe, Ti for the point 1.5 m m (0.06 in) below
open data file of CCT (Continuous Cooling Transforma-
the surface, and Tc for the center of the probe. TypiccJ cool-
tion) diagrams in which the user may store u p to 60 CCT
ing temperature-time profiles for each of these points is il-
diagrams of his own choice. This program enables the user
lustrated in Fig. 58. The temperature gradient between Ti
to superimpose every calculated cooling curve on the CCT
and Tn is calculated from these cooling curves by multiply-
diagram of the desired steel. From the superimposed cool-
ing the corresponding data by the temperature-dependent
ing curves (shown on the CRT monitor during analysis)
thermal conductivity, and the heat flux density versus time,
the u s e r can select the percentage of microstructural
q = fit) (see Fig. 58b) and the heat flux density versus sur-
phases transformed and the hardness value at the selected
face temperature, q = f{T„) (see Fig. 58c) are calculated.
point within the cross section after hardening as illus-
Calculation of the differences between each thermocou- trated in Fig. 61. For a cross section of the selected diame-
ple location versus time, AT — f(t), provides the functions ter, cooling curves are calculated at three or five charac-
illustrated in Fig. 59d. Calculation of the integral under the teristic points (surface, 3/4R, 1/2R, 1/4R and center), using
heat flux density curve (which represent the a m o u n t of the HEAT-TRANSF module. The CCT-DIAGR module en-
heat extracted) from the beginning of immersion until a ables the user to d e t e r m i n e hardness values at these
predetermined time, provides the functions shown in Fig. points, which will permit prediction of the hardness distri-
59e. For heat extracted from the probe, the curve desig- bution curve.
nated by "(" (i.e., for the surface layer of 1.5 m m thickness)
is valid. In each point where thermocouples are located, Note 17: In the case of delayed quenching, where a
the cooling rate curves versus surface temperature: dT/dt = discontinuous change of cooling rates occur, the predic-
fiT„) are calculated as shown in Fig. 59f. tion of microstructural transformations and hardness
TCXTJi .«CC TCST2*-ncc
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^^ Time I tsl
i i u r f o c e l e m p e r o t u r e ; Ti« t « m p e r o l u r e l . S m m b e l o w l h « s u r f o c c ;
(a) • t e m p e r o i u r e in t h e c e n t e r ot t b e probe T„ = s u r f a c e f e m p e r o t u r e ; T; « t « m p e r o t u r e 1.5 mm b e l o w t h e s u r f a c e :
t e m p e r a t u r e in t h e c e n t e r of t h e p r o b e .
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"o too aoa >oo 400 9 6O «00 TOlo s o o lac >oo xooo xxoo jiioo
(c) T«mperolure Tn 1*01 T » r o p « r a t u r « Tn I'Cl.
FIG. 58—Graphical Display from Module 1 (TEMP-GRAD) when quenching the LISCIC/NANIVIAC probe into a 20°C mineral oil bath
without agitation (left row, vertically) and a 25% aqueous polyalkylene glycol quenchant solution at 40°C bath temperature and 0.8
m/s agitation rate (right row, vertically), (a) Measured and recorded temperature versus time, T = f{t); (b) Calculated heat flux den-
sity versus time q = f{t),; and (c) Calculated heat flux density versus surface temperature, q = f(T„).
rcxTi.nee
(d) »l-^ >c-l
rcsTi.ncc TE&TZtc .nee
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TOO «OO 9OO AOOO a&oo txoo 1.00 too >00 400 900 coo 700 MOO «00 lOOO llOO IXOO
Tempefotore T^ C*C1 T » m p » r o l o r e T„ I ' C l
(f)
FIG. 59—Graphical display from Module 1 (Temp-Grad) when quenching the LISCIC/NANMAC probe into a 20°C mineral oil bath
without agitation (left row, vertically) and a 25% aqueous polyalkylene glycol quenchant solution at 40°C bath temperature and 0.8
m/s agitation rate (right row, vertically), (d) Calculated temperature difference versus time, AT= i(t); (e) Calculated integral of the
heat flux (heat extracted) versus time, Iqdt = f(t), and 1. Calculated cooling rates versus temperature, dT/df = 1{J,^.
2000 2000
a ^ . ^ i Z B w;m»K o„, . 595 W/m'K
gi800 5 1800
"6
J 1600 ? 1600
"UOO ", I t O O
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Time/ s
Time /s
2000 2000
Siaoo _ 1800
Sl600 S: 1600
5 d itOO
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100 200 300 400 500 600 700 800
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Tempcrature/»C Temperature/*<;
900 900
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(C) 0.01 0.1 1 10 100 1000 1000
0.01 0,1 1 10 100
Timc/s
Time/s
FIG. 60—Graphical display from Module 2 (HEAT-TRANSF), when quenching the LISCIC/NANMAC probe into a 20°C mineral oil
bath without agitation (left row, vertically) and a 25% aqueous polyalkylene glycol quenchant solution at 40°C bath temperature and
0.8 m/s agitation rate (right row, vertically), (a) Heat transfer coefficient versus time, a = f(t); (b) Heat transfer coefficient versus
surface temperature, a = f(r„); and (c) Comparison of measured and simulated cooling curves for the center of the quench probe
(50 mm diameter).
Chemicot C Si Mn P S Cr Cu Mo Ni V
Composition 0.38 0.23 0.64 0.019 0.013 0.99 0,17 0.16 0,08 «0.01
1000
Times
FIG. 61—CCT diagram of AISI4140 steel with superimposed calculated cooling curves for sur-
face (S), three-quarter radius (3/4 R), and center (C) of a round bar of 50 mm diameter.
values after hardening ft-om an ordinary CCT-diagram is tracted. However, immediately after that period, between 50
not correct, because the incubation time consumed (at and 100 s, the heat extracted in Case A has increased only
any point on the cross section) before the coohng rate from 50 to 55 MJ/m^, whereas in Case B, the heat extracted
was abruptly changed, has not been taken into account. has increased from 20-86 MJ/m^. This shows that in Case B,
For a detailed explanation see Ref 94. the thick polymer film has prevented the heat extraction for
a relatively long time at which point the insulating polymer
Hardware Requirements—For the system being described film surrounding the cooling probe burst and a sudden in-
here, the hardware requirements are relatively modest and crease of heat extraction occurred.
include: IBM compatible PC (286/386/486/Pentium), 640
By comparing the time required to decrease the heat flux
Kbytes RAM, a color graphic system, 2 MB free hard disk density from its m a x i m u m to a low value, e.g., 100 KW/m^ as
space plus additional space for files to be stored, printer port, shown in Fig. 58b, it is observed that in Case A, 45 s is neces-
cind disk drive. sary, whereas in Case B, only 28 s is necessary. This illus-
trates that Case B is a quenching process in which after the
Example of a Quenching Process Analysis s u d d e n burst of the thick polymer film surrounding the
Two different quenching processes are illustrated in Fig. 58 probe, there is practically n o boiling, as observed in oil
and Fig. 59; Case A and Case B. Case A is a quenching process quenching, but an abrupt change in the convection cooling
in a mineral oil at 20°C (68°F) without agitation. (All associ- stage.
ated diagrams are on the left side of the figure.) Case B is a A discontinuous cooling change is inherent to such a
quenching process in a 2 5 % aqueous polyalkylene glycol quenching regime. It is interesting to analyze cooling rate
(PAG) solution at 40°C (104°F) and 0.8 m/s agitation rate. (All versus surface temperature as shown in Fig. 59f. While in
of the diagrams for this process are on the right side of the Case A (oil quenching), the cooling rate at the surface of the
figure.) probe "o" exhibits a greater m a x i m u m cooling rate t h a n
By comparing the diagrams of the heat flux density versus the cooling rate at 1.5 m m below the surface ( ). In Case B,
time in Fig. 58b, it is shown that Case B exhibits delayed the maximum cooling rate at 1.5 m m below the surface (dur-
quenching because in Case A, the time required for meixi- ing the period of 350°C to 300°C of surface temperature) is
m u m heat flux to occur (f^max) is only 15 s, whereas in Case B higher than the m a x i m u m cooling rate at the surface itself!
it is 72 s (due to the thick PAG poljmer film). In Case A (oil This is also evident from the cooling curves illustrated in Fig.
quenching). Fig. 59e shows that by 20 s after immersion, 34 58a for Case B where at 570°C, a discontinuous change of
MJ/m^ has already been extracted and by 50 s, 50 MJ/m'^ heat cooling curve slope of Ti occurs, and between 500°C a n d
has been extracted. In Case B, (quenching in a high concen- 300°C, this slope is greater t h a n the slope of the cooling curve
tration of a PAG quenchant solution), by 20 s after immer- for the surface (T^). This is an experimental proof of the the-
sion, only 5 MJ/m^ and by 50 s, only 20 MJ/m^ has been ex- oretical calculation described in Ref 95, that in delayed
quenching, cooling rates below the workpiece surface can be 500

higher than at the surface itself.
Another analysis, with respect to thermal stresses during
quenching (on which residual stresses and possible distor-
tion depend), is possible by comparing Fig. 59d. This com-
parison shows that quenching in an aqueous PAG quenchant
solution of high concentration (Case B) compared to oil
quenching (Case A), resulted in 27% lower maximum tem-
perature difference between the center and the surface of the
probe (o). Whereas in Case A, the maximum temperature dif-
ference between the center and 1.5 mm below the surface (A)
1 10| 1000 (a)
is higher than the maximum temperature difference between log t tsl ""
the point 1.5 mm below the surface and the surface itself ( );
500
in Case B, the maximum temperature difference between the
point 1.5 mm below the surface and the surface itself ( ) is
slightly higher than the maximum temperature difference be- 388
tween the center and the point 1.5 mm below the surface (A), ^333
which is reached about 20 seconds later. This analysis also J 277
o
.^^
shows an abrupt heat extraction when the polymer film ^ 222 /
bursts. 166 /
However, Figure 59d shows that in oil quenching, the max- /
imum temperature difference between the center and the
surface (o) occurs 20 s after immersion when the surface
temperature is 450°C (See Fig. 58a for Case A), i.e., above the
55
— i - i 1 mil—i-f-rnm
1.01 0.1 1
/
i i i iim
10
11
1
iiVu
100
J-t-W-lIU
1000 (b)
martensite start temperature (Ms)- In an aqueous solution of log t Is)
a PAG polymer quenchant at high concentration, the maxi- 500
mum difference between the center and the surface (o) oc-
curs much later, i.e., after 80 s when the surface temperature _388
has already decreased to 350°C (see Fig. 58a for Case B). Be-
"e 333
cause of this, when working with steels with high Ms tem-
peratures, there is a greater possibility of overlapping ther- I 277
o
mal stresses with those created due to austenite - to -222
martensite transformation. 166
The probability of crack formation can be observed by

comparing the surface temperature of the probe at the mo- 55
1 1 iii!i}~—t_J-llllll
ment when maximum heat flux density occurs (Tqmax,)- As 1 1 llllll 1 1 1 IIITI 1 1 llllll
0.01 0.1 1 10 ,100 1000 (c)
seen in Fig. 58c for oil quenching, Tqmax is 515°C, while for log t Isl
the aqueous PAG quenchant solution at high concentration
(Case B) this occurs at 380°C. The lower the value of Tqâx, FIG. 62—Calculated heat flux densities versus time, when
the greater the risk of crack formation, especially with steels quenching the LISCIC/NANMAC probe into an aqueous
with high Ms temperature. polyalkylene polymer solution at 40°C and 0.8 m/s agitation
rate, but having concentrations: (a) 5%, (b) 15%, and (c) 25%.
When comparing two different processes with continuous
cooling (for the same workpiece and the same steel grade), to
determine which will provide the greater depth of hardening, quenchant concentration) changes a normal quenching pro-
the following analysis may be used (see Fig. 58b). The larger cess to a delayed one.
the value of gâx, and the shorter the time (fqmax), the greater This example illustrates the possibiUties that are available
will be the depth of hardening. In the case of a quenching for simulation of production quenching processes using ad-
process with discontinuous (delayed) quenching such rea- vanced data acquisition and analysis techniques.
soning is not valid.
The sensitivity of the method to variation of quenching pa-
rameters is demonstrated in Fig. 62, which shows the calcu- ASTM STANDARDS
lated heat flux densities versus time for the LISCIC/NANMAC
quench probe, all experiments performed in the same aque- No. Title
ous PAG polymer quenchant solution of 40°C bath tempera- A 255 Standard Method for Determination of Hardenabil-
ture and 0.8 m/s agitation rate. The only parameter that was ity of Steel
changed was the polymer concentration from: a) 5% to b) D 91 Test Method for Precipitation Number of Lubricat-
15% to c) 25%. This figure illustrates how increasing polymer ing Oils
quenchant concentration decreases the heat flux density, i.e., D 92 Standard Test Method for Flash and Fire Points by
quenching intensity. Shifting the heat flux density maximum Cleveland Open Cup
to a longer time (because of increasing thickness of the insu- D 93 Standard Test Method for Flash-Point by Penske-
lating polymer film surrounding the probe with increasing Martens Closed Cup Tester
D 94 Standard Test Method for Saponification Number D 6482 S t a n d a r d Method for Cooling Curve Analysis of
of Petroleum Products Aqueous Polymer Q u e n c h a n t s by Cooling Curve
D 95 S t a n d a r d Test Method for Water in Petroleum Analysis with Agitation (Tensi Method)
Products and Bituminous Materials by Distillation D 6549 S t a n d a r d Method for Cooling Curve Analysis of
D 189 S t a n d a r d Test Method for Conradson Carbon Aqueous Polymer Q u e n c h a n t s by Cooling Curve
Residue of Petroleum Products Analysis with Agitation (Drayton Method)
D 287 S t a n d a r d Test Method for API Gravity of Crude D 6666 Stcindard Guide for Evaluation of Aqueous Polymer
Petroleum and Petroleum Products (Hydrometer Quenchants
Method) D 6710 Standard Guide for Evaluation of Hydrocarbon-
D 445 Standard Test Method for Kinematic Viscosity of Based Quench Oil
Transparent and Opaque Liquids (the Calculation E 112 Standard Test Methods for Determining Average
of Dynamic Viscosity) Grain Size
D 482 S t a n d a r d Test Method for Ash from Petroleum E 131 Standard Terminology Relating to Molecular Spec-
Products troscopy
D 653 Standard Terminology Relating to Soil, Rock, and E 349 Standard Terminology Relating to Space Simula-
Contained Fluids tion
D 664 S t a n d a r d Test Method for Acid N u m b e r of E 686 Standard Method for Determination of Antimicro-
Petroleum Products by Potentiometric Titration bial Agents in Aqueous Metalworking Fluids
D 892 Standard Test Method for Foaming Characteristics E 930 Standard Test Methods for Estimating the Largest
of Lubricating Oils Grain Observed in a Metallographic Section (ALA
D 974 Standard Test Method for Acid and Base Number Grain Size)
by Color-Indicator Titration E 979 Standard Method for Determination of Antimicro-
D 1298 Test Method for Density Relative Density (Specific bial Agents as Preservatives for Invert Emulsions
Gravity) or API Gravity of Crude Petroleum and and Other Water Containing Hydraulic Fluids
Liquid Petroleum Products by Hydrometer Method E 1181 Standard Test Methods for Characterizing Duplex
D 1310 S t a n d a r d Method for Determination of Flash Grain Sizes
Point and Fire Point in Liquids by Tag Open-Cup E 1382 Standard Test Methods for Determining Average
Apparatus Grain Size Using S e m i a u t o m a t i c a n d Automatic
D 1744 Standard Test Method for Determination of Water Image Analysis
in Liquid Petroleum Products by Karl Fischer
Reagent
D 1747 Standard Test Method for Refractive Index of Vis- OTHER STANDARDS
cous Materials
D 2624 Standard Test Method for Electrical Conductivity SAE J406 Methods of Determining Hardenability
of Aviation and Distillate Fuels of Steel
D 3519 Standard Test Method for Foam in Aqueous Media DIN 50191 Hardenability Testing of Steel by End-
(Blender Test) Quenching
D 3 5 20 Standard Test Method for Quenching Time of Heat- IP 34 Determination of Flash Point - Penske-
Treating Fluids (Magnetic Quenchometer Method) Martens closed cup method
D 3601 Standard Test Method for Foam in Aqueous Media IP 71 Petroleum products - Transparent Eind
(Bottle Test) opaque liquids - Determination of
D 3867 Standard Test Method for Determination of Nitrite- kinematic viscosity and calculation of
Nitrate in Water dynamic viscosity
D 3946 Standard Test Method for Evaluating the Bacteria IP 123 Petroleum products - Determination of
Resistcince of Water-Dilutable Metalworking Fluids distillation characteristics at a t m o -
D 4007 Standard Test Method for Water and Sediment in spheric pressure
Crude Oil by Centrifuge Method (Laboratory Proce- IP 160 Crude petroleum and liquid petroleum
dure) products - Laboratory determination
D 4327 S t a n d a r d Method for Determination of Anions of density - Hydrometer method
in Water by Chemically Suppressed Ion Chro- IP 226 Petroleum p r o d u c t s - Calculation
matography of viscosity index from kinematic
D 5296 Standard Method for Determination of Molecular viscosity
Weight Averages and Molecular Weight Determina- ISO 642 Steel Hardenability Test by E n d
tion of Polystyrene by High Performance Size Ex- Quenching (Jominy Test)
clusion Chromatography ISO 6743 Part 14: Family U (Heat Treatment),
D 6161 Standard Terminology Used for Crossflow Microfil- Lubricants, Industrial Oils & Related
tration, Ultrafiltration, Nanofiltration, and Reverse Products (Class U)
Osmosis Membrane Processes ISO 9950 Industrial Quenching Oils-Determina-
D 6200 S t a n d a r d Method for Determination of Cooling tion of Cooling Characteristics-Nickel-
Characteristics of Quench Oils by Cooling Curve Alloy Probe
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ments," Industrial Heating, November 1989, pp. 23-24. cesses, Vol. 149, No. 6, 1996, pp. 64AA-64DD.
[64] Totten, G. E., Bates, C. E., and Clinton, N. A., "Chapter 5-Poly- [86] Mueller, E. R., "Polyglycol Quenchant Cleanliness: Are There
m e r Quenchants," Handbook of Quenchants and Quenching Benefits," Heat Treating, October 1993, pp. 24-27.
Technology, ASM International, Materials Park, OH, 1993, pp. [87] Jarvis, L. M., Blackwood, R. R., and Totten, G. E., "Thermal Sep-
161-190. aration of Polymer Quenchants for More Efficient Heat Treat-
[65] Totten, G. E., Webster, G. M., Tensi H. M., and Liscic, B., "Stan- ments,"/nrfwiina/Heafrng, November, 1989, pp. 23-24.
dards for Cooling Curve Analysis of Quenchants," Heat Treat- [88] HiU, E. C. and Hill, G. C , "Biodegradable After Use But Not In
ment of Metals, 1997, No. 4, pp. 92-94. Use," Industrial Lubrication & Tribology, Vol. 46, No. 3, 1994,
[66] "Laboratory Test for Assessing the Cooling Curve Characteris- pp. 7-9.
tics of Industrial Quenching Media," Wolfson Heat Treatment [89] Hill, E. C , "The Significance and Control of Microorganisms in
Rolling Mill Oils and Emulsions," Metals Materials, No, 9, 1967, Treating-Proceedings of the 20th Conference Vol. 2, K. Funatani
pp. 294-297. and G. E. Totten, Eds., 9-12 October 2000, ASM International,
[90] Anon., "Microbiology of Lubricating Oils," Process Biochem- Materials Park, OH, pp. 688-695.
istry, May 1967, pp. 54-56. [94] Shimizu N. and Tamura, L, "Effect of Discontinuous Change in
[91] Passman, F. J., "Biocide Strategies for Lubricant Rancidity and Cooling Rate During Continuous Cooling on Pearlite Transfor-
Biofouling Prevention," Proceedings of the AISE Annual Conven- mation Behavior of Steel," Transactions ISIJ, Vol. 17, 1977, pp.
tion, Vol. 1, Association of Iron and Steel Engineers, 1996, pp. 469-476.
413-428. [95] Chen, M. and Zhou, H., "Numerical Heat Transfer Ansdysis on
[92] Kobasko, N. I., "Teplovie Procesi Pri Zakalke Stall," Metalovede- the Effect of Enhancing the Thickness of the Hardened Layer by
nie I Termiceskaja Obrabotka Metalov, 1968, Vol. 3, pp. 2-6. Delayed Quenching," Jinshu Rechuli Xuebao, (Transactions of
[93] Liscic, B. and Dowding, K., "Calculation and Measurement of Metal Heat Treatment), Vol. 14, No. 4, 1993, pp. 1-6. (in Chi-
the Workpiece's Surface Temperature During Quenching," Heat nese).
Section IV: Performance/Property Testing Procedures
Steven R. Westbrook and Rajesh J. Shah, Section Editors

MNL37-EB/Jun. 2003
Static Petroleum Measurement

Lee Oppenheim^
STATIC PETROLEUM MEASUREMENT CAN BE BEST SUMMED UP as the termine the quantity of. The measure is linear (meters, feet).
procedures and methods used to determine the quantity of liq- Along the way, it is necessary to determine the a m o u n t of sed-
uid in a storage tank, marine vessel, road transport vehicle, or iment and/or water on the bottom of the tank and depending
a rail tank car. In determining the quantity of the liquid in the on the product, the amount of entrained material within the
container, there may be other things in the container that de- liquid to be measured. While doing so, a sample is obtained
tract from determining the quantity of useable petroleum or to determine its density. A temperature of the product is also
petroleum products. They do take u p space in the container tctken at the same time. When the basic steps are completed,
and therefore must be desilt with as peirt of any measurement calculations side of static petroleum measurements are per-
procedure. These can include water, sediment, sludge, rust formed. Linear measures are converted to volumes, sediment
scale, and sand to n a m e just a few. As used here, petroleum and water found at the bottom of a tank is eliminated from
refers to crude oil, therefore the continuous reference to our quantity, entrained sediment and water (S & W) mixed in
petroleum and petroleum products. Petroleum products as the product is subtracted, and then the product density and
used here are the liquid stocks (e.g., naphtha, kerosene, fuel temperature of the product at time of measurement is used to
oils) derived from the refinery processes from crude oil. It is produce a net volume at the specified reference temperature
important to know the total of the liquids and solids in a tank (60°F in the U.S.). A small error may cost either the buyer or
to prevent a tank from overflowing during a receipt. However, the seller to gain or lose much with a significcuit effect on a
the more exacting science of static petroleum measurement is company's bottom line. In a small way, this chapter will help
concerned with determining a n accurate measure of the unravel the mystery of determining the quantity of petroleum
quantity of petroleum Eind petroleum products used in the in a bulk container, and also provide a n understanding of the
purchase, sale, or inventory control of the commodity. This importance of each step in the process.
section on static petroleum measurement will deal primary Petroleum and petroleum products expand and contract as
with manual gauging techniques and the related sampling the temperature changes. The rate of this expansion may vary
and quality tests needed to obtain accurate petroleum and depending on the type of product encountered. An underly-
petroleum product quantity measurements. Automatic tank ing principle used in static petroleum measurenaent is the
gauging, not discussed in this chapter, relies on the manued volume of petroleum at a specified standard temperature.
gauging methods for calibration purposes. Newer techniques This standard temperature is a means of common reference
for leak detection combine a form of static petroleum mea- and helps to avoid the misunderstcuidings that occur when
sureraent with inventory control to assure that tanks and lines comparing unlike items. It is important to understand what
storing and moving the products are tight. Leak detection temperature is being used as the reference temperature. In
procedures primarily combine automatic gauging methods using the System Internationale, sometimes referred to as the
with computer programming. This chapter is designed to ex- metric system, the standard temperature is usually 15°C and
plain h o w to accurately m e a s u r e the petroleum and sometimes 20°C. Using the American measurement system,
petroleum products, why certain procedures are necessary, 60°F is used. This does not imply that volumes at ambient
sampling and testing processes, and the basics of converting temperatures cannot be used for the sale of a product. Small
these measures into quantity m e a s u r e m e n t s used in the quantities such as those sold using meters at an automotive
industry. service station or at a single user fleet dispensing location are
The primary reference for static petroleum measurements usually determined at the ambient (surrounding air) temper-
is the American Petroleum Institute (API) Manual of ature.
Petroleum Measurement Standards (MPMS). Increasingly, Storage and transport tanks have several openings from
the s t a n d a r d s and practices are standardized with other which measurements may be taken. However, only specially
Standards bodies such as ASTM International (ASTM), Insti- designated locations on the tank are to be used. This is be-
tute of Petroleum (IP), and the International Organization of cause calibration of the tank volume has been made from this
Standards (ISO) as well as other national standards organi- point or a combination of several designated points. Smaller
zations. Yet, static petroleum measurements normally do not transport tanks may have volume measurements scribed on
even measure the volume of the product we are trying to de- an approved measurement rod, commonly referred to as a
dipstick. These calibrated dipsticks are only for use on the
' Chief, Quality Operations Division, Defense Energy Support Cen- specified tanks conforming to the originjd construction of the
ter, Ft. Belvoir, VA 22060-6222. tanks. The majority of manual measurements are taken using
635
a linear measure from a properly designated gauging point plate may be attached to the side of the tank or the bottom of
on the tank. The linear measure is converted to a volume the stillpipe. The datum plate is fixed in a level position on the
measure by use of the certified calibration table (or tank ca- floor of the tank directly underneath the reference gauge
pacity tables or strapping table/chart as it may be referred to) point. It is between these two locations that we take the lin-
for that tank. A strapping chart contains the official conver- ear measurement. The datum plate may be raised off the
sion of the linear measure to a volume measure within that floor. In such cases a reading of zero does not indicate that
tank. Tank calibrations are performed using API MPMS the tank is empty as product may be below the measuring
Chapter 2 criteria. Tajik bottoms may slope in various ways, point. When this occurs, the strapping chart will have an in-
changing the shape of the bottom. Taking measurements dicated volume for a measurement of zero. It takes that much
from a point not designated as the gauging point will most product just to reach the zero point. If a tank does not have a
likely mean a change to the linear measurement needed for datum plate, the reference height is from the reference gauge
accurate quantity measurements. Tank calibrations take into point to the floor of the tank. Again, this may not be the low
account internal structures such as supports and piping, point of the tcink and a zero reading may account for a cer-
change in tank diameters, as well as deductions for floating tain fill quantity. This is particular true of cone down type
roofs. Each tank requires a certified calibration table or tank bottom construction with side gauging points, but exists
strapping chart when performing static petroleum measure- in other tank styles cdso.
ments. It will contain much needed information for the per- Between the reference gauge point and the datum plate,
formance of accurate measurement and validation should the distance is called the reference gauge height. This distance
the need arise. will be indicated on the strapping chart and may also be
To begin the process of understanding how to measure and marked on the top of the tank by the gauging point. During
quantify a large tank or marine vessel compartment, it is nec- the measurement process, knowing whether the sediment,
essary to start with some basic terminology. Beginning at the water, and product heights are accurate requires knowledge
tank where the product resides, use Fig. 1 to describe the of the reference gauge height. This will be especially true for
terms. Each tank to be measured has designated a place tanks that may contain sufficient sediment or sludge, pre-
where gauging is to occur, or reference gauge point. Normally venting the measuring device from hitting the datum plate or
a gauge hatch is designated for this purpose. Check the strap- bottom of the tank.
ping chart for the point or points so designated. Some gauge A tape and bob combination is used to make the linear
hatches, primarily those in stationary shore tanks, have a slot measurement. There are several different styles of tapes and
or mark where the measuring tape can be inserted. These bobs (Fig. 2). It is important that the correct combination is
slots or marks designate which side of the gauging tube is to used. We must therefore understand the difference between
be used. If there is no indication on the strapping chart des- the two measurement styles: innage and outage. Innage is the
ignating a specific location, gauging should be performed op- measurement of the liquid and solids from the bottom of the
posite the hinge on the gauging hatch for uniformity. Be- tank to the upper level of the product. Most refined products
neath the gauging point, there may be a datum plate, in shore tanks, road transport vehicles, and rail tank cars are
preferably on the floor of the tank. Occasionally a datum measured in this manner. If the measurement device can get
through the sediment, sludge, and water in the tank (the ref-
erence gauging height is obtained at the reference gauge
point), then the innage method ccin be used to determine the
nonproduct or nonmerchantable part of the tank. Outage,
GAGING TAPE GAGING TAPE sometimes referred to as ullage, especially on marine vessels,
REFERENCE REFERENCE
POINT GAGING HATCH POINT / GAGING HATCH is the measurement of the void space in the tank. Most ma-
READING READING
rine vessel compartments are strapped using the ullage
method. The outage method is also preferred to determine
the amount of fuel oil or heavy, viscous products. These
products may prevent the tape and bob from getting to the
OUTAGE bottom in a straight line, increasing the total linear distance.
It is also very messy having to clean the tape and bob after
TAPE BOB
CUT CUT LIQUID
each measurement. The innage and outage methods may be
LIQUID TANK
TANK
^ LEVEL SHELL
LEVEL used together for different purposes. An outage measurement
SHELL
may be taken for the product, but an innage taken for sedi-
ment, sludge, and water measurements. Whether an innage
or outage gauge is taken, always remember to check the
INNAQE strapping chart to determine which method to use for con-
verting from a linear measurement to a volume measure. You
can compensate taking an innage when an outage is required
(or vice versa) by remembering the simple relationship be-
tween innage and outage.
innage height + outage height = reference gauge height
For example, take an innage gauge with a total height of
INNAGE OUTAGE
7.500 m. The Reference gauge height is 19.670 m. An outage
FIG. 1—Gauging diagram. gauge is required when the strapping chart is used. This
CHAPTER 23: STATIC PETROLEUM MEASUREMENT 637
S t a l l T a p « i tob«^^« or *^t in.

w l o , O D O S lo 0.012 In. thick
Bobs l o b * mode of
coriDsion-rislstQnt m e t a l
A
r-B II
r-ll •»
IS
'OUTAGE TAPE- -H
r-ll i—n
10"
r-J
X INNAGEtOa SCALE
ZERO Z
EXTCNSION PIAIM DEEP
OUTACe — OUTASE— GROOVED—
SOB SOB OUTAGE
BOS
bC^ \f \ /
FIG. 2—Tapes and bobs.
shows that the pregauging review was not performed. Using the top of the outage bob where the tape latches onto the
the formula reference gauge height — innage height = outage bob. The bob will then be graduated from the top of the bob
height or downwards. An extension outage bob is designed to be at-
tached to an innage tape. Below where the zero point would
19.670m - 7.500m = 12.170m for the outage height. be if an innage bob was attached is a metal extension. Read-
A bob is a heavy metal (usually brass) weight with linear ings begin at the zero point and increase below the zero
measurements on it. The heavy weight is designed to keep point. When using an outage tape, readings on the bob be-
the tape stretched in a straight line below the gauging point. low the zero point are added to the reading tciken at the ref-
Each bob is specifically designed for various tapes. An in- erence gauge point. Treat the tape properly as the linear
nage bob begins at the bottom with zero and provides the measure is a critical step in getting the quantity accurate.
linear measure upwards towards the tape. It will have some Kinks in the tape are to be avoided. Tapes that have been
means for the bob to be attached to the tape. The latching spliced together shall not be used when gauging for custody
area is normally without linear gradients so measurement transfer purposes as it may change the measurement above
should not occur in this area. The tape continues the linear the splice point. A bob showing wear at the tip may affect
measurement up to the reference gauge point. It is impor- gauging accuracy.
tant to use the corresponding bob cind tape to provide for a Where primarily water and small amounts of soft sediment
continuous linear measurement. Some bobs are 6 in. with a may be the contaminant, a water gauging bar may be used to
dead area of 2 in. between the latching area and the begin- measure the water that has settled to the bottom of the tank.
ning of the linear tape gradients. Other bobs may be 10 in. One drawback is if the bar is not attached to a corresponding
Check and validate that the measurement from the tip of tape, it is not possible to obtain a reading of the reference
the bob up past the beginnings of the tape linear gradients height gauge. Therefore if the bar did not hit the datum plate
are continuous. Outage bobs can be designed to work with or floor of the tank, the gauger will not know if the bar actu-
either an innage tape or and outage tape. An outage bob ally reached the datum plate or the floor.
with an outage tape is designed so that the zero point is at A new tape and bob should be checked before use. Inspect
the entire length to assure that the n u m b e r s are clcEirly indi- a readout of the temperature. These must be calibrated o n a
cated in the correct order and the graduation meirks between yearly basis or as recommended by the manufacturer. Cali-
the numbers are present. Tapes should be made of steel or bration should cdso be accomplished whenever there is reason
corrosion resistant material. Meike sure the snaps and eyes to doubt the accuracy of the measurement. Other temperature
between the tape and the bob afford for proper fit and accu- measuring devices may be temperature dials placed in the
racy for measurement purposes. Tapes and bobs should be wall of the tank. These are placed strategically at various
checked daily w h e n in use. Check the tape for kinks and heights, normally along the stairs going u p to the tank roof. If
splices, which would make the apparatus unsuitable for ac- a tank is not full, care must be taken only to read those ther-
curate gauging. The tape and bob fittings should provide for mometers on the tank side weJl that are immersed in product.
an accurate measure. Also ensure that the bob tip has not One disadvantage to the dial type is that the probe may not ex-
been worn down or damaged, which would create another tend sufficiently into the tank. They would then be very sensi-
measurement error. Lastly, make sure the tape and bob Eire tive to the environmental factors at the wetll surface. For ex-
fit for the purpose to be used. A tape and bob shall not be in- ample, with the sun on the tank wall, it may have warmed up
troduced into another product where the residue on the tape the product within 6 in. of the wall, yet the remainder of the
and bob would contaminate the product to be measured. A tank remains cooler. Using these readings would obtain a
s t a n d a r d operating procedure to r e m e m b e r is t h a t crude higher temperature t h a n if a thermometer was used within
oil/residual fuel oil tapes should not be used to measure dis- the middle of the tank. These differences could have a signif-
tillate products. Many specialty petrochemical products are icant effect on the volume correction factor, resulting in
very sensitive to extremely small levels of contamination. Ei- greater than anticipated quantity variations at the agreed tem-
ther separate tape and bobs may be necessary or the tape and perature. Other temperature devices may also be used in the
bob may require special cleaning before use. tank with electronic readouts at the tank itself, or more likely
a control room.
There are still several items needed before a linear mea-
surement is m a d e at the tank. Remember several other fac- When performing manual temperature readings using a
tors m u s t be accounted for to obtain accurate petroleum mercury in glass thermometer, a thermometer assembly or
measures. The first to be discussed is what is needed in de- holder is also required. These assemblies protect the ther-
termining the temperature of the product to be measured. A mometer from being broken in the course of being lowered
thermometer or temperature measuring device is required. and raised. More importantly, they provide for a reservoir of
The industry standard for reference is API MPMS Chapter 7, product to surround the thermometer bulb. Thermometers
Method of Measuring the Temperature of Petroleum and have a tendency to react quickly to temperature changes.
Petroleum Products. The temperature of the product is criti- Without a product reservoir, by the time the thermometer is
cal to correct the measured quantity to the standcird temper- raised and turned to determine the reading, it would have
ature. changed temperatures first with the variation within the tank,
The temperature in a tank may vary greatly, especially for but more importantly with the ambient air temperature.
crude oil and residual fuel oils that are heated to higher tem- Several types of assemblies are in use. Several basic t5?pes
peratures to maintain fluidity and preventing gelling of the are the cup case, flushing cup, and armored case (Figs. 3-5).
product. The heating coils are near the floor and heat con- Flushing cups are not referenced in the current MPMS Chap-
vection helps swirl the product in the tank. It may not, how- ter 7, but occasionally may be found in use. As the assembly
ever, provide for a uniform t e m p e r a t u r e within the tank. is lowered into the product to be measured, it quickly fills
Even distillate products in tanks have t e m p e r a t u r e varia- with product. The assembly is lowered to the height required
tions. After distillation and condensation of the product, it for the temperature reading and it is allowed to equilibrate
enters a storage tank. If measurements are made soon after for at least 5 min at that level. Products having viscosities
that, there may be a temperature gradient within the tank. greater thein 100 Saybolt Universal Seconds may require 15
The equilibration of the product has not occurred. Another or 30 min before equilibration occurs. By raising the assem-
factor affecting the temperature within a tank is the external bly rapidly, the p r o d u c t in the reservoir is more likely to
environmental conditions. If gauging is performed on a side maintain the temperature at the level to be measured. Tem-
of the tank were the sun is shining, it may indicate a higher perature readings therefore need to be taken as soon as pos-
temperature than if the gauge was taken on the shady side of sible after the assembly is raised. Conversely, temperature
the tank. Rapid ambient temperature cheinges may also in- probes with electronic readouts may not require any time for
crease the t e m p e r a t u r e variation within a tank. Product equilibration. Readings may be tciken shortly after reaching
within the tank may not have h a d a chance to equilibrate. In- the desired level, reading when the read-out is stable.
creased temperature readings are advisable where tempera- Steps needed before going to the teink. Check that the ther-
ture stratification is found within a tank. mometer is not broken. Make sure that the liquid in the col-
The temperature within the tank is measured using a ther- u m n has not separated. Do not use thermometers with these
mometer or an electronic temperature probe (thermoprobe). defects. Ensure that the thermometer is within the tempera-
Thermometers must meet ASTM E l , ASTM Thermometers ture range of the product to be measured or obtain a correct
specifications for the range of temperatures cinticipated in the thermometer. Lastly, ensure that the assembly adequately
product to be measured. Thermometers shall be calibrated at holds the thermometer in place and that the bulb of the ther-
least yearly against a thermometer traceable to a certified namometer is placed within the reservoir. The reservoir should
tional standard thermometer. In the U.S., the Standard body not have holes or openings that would prevent the retention
is the National Institute of Standards and Technology (NIST). of the product in the reservoir. Replace the assembly if
Thermoprobes rely on electronic instrumentation to provide defective.
CLAMP.
ASTM-
THERMOMETER
CORROStON-
RCSBTANT
METAL
CD
CUP CASE
FIG. 3—Cup case Thermometer.
MAX.p
FIG. 5—Armored cup

case.
ASTM
THERMOMETER
Free water is defined as the water present in a tank that is
not in suspension or dissolved in the petroleum. To measure
free water, something is needed so that the water level after
drawing the bob or bar through the product can be observed.
To detect the free water, a water finding paste is used to dis-
tinguish between the petroleum and petroleum product layer
and the water level. For crude oils and many residual fuel
oils, the bob or bar may retain a significant coating of the
crude or product, hindering our ability to see the watermark
to be read. In these cases, a petroleum solvent may be needed
to rinse the bob or bar. Care must be taken not to disturb the
water finding paste when rinsing the bob or bar with the
petroleum solvent. This procedure also requires advance
planning so that the proper solvent can be taken to the tank
and equipment needed to preclude environmentcJ and safety
problems with the rinse are available.
It is also necessary to have a water finding paste that is suit-
FLUSHING CASE
able for the product to be measured. Some products have wa-
FIG. 4—Flushing cup case. ter soluble additives that leach out of the product into the wa-
ter layer. The water paste must therefore be able to register
the water/additive mixture as well as free water. An example
of this interaction is fuel system icing inhibitor (FSII) (some-
times referred to as anti-icing additive). It is only slightly sol-
uble in aviation turbine fuel but very soluble in water. The representative sample of the product to be sampled. Distil-
water finding paste for these applications must be sensitive to late products and finished lubricating oils from a single
a 50% water/50% FSII mixture. One way to test whether the batch are normally considered to be homogenous. That is, a
water finding paste is still working is to place a drop of water sample from anywhere in the product should be uniform
on a bob with the paste. This will show a color change. Pastes and, in theory, represent the product. In reality, slight
are different, some changing from pink to blue, others one changes in the refining or manufacturing process may cause
shade of pink to another, etc. By testing the paste before go- some variation in the product. A permitted testing variation
ing u p to the tank, a new ganger will understand what is on specified parameters determined by prior agreement
about to be seen when gauging for water. Remember, it will would provide for agreement that the batch tank is deemed
not tell if the water paste is working in water/other product homogeneous for quality and quantity procedures. Not dis-
mixtures. These must be tested in a laboratory at the pre- cussed in this chapter is the automatic in-line sampling pro-
scribed mixture ratios. cedures covered by API MPMS Chapter 8.2 (ASTM D 4177),
The measurement of sediment uses the same bob or bar Automatic Sampling of Petroleum and Petroleum Products.
used for the detection of free water. Water should sit on top of While previously used to determine the quality of crude oil
the sediment. While both are subtracted from the calculations and residual fuel oils in the past, they are increasingly being
of product quantity, it is necessary to know the level of sedi- used for automotive gasolines, aviation fuels and diesels
ment in the tank. Distillate product tanks have less sediment both for quality control purposes and environmental regu-
layering them do crude oil and residual products. Therefore, lation compliance.
noticing sediment building u p on the floor may indicate it is The tools needed for manual sampling include a sample
time to clean the tank before a quality problem occurs with bottle(s) and sampling cage or a weighted beaker (Figs. 6 and
the product. Crude oil and residual fuel tanks may have larger 7). A sample receiver or receptacle is a container in which all
quantities of sediment and sludge. Should the level become sample bites are collected during the sampling operation. The
too high, it could affect the ability of the p u m p s to draw prod- n u m b e r of bottles and sample receivers needed must be de-
uct out of the tank. The other problem it creates is that ship- termined before going out to sample. Bottles and weighted
ment of the contaminates decreases the value of the product. beakers must be properly cleaned so as not to contaminate the
For most distillate products, sediment and water quickly sample before taking the samples. Sample bottles and con-
falls to the bottom of the tank. A visual appearance of the fuel tainers may be clear or brown glass. Ccins used must have their
determines that the water and sediment have settled to the seams soldered on the exterior surfaces to preclude contami-
bottom of the tank and we do not have to worry about it for nation with flux used in their manufacture. Polyethylene un-
calculation purposes. However, for crude oils and residual pigmented linear plastic bottles can be used for gas oil, diesel
fuel oils, sediment and water may also be suspended or oth- oil, fuel oil, and lubricating oils. These plastic bottles should
erwise in the product to be measured. The buyer of the prod- not be used for gasoline, aviation jet fuel, kerosene, crude oil,
ucts may not want to pay for these contaminants and there- white spirit, medicinal white oil, and special boiling-point
fore require an accurate measure of them. For crude oil and products unless testing indicates there is no problem with sol-
residual fuel oils, there is an anticipation that these contam- ubility, contamination, or loss of light ends. The container clo-
inates will be received and dealing with them requires ad- sure must be clean and ensure a good tight seal. Loss of light
vance knowledge of the levels of each. ends have an effect on the density of petroleum and petroleum
If not already determined, a sample for the density mea- products, which is an important element for petroleum mea-
surement is required. The density is necessary as product ex-
pansion and contraction is affected not only by the tempera-
ture, but the product type and its density. This relationship
will be explained later in this chapter. Crude oil and residual
fuel oils are more likely to be non-homogeneous and proper
sampling is more critical so that an accurate picture of the
product quality can be determined through the testing pro-
cess. Automatic sampling is the preferred method for sam-
pling crude oils cind residual fuel oils because of this prob-
lem. In some cases, the density, water, a n d sediment for
official custody transfer purposes will be determined based
on in-line sampling at the time of shipment. By agreement, or
to protect one of the parties, a manual sample may still be
taken in case of a failure of the automatic in-line sampler. Au-
tomatic in-line samplers are recommended for custody trans-
fer purposes as they may better represent petroleum and
petroleum products that would normally contain suspended
(entrained) S & W. Manual sampling may not be as accurate
in sampling for these contaminants, which are present in the
1-Lllre (1 qt.)
product in a non-uniform manner. Sample Weighted Cage
(can be (abricated
Manual sampling of the tanks is covered by API MPMS to HI any size bottle)
Chapter 8.1 (ASTM D 4057), Manual Sampling of Petroleum
and Petroleum Products. The object of sampling is to take a FIG. 6—Weighted bottle sampler.
When any sample is taken where the loss of volatile com-

Copper ponents would affect the sample result, the procedures in API
MPMS Chapter 8.4, ASTM D 5842, Standard Practice for
handle Manual Sampling and Handling of Fuels for Volatility Mea-
surement, should be used. The object is to take and handle a
sample without losing the light hydrocarbons. For instance,
Copper
wire when a density is to be run, the loss of the light ends will in-
lugs crease the density (lower the API Gravity) of the tested sam-
hitah
ple. This is t u r n m a y affect the volume correction factor
(VCF) used in determining the net quantity of fuel at the stan-
dard temperature. Basic technique requires the sample con-
tainer to be filled to the 80% fill level, capped quickly, kept
cool, and delivered to the laboratory for testing promptly.
Volatile samples taken from taps should use an extension
Sheet
lead that can reach close to the bottle of the sample container.
This will preclude splashing and the generation of vapors
leading to light end loss. Brown or a m b e r bottles or sample
Cork arrangements Beaker cans must be used when taking samples of petroleum prod-
ucts that are light sensitive. Failure to use the appropriate
1-Litre {1 qt) Weighted Beaker container could cause changes to the quality of the product
before testing of the product is accomplished. This could lead
FIG. 7—Weighted beaker sampier.
to inappropriate results that may affect the quantity determi-
nation also.
When taking spot samples to be composited for a repre-
surement. A sampling cage with a bottle is preferred for sentative sample, a standard way to take samples is as fol-
volatile products to preclude the loss of light ends created by lows: For tanks over 1000 barrels that contain more than 15
other techniques during product transfers. Poorly taken sam- ft. of oil, an upper, middle and lower sample are taken and
ples provide inaccurate sediment and water results. Taking combined in equal volume to make a composite sample. For
and protecting the samples is critical both for proper sam- tanks over 1000 barrels which contain between 10 and 15 ft
pling technique, to provide accurate data for petroleum cal- of oil, a middle sample from the top half and a middle sam-
culations, and to prevent disputes. ple from the bottom half are taken and composited. A single
What samples should be taken? An official sample is taken sample is taken normally when the level of the oil is less than
at the point of custody transfer and is used for custody trans- ten feet. For tanks smaller than 1000 barrels, either a single
fer properties. The location where this sample is taken is by sample or multiple spots can be used. Again make sure the
mutual agreement between the buyer and seller. The object parties involved agree on the t3rpes of samples in advance of
for obtaining accurate samples is to have a sample repre- the sampling process. Other spot samples can be designated
senting the entire contents of the tank. A representative sam- or taken upon mutucd agreement for custody transfer pur-
ple is a sample representing a small portion of the tank vol- poses. A bottom sample is one that obtains material from the
u m e (that is, for tanks, ships' c o m p a r t m e n t s , containers, bottom surface of the tank or container at its lowest point. A
pipeline tenders, a n d so forth) obtained with a precision
equal to or better t h a n that of the laboratory m e t h o d by
which the sample is to be analyzed. Other samples are taken Hatch
for Vcirious process, custody, inventory, a n d quality reasons.
These samples can be taken as a single sample or as various
spot samples as agreed upon. Some of the various types of
samples that can be taken as shown in Fig. 8. A spot sample r
rj
•15 cm (6")
Top sample
is one taken at a single location in a tank. It represents only
material at that location. Examples of spot samples are: top, TH Upper sample Upper third
upper, middle, lower, and outlet samples. Tank
• Top sample is one taken at spot six inches below the top contents - Middle sample Middle third
surface of the liquid.
• Upper sample is one taken from the middle of the upper
third of the tank contents. Lower sample
Lower third
Outlet sample
• Middle sample is one taken from the middle of the tank con-
Outlet
tents and should be half the distance between the upper Bottom sample
and lower samples. NOTE 1—TTie location shown tor the outlet sample appfes only to tanks with
• Lower sample is one taken at the middle of the lower third side Qutltta. It doea not apply whaa ttn outiat comas from the tkxx of the tani( or
of the tank contents. turns down into a sump. Bottom sample location must tie specified.
NOTE 2—Samples shoiid t » otitained from within solid stand pipes as the
• Outlet sample is one taken at the level of the bottom of the materials normaiiy not representative of the material in the tanit at that point.
tank outlet, but not more than one meter from the bottom
of the tank. FiG. 8—Sampiing terms.
bottom water sample is a spot sample of free water taken be- They represent the product at a particular moment of sam-
neath the petroleum contained in a tank or marine vessel pling. Several pipeline spot samples can be combined to
tank. These last two samples are used as indicators of the make a pipeline composite sample to represent the product
contamination accumulating on the bottom of a tank, to de- in question. The number of samples required should be
termine where water came from (process water or sea water), agreed between buyer and seller when used for custody trans-
or to detect bacteriological or fungal growth. fer purposes. Changes in flow rates have little effect on the
Combining agreed upon spot samples is one acceptable amount of sample being taken. Care must be taken to pre-
method as is testing individual spot samples and averaging clude overfilling samples taken from a pipeline. To get a truly
the results. A composite spot sample is a blend of spot samples representative sample from a pipeline, the product must be
mixed volumetrically proportionally for testing. For instance flowing at a turbulent flow rate. Turbulent flow promotes
a multiple-tank composite tciken from marine vessel compart- product and contaminants distributed equally throughout
ment tanks is a mixture of individual samples from several the pipeline cross section. When product has a laminar flow,
compartments, each of which contains the same grade of there is a faster section moving above a slower section. Con-
petroleum material. The mixture is blended in proportion to taminants such as sediment and water can settle to the lower
the volume of material in each compartment (weighted aver- section of the pipeline or at the low points. Samples taken at
age method). API MPMS Chapter 8.3, ASTM D 5854, Stan- laminar flow tend not to be representative.
dard Practice for Mixing and Handling of Liquid Samples of Before climbing the tanks, determine if control of the vol-
Petroleum and Petroleum Products, should be used for this umes in the pipeline are required. For custody transfer pur-
process. This blending should be performed in a laboratory. poses, the condition of fill of the pipelines to be used must be
Some tests may be made on the spot samples before blending known, both before and after the movement. If the pipelines
and the results averaged. are stated as full, validate by pressure or other means that the
Two types of samples can be taken that represent the col- line is full. One reference for this operation can be found in
umn of petroleum or petroleum product in the tank. Each API MPMS Chapter 17.6, Guidelines for Determining the Full-
has drawbacks as to its being a representative sample. They ness of Pipelines Between Vessels and Shore Tanks. If empty,
are used primarily for homogeneous product. First is an all- confirm as best as possible. If there is a difference in the con-
level sample. An all-level sample is taken by submerging a dition of the pipeline fill before and after a movement, the dif-
stoppered bottle or beaker as near as possible to the draw-off ferences must be accounted for in the product calculations.
level, and then opening the sampler, and raising the sampler It's time to climb that tank or go to the marine vessel to
at a uniform rate such that it is about three-fourths full as it take samples and to gauge the tanks. What is the proper or-
emerges from the liquid. A running sample is one obtained by der to perform the water cut, product gauge, temperature,
lowering an unstoppered beaker or bottle from the top of the and sampling? If water cut is done first, the oil column above
oil level to the level of the bottom of the outlet connection and the water layer may become contaminated. This would lead
returning it to the top of the oil at a uniform rate of speed so to erroneous results coming from the contaminated samples.
that the beaker or bottle is about three-fourths full when it Therefore the order should be to take the samples first.
breaks the surface of the oil. Both a running sample and an Which samples should be taken? For the same reason, taking
all-level sample may not be a true representative sample, be- the bottom water cut measurement, samples are taken start-
cause the tank volume may not be proportional to the depth ing from the highest in the tank. If a top sample is needed,
or because the operator may not be able to maintain the vari- take that first. Then the upper, middle, lower, outlet, and bot-
able rate required for proportional filling. The rate of filling tom samples. If after these samples an all-level or running
is proportional to the square root of the depth of immersion sample is required, take these after the spot samples. The or-
also affecting sample representativeness. The lower the der of taking the samples is the same from compartments on
beciker or bottle, the faster liquid flows into the beeiker or bot- a marine vessel. When homogeneous product is on board a
tle. vessel, a single middle spot sample may only be required. At
Pipeline samples can be of several t3rpes. Automatic sam- other times the individual compartment may only require an
plers are covered by API MPMS Chapter 8.2 (ASTM D 4177), all-level sample. However, when crude and heavy fuel oils
Automatic Sampling of Petroleum and Petroleum Products. that contain water and sediment in a non-homogeneous
Automatic samplers are designed to take a representative manner are sampled, several spot samples may be required
sample from liquid flowing through a pipeline. It consists and/or a running or all-level sample. Samples are taken and
generally of a probe, an extracting mechanism, a controller properly labeled with a marker that will not be affected
that determines when to extract the sample bites, and a sam- should the oil splash or be introduced onto the label. The la-
ple receiver. Flow proportioning samplers adjust to product bel must be affixed to the sample bottle or containers imme-
volume changes resulting from changes in the flow rate. This diately after the sample is taken. This is extremely important
is the best way to get a representative sample from a pipeline. when several different samples are taken from one tank. Al-
Another tjê is a time controlled automatic sampler. It takes ways check that any labels, especicilly preprinted ones, are
a sample bite at preset time intervals. Manual samples from put on the correct sample. Ensure that all relevant details are
pipelines, sometimes called drip samples, can be taken. A on the sample label. No one wants to climb a tank a second
valve is cracked leading to a sample receiver so that over the time because the results from the testing indicate a problem.
duration of the movement, product slowly fills the sample re- Side tap samples along the staircase can be taken either go-
ceiver so that it fills the container over the determined pe- ing up or going down. However, if samples are taken on the
riod. This does not provide for a truly representative sample. way up, it will make the carrier weigh more as you ascend the
Pipeline spot samples are another tjê of manual samples. staircase. Recommend tEiking the samples on the way down
after gauging is complete. When using the side taps, know crude oils, and other dark viscous products as they do not
how high the product is in the tank and make a determina- evaporate or rise up the tape. Talc and chalk may not be used
tion on which taps are needed from that information. On a if the product has a tendency to creep up the powdered tape
full tank, the upper, middle, and lower samples are easily from the true reading giving erroneous readings. Place the
judged. When the tank is not full, the requirement for two tape against the reference point on the gauge hatch. This re-
sets of more than five taps on a tank can be understood. By leases static charge, which may build up. Lower the bob
knowing the height of the product in the tank, appropriate slowly through the product. While lowering the tape and bob,
level samples can be taken. Some sample taps include exten- try not to disturb the liquid level greatly. Motion at the top of
sions that enable sampling from the base of the tank. When the liquid level causes an inaccurate reading. The waves
these are encountered, make sure the tubing is flushed com- caused by the disturbance or the wind can result in an in-
pletely before taking samples. Otherwise, a prior batch left in crease in the total liquid height measured.
the extension tubing will be sampled. For an innage gauge, lower the tape until the length in the
At the top, the gauging and sampling tubes should be tank is close, but not over, the reference height. Remember it
clearly marked. In most cases they are the same point. Sam- is most likely stenciled or written by the gauge hatch. Just
pling and gauging tubes must be appropriately slotted in or- compare it to the tape reading and when they are close (that's
der to obtain accurate samples and gauges. The gauging the point to pay close attention) be very careful, lowering the
hatch or hatches should have the reference height marked on tape until you feel the bob hit the datum plate or floor of the
or near the hatch. While this must be validated from the cer- tank. It is very important to come to a full stop when this is
tified capacity tables, it is a good reference while on top of the felt. Lowering the tape any further results in the bob and the
tank. Take the required number of samples in accordance tape arching in the tank. The bob leans to one side and more
with API MPMS Chapter 8.1 and Chapter 8.4 when taking tape goes into the product. Both measurements will have in-
volatile samples. After the samples are taken, go to the gaug- creased by some amount. If you go far enough, the bob will
ing. actually be resting horizontally (flat on the floor or datum
When using thermometers, place them at the appropriate plate). Maintain the tape in the stop position. Record the to-
levels now if they will not be in the way for the gauging oper- tal height that the tape is out. This should be equal to the ref-
ation. This will give them time to equilibrate to the sur- erence height. If it is not, then when performing the calcula-
rounding temperatures. Table 3 of API MPMS Chapter 7.1, tions, some adjustment may be needed to the product height.
Static Temperature Determination Using Mercury-in Glass The length of time the stop position must be held is depen-
Tank Thermometer, provides for the minimum number of dent on the product in the tank and the amount of water.
readings required based on product height. Where the depth Heavy products tend to coat the bob and water finding paste
is greater than 10 feet, three temperatures are required, one before the bob enters the water layer. This type of product re-
each from the middle of the upper, middle, and lower sec- quires the bob to rest longer in position for accurate water
tions of the tank. For depths less than 10 feet, a single tem- readings. It is appropriate for clean light products to main-
perature taken at the middle of the liquid is required. Tables tain this position for 10 s. For heavy crude oils and fuel oils,
4A and 4B of Chapter 7.1 provide for the minimum immer- it is appropriate to maintain this position for 1-5 min.
sion time for these thermometers. The immersion time is If there is a large body of sediment and sludge on the bot-
based on the density of the product and whether the ther- tom, using the innage method may be impractical as the bob
mometer is stationary at the required level or in-motion will never reach the bottom of the tank or datum plate. The
(raised cind lower one foot above and below the designated bob is unable to cut through it. More than likely, an experi-
level). Table 2 of API MPMS Chapter 7.3, Static Temperature enced gauger will be able to discern the problem by the way
Determination Using Portable Electronic Thermometers, pro- the tape feels as it hits the sediment and sludge. But more
vides recommended immersion times for electronic ther- practically, the reference height will be greater than the tape
mometers. The times again vary based on the density of the reading at the reference point when this occurs. When there
product and whether the thermometer is held stationary or is sediment and sludge precluding the bob from reaching the
kept in-motion as described above. Check these publications bottom, the outage method of gauging is required. The outage
for the appropriate immersion times. method may be required for both the product and water cuts.
When gauging for custody transfer purposes, there is, by However, there are occasions when a bob is unable to cut
necessity, an opening gauge and a closing gauge. When through sediment and sludge, but a water gauging bar or rod
standing on a roof, your weight and the weight of those can. As long as the bar or rod hits the bottom, gauging using
watching or helping you may depresses the roof. It is impor- an innage method of the total sediment and water is appro-
tant that the same number of persons, hopefully of the same priate. One other problem occurs with tanks that have a large
approximate weight, accompany the gauger for each mea- bottom sediment and sludge layer. The solid material may not
surement. Encourage everyone to stand in the same relative be layered in the tank. Rather, pejiks and valleys may have de-
positions (at the side) to keep these factors constant. If a wa- veloped due to the dynamics in the tank. Close to the inlet, the
ter gauge and product gauge will be taken at the same time, sediment may have been pushed up forming peaks away from
apply the water finding paste to the bob and a thin coating of the inlet. Conversely, d5mamics at the suction point results in
product finding paste along the anticipated levels. When washing away of the sediment building up. Again a valley may
gauging crude oils or heavy fuel oils, it may help to coat the be formed here. Several measurements for sediment at vari-
water finding paste and the bob with a light lubricating oil in ous levels may be necessary to discern these anomalies.
order to help shed the oil after its return to the top for read- There are several schools of thought on gauging total
ing. Product finding paste is not needed for heavy fuel oils. height of the liquid at the same time as the free water mea-
surement. First, gauge the free water, first getting the refer- on the u p side of the tape. In this case, subtract the product
ence height estabhshed once. This is only done once. Then reading from total distance the tape was lowered into the tank.
proceed on with gauging for the total height of the liquid in Of course, if you used an extension outage bob designed for
the tank. Second—Perform b o t h the free water and total an innage tape there is a section where n o linear measure-
height of the liquid simultaneously. Assure that an agreement ments are encountered on the bob. Just clean the bob and redo
has been reached on this point between the buyer and seller the measurements. As in the innage method, two consecutive
or as a company policy and then advise the ganger and/or in- readings are required to be identical. Otherwise use the same
dependent surveyor of the agreed procedure. innage rule for obtaining gauged measurements.
Continuing on with the innage method using the second Taking an outage gauge with an innage gauge and bob fol-
school of thought, raise the tape until the product cut can be lows the same procedures as an outage gauge. Ground the
seen. Read the location of the product, referred to as a cut, to tape and bob to the tank by placing the tape against the tank
the nearest millimeter (or 1/8 in). Record the product cut. rim. Lower the tape and bob just barely into the product.
Raise the tape and bring the bob to be viewed. Be careful Lower the tape to the next whole increment on the tape. Read
when bringing the bob u p and out so as not to disturb the wa- and record the total tape height let out. Bring the tape and
ter finding paste. Read the water cut and record it also. For bob back u p to the top and read the product cut on the tape
tanks with crude oil and heavy fuel oils, it may be necessary or bob. If the reading is within the eye or eye hook area where
to rinse the oil off the bob to view the water cut. Use an ap- no linear markings are, clean the tape and bob and redo the
propriate solvent to clean the bob. Take care in rinsing with measurement using a different lowered distance. For innage
a solvent so as not to push the water line u p or down. Be en- tapes and bobs, the outage is figured by subtracting the lower
vironmentally friendly when performing these actions. Addi- tape or bob reading from the total height the tape and bob
tionally, do not blow or wipe the petroleum or petroleum were lowered into the tank.
products off the bob as this too may distort the water cut and
thereby give incorrect readings.
E x a m p l e 1: O u t a g e T a p e a n d B o b
Perform the gauging actions again. They should be identi-
cal. If not try once more. If all three are within 3 m m (1/8 in) a) Total height of tape p u t into the tank read at the tank
of each other and two are identical, then the two identical gauging point = 7.450 m
readings are reported as the official gauge. If not within 3 b) Measurement found o n the bob when raised = 0.090 me-
m m (1/8 in), continue gauging until three consecutive gauges ters. Add (a + b).
are within 3 m m (1/8 in) of each other. If none are identical, c) Outage Gauge for total liquids in the tank = 7.540 m
averaging of the gauges m a y be permitted. Averages are to
the nearest millimeter or 1/8 in, depending on the unit being
E x a m p l e 2: I n n a g e T a p e a n d O u t a g e B o b
used. Other a r r a n g e m e n t s are permitted by agreement.
Smcdler tanks or tanks gauged in windy conditions may pre- a) Total height of tape p u t into the tank read at the tank
clude the level of accuracy desired as the product level in the gauging point = 7.450 m
tank is unstable. Small waves are created by the wind and the b) Measurement found on the bob when raised = 0.090 me-
differences in the wave heights between each measurement ters. Add (a + b).
create the inaccuracy in measuring the product height. Once c) Outage Gauge for total liquids in the tank = 7.540 m
completed it is time to return to the office to perform the cal-
culations. However, before coming down off the tanks, if sev-
eral people are gauging or witnessing the gauging, agree on E x a m p l e 3: Innage T a p e a n d B o b or a n Outage
the gauges before coming down. This precludes disagree- Tape a n d B o b Reading above the Zero Mark or an
ments after the fact. Innage Tape with an Extension Outage Bob
Reading above the Zero Mark o n the B o b
Most marine measurements are not used for custody trans-
fer purposes, but primarily for inventory control purposes. a) Total height of tape p u t into the tank read at the tank
Let us look at performing a n outage or ullage gauge. This is gauging point = 7.450 m
used for most heavy dark oils and is the preferred method for b) Measurement found on the bob when raised = 0.090 m.
marine vessel gauging. The basic difference is that the bob Subtract (a — b).
does not reach the bottom of the tank. When using an outage c) Outage Gauge for total liquids in the tank = 7.360 m
tape and bob, ground the tape and bob to the tank. Lower the After performing the total liquid measure in the outage
tape and bob into the product. Lower the bob into the prod- method, a measurement for water and sediment is still re-
uct only slightly. Remember, the object of a n outage tape and quired. This can be done by the innage method as described
bob is that the product reading is on the bob between the zero above provided the bob or rod can reach the bottom of the
cmd the plus side (lower end of the bob). At the reference point, tank. For tanks that may contain sediment and sludge, make
have the tape come to a whole increment, either centimeter or sure the bottom is reached. When the reading is tciken, esti-
inch. Note the distance the tape has been lowered into the mate the level of sediment and sludge by looking for its ad-
tank. Bring the tape back to the surface emd read the bob. If herence to the water finding paste. There will then most
within the correct reading zone, the bob reading is added to likely be a section where the water finding paste turned the
the distance the tape was measured as being lowered into the appropriate color without any sediment. Both measurements
tank. Unfortunately, there are occasions when the gauger for are important information, be it for unpumpable bottoms, or
any n u m b e r of reasons lowers the tape too far. When you levels that would indicate a possibility that the water and sed-
bring the tape and bob back up, you can read a measurement iment would be pumped from a tank.
However an outage measure can be performed to obtain using an acousticcJ sound. The device measures the elapsed
the height of the water cind sediment. This is a little tricky as time of the sound and the return of its echo. These are a few
some trial and error may be necessary. Apply the water find- of the automated gauging types. Some ATGs are also able to
ing paste to the bob and if the water layer is believed to be measure the water/ product interface.
greater than 15 cm (6 in.), apply the water finding paste to the To be truly accurate, at least one more measurement is
tape for an appropriate distance. Ground the tape and bob to needed. The ambient air temperature just on the outside of
the tank top and then lower until you believe you are in the the tank is needed for use in the correction for steel of the
water layer. Remember the problems that occur if the tape tank shell calculations. The ambient air measurement is
and bob hit sediment or sludge cire identical to going too far made at least 3 ft. off the ground on the shady side of a tank.
in the innage gauge procedure. If you hit a solid layer of sed- It should be taken by the gauger either just before or just af-
iment and sludge, the bob could lean. If this happens and the ter the tank gauges. Allow enough time for the thermometer
gauger shows that the tape and bob have leaned or arched, to equilibrate with the ambient air before reading.
bring the tape and bob back up, clean the equipment and Measurements on marine vessels are taken identically as on
lower the tape and bob a little shorter. Lower the tape to the land. There are two additional factors that are required. On
next whole number on the tape and record the reading. Bring marine vessels, the vessel may not be level in two directions.
the tape and bob up. It may be necessary to use an appropri- The front to back slope on a marine vessel is called trim while
ate rinse to clear heavy oils off of the section to be read. Use the right to left tilt is called list. These are needed because the
the same precautions as discussed under the innage method. strapping charts are prepared for vessels that are level. When
Read the water cut before the calculations as above. Depend- the vessels become out of level, the liquid level remains paral-
ing on the tank strapping chart, this reading may have to be lel to the pull of gravity, changing the gauge readings at the
converted to an innage gauge. Remember that the reference point where it is normally taken. To understand this concept,
height of the tank minus the outage gauge equals the innage take a glass of water filled only half way. Tilt the glass in any
gauge. direction. The liquid level remains parallel to the ground. The
A quick mention of automatic tank gauging is needed. API steeper the tilt either forward or backwards or side to side can
MPMS Chapter 3.IB covers the Standard Practice for Level place a liquid surface close to the edge of at the top while the
Measurement of Liquid Hydrocarbons in Stationary Tanks by other side gets close to the bottom of the glass. Marine vessels
Automatic Tank Gauging. These instruments require calibra- have calculated values contained on the strapping cheirt for
tion before use. Manual gauging in accordance with API trim and list. It is therefore necessary to determine the trim
MPMS Chapter 3.1 A is recommended for most calibration and list. Marine vessels have markings on the side of the ves-
procedures. Additionally, some may not have the accuracy sel near the bow, middle, and stem to indicate how far into the
required for custody transfer purposes. Use of an automated water they are. These draft markings are used to determine
tank gauge (ATG) requires agreement by the parties prior to the trim. Read the draft markings as best as possible. If the
their use. ATGs can have remote readouts, gauge readers at bow is higher than the stem, the vessel is down by the stem.
the bottom or the top of a tank and sometimes an external Should the bow be lower than the stem, the vessel is down by
marker on the side of a tank. Even with ATGs, slotted stand- the head. Note that the higher the draft, the lower the vessel is
pipes when used are recommended. Solid stilling wells ("still" sitting in the water at that point. The middle draft is used to
pipes) used for environmentetl reasons are not recommended determine whether the vessel is arching or bowing in the wa-
for custody transfer purposes as they can lead to inaccuracies ter. Weight is not always equal at every point within the ves-
of the level and temperature measurements. There are sev- sel and some hog or sag is expected. Additionally, the vessel
eral types of ATGs in use currently. A float operated ATG con- may lean to the right (starboard) or left (port). A vessel's in-
tains a float, which travels along one or two wires. The floats clinometer, usually on the bridge, is used to measure the ves-
are designed to be buoyant at certain densities. They will sel's list. If the inclinometer is not available, the list can be cal-
therefore remain on top of the product intended. Turbulence culated from the midpoint port and starboard draft readings.
in a tank can put the float out of calibration. When used in The measurement of the trim and list must be made at the
floating roof tanks, wind can stretch the wire holding the time the vessel gauging is performed. Otherwise the correc-
float cind provide inaccurate readings. A servo-operated auto- tions applied to the actual vessel gaugings will be inaccurate.
mated tank gauge is another type that uses a small displacer That is one reason why gauging should occur after completion
into the liquid level from a flexible cable or tape. These are of loading or discharge. During the transfer operations, the
normally located at the top of a tank in a still pipe. Hydro- trim and list may change. The corrections are added or sub-
static tank gauges use precision pressure measurement de- tracted to the observed gauges based on the instructions con-
vices located at several levels of the tank. These gauges mea- tained in the strapping chart.
sure the hydrostatic head pressure at each point and use
strapping chart data to calculate the mass, density, volume, In a marine vessel, on-board quantity (OBQ) and remain-
and level within the tank. Temperatures are tcJcen and fed ing on board (ROB) quantity must be measured. As long as
into the automated calculation and readout system. This sys- these volumes cover the entire bottom surface and all four
tem is prone to inaccuracies caused by product stratification, walls, the strapping chart applies. There are times when this
especially density stratification. Another type of ATG is the does not occur, but measurements must be tsiken. A wedge
radar tank level gauge. Radar waves are used to determine the formula is used to calculate the OBQ or ROB. Some linear
distance remaining in the tank. It measures the time it tcikes measurements of the cargo compartment are needed. For
for a radar wave to go to the liquid surface and return. Then use of the wedge formula, use API MPMS Chapter 17.4
there are sonic and ultrasonic tank level gauges. These operate Method of Quantification of Small Volumes on Marine Vessels
(OBQ/ROB). Where a solid or nearly immovable substance is
layered on the bottom of a marine vessel, trim and list cor- would float. Getting liquid above this position on the hydrom-
rections are not applied. Rather for this layer, it can be con- eter stem can result in slightly inaccurate readings as the liq-
sidered as layering the bottom of the vessel as a solid sheet. uid may be retained above the level of the product depressing
Use the strapping chart to obtain this quantity as if the vessel the hydrometer slightly. Spin the hydrometer to disperse air
were on even keel. bubbles on the bottom of the hydrometer. Allow the hydrom-
Nov*? for the really easy pEirt, the calculations back in the eter to come to rest. Read the hydrometer to get the observed
shore office or the ship's office. The calculation procedures density. As quickly as possible read the thermometer to obtain
are governed by API MPMS Chapter 12.1, Calculation of the temperature that the observed density was taken. When us-
Static Petroleum Quantities. We will be taking the linear mea- ing separate hydrometer and thermometer, remember to allow
surements and converting them to volumes now. In doing so, the thermometer time to equilibrate in the liquid before read-
we need to define some terms. ing it. To convert density at observed temperature to density
• Total Observed Volume (TOV) is the volume found from the (API Gravity) at standard temperature, follow the procedures
measured total liquid height. It includes all petroleum liq- in API MPMS Chapter 11.1 (ASTM D1250 or IP 200) and the
uids, water, and sediment in the product, free water, and appropriate table designations. There are tables for specific
bottom sediment. range of products. Table A is used for crude oil and naphtha
• Free Water (FW) means all free water and bottom sediment. based aviation turbine fuels. Table B is used for most other
This is the water cut measurement converted to a liquid petroleum fuels. Table D is used for lubricating oils. For those
volume. It includes the bottom sediment a n d sludge, if pre- that wish to perform the coefficient of expansion tests each
sent, as the measurement includes it. Additionally, the free time a VCF is needed for a specified product, use table C. Tests
water and the sediment and sludge have different volume for S & W include centrifuge method, water by distillation, wa-
correction factors from petroleum products. ter by Karl Fischer and Sediment by extraction. Round values
• Gross Observed Volume (GOV). This is the total volume of to the precision required as stated in API MPMS Chapter
petroleum liquids and sediment and water in the product 12.1.1, paragraph 6.2 and Table 1. You can do the calculations
less the free water volume. (GOV = TOV — FW). or a computer may be able to do them if programmed appro-
• The Volume Correction Factor (VCF) is correction for tem- priately Eind the correct numbers are entered into it.
perature of the liquid to a standard temperature. It may For shore tanks, take the total liquids gauged measurement
also be referred to as the Correction for Temperature of the and go to the strapping chart. The volume obtained is the
Liquid or CTL. TOV. For marine vessels, the trim and list factors must be ap-
• Gross Standard Volume (GSV) is the GOV times the VCF plied to t h e total liquids gauged. This will b e contained
(GOV X VCF). within the strapping chart. Based on the trim and list, the
• Net Standard Volume (NSV) is the total volume of all strapping chart will advise you to add or subtract some linear
petroleum liquids, excluding S & W and free water, cor- measurement to the observed reading. From this correct lin-
rected by the appropriate VCF. (G.S.V. - S & W = N.S.V.) ear measurement, obtain the TOV from the strapping chart.
For sales, this is the value required. However for inventory Whether a shore or marine tank, free water is normally ob-
purposes and storage, shipping, and handling, we need to tained as an innage value. Look u p the total volume of free
know and understand the other definitions. water (remember this includes the b o t t o m sediment) and
A tank may be able to contain the NSV, but not the TOV. record this volume as FW. There may be occasions when the
Remember that petroleum products expand when the tem- level or type of free water and sediment necessitated an out-
perature of the product increases. Leave enough room in the age gauge. If the chart is in innage measurements, convert
tank for said expansion. Volumes in pipelines also expand the outage gauge to a n innage gauge and look u p the FW vol-
and contract. Static lines may not be full if several expan- ume. If the volume of free water and b o t t o m sediment is
sion/contraction cycles caused by day/night t e m p e r a t u r e great, using the outage gauge table may be appropriate. On
variations have occurred. Some product may have moved to marine vessels, remember trim and list corrections when the
another tank through the pressure relief system. bottom layer is fluid.
From the laboratory tests we receive the density at 15°C (API For true corrections, the correction for temperature of the
Gravity at 60°F) and the tested S & W contained in the product shell (CTsh) is needed. This compensates for the expansion
as a percent reading. Performing a density or API Gravity test, and contraction of the tank shell caused by the temperatures
follow the procedures in API MPMS Chapter 9 Density Deter- of the product and the ambient air. Tanks are strapped as-
mination. Several ASTM test methods are D 5002 (Crude Oil suming a specified temperature range. The CTsh is used to
by Digital Density AnjJyzer), D 4052 (Liquids by Digital Den- bring the liquid volume back into calibration. In accordance
sity Meter), and D 1298 (Hydrometer Method). The basic prin- with API MPMS Chapter 12.1.1, Section 9.1.3 the adjustment
ciple for the manual method is to take the sample and place it used is CTsh = 1 - 1 - 2aA T + a^\^. The symbol a equals a lin-
in a hydrometer cylinder. Make sure all air bubbles Eire elimi- ear coefficient of expansion of the tank shell, with Appendix
nated from the top of the liquid. Use a hydrometer with an ap- B-2 containing several coefficients for various metals. The AT
propriate scale reading. Some hydrometers have a thermome- equals the Tank Shell Temperature — Base Temperature. The
ter as p a r t of the hydrometer. Otherwise, a separate base temperature is the temperature that the strapping chart
thermometer is required. It is best to have the product being was calibrated at. The tank shell temperature for an insulated
measured equilibrate with the ambient temperature as it pre- tank is assumed to be the temperature of the product. For
cludes temperature drift during the measurement. Especially noninsulated tanks, use the formula in Appendix B of API
in the field, this may not also be possible. Lower the hydrom- MPMS Chapter 12.1.1.
eter into the liquid to a position close to where the hydrometer Calculations for a floating roof tank include a floating roof
adjustment (FRA). Remember that a floating roof displaces needed is to confirm all the adjustments have been made for
product due to its weight. Some strapping charts contain the FRA, CTsh, FW, and sediment and water. As noted earlier,
formula for this adjustment. Others just provide the weight of the calculation psirt of static petroleum measurement is re-
the roof and the FRA must be calculated. Check this carefully ally the easy part.
w h e n performing the CcJculations. The basic principle is that Let u s perform a sample calculation here. Information
the roof correction = weight of the roof / (density X VCF). from the tank and lab are provided:
The displacement a m o u n t was also determined at a specified
density and part of the correction includes an adjustment for Product Crude Oil API Gravity = 28.5
the difference between the observed density and the density TOV = 10,250,500 USG FRA = - 7 5 . 5 5 USG
used in the calibration, most likely 15°C or 60°F. Now we can FW = 765 USG CTsh = 1.00009
Sediment and water = 2.25% VCF (Table 6A) = 0.9969
determine the GOV. Product Temperature == 67°F WCF (Table 11) = 0.13808
For shore tanks, the GOV is the [(TOV - FW) X CTsh] ± LT/BBL
FRA. The FW is deducted before the FRA because water and TOV 10,250,500 USG
s e d i m e n t compress differently t h a n petroleum a n d minus FW 765
petroleum products. For most purposes, it is assumed not to equals GOV 10,249,735 USG
have a compression factor and therefore is ignored in the cal- times CTsh X 1.00009
culations. For marine vessels the GOV = (TOV ± Trim/List
Corrections) — FW. This now gives the total liquid volume to equals 10,250,657 USG
FRA - 76 USG
be sold or moved. The next step is to convert this volume at
an observed temperature to a volume at the standcird tem- 10,250,581 USG
perature, referred to as the Gross Standard Volume (GSV). times VCF table 6A x 0.9969
The GSV = GOV X VCF. For distillate fuels and lubricating
oils, the trace amounts of entrained water and sediment are GSV 10,218,804 USG
Note: (S = Standard temperature, in this example it is 60°F)
accepted without adjustments to the quantity. Therefore for times CSW (1-0.0225) 0.9775
distillates and lubricating oils, we also have the Net Standard
Volume (NSV). In fact for these products, we normally do not equals NSV 9,988,881 USG
refer to a GSV, only the NSV in the CcJculations. Divided by 42 USG/barrel equals 237,830.50 barrels
times WCF (table 11) 0.13 808 long
However, in the case of crude oil and some heavy heating tons/barrel
oils, a deduction is made for the amount of S & W contained
in the product. From the laboratory, the water and sediment Long Tons 32,839.64 long tons
value is provided as a percentage. The NSV is therefore the
GSV times a correction for the sediment and water (CSW). Using this information requires an understanding of the
To obtain the CSW, convert the sediment and water percent- purpose of the measurement and its relationship to other
age into a decimal and then subtract that value from one measurements. In the petroleum industry, careful control of
(1.0000). For example, if the sediment and water contained in quantities is expected. First, the profitability of a company
a crude oil is 4.25%, converting to a decimal gives 0.0425. depends on accurate measures for sales and purchases.
Then (1.0000 - 0.0425) = 0.9575 as the CSW. Then the Losses affect the company's bottom line. If you obtain a
NSV = GSV X CSW. Conversely, use the converted sediment gain, someone else has taken the loss. Second, inventory
and water decimal and multiply it times the GSV. This will control procedures use these quantities to determine theft
give a volume of sediment and water contained in the GSV. during movements or spills and leaks during storage or
Then the NSV = GSV minus the volume of sediment and wa- movement. The accuracy of these determinations affects the
ter CcJculated. This concludes volume calculation. time spent in investigating the loss or gain. Losses may re-
Lastly, many users of this information also require the ap- quire an expenditure of funds in investigating the loss, some
parent mass or weight in air of the product. For this we use a internally m a n d a t e d , b u t m a n y regulatory mandated.
Weight Conversion Factor (WCF), which is a relationship be- Within the industry, it is recognized that the measurements
tween the density of the product and its weight in air. There between two points contain some vjiriation. The principle
are m a n y tables contained in Volume XI a n d XII of API causes of these differences are contained in the measure-
MPMS Chapter 11.1 that give these relationships. There are ment precision of the methods used in determining the lin-
also numerous methods to convert from volume to weight. It ear gauge, temperature, automated gauging precision, den-
is preferable to approach the ceJculation process from the sity measures, evaporation loss, and others. These slight
simplest, most direct direction. Using different approaches variations may give slightly different volumes between two
results in slightly different weights. It is best to obtain agree- different measurements. One source of error is slowly being
ment on the conversion process as part of the agreement be- displaced by the use of precision equipment. A temperature
obtained using a thermometer will have an error caused by
tween buyer and seller or as a company policy for internal
our ability to discern between the graduation marks. The
use. This will preclude problems by those performing the cal-
electronic versions provide the temperature more accu-
culations or inventory control reviews.
rately. These changes reduce the variation expected. Agree
The order of calculation is TOV to GOV to GSV to NSV to
on the variation due to measurement errors in adveince or
Weight in Air. The exception is when the tank measurement
have company policy clearly explain that some variation is
is by a direct mass method, for example a hydrostatic tank expected. However, losses that can be determined, such as
gauge. The reading is already in mass units and the calcula- spills, leaks, and thefts are not contained in the variation.
tions are performed within the little black box. All that is
These need to be identified and explained, and procedures D5854 Mixing and Handling of Liquid Samples of
should be developed to eliminate them. Volatile hydrocar- Petroleum and Petroleum Products
bon losses can be calculated. With increased attention on El ASTM Thermometers
the environment, environmental groups are mandating re-
ductions in the release of volatile organic hydrocarbons.
These normally require some sort of engineering changes to
the tanks and facilities. OTHER STANDARDS
The true measure of successful static petroleum measure-
ment is the care and practice of the techniques described in American Petroleum Institute (API) Manual of Petroleum
obtaining the required data. The calculations are easy and Measurement Standards (MPMS), Chapter 3.1
straightforward. However, with incorrect data, all that is ob- API MPMS Chapter 7, Method of Measuring the Tempera-
tained is incorrect volume eind weight measurements. Take ture of Petroleum and Petroleum Products
the time to train the samplers and gaugers to perform the re- API MPMS Chapter 8.1, Manual Sampling of Petroleum and
quired steps in accordance with the defined procedures. Petroleum Products
Make sure they understand how important they are to the API MPMS Chapter 8.2, Automatic Sampling of Petroleum
health and financial success of your operation. and Petroleum Products
API MPMS Chapter 8.3, Standard Practice for Mixing and
Handling of Liquid Samples of Petroleum and Petroleum
ASTM STANDARDS Products
API MPMS Chapter 8.4, Standard Practice for Manual Sam-
No. Title pling and Handling of Fuels for Volatility Measurements
D 1250 Petroleum Measurement Tables API MPMS Chapter 10, Density Determinations
D 1298 Hydrometer Method API MPMS Chapter 11.1, Physical Properties Data
D 4052 Liquids by Digital Density Meter API MPMS Chapter 12.1, Calculation of Static Petroleum
D 4057 Manual Sampling of Petroleum and Petroleum Quantities
Products API MPMS Chapter 17.4, Method of Quantification of Small
D 4177 Automatic Sampling of Petroleum and Petroleum Volumes on Marine Vessels (OBQ/RBOB)
Products API MPMS Chapter 17.6, Guidelines for Determining the
D 5002 Crude Oil by Digital Density Analyzer Fullness of Pipelines Between Vessels and Shore Tanks In-
D 5842 Sampling and Handling of Fuels for Volatility ternational Petroleum (IP) 200, Petroleum Measurement
Measurement Tables
MNL37-EB/Jun. 2003
Hydrocarbon Analysis
James C. Fitch^ and Mark Barnes^'•^
THE AIM OF THIS CHAPTER IS TO BRIEFLY PRESENT SIX ANALYTICAL Basic Principles of NMR Spectrometry
METHODS for characterizing hydrocarbon compounds found
in fuels and lubricants. The methods presented are NMR Absorption spectrometry works because applied electromag-
spectrometry, gas chromatography, liquid chromatography, netic radiation of an appropriate frequency induces a transi-
ultraviolet spectroscopy, mass spectrometry, and infrared tion from one (lower) energy level to another (higher) energy
level within the molecule, causing the radiation to be ab-
spectroscopy. The analysis of hydrocarbons deploying these
sorbed by the sample. In IR and UV spectrometry, these en-
methods is well-founded in scientific laboratories and is the
ergy levels are the vibrational and electronic energy levels of
basis of numerous ASTM standards.
the molecule, whereas in NMR the energy levels are associ-
Because of the large body of published work on these
ated with the nuclear spin of the nuclei that make up the
methods, it is not the intention of the authors to attempt molecule. For the purpose of detailing how NMR works, we
complete coverage of all methods, but rather to provide an will focus on the most commonly studied nucleus, the hydro-
overview of their use in the analysis of fuels and lubricants. gen nucleus 'H, which has a nuclear spin of li.
Following each section are summaries specific to ASTM D 02
standards where the analytical method is deployed in the ar- A nucleus such as 'H with a spin of 'A possesses two nuclear
eas of fuels and lubricants. spin states, +'A and —'A. Under normal circumstances, these
spin states have the same energy and are said to be degener-
ate. However, in the presence of a strong magnetic field (typ-
ically 2.33 tesla (T) for the ^H nucleus), the two nuclear spin
NUCLEAR MAGNETIC RESONANCE (NMR) states split into two energy levels, their separation being pro-
SPECTROSCOPY portional to the applied magnetic field as shown in Fig. 1 [1].
Applying a source of electromagnetic radiation and slowly
Introduction scanning the frequency can induce absorption when the ra-
diation frequency matches or is in resonance with the energy
Nuclear magnetic resonance (NMR) spectroscopy is one of separation of the two nuclear spin states under the applied
the most widely used analytical tools in chemical analysis. magnetic field. The frequency of radiation that must be ap-
Just like infrared (IR) and ultraviolet (UV) spectroscopy, plied to induce such a transition is typically in the radio fre-
NMR is a form of absorption spectrometry, whereby the quency (rf) range. For a ^H nucleus under an applied mag-
amount of absorbed electromagnetic radiation at a given fre- netic field of 2.33 T, the resonance frequency is around 100
quency can be related to the concentration of certain chemi- MHz [2]. For practical reasons, NMR spectrometers usually
cal species that absorb at that frequency. However, unlike IR work in the opposite sense, with a fixed electromagnetic ra-
spectroscopy, which looks at functional groups within a diation frequency (commonly 100 MHz for ^H NMR) and a
molecule, or UV spectroscopy, which looks at the molecule as scanning magnetic field [3]. However, the same principle ap-
a whole, NMR is used to determine the concentration of spe- plies: the magnetic field is scanned until the energy separa-
cific atoms within a sample. tion of nuclear spin states induced by the field comes into res-
It is not the mandate of this chapter to provide a detailed onance with the applied electromagnetic radiation.
quantum physical explanation of NMR or any other analyti- In reality, the magnetic field that must be applied to bring
cal method described herein. However, the basic theory be- a nuclear spin transition into resonance with the applied
hind NMR spectroscopy will be outlined in this section, so electromagnetic radiation varies slightly with the chemical
that the reader can obtain an understanding of NMR and environment of the nuclei in question. This phenomenon is
how it can be applied to the analysis of large hydrocarbon known as shielding and can be attributed to the effects of the
molecules typically found in fuels and lubricants. electrons surrounding a particular nucleus, shielding the nu-
cleus from the effects of the magnetic field [2]. Because the
electron density surrounding a particular nucleus is directly
related to the chemical structure of the molecule, the electron
distribution within the molecule gives rise to shielding ef-
1 Noria Corporation, 1328 E. 43''' Court, Tulsa, OK 74105.
^ Technical Editor, Practicing Oil Analysis Magazine, Tulsa, OK fects, which are typically called the chemical shift, which can
74105. be used to differentiate between the same nuclei (for example
649
' H ) in different chemical environments. Take for example the will thus be split into two groupings, one associated with the
molecule toluene: methyl hydrogen nuclei, t h e second with the aromatic hy-
drogen nuclei. The relative intensities of the absorption pesiks
H for the two groups will be in the ratio 3:5 corresponding to
the relative ratios of the nuclei in the two environments. The
' H NMR spectrum for toluene is shown in Fig. 2 [4].
H C _ H The chemical shifts reported in NMR spectrometry are
usually expressed as the pEtrts-per-million (ppm) shift from
the r e s o n a n c e frequency of a reference standard, usually
H H tetramethylsilane (IMS). The chemical shift c a n be calcu-
lated using the following formula [5]:
Chemical shift (in p p m ) = (RFS-RFTMS)/RFTMS X 10*
Where RFs is t h e resonance frequency of t h e sample a n d

RFTMS is t h e resonance frequency of t h e TMS reference.
H H Some typical chemical shifts for ' H in hydrocarbon
molecules are shown in Table 1 [5].
The key to using NMR spectrometry in t h e analysis of hy-
drocarbon molecules is to recognize the chemical shifts ob-
served in the NMR spectra £ind relate the relative concentra-
Toluene h a s t w o types of protons, either as part of t h e tions of nuclei in these different environments to help
methyl group, or attached t o a n aromatic carbon. Because elucidate the bulk properties of a hydrocarbon sample, for
the shielding experienced by these two different types of pro- example the concentration of aromatic molecules in a hydro-
tons will depend on both electron density and ring current ef- carbon oil.
fects, the resonance frequency for interaction with the ap-
plied field will be different. The NMR spectrum for toluene
" C NMR Spectrometry
NMR spectrometry is not limited to just hydrogen nuclei. In
fact, any nucleus with a n odd s u m of protons a n d neutrons
will possess a magnetic m o m e n t and can thus be analyzed us-
ing NMR. Aside from 'H, the second most commonly studied
nucleus is '^C, which like ' H has a nuclear spin of'/. Carbon
exists in two naturally occurring isotopes ^^C a n d '^C, with
Relative Magnetic
Field of relative natural abundances of 98.9% and 1.1%, respectively.
Energy
Strength Although '^C has a n even s u m of protons a n d neutrons a n d
thus does not possess a magnetic moment, with sufficient ex-
TABLE 1—Typical chemical shifts for 'H nuclei in

hydrocarbon molecules.
' H Nucleus Environment Chemical Shift/ppm
Absorbed
CH2 and CH3 H atoms far from 0.5-2.0
Energy
aromatic rings
• Increasing Frequency CH2 and CH3 H atoms in the a 2.0-4.0
position relative to an aromatic rings
FIG. 1—The separation of proton nuclear spin states under H atoms in monocyclic aromatic rings 6.0-7.2
H atoms in Polycyclic aromatic rings 7.2-9.0
an applied magnetic field.
aromatic hydrogen
resonance
methyl hydrogen
resonance
7 6 5 4 3 2
FIG. 2—^H NMR spectrum for toluene.

CHAPTER 24: HYDROCARBON ANALYSIS 651
TABLE 2—Typical chemical shifts for '^C nuclei in where S is the total integrated hydrogen signal from the sam-
hydrocarbon molecules. ple, R is the integrated signal from the n-dodecane reference,
" C Nucleus Environment Chemical Shift/ppm Wn is the weight of n-dodecane used, Ws is the weight of sam-
Aliphatic and naphthenic carbon atoms 10.0-60.0 ple used, and 15.39 simply reflects the percentage by mass of
Carbon atoms in terminal CHj groups 14.1 hydrogen in the n-dodecane reference standard. The accu-
Carbon atoms in CH2 groups in the middle 29.2 racy of this test method is around 0.2-0.4% for a typical hy-
of a chain drogen content of 14% [5]. Other variations on this method
Carbon atoms in aromatic rings 110-160 have also been used, which involve pulsed FT NMR, which
are capable of errors as low as 0.05% [6, 7].
Hydrocarbon oils made by the refining of crude petroleum
perimental resolution, the NMR spectrum of samples con- are generally classified parafHnic or naphthenic depending
taining '•'C nuclei in natural abundance can be recorded and on the predominant class of hydrocarbon compounds found
analyzed, in much the same way as 'H NMR spectra can be in the oil [8]. Despite this, most oils of this type contain a sig-
analyzed to determine key structural properties of the nificant proportion of aromatic hydrocarbons. The aromatic
molecules that comprise the bulk sample. content of an oil can affect a number of physical and chemi-
Just like ' H NMR, the resonant frequency of the ^•'C nuclei cal properties such as boiling range, viscosity, stability, and
are influenced by the chemical environment in which they compatibility. For this reason, it is important to be able to de-
are surrounded and again, chemical shifts can be calculated termine to amount of aromatic hydrocarbon content in a hy-
in ppm relative to a calibration standard such as TMS using drocarbon oil [9].
the same formula used to calculate 'H chemical shifts. Chem- One way of characterizing the aromatic content is to count
ical shifts for '^C nuclei tend to be somewhat larger than 'H the number of aromatic carbon and hydrogen atoms in a
shifts in hydrocarbon molecules. Some typical chemical bulk sample. Because NMR is capable of separating signals
shifts for '^C nuclei in hydrocarbon molecules are shown in from different atoms within molecules based on their chem-
Table 2 [5]. ical structure and environment using the concept of chemical
Because the natural abundance of ^^C is so low, the exper- shifts, NMR is a natural for this type of determination: this is
imental measurement of '^C NMR spectra is slightly more the basis behind ASTM D 5292. In this case, the test method
difficult than 'H NMR spectra because the spectra tend to be is even simpler than measuring total hydrogen content. The
much weaker. To overcome this difficulty, the spectra are sample is analyzed using pulsed FT NMR and the total aro-
recorded not by scanning the frequency as for *H NMR (a matic ' H and "C content determined by taking the ratio of
technique often called continuous wave or CW) but by puls- the aromatic carbon or hydrogen nuclei integrated signal to
ing a series of short pulses of broad band radiation (of the or- the corresponding aliphatic signal. For the purpose of as-
der of 0.5-50 fjis) and monitoring the free induction decay of signing ' H nuclear environments, peaks in the chemical shift
the signal from the '^C nuclei. This time domain single is range —0.5 to 5.0 ppm are considered aliphatic hydrogen,
then converted into the frequency domain using Fourier while those in the 5.0-10.0 ppm range are considered aro-
Transformation [2]. This, coupled with other techniques too matic. A t5îcal NMR spectrum of this kind is shown in Fig.
advanced to discuss here, have made the recording and in- 3. For " C NMR, peaks in the —10 to 70 ppm range are con-
terpretation of '^C NMR spectra commonplace [5]. sidered aliphatic, while those in the 100-170 ppm range are
considered aromatic carbons [9].
The Use of ^H and " C NMR in the Analysis of The biggest drawback with NMR is the expense of pur-
Hydrocarbons chasing and running an NMR instrument. However, in cir-
cumstances where the determination of the relative propor-
Because 'H and '^C are the two nuclei most commonly ana- tions of various constituents of a bulk sample in different
lyzed by NMR spectrometry, it stands to reason that NMR chemical environments at high precision are required, NMR
has proven useful in hydrocarbon analysis. There are two offers a quick simple means of obtaining quick, accurate
main areas where NMR has been used for hydrocarbon fuel data. For this reason, the use of NMR as a tool for hydrocar-
and lubricant aneJysis, specifically the identification of hy- bon analysis will continue to grow.
drogen content in aviation fuels (ASTM D 3701) and
petroleum distillates (ASTM D 4808), and in determining the
aromatic hydrogen and aromatic carbon content using 'H ASTM Petroleum Products and Lubricants NMR
and " C NMR spectrometry (ASTM D 5292). Test Standards Under Subcommittee D 02.04
The determination of hydrogen content is an important Aromatics in Hydrocarbon Oils by High Resolution
property of a fuel or lubricant because it is closely related to Nuclear Magnetic Resonance (HR-NMR)
key performance characteristics and can be used as a mea- (ASTM D 5292)
sure of quality control both during and after production.
Both test methods (ASTM D 3701 and ASTM 4808) work by This method is applicable to a wide range of hydrocarbon oils
taking the ratio of the total integrated hydrogen signal from that are completely soluble in chloroform and Cctrbon tetra-
the sample NMR spectrum to a known n-dodecane standard chloride at ambient temperature. The data obtained by this
run on the same NMR instrument. In each case, the total hy- method can be used to evaluate changes in aromatic contents
drogen content by mass (H%) is then calculated using the of hydrocarbon oils due to process changes. Hydrogen ('H)
formula, NMR spectra are obtained on sample solutions in chloro-
form-d using a continuous wave or pulsed FT high resolution
H(%) = S/R X (WR/WS) X 15.39 NMR spectrometer. Carbon ('^C) NMR spectra are obtained
bon analysis rely on gas-liquid chromatography, we will fo-

cus exclusively on this method, although the same basic prin-
1HFTNMR
cipals apply to both methods.
In gas-liquid chromatography, it is the interaction between
the gaseous sample being carried t h r o u g h the column by
means of an inert gas (the mobile phase) and a standard liq-
uid (the stationary phase), which causes the separation of dif-
ferent molecular constituents. The stationary phase is either
a polar or nonpolar liquid, which either coats the inside of
the column, in the case of a capillary column, or is impreg-
nated onto an inert solid, which is then packed into the GC
column [ 11 ]. A schematic layout of a GC instrument is shown
in Fig. 4. The basic components are a n inert carrier gas, most
commonly helium, nitrogen or hydrogen, a GC column,
which will be described below, held inside an oven that al-
PPM lows for precise temperature control, and some type of de-
tector capable of detecting the sample as it elutes from the
FIG. 3—^H NMR spectrum of gas oil showing thie aliphatic
column.
(-0.5 to 5.0 ppm) and aromatic (5.0 to 10.0 ppm) hydrogen
peaks. Reprinted from ASTM D 5292-93. Gas-liquid GC works because the molecules in the samples
are carried along the column in the carrier gas and partition
between the gas phase a n d the liquid phase. Because this par-
titioning is critically dependent on the solubility of the sam-
on the sample solution in chloroforni-<i using a pulsed FT ple in the liquid phase, different molecular species travel
high resolution NMR. along the column a n d exit or elute at different times. Those
molecules that have a greater solubility in the liquid phase
take a longer time to elute and thus are measured at a longer
GAS CHROMATOGRAPHY (GC) time interval. Because solubility is dependent on the physical
and chemical properties of the solute, separation between
different components of the sample occurs based on molecu-
Introduction
lar properties such as relative polarity (for example, oxy-
GC is one of the most widely used analytical tools in the eval- genated molecules, aromatics and nonaromatics) and boiling
uation of petroleum products, as witnessed by the n u m b e r of point. A tjTDical gas chromatogram is shown in Fig. 5.
relevant standcirds summarized at the end of this section that In order to create this separation, a n u m b e r of different
use GC. Its principal value lies in the fact that the technique liquid phase materials are used that can be broadly classified
can b e used t o separate complex mixtures of different as either polar or nonpolar. For hydrocarbon analysis the two
molecules or groups of molecules based on their physical most commonly used liquid phase materials are TCEP (1,2,3-
properties, which is precisely w h y it is such a valuable tris(2-cyanoyethoxy)propane) for polar columns, and methyl
method for fuel a n d lubricant analysis. silicone for nonpolar columns, although a multitude of dif-
Because GC involves first getting the sample into the gas ferent polar and nonpolar columns suitable for hydrocarbon
phase, it is used in the analysis of the more volatile compo- analysis are commercially available. I n general, polar
nents of fuels and lubricants. Less volatile fractions are typi- columns are used to separate aromatics from nonaromatics,
cally analyzed using the related technique of Liquid Chro- while nonpolar columns are used to sepeirate hydrocarbon
matography, which will be discussed in the following section. components by their boiling point.
GC is also used to simplify several spectrometric techniques There are two basic ways in which GCs are used for hydro-
such as Mass Spectrometry (MS) a n d Fourier Transform In- carbon analysis, either to separate different components of
frared Spectroscopy (FTIR) by first separating the sample the sample based on their differing chemical characteristics
into different molecular component types. The use of GC in (for example, aromatics versus nonaromatics), or to separate
GC-MS and GC-FTIR is covered under the relevant spectro- different chemically similar fractions based on their boiling
scopic technique. The direct application of Gas Chromatog- point. To separate molecules based on their chemical prop-
raphy (GC) to the evaluation and analysis of hydrocarbons erties, a GC is run in the method described above, with a po-
will be discussed in this section. lar column used to provide longer retention times for com-
pounds such as aromatics relative to paraffins and olefins.
For accuracy, it is vital that the oven temperature in which
Gas Chromatography the GC column is housed is precisely controlled. This method
Gas Chromatography can be subdivided into two categories, is called isothermal GC analysis [10].
gas-liquid chromatography a n d gas-solid chromatography GCs can also be used in another mode called temperature
[10]. In each case, the technique involves the separation of programming. In temperature programming, the oven tem-
components of a gaseous sample using a stationary phase, ei- perature is slowly swept from an initially low temperature
ther a liquid in the case of gas-liquid chromatography, or a ( s e e ) to a much higher temperature (typically 350-400°C) at
solid in the case of gas-solid chromatography. Because the a CcirefuUy controlled rate [12]. The effect is to cause an in-
overwhelming majority of test standards used for hydrocar- creased separation of chemically similar species based on
OVEN VENT
CARRIER
GAS • ••^ RECORDER
INJECTION
PORT
COLUMN
R s REFERENCE
S s SENSING
FIG. 4—GC Instrument with a thermal detector.
their boiling point; those low boiling fractions eluting at a

faster rate than fractions with higher boiling points. Temper-
ature programming is used in hydrocarbon GC ancJysis to
determine boiling point ranges for various crude and refined
petroleum fractions.
Whether isothermal or temperature programmed GC anal-
ysis is used, a detector capable of measuring molecules as
they elute is required. For hydrocarbon analysis, the two
most c o m m o n types of detectors are flame ionization and
thermal conductivity [13]. In flame ionization type detectors,
the column effluent is mixed with hydrogen and air and ig-
nited. This flame b u m s any organic material (such as hydro-
carbons) when they elute from the column producing, among
other things, ions and electrons. This increase in charged u_
particle concentration causes an increase in current between TIME. MINUTES
the tip of the burner, which is held at a high electrical poten-

FIG. 5—Gas chromatogram of C^ to C^ species in gasoline.
tial, and a collector electrode above the flame. It is this in-
Reprinted from ASTM D 2427.
creased current that is used to measure the elution of sample
molecules from the column. An illustration of a flame ion-
ization type detector is shown in Fig. 6.
Thermal conductivity detectors contain a tungsten fila- — 1 | ^ e ^ 1—
ment that is heated using a constant current [10]. The elution
of pure carrier gas (helium) has a cooling effect on the fila-
ment, which controls the temperature and hence the resis- -Collector electrode
Flame ignition
tance of the filament to the applied constant current. As hy- coil +300V
drocarbon molecules elute, they have less of a cooling effect
Polarising voltage
than the carrier gas, resulting in an increased temperature.
Sample molecule elution is determined based on a change in
resistant of the filament, c o m m o n l y m e a s u r e d using a
Wheatstone bridge electrical circuit [10].
For specialized applications where element specific detec-
tion is required (for example, the determination of sulfur
content in hght petroleum liquids by GC (ASTM D 5623)), Hydrogen
other detection systems are used such as atomic emission
(AED) and chemi-luminescence. These will not be covered in Column
detail in this chapter.
FIG. 6—Flame ionization detector.
T h e U s e o f GC i n H y d r o c a r b o n Analysis
using temperature programming, and the detection of cer-
The use of GC in the analysis of petroleum products falls into tain contaminants such as diesel fuel or ethylene glycol in en-
three genereJ categories: the eveJuation of the relative con- gine oil or oxygenated additives such as MTBE.
centrations of different types of molecules (for example, aro- The determination of the aromatic content of hydrocarbon
matics, olefins, naphthenes etc.), the determination of boil- fuels is a n important application of GC because benzene,
ing point ranges and carbon numbers in fuel and lubricants toluene, and other aromatics pose a serious heedth threat and
is carefully regulated in gasolines and other petroleum prod- 1100 600

ucts. There are a n u m b e r of test methods that use GC for this
purpose, all of which follow the same basic principle (see
ASTM D 3606, D 4420, and D 5580). In each case, a sample
containing an internal calibration standard is injected into a
GC instrument equipped with two columns, one containing a
nonpolar liquid phase such as methyl silicone, the second us-
ing a polar liquid phase such as TCEP. The polar liquid phase
separates aromatics and nonaromatics because aromatics
take longer to elute from a polar column, while the nonpolar
column separates the aromatic components by their boiling
point, allowing the concentrations of benzene, toluene, and
heavier aromatics to be determined. In each case, the mea-
surements are carried out isothermally (that is at a fixed col-
u m n temperature). A tjrpical gas chromatogram of the aro-
matic components of gasoline using this method is shown in
Fig. 7.
Another i m p o r t a n t application of GC to h y d r o c a r b o n
analysis is the simulated distillation of crude petroleum [13].
Determining the boiling point range of petroleum fractions
has a variety of uses, from determining the composition of
feed stocks to evaluating the presence of volatile components,
which may have implications on the performance or safety
cheiracteristics of finished hydrocarbon fuels and lubricants.
Historically, the boiling point range of petroleum fractions 10 15 20 25 30 35 40
has been determined by trial distillations in the laboratory. Retention Time, Minutes
While this method still has some validity, and in some cir- FIG. 8—^Typical boiling point ranges of n-paraffins as a func-
cumstances may be advantageous, the use of gas chromatog- tion of column retention time. Reprinted from ASTM D 5307.
raphy offers a quick, simple alternative for controlling refin-
ing processes and product evaluations.
Boiling point range determination of petroleum products
pie fractions converted to boiling points using the calibration
using GC involves injecting a sample into a nonpolar column,
curve shown in Fig. 8. An example of the simulated distilla-
which is housed in a temperature programmable oven. The
tion of a crude oil s a m p l e using gas c h r o m a t o g r a p h y is
GC is first calibrated using a calibration solution containing
shown in Fig. 9.
known concentrations of normal paraffins. The temperature
The third area where GC has an increasingly important role
of the column is increased at a known rate and the retention
to play is in the determination of certain contaminants in used
time of the n-paraffins is plotted against their known boiling
oil samples, such as ethylene glycol, used as a coolant in many
points, as shown in Fig. 8. The crude sample is then analyzed
combustions engine, and fuel dilution in diesel engine sam-
in the same way, and the retention times of the eluting sam-
ples. While used oil analysis is a subject unto itself, it is in-
structive to review how GC is applied in this area.
The determination of fuel dilution in engine oil samples is
of prime importance because it can impair the performance
of the lubricating oil [14]. Because diesel fuel is chemically
<-8
Toluene aromatics very similar to the oil itself, it is almost impossible to quan-
tify fuel dilution by conventional wet chemistry tests. While
other physical tests such as changes in viscosity, FTIR, and
flash point offer means of determining the presence of fuel in
a lubricating oil, GC is generally a more precise and reliable
0}
c Switch to forward flow means of determining fuel dilution based o n the temperature
m (Time T2)
N programmed elution of fuel relative to the larger (higher boil-
Non-aromatics • aromatics
ing point) fractions of the lubricating oil.
The same can be said for ethylene glycol coolant detection.
t—^r^ Ethylene glycol is an insidious c o n t a m i n a n t in engine oil
samples that can result in catastrophic engine failure if left
unchecked [15]. Again a n u m b e r of wet chemistry tests
(ASTM D 2982) and physical tests (FTIR) are available, but,
again, GC offers superior detection limits. Because ethylene
glycol is a polar molecule, GC analysis is performed by first
10 15 25 extracting the glycol from the used oil sample with water.
Time, minutes The water extract is then run directly on a n isothermal GC
FIG. 7—Typical gas chromatogram of the aromatic column against calibration standards containing known con-
fractions of gasoline. Reprinted from ASTM D 4420. centrations of ethylene glycol in water. The sensitivity of GC
23500- AIS = AREA OF CRUDE PLUS

INTERNAL STANDARD
21500
19500
17500-
V) 538°C (1000°F)
Z 15500
O
0.
tU 13500
OC
11500
9500 BASELINE
7500 JIMMAAAAMA^
AIS •
5500
1 r 1 1 1
3500 •o O 00 CO
CM P4 M
TIME
A. CRUDE + INTERNALSTANDARD
B = TOTAL ELUTED AREA

19500 UPTO538*C(1000°F)
B' = AREA CORRESPONDING TO
NON-ELUTED SAMPLE
BIS " AREA OF SEGMENT WHERE
INTERNAL STANDARD ELUTES IN
FIGURE 9A
538''C(1000''F)
BASELINE
yUwiiUAAAz/AAx^
I BIS
TIME
B. CRUDE ONLY
FIG. 9—Gas chromatogram of calibration mixture and crude oil sample used to deter-
mine boiling point range. Reprinted with permission from ASTM D 5307.
to detecting contaminants in used oil samples makes it an with complex mixtures such as fuels and lubricants. How-
ideal test where high precision test data is required. ever, one way of addressing this issue is to couple GC with
Whether it is used for evaluating different molecular com- some other applicable method that is capable of not only de-
ponents of gasoline, determining boiling point ranges for tecting eluting fractions, but can also identify their chemical
crude oil fractions, or detecting contaminants, one of the ma- composition. For this reason, the dual combination of GC
jor drawbacks with GC is that while its is excellent at quanti- with mass spectrometry (GC-MS), infra-red spectrometry
fying the relative concentrations of various eluted fractions, (GC-FTIR), and atomic emission (GC-AES) will continue to
it cannot determine empirically what those fractions actually grow in importance in the quantitative analysis of hydrocar-
are [11]. Without the application of suitable cetlibration stan- bon fuels and lubricants [16,17]. The application of GC to MS
dards, which requires at least some knowledge of the sample and FTIR is covered in the appropriate spectrometric analy-
constituents, this problem could severely limit the use of GC sis sections of this review.
A S T M P e t r o l e u m P r o d u c t s a n d L u b r i c a n t s GC time axis from a calibration curve, obtained under the same

Test Standards conditions by running a known mixture of hydrocarbons cov-
ering the boiling range expected in the sample.
Aromatics in Finished Gasoline by Gas
Chromatography (ASTM D 4420) Diesel Fuel Diluent in Used Diesel Engine Oils by Gas
This test method determines benzene, toluene, Cs, C9, and Chromatography (ASTM D 3524)
heavier aromatics, and total aromatics in finished m o t o r This test method covers the determination of diesel fuel as a
gasoline and gasoline blending components. A two column contaminant in used lubricating oil. A mixture of n-decane
chromatographic system connected to a dual filament ther- and used lubricating oil is introduced into a gas chromato-
mal conductivity detector (or two single filament detectors) graphic column that separates hydrocarbons in the order of
is used. their boiling points.
Aromatics in Finished Gasoline by GC (ASTM D 5580) Estimation of Engine Oil Volatility by Capillary Gas
Aromatics in the following concentration reinge can be deter- Chromatography (ASTM D 6417)
mined by this test method; benzene 0.1-5; toluene 1-15; in- The determination of engine oil volatility at 371°C is a re-
dividual Cg aromatics 0.5-10; total C9 and heavier aromatics quirement in some lubricant specifications. A sample aliquot
5-30; and total aromatics 10-80 liquid volume percent. The diluted with a viscosity reducing solvent is introduced into
aromatic hydrocarbons are separated without interference the gas chromatographic system, which uses a nonpolar open
from other hydrocarbons in the finished gasoline. A two col- tubular capillary gas chromatographic column for eluting the
u m n c h r o m a t o g r a p h i c system equipped with a column- hydrocarbon components of the sample in the order of in-
switching valve and a flame ionization detector is used. creasing boiling point.
Benzene/Toluene in Gasoline by Gas Chromatography Ethanol Content In Denatured Fuel Ethanol by GC

(ASTM D 3606) (ASTM D 5501)
This test method determines benzene and toluene in finished This test method covers the determination of ethanol content
m o t o r and aviation gasoline by gas chromatography. The of d e n a t u r e d fuel ethanol by gas chromatography. A fuel
sample is doped with an internal standard, methyl ethyl ke- ethanol sample is injected into a gas c h r o m a t o g r a p h
tone (MEK), and is then injected into a gas chromatograph equipped with a methyl silicone bonded phase fused silica
equipped with two columns connected in series. capillary column.
Ethylene Glycol in Used Engine Oil (ASTM D 4291)

Boiling Range Distribution of Crude Petroleum by Gas
This test m e t h o d provides for early detection to prevent
Chromatography (ASTM D 5307)
coolant from accumulating and seriously damaging the en-
The method covers boiling range distribution of water-free gine. The sample of oil is extracted with water and the analy-
crude petroleum through 538°C (100°F). A solution of crude sis is performed on the water extract, which is injected into a
oil in carbon disulfide is injected into a gas chromatographic gas chromatograph using on-column injection. The eluting
column that separates hydrocarbons by their boiling point compounds are detected by a flame ionization detector.
order.
Engine Oil Volatility by GC ASTM (D 5480)
Boiling Range Distribution of Gasoline Fractions by
This test method provides the determination of the amount
Gas Chromatography (ASTM D 3710)
of engine oil volatilized at 700°F (371°C). The sample is
This test method is designed to measure the entire boiling mixed with an internal standard and a dilute tetracosane so-
range of gasoline with either high or low Raid vapor pressure. lution, and injected into a gas chromatograph.
The sample is injected into a gas chromatographic column,
which separates hydrocarbons in boiling point order. Gasoline Diluent in Used Engine Oils Gas
Chromatography Method (ASTM D 3525)
Boiling Range Distribution of Petroleum Distillates by
This test method uses gas chromatograph equipped with a
Gas Chromatography (ASTM D 6352)
flame ionization detector and a programmable oven.
The gas c h r o m a t o g r a p h i c (GC) determination of boiling
point ranges is used to replace conventional distillation Hydrocarbon Types in Gasoline by Gas
methods for control of refining operations. A nonpoleir open Chromatography (ASTM D 2427)
tubular capillary GC column is used to elute the hydrocarbon This test method provides information on C2 through C5 ceir-
c o m p o n e n t s of the sample in order of increasing boiling bon paraffins and mono-olefins in gasolines. The sample is
point. injected into a gas-liquid partition column. The components
are separated as they pass through the column with an inert
Boiling Range Distribution of Petroleum Fractions by carrier gas and their presence in the effluent is detected and
Gas Chromatography (ASTM D 2887) recorded on a chromatograph.
The d e t e r m i n a t i o n of the boiling range distribution of
petroleum fractions by gas chromatography is effective as a Methyl Tert-Butyl Ether in Gasoline by GC
rapid anal5îcal tool. The sample is introduced into a gas (ASTM D 4815)
c h r o m a t o g r a p h i c column that separates hydrocarbons in This test method determines ethers and edcohols in gasoline
boiling point order. Boiling temperatures are assigned to the by gas chromatography, a n d is applicable to both quality
control in the production of gasoline and the determination hydrocarbon petroleum products, specifically, absorption
of deliberate or extraneous oxygenate additions or contami- chromatography, high performance liquid chromatography
nation. A gasoline sample is doped with an internal standard (HPLC), fluorescent indicator absorption (FIA) and super
such as 1,2-dimethoxyethane, and is injected into a gas chro- critical fluid chromatography (SFC).
matograph equipped with two columns and a column switch-
ing valve. The eluted components are detected by a flame ion-
L i q u i d C h r o m a t o g r a p h y (LC)
ization or a thermal conductivity detector.
In classical LC, a liquid sample is introduced either neat or
Olefins In Engine Fuels by GC (ASTM D 6296) diluted with a n a p p r o p r i a t e solvent into a glass column,
This test method can determine olefins in the C4 to Cio range which has been prepacked with an appropriate solid material
in spark ignition engine fuels or related hydrocarbon streams such as silica, alumina, or some other solid medium. The
such as naphthas and cracked naphthas. A sample fuel is insample is then washed down the column using a flowing
jected into a computer controlled gas chromatographic sys- stream of solvent, starting with a relatively low strength sol-
tem, which consists of a series of columns, traps, and switch- vent and progressing to stronger and stronger solvents until
ing valves operating at various temperatures. The final eluted the sample has been washed out or eluted from the column
olefins are detected by flame ionization detector. [18]. Depending on the nature of the interaction between the
sample (the mobile phase) and the column material (the sta-
Oxygenates in Gasoline by Gas Chromatography tionary phase), mixtures can be separated by retention time
(ASTM D 5599) in the column; those molecular species present in the mobile
This test method provides sufficient oxygen-to-hydrocarbon phase which have a greater affinity for the stationEiry phase
selectivity a n d sensitivity to allow d e t e r m i n a t i o n of oxy- material take a longer time to elute t h a n those that have little
genates in gasoline samples without interference from the or n o affinity for the stationary phase. This is called absorp-
bulk hydrocarbon matrix. An internal standard of a nonin- tion chromatography and the columns used for this kind of
terfering oxygenate (for example, 1,2-dimethoxyethane) is methodology are absorption columns.
added in a quantitative proportion to the gasoline sample. An An illustration of absorption liquid c h r o m a t o g r a p h y is
aliquot of this mixture is injected into a gas chromatograph shown in Fig. 10. In this example, a mixture of two com-
equipped with a capillary column operated to ensure separa- pounds, X and o, Eire added to an LC column packed with a
tion of the oxygenates. Oxygenates are detected with the oxy- stationary phase that has a greater affinity for compound x
gen-selective flame ionization detector. than compound o. The mixture is washed down the column
with a suitable solvent, however, because compound x has a
Oxygenates O-PONA Hydrocarbons in Fuels by greater affinity for the stationary phase than compound o, it
GC (ASTM D 6293) will take a longer time to exit or elute from the column. Sep-
This test method provides for the quantitative determination ciration is thus affected between the two compounds, which
of oxygenates, paraffins, olefins, naphthenes, and aromatics can then be monitored as a function of their elution times by
in low-olefin speirk-ignition engine fuels by multidimensional a suitable detector. This methodology is called absorption
gas chromatography. A fuel sample is injected into a com- chromatography Eind is the most commonly used method for
puter-controlled gas chromatographic system consisting of hydrocarbon emalysis. In certain circumstances, absorption
switching valves, columns, and a n olefin hydrogenation cat- by the stationary phase is so effective that the absorbed com-
alyst, all operating at various temperatures. The eluted hy- ponents of the sample can only be removed by washing with
droccirbons are detected by flame ionization detector. a solvent that has a stronger affinity for the absorbed sample
component than the stationary phase.
Sulfur Determination by GC-Sulfur Detector Two other types of LC columns exist, specifically partition
(ASTM D 5623) columns and exclusion columns. Pcirtition columns work in
This test method covers the determination of volatile sulfur m u c h the same way as GC columns. In peirtition chromatog-
compounds in light petroleum liquids. The sample is ana- raphy, instead of being filled with a solid stationary phase,
lyzed by gas chromatography with an appropriate sulfur se- the LC column contains a liquid, which is coated or chemi-
lective detector. cally bonded onto a solid medium contained within the col-
LIQUID C H R O M A T O G R A P H Y (LC)
TIME
Introduction XOXOI
oxox X X
The technique of liquid chromatography (LC) is closely allied xoxo oxox
oxox xoxo
X X
X X X X X X
with gas chromatography (GC) and other chromatographic oxox xoxo X X XX X X
o 0 X X X X
methods. Just like GC, liquid chromatography separates dif- oxox X X
0 0 oxox X X
X X
ferent molecules or molecular groups based on their physical 0 0 0 0 0 0
X X
|0 O 0 0
and chemical properties. However, unlike gas chromatogra- 0 0 0 0 O 0
phy, LC as the name implies the use of a liquid mobile phase O 0 O 0
0 0
to analyze samples. The field of liquid chromatography is 0 0
very broad ranging and is used in many different areas of an-
aljîcal chemistry. In this section, we will cover just those ar-
eas of liquid chromatography that Eire used in the analysis of
•U 1/ W U \J
FIG. 10—The chromatographic process.
u
umn. Separation is affected by the interaction between the UV absorption of organic molecules as they elute from the
Hquid mobile phase and the liquid stationary phase (often column; refractive index (RI) detectors, which record a
called the partitioning phase), which separates components change in RI as sample molecules elute relative to the solvent
of the sample based on their relative solubilities in the parti- being used; and flame ionization (FID) detectors, which mea-
tioning liquid [19]. This method is often referred to as liquid- sure a change in conductivity through a hydrogen flame as
liquid chromatography. It is less commonly used for hydro- the eluting molecules are ionized in the flame.
carbon analysis, but can be used to separate hydrocarbons of
the same family, which differ only by their substituents [20]. The Use of LC in Hydrocarbon AniJysis
Exclusion column chromatography is another form of Like gas chromatography (GC), LC is used for the analysis of
solid-liquid chromatography, like absorption chromatogra- petroleum fuels and lubricants because of its ability to sepa-
phy. However, instead of separation being affected by the rate complex mixtures based some physical or chemical
rate of absorption (and desorption) by the solid stationary property. Although lower in sensitivity than GC, LC has sev-
phase, exclusion columns are packed with porous materials eral distinct advantages, which make it more widely applica-
with carefully controlled pore sizes. In this case, the rate of ble to hydrocarbon analysis. Some of these advantages in-
elution is controlled by molecular size, and the ability of the clude [21]:
sample molecules to enter the pores of the stationary phase
• Shorter analysis times
material. In general, very small molecules, which are smaller
on average than the pore of the stationary phase material be- • Higher precision for identifying and quantifying compo-
come trapped in the column and take longer to elute, while nents
larger molecules cannot fit inside and thus elute faster than • Analysis in series using the same column
smaller molecules. This method is typically used to separate • Selectivity for certain classes of hydrocarbons
large polymeric additives, such as viscosity index (VI) im- • Ability to measure high molecular weight and high boiling
provers from base oils [21,22]. point compounds
The main application of chromatographic techniques to
Liquid chromatography can be further subdivided into two
hydrocarbon analysis is the separation of different fractions
categories: open column liquid chromatography (OCLC) and
that possess wildly different physical and chemical proper-
high performance liquid chromatography (HPLC). With
ties such as polar compounds, aromatics, and saturates. This
OCLC, the mobile phase (sample and solvent) is forced
is the principle behind ASTM D 2007, which is used to define
through the column either under gravity, or a small head
API base stock categories and engine oil interchangeability
pressure of gas, typically 25 psig or less [19]. Most modem
rules [24].
analytical instruments now use HPLC. Originally standing
for "high-pressure liquid chromatography," HPLC or high In this test method, a dual column apparatus is used con-
performance liquid chromatography uses significantly taining two columns in series. The first column contains clay,
higher pressures than OCLC to force the mobile phase which retains any polar compounds allowing both saturates
through the column, resulting in shorter analysis times. A and aromatics to pass through using n-pentane as a solvent.
schematic illustration of the basic components of an HPLC The second column contains clay and silica gel, which retains
instrument is shown in Fig. 11. A detailed review of HPLC in- aromatics but again allows saturates to pass through. Col-
strumentation can be found in Ref 23. lecting the total effluent through both columns allows the
percentage by mass of saturates to be calculated as a function
Whether an absorption column, partition column or exclu- of total sample mass, because both polar compounds and
sion column is used, or whether gravity (OCLC) or high pres- aromatics are stripped from the sample by the two columns.
sure (HPLC) is used to push the mobile phase through, a de- The clay column is then removed and washed with a toluene
tection system is required to measure the sample fractions as acetone mixture allowing the absorbed polar compounds to
they elute from the column. The most common methods in- elute. The percentage by mass of polar compounds can then
clude UV spectrometers, used to measure the characteristic be calculated as the total polar effluent from the toluene-ace-
tone washed column, again as a function of the total sample
mass. Finally, the silica gel/clay column is rinsed with
toluene, which eJlows the aromatics to elute, again allowing
their percentage by mass to be calculated. The precision of
SOLVENT RESERVOIR determining the saturate and aromatic content using this
method (as per API 1509) is around 2% [25].
5=
• INJECTION POINT
A similar method is used in ASTM D 2549, this time to sep-
arate aromatic and nonaromatic components of high boiling
DETECTOR oils. In this method, a single absorption column containing
activated bauxite and silica gel is used. Initially, n-pentane is
used as a solvent, allowing nonaromatics to pass through the
column. These are then collected and expressed as a percent-
RECORDER age by mass of the initial sample, after evaporation of the n-
pentane solvent. The column is then washed with diethyl
COLUMN-
\J THERMOSTAT
ether, chloroform, and ethyl alcohol which allows the elution
of the aromatics compounds, which are then weighed and ex-
pressed as a percentage by mass of the initial sample mass. A
FIG. 11—An HPLC instrument. number of related techniques have been used to achieve sim-
240
_ A = Start integration of IMAIHs
i B = End integration of IMAHs/Start integration of DAHs

210
1 C = End integration of DAils
180
1
>
E ISO
1
1 3i-Aromatic Hydrocarbons
!& CO c1
c ^ 1
o
j!l20
c o
sQ \
o "°
>• 11
_ ^ I
90 - X X- 1
I \
o to 1
" 13 E 1
E o I
60
8
•^
6 1
1
I
<= £ I
\ C
- i\î M
30 1 1 > 1 1 1 " 1 ' 1 • 1 1 1 1 1 1 1 1 1 I l l
Time (minutes)
FIG. 12—^The use of liquid chromatographic separation to differentiate mono and di-aro-
matics in aviation fuel. Reprinted with permission from ASTM D 6379.
ilar separations, which differ simply by the column material mixture of dyes. The dye mixture is carried along the column
and solvents used [21]. with the petroleum sample, which stcirts to separate because
These simple absorption techniques under atmospheric the saturates have less of an affinity for the silica gel than the
pressure have, to a large part, been superceded by high per- olefins, which in turn have less of an affinity than aromatics.
formance liquid chromatography (HPLC), principally be- The dye mixture contains three different components, one
cause of the much shorter analysis times afforded with HPLC which has an affinity for silica gel, which is greater than that
[21]. However, just like absorption chromatography, HPLC is of the saturates, but less than that of the olefins. This dye
used mainly as a tool for separating samples based on physi- component thus marks the interface between saturate
cal and chemical properties. molecules and olefins as they move through the column be-
Just like absorption chromatography, separation of com- cause the dye's retention time will be between the saturates
plex mixtures into saturates and aromatics is possible with and olefins. A second dye component has an affinity for silica
HPLC, as well as differentiating between similar molecules somewhere between that of olefins and aromatics and thus
such as mono-ciromatics (MAHs) and diaromatics (DAHs). marks the olefin-aromatic boundary, while a third dye com-
This method is used in ASTM D 6379 to determine MAH and ponent falls between aromatics and the isopropyl alcohol
DAH content in petroleum products. In this case, an amino used as the solvent, marking the final boundary. By measur-
bonded stationary phase is used, together with n-heptane, as ing the separation of each dye, the relative proportions of sat-
the solvent to resolve different compounds based on elution urates, olefins, and aromatics can be determined to within
times. An example of a chromatogram of this type is shown 1-2% depending on conditions. This test is described under
in Fig. 12. ASTMD 1319.
Aside from absorption chromatography and the related
technique of HPLC, there are two other LC methods used for
hydrocarbon analysis that are worth mentioning, specificedly Super Critical Fluid Chromatography (SFC)
fluorescent indicator adsorption (FIA) and supercritical fluid Although not strictly a liquid chromatography technique,
chromatography (SFC). SFC shares many of the same basic principles of HPLC. The
principal difference between SFC and HPLC is that the mo-
bile phase containing the sample is neither a liquid, as used
Fluorescent Indicator Adsorption (FIA)
in HPLC, or a gas, as used in gas chromatography, but is a su-
Despite its rather grandiose name, FIA is a relatively simple percritical fluid, most commonly CO2 [23]. A supercritical
technique. First developed in the early 1940s, it is used to de- fluid is one that has been heated above its critical tempera-
termine the relative amounts of ciromatics, olefins, and satu- ture and pressure such that it exists in a new state of matter,
rates in petroleum fractions [18]. The technique involves with properties between that of a gas and a liquid. In partic-
standard OCLC using a silica gel column. However, in addi- ular, supercritical fluids have greater mobility (are less vis-
tion to being packed with silica gel, the column contains a cous) than liquids, but are denser than gases. This property
small portion of the gel towards the top that is doped with a of supercritical fluids has great advantages as the mobile
phase Ccuxier over conventional HPLC or gas chromatogra- umn and eluted using supercritical carbon dioxide mobile
phy (GC). phase. The detector response to hydrocarbons is recorded
For hydrocarbon analysis, SFC has an advantage over GC throughout the analysis time corresponding to the mono-,
for fuel samples because it uses much lower temperatures polynuclear, and nonaromatic components determining the
than GC and is thus less likely to cause thermal decomposi- mass percent content of these groups.
tion. SFC also typically offers high resolution than HPLC,
making it a more accurate test for determining different
moleculcir components in hydrocarbon fuels [26]. ULTRAVIOLET S P E C T R O S C O P Y
ASTM Petroleum Products and Lubricants Introduction

LC Test Standards Ultraviolet (UV) spectroscopy, also known as UV spectrome-
Hydrocarbon Types by Fluorescent Indicator try, was one of the first spectroscopic techniques used to
Adsorption (ASTM D 1319) quantify chemical composition [27]. Like other spectro-
scopic techniques, it is used to identify characteristic molec-
This test method determines hydrocarbon types in the range ulEir fingerprints enabling the quantitative detection of spe-
of 5-99 volume percent aromatics, 0.3-55 volume percent cific molecules or molecular species in complex mixtures. UV
olefins, and 1-95 volume percent saturates in petroleum frac- spectroscopy is most commonly used in hydrocarbon analy-
tions that distill below 315°C. sis as a detection tool after high performance liquid chro-
Hydrocarbon Types Aromatic Hydrocarbon Types in matography (HPLC).
Aviation Fuels and Petroleum Distillates
(ASTM D 6379) Basic Principles of UV Spectroscopy
This test method is intended for use as one of several possible In order to understand UV spectroscopy, we need to first un-
aJtemative instrumental test methods that are used for quan- derstand the electronic structure of molecules. While a de-
titative determination of hydrocarbon t5rpes in fuels. This test tailed quantum mechanical explanation of molecular elec-
method determines mono- and di-aromatic hydrocarbon con- tronic structure is beyond the scope of this book, there are a
tents in aviation kerosenes and petroleum distillates boiling in few simple concepts that will allow us to understand the ba-
the range from 50-300°C, such as Jet A or Jet A-1 fuels. The sic theory behind UV spectroscopy.
sample is diluted 1:1 with a solvent such as heptane, cind a The total energy of a molecule is given by the sum of the
fixed volume of this solution is injected into a high perfor- electronic energy, vibrational energy, and rotational energy,
mance liquid chromatograph fitted with a polar column. with the electronic energy being significantly greater than the
vibrationed energy, which in turn is significcuitly greater than
Aromatics and Polynuclear Aromatics in Diesel and rotationed energy. While rotational energy levels are only of
Aviation Turbine Fuels By SFC (ASTM D 5186) significance in gas phase spectroscopy, the electronic and vi-
The aromatic hydrocarbon content of motor diesel fuels af- brational energy levels will be important in solution phase
fects their cetane number and exhaust emissions. The aro- spectroscopy such as FTIR and UV spectroscopy. An illustra-
matic hydrocarbon and the naphthcdene content of aviation tion of the electronic and vibrational energy levels of a
turbine fuels affects their combustion characteristics and molecule is shown in Fig. 13.
smoke forming tendencies. In the test, a small aliquot of the Under normal conditions, most of the molecules in a sam-
fuel sample is injected onto a packed silica adsorption col- ple will be in the ground (lowest energy) electronic state. By
i k
excited electronic state ^ k i L
i k i k ^
electronic energy levels,

increasing
> measured using UV spectroscopy
energy
J
4 vibrational energy levels,
A measured using FTIR spectroscopy
ground electronic state
A
FIG. 13—^The electronic and vibrational energy levels of a molecule.
passing infrared light through the sample at the exact fre- lamp
quency corresponding to the difference in energy of the vi-
brational levels, transitions within the vibrational levels of
the ground state can be induced, which is the principle be-
hind FTIR spectroscopy. entrance
For the same reason, passing light through the sample at an slit
appropriate frequency corresponding to the separation of the
electronic energy levels can induce a transition between these
levels, resulting in absorption of the light. For some
molecules, the frequency of light required to induce electronic
transitions is in the visible region of the electromagnetic spec- diffraction
trum, however, for most hydrocarbon molecules, the energy grating
that is required is much higher and requires ultraviolet radia-
tion. This is the principle behind UV spectroscopy. photo cell
For hydrocarbon analysis, the most important factor deter- detector
mining the energy separation of the electronic energy levels is FIG. 14—UV spectrometer.
what is often referred to as the molecular chromophore [28].
A chromophore is simply a covalently unsaturated bond or
group of bonds that is responsible for electronic absorption.
In tjrpical hydrocarbon fuels and lubricants, the most com-
mon types of molecules to possess a chromophore will be aro- max
matic molecules, which have characteristic absorption bands
in the 185^00 nm wavelength range [28]. This range of the
electromagnetic spectrum is typically called the near-UV.
Beer's Law
In order to use UV spectrometry as a quantitative tool, we
need to understand the relationship between the concentra-
tion of specific molecules and the amount of light they ab-
sorb. This fundamental property is determined by Beer's
Law:
A = d)c
where A is the absorbance, e is the molar absorptivity, b is the
cell path length containing the sample, through which the UV
light passes, and c is the concentration in mol/L [27]. Because 'max
the molar absorptivities of most molecules of interest have
FIG. 15—Typical UV absorption spectrum.
been measured, and i> is a known quantity based solely on in-
strument design, measuring the amount of light absorbed by
the sample (A in the above equation) allows the concentra-
tion c to be determined simply by rearranging the Beer's law
equation. The Use of UV Spectrometers in the
Analysis of Hydrocarbons
UV Spectrometers UV spectrometers are used both directly and in conjunction

with high performance liquid chromatography (HPLC) in-
A schematic illustration of a UV spectrometer is shown in Fig. struments, principally to detect aromatics because they typi-
14. The main components are a white light source, which is fo- cally have strong UV absorption bands in the near UV region
cused onto the entrance slits of a spectrometer, a cuvette or cell (200-400 nm). The specific maximum absorption wavelength
containing the sample to be analyzed, and a photocell detector and absorptivity is determined by a molecule's electronic
to measure light intensity. The spectrometer is equipped with structure, however, in general it is found that mono-aromat-
a diffraction grating, which acts much like a prism to split the ics (those with a single aromatic ring such as benzene and
white light into discrete wavelengths. Because the angle of toluene) have an absorption maximum around 197 nm, di-
diffraction is defined by the wavelength of light, slowly chang- aromatics have absorption maxima around 230 nm, while
ing the angle of the grating relative to the incoming light allows piclyaromatics absorb around 260 nm [29].
the wavelength of light that exits the spectrometer through the One application of this method, employed by several oil
exit slits to be slowly scanned, allowing an absorption spec- companies, follows the work of Burdett [29, 30]. A typical UV
trum to be recorded, as shown in Fig. 15. The amount of light absorption spectrum of mono-, di-, and tri-aromatics is
absorbed at the maximum excitation wavelength (Amax). will shown in Fig. 16. The method of Burdett employs UV spec-
be dependent on the concentration c, path length b, and molar trometry to record the absorption spectrum in the range
absorptivity Smax as per Beer's Law. 175-270 nm. The molar absorptions is then recorded at the
Molar Absorption trofiuorometry [29]. The principle behind spectrofluorome-

1
|Di 1 try is illustrated in Fig. 17, which shows theoretical absorp-

100,000 1 Mono 1 1
[ Tricycli
tion spectra for two different polyaromatic molecules
1 \
-/^ 1 \ ^
(molecules A and B), together with the corresponding fluo-
/ / N j ™ /^(~" \ 'iTriX/ 1 rescence spectra. Because both molecules are polyaromatic,
1
)1 the absorption spectrum for each will show a meiximum
10,000 —^ ' \ around 260 nm. Recording the absorption spectrum for a
1
^—-^ |Di \' \. Dicyclics mixture of molecule A and molecule B will not allow the rel-
VMono
\ ^ ^— ative concentrations of each to be determined because both
\ ^ absorb simultaneously at 260 nm. However, after excitation
11
1,000 1
1 at 260 nm, both molecules are in an excited electronic state
1
1 Monocyclics
etnd will emit radiation to return to a lower lying electronic
11
1
1
1,,^ state, typically in the form of light. Because molecule A and
1 I
1 / 1 molecule B possess different electronic structures, the en-
1 / 1
100
1
1 t yf
/ 1
1
ergy of the lower lying electronic states will not necessarily
1 \
1 \ /
/ 1
1 be the same. Because the emitted radiation is quantized,
1 \ ^ / 1
1
1
1 measuring the emission (fluorescence) spectrum as opposed
1
1 1 to the absorption spectrum allows the concentration of two
1
10 • • ' I 1
—1 ' k.
molecules to be determined independently of each other.
180 190 200 210 220 230 240 250 260 A(nm) Used in conjunction with LC, spectrofluorometry is an ex-
tremely sensitive technique capable of detecting concentra-
FIG. 16—UV absorption spectrum for monocyclic,
dicyclic and tricyclic aromatic hydrocarbons.
tions of polycyclic aromatics and other species as low as
picograms [32].
three characteristic absorption maxima, 190, 230, and 260

nm corresponding to mono-, di-, and poly-aromatics and can ASTM Petroleum Products and Lubricants UV
be converted to a percent by weight of each type of molecu- Test Standards
lar species using a simple formula based on moleculcir mass,
and the average molar absorptivity of each species at the Naphthalene Hydrocarbons in Aviation Turbine Fuels
three wavelengths. Details of this procedure can be found in by Ultraviolet (UV) Spectrophotometry (ASTM D 1840)
Ref. 29. This test method covers the determination of the total con-
One of the most common applications of UV spectrometry centration of naphthalene, acenapthene, and alkylated
to the analysis of hydrocarbon fuel and lubricants is its use in derivatives of these hydrocarbons in straight-run jet fuels
determining the amount of toxic impurities, particularly containing no more than 5% of such components and having
PAHs (polyaromatic hydrocarbons). The term PAH covers a end points below 600°F. The total concentration of naph-
multitude of different hydrocarbon molecules, with one com- thalenes in jet fuels is measured by absorbance at 285 nm of
mon theme: the presence of multiple aromatic rings. A num- a solution of the fuel at known concentration.
ber of different PAHs, which are known to be present in hy-
drocarbon fuels and lubricants, have been found to be
carcinogenic. For this reason, the EPA and other regulatory MASS SPECTROMETERY
bodies have established limits for PAH concentrations in fu-
els, lubricants, and other media. Because UV spectrometry is Introduction
capable of detecting polyaromatic species such as PAHs in
hydrocarbons by their characteristic absorption at 260 nm, it Mass spectrometry is used to detect the presence of different
is only natural that it has been used in this manor for deter- molecules in bulk samples. The technique involves the gas
mining PAH concentrations and carcinogen content in hy- phase cinalysis of samples that are either already gases, or are
drocarbon oils [31]. liquids or solids that can be vaporized prior to mass spectro-
While UV absorption is incapable of differentiating be- metric analysis. In conventional mass spectrometry, the gas
tween two different molecules that may have absorption phase sample is ionized to form various primary and frag-
bands in the same region (for example, two different PAH mentation ions, which are then analyzed according to their
molecules, both of which will absorb at 260 mm), the use of mass-to-charge ratio. The mass spectrum thus generated can
separation techniques such as liquid chromatography (LC) then be used as a cheiracteristic fingerprint to detect the pres-
or gas chromatography (GC) can be employed to differenti- ence of certain molecules with the relative intensity of the
ate between different molecular species. In this case, the UV mass spectra allowing an estimate of the concentration of the
spectrometer is fixed at a known absorption wavelength (for molecule or molecular species within a bulk sample. The ap-
example, 197 nm for mono-aromatic species), and is used to plication of Mass Spectrometry (MS) to the analysis of hy-
measure different molecular species as they elute from the drocarbon fuels emd lubricants is outlined in this section.
GC or LC column; this provides a more molecule specific
means of detection than flame ionization or thermal detec-
tors tjîcally used with GC and LC instruments. MS Theory
One other technique closely related to UV absorption As previously mentioned, MS works on the principal of sepa-
spectrometry that is used in hydrocarbon analysis is spec- rating primary and fragmentation ions according to their
mass-to-charge (m/z) ratios. Take for example the w a t e r of hydrocarbons typicedly found in petroleum fuels and lu-
molecule H2O. Bombarding water vapor with a high-energy bricants. With many thousands of different components in-
electron source will create both primary ions and fragmenta- cluding paraffins, branched paraffins, naphthenic molecules,
tion ions as follows: and aromatics, the m a s s spectrum of a typical petroleum
fraction is extremely complex. Nevertheless, mass spectrom-
HOH >HOH+ + OH+ + 0+ + H+-F3e~
etry can and has been successfully applied to the analysis of
I • . complex petroleum mixtures as will be discussed later.
primary ion secondary ions
m/z = 18 m/z = 17 m/z = 16 m/z = 1 MS Instrumentation
Recording the mass spectrum of a bulk sample and mea- The basic components of a mass spectrometer are shown in
suring the relative intensities of the m/z = 1, 16, 17, and 18 Fig. 19. The system comprises an inlet source, which is de-
peaks will allow the presence of water to be determined, and signed to introduce the sample in the vapor phase to the spec-
by inference its concentration, provided a suitable calibra- trometer, a n ionization source that serves to ionize the sam-
tion standard has been determined. ple, a mass analyzer which separates the ions by their m/z
The biggest drawback with MS is that the complexity of the ratio, and an ion detector for detecting the ions once they
m a s s s p e c t r u m increases exponentially with increasing have been mass selected. The inlet system for most basic
molecular size (molecular mass). Take for example benzene, mass spectrometers is called a batch inlet and comprises a
a relatively simple hydrocarbon. The electron ionization means of injecting a gas, or more commonly a liquid sample
mass spectrum of benzene (Fig. 18) has 17 different peaks under reduced pressure and elevated temperatures such that
corresponding to m/z values ranging from 27-79, which in- the sample can be vaporized for presentation to the spec-
clude primary and fragmentation ion mass peaks, as well as trometer [34]. In m o d e m instruments, the liquid is com-
peaks associated with the naturally occurring isotope '^C monly injected into the vacuum chamber using a hypodermic
[35]. Now consider applying mass spectrometry to a mixture syringe arrangement called a probe [35].
-*• energy
UV absorption (A&B)
Amaxs260nm
absorption
molecule A
emission
emission spectrum (A)
absorption
molecule B
emission
emission spectrum (B)
FiG. 17—Tlieoretical fluorescence emission spectrum of two different poiyaromatic

moiecuies, A and B.
<n
1) 60-
U 40
a:
20
1111 111 111 1111111 1111111 11 M 111 111 111 11 "i""|i il'i""i"'lMl'h
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
m/z
FIG. 18—Mass spectrum of benzene.
Sample Ionization Ion The usual way in which GC-MS is used for the analysis of
Inlet Source Mass Analyzer —• petroleum products is to fix the mass spectrometer to detect
Detector
one specific ion peak, for example m/z = 78, corresponding
to the primary ion peak for benzene. The ion intensity at
FIG. 19—Basic components of a mass spectrometer. this fixed m/z ratio is then measured for different retention
time in the GC. The retention time is simply the time taken
for a specific molecular component of a complex mixture to
Once in the gas phase, the sample is drawn into the ioniza- emerge or elute from the GC column, which in turn is re-
tion section of the instrument where it is intersected at right lated to the physical and chemical properties of the
angles by a high-energy electron beam created by a hot fila- molecule. By separating the signal in the m/z = 78 into dif-
ment. This is called an electron ionization mass spectrome- ferent elution times, the true signal due to benzene can be
ter. The electron beam ionizes the sample into primary and differentiated from other fragmentation ions from different
fragmentation ions, which are accelerated into the mass an- molecular species that may have an m/z ratio of 78, but
alyzer section using an electrostatic field formed by a series have different retention times in the GC column. This
of electrodes, which serve to focus and accelerate the ions makes the difficult task of interpreting the MS data signifi-
into the mass analyzer. cantly less complicated.
There are many different types of commercial mass spec-
trometers available. They all differ slightly in their design,
The Application of MS t o Hydrocarbon Analysis
but all use one of three basic methods to mass analyze the
ionized sample, namely magnetic field deflection, Mass spectrometry is an important tool in the analysis of
quadrupole mass spectrometry, or time-of-flight [35]. A de- petroleum products because it can give information that can-
tailed explanation of these different types of mass analyzers not be obtained by other means. Just like other spectromet-
is beyond the scope of this chapter, but an excellent descrip- ric techniques, it gives important information on the chemi-
tion of these different methods can be found in Ref. 35. No cal composition of complex mixtures of hydrocarbons
matter what type of mass analyzer is used, they all separate commonly found in fuels and lubricants, particularly when
ions according to their m/z ratio, with the ion signal being de- coupled with other techniques such as gas chromatography.
tected, amplified, and recorded as a function of their mass- The most common application of mass spectrometry to hy-
to-charge (m/z) ratio. drocarbon analysis is in determining the composition of dif-
ferent process stream and boiling fractions during the refin-
ing process. There are a number of ASTM test procedures that
Gas Chromatography-Mass Spectrometry (GC-MS)
cover the use of MS in this area, which are listed in Table 3.
One adaptation, which has served to simplify the interpreta- In each case, chemical composition is determined by cal-
tion of MS data, is to use a standard Gas Chromatograph (GC) culating mass groupings, which correspond to the summa-
as the sample inlet source for the mass spectrometer. As ex- tion of characteristic mass peaks for different classes of
plained earlier in this chapter, a gas chromatograph is an in- molecules that are likely to be present.
strument that separates complex mixtures of chemicals into The m/z peaks that are used to calculate the different mass
single molecular components, or groups of components with groupings in the ASTM procedures listed in Table 3 are sim-
similar physical properties. By combining MS with GC, the ply based on the known primary and fragmentation ions pat-
analysis of complex mixtures of chemicals such as hydrocar- terns using mass spectrometry for different molecules under
bon fuels and lubricants has become greatly simplified. controlled laboratory conditions. For example, in ASTM D
TABLE 3—ASTM test procedures that use mass spectrometry for a function of elution time. This can either be done directly by
determining the composition of different fractions. recording the signal in a fixed mass channel, or by scanning
ASTM Test Procedure Significance the spectrometer across cJl mass ranges and reconstructing
D 2425 Saturates and aromatics in middle distillates the signal in a single mass channel using softweire. The latter
D 2786 Saturates in gas oil fractions is the method used u n d e r ASTM D 5769. In this method, sep-
D 2789 Hydrocarbon types in low olefinic gasoline aration of molecular species according to their characteristic
D 3239 Aromatics in gas oil fractions p r i m a r y a n d fragmentation ions allows a more complete
analysis to be performed. This is illustrated in Fig. 20. In this
case, by combining the selectivity of GC in separating differ-
ent molecular species with the mass specificity of MS, the dif-
2786 that is based on the Hood and O'Neal method, the mass
ferent molecular concentrations of specific molecules such
grouping E71 is defined as the sum of peaks at m/z = 71,85,
as benzene, toluene and other aromatics can be determined.
99, and 113 and is used to determine alkane content [37,38].
Without this mass selectivity, the gas chromatogram would
The difference in masses between each peak in the summa-
be extremely complex, with no guarantee that the elution
tion is simply the extension of the aJkane chain by one CH2
peak corresponds to a specific molecule such as benzene or
unit, with a corresponding increase in molecular mass of 14
toluene.
atomic mass units. The biggest drawback with this method,
and indeed MS in general, for the analysis of hydrocarbons is Although limited by its ability to resolve information from
that the n u m b e r of mass peaks that must be considered in- complex mixtures of chemicals typically found in petroleum
creases significantly with molecular size. To illustrate this products, mass spectrometer, particularly when combined
complexity, consider the complete list of mass groupings, with other separation techniques such as LC and GC is an im-
which must be considered under ASTM D 2786, and the cor- portant tool in the analysis of hydrocarbons.
responding molecular types they represent;
S71 = 71 + 85 + 99 -F 113 alkanes ASTM Petroleum Products and Lubricants M S

Test Standards Under Subcommittee D02.04
1 6 9 = 69 -I- 83 + 97 + 111 -F 125 + 139 1 ring naphthenes
E109 = 109 -I- 123 + 137 -I- 151 + 165 Hydrocarbon Types in Gasoline by Mass Spectrometry
-I- 179 -I- 193 2 ring naphthenes (ASTM D 2789)
X149 = 149 + 163 + 177 + 191 -I- 205 This test method covers the determination by mass spec-
t r o m e t r y of total paraffins, monocycloparaffins, dicy-
+ 219-I-233-(-249 3 ring naphthenes
cloparaffins, alkylbenzenes, indans, or tetralins or both, and
S189 = 189 + 203 + 217 + 231 + 245 n a p h t h a l e n e s in gasoline. Samples are analyzed by m a s s
+ 259 + 273 + 287 + 301 4 ring naphthenes spectrometry, based o n the s u m m a t i o n of characteristic
X229 = 229 + 243 + 257 + 271 -I- 285 mass fragments, to determine the concentration of the hy-
drocarbon types.
+ 299 + 313 + 111 + 341 + 355 5 ring naphthenes
1269 = 269 + 283 4- 297 -F 311 + 325 Aromatics in Gasoline by Gas Chromatography-Mass
-I- 339 + 353 -1-367-1-381 6 ring naphthenes Spectrometry (GC-MS) (ASTM D 5769)
-F 395 + 409 This test method can be used for gasolines that contain oxy-
S91 = 91 -F- 105 + 117 -I- 119 + 129 genates such as alcohols and ethers as additives. They do not
interfere with the analysis of benzene and other aromatics by
+ 131 4- 133 -I- 143 + 145 -I- 147 Mono-aromatics
this test method. The sample is injected either through the
+ 159-1- 171 capillary splitter port or a cool-on-column injector into a gas
Because of this, it is not surprising given the complex nature c h r o m a t o g r a p h equipped with a dimethylpolysiloxane
of different hydrocarbon fractions, each of which may con- WCOT column interfaced to a fast scanning mass spectrom-
tain several thousand different types of molecules, that the eter. The mass analyzer processes the signal at specific m/z
precision of using MS in this mode for different samples values corresponding to the principal ion masses for various
types is at best 10% [36]. components allowing benzene, toluene, and total aromatic
To circumvent these difficulties, MS is often used in con- content to be measured in gasolines.
junction with other techniques such as gas chromatography
(GC) or liquid c h r o m a t o g r a p h y (LC). In this case, chro-
m a t o g r a p h y is used to reduce the n u m b e r of different INFRARED SPECTROSCOPY
molecule types that enter the mass spectrometer, reducing
the n u m b e r of mass peaks observed, and hence the complex- Infrared spectroscopy is a widely applied, nondestructive test
ity of interpreting the data accurately. In fact, separation of method for assessing a variety of molecular physical qualities
the sample into aromatic and nonsiromatic fractions using of a lubricant or fuel sample. The spectrum analyzed by the
liquid chromatography (ASTM D 2549) prior to MS analysis method is considered a distinct physical property of the sam-
is a prerequisite for ASTM D 2425 [39]. ple and, as such, is unique from other physical and chemical
One way in which MS Ccin be combined with GC is in fact properties, such as viscosity, specific gravity, flash point, etc.
not to record a complete mass spectrum of the sample, but From the spectrum, in most cases, a positive identification of
rather to fix the mass (or more strictly the m/z ratio) of the the sample and its greater molecular constituents can be ob-
spectrometer to a known ion peak, and monitor this mass as tained [40].
Most p e t r o l e u m products, a n d more specifically, lubri- groups, which make u p part of a molecule's structure, give
Ccints, fuels, additives, and contaminants are mixtures, which rise to absorption at specific infrared frequencies but more
results in the spectrum being a composite of m a n y different typically spectral b a n d s comprising a broader range of wave-
spectral components that are additive. Nevertheless, for most lengths. These cire commonly referred to as group frequen-
fluids, the spectrum is sufficiently characteristic to enable cies. For example, a well-defined group frequency is associ-
the identification of the unique spectred features of individual ated with C = 0 at around 1700 wavenumbers (cm~').
components. Still, in certain cases, a physical or chemical
separation of the tcirget components from the rest of the sam-
ple, such as gas chromatography, m a y be desirable to im- Wavelength, Wavenumber and Frequency
prove detection limits and resolving power of the technique. The frequency or energy at which unique infrared absorp-
The infreired spectrum of a substance is produced when a tions occur is usually expressed as wavelength in microme-
portion of a beam of infrared energy passing through a fixed ters (fjim) or wavenumbers in reciprocal centimeters (cm~').
path length of the sample is absorbed by a specific functional Studies have shown that a tjrpical organic molecule requires
group within a specific molecule present in the sample. This an average energy of 1.6 X lO"'^" joules (J) for vibrational ex-
absorption has unique wavelength dependencies relating to citation, which corresponds to 12 fji,m of infrared radiation.
the sample's molecules. Most molecules are in constant The reciprocal of the wavelength is referred to as wavenum-
modes of rotation, stretching, and bending at unique and of- bers and represents the n u m b e r of cycles passing a fixed
ten multiple frequencies. In addition, these vibrational fre- point per unit of time. The scale in Fig. 21 shows the conver-
quencies will vary as the bonded atoms, functional groups, sion of wavelength to w a v e n u m b e r s [42]. The use of
a n d bond strengths are changed. These differences in ab- wavenumbers (cm~^) in infrared spectroscopy is preferred to
sorption at certain wavelengths in the mid-infr£ired spectrum a scale of wavelengths (jj-m) because wavenumbers Eire linear
collectively describe the quality and quantity of molecular a n d proportional to the energy a n d frequency being ab-
makeup of the sample [41]. sorbed. Wavenumbers are sometimes incorrectly referred to
Infrared spectroscopy is especially well suited for the anal- as frequencies, a n error because the w a v e n u m b e r is ex-
ysis of organic c o m p o u n d s comprised of characteristic pressed in reciprocal centimeters (cm~^) and frequency is ex-
molecular structures. The various groups, called functional pressed in units of reciprocal time (s~') [42].
Abundance.,
80000: ION 128
70000.
60000.
SCOOO.
NAPHTHALENE
40000:
30000'
20000-
10000
^
0
Time » 18 00
Abundance
18.50 I19.00 19.50 20.00 20.50 21.00 21.50 22.00
50000 ION 142

4S000
2-METHYmAPHTHALENE
40000
39000:
1-METHYL-NAPHTHALENE,
30000
2SOO0' ""-*
20000
15000-
10000-
5000;
0^ ,
Time -• 18 00 18.50 19.00 19.50 20.00 20.50 21.00 21.50 22.00
MINUTES
FIG. 20—^Typical mass selected gas chromatogram showing the abil-

ity of GC-MS to separate molecular species by their elution time and
characteristic ion mass peak. Reprinted with permission from ASTIVI D
5769-98.
Wavenumber Wavelength The reference and sample beams are then passed ahema-
4000- - 2 . 5 - 1
tively by a rotating half mirror to a dispersive device, which
separates the radiation into specific frequencies (wave-
3500- lengths). A prism is one type of dispersive device that sepa-
-3 Functional rates radiation in different wavelengths based on differences
3000-
; •
group in refractive indexes at different wavelengths. Since glass will
absorb infrared radiation sodium chloride, other materials
2500- ^ 4 region cire required. Alternatively, a grating can be used as a disper-
2000- ^ 5 sive device using a series of closely spaced parallel grooves
1800^ etched into a flat surface. The grating simply reflects the
-1 : L-e /Am diffracted light from its surface and absorbs very little radia-
cm 1600 — L (micrometei) tion. Many infrared spectrometers require special tempera-
1400- f-7 ture cind/or desiccants to prevent moisture damage to the op-
|-8 tics in the monochromator [42].
1200-
^9
Fingerprint
The monochromator directs the radiation reflecting
1 0 0 0 - |-10 region from the grating through a series of narrow slits, which lu-
8 0 0 - |-12
tl5 — minate onto a detector, for example, a thermocouple. This
elength goo —
conversion scale for
efor P-20 quantifies the intensity of the energy at only the desired
infrared data.
1. 400 - F 3 0 band of frequencies. Many dispersive-type infrared spec-
2 0 0 - ^50 trometers are of the double-beam optical null type. In such
Frequency •Wavele ngth cases, the radiation passing through the reference beam is
reduced or attenuated to match the intensity of the sample
FIG. 21—Conversion scale for infrared data. beam [42].
Beer-Lambert Law Fourier Transform Infrared Spectroscopy

A good place to begin the discussion of using infrared spec- Compared to the dispersive spectrometer, the Fourier trans-
troscopy for quantitative analysis of fuels and lubricants is form spectrometer provides improved speed and range of
the Beer-Lambert Law. It relates the amount of infrared light spectral sensitivity in making infrared measurements. The
absorbed by a given sample to the concentration of the target Michelson interferometer is a basic component of the
compound and path length. More to the point, the law states Fourier transform instrument. Unlike the dispersive spec-
that concentration is directly proportional to absorbance at a trometer, the interferometer has no slits or grating. Instead,
given wavelength and path length at a specified temperature it consists of two mirrors and a beam splitter. The beam
and pressure. splitter transmits half of all the incident radiation from a
source to a moving mirror and reflects half to a stationary
A = abc = logio I°/I (1)
mirror. Each component reflected by the two mirrors re-
A = absorbance turns to the beam splitter where the amplitudes of the
/ = IR power-reaching detector with sample in beam waves eire combined to form an inteferogram, which is
7° IR power-reaching detector with no sample in beam Fourier-trEinsformed into the frequency spectrum. The in-
a = absorption coefficient of pure component of interest at terferometer scans the infrared spectrum in just fractions of
anal54ical wavelength; the units depend on those chosen a second at moderate resolution. The resolution is uniform
for b and c across the optical range. Multiple scans can be co-added to
b = sample path length reduce background noise [42].
c = concentration of sample component
This linearity permits simple calibration plots of known Analysis of Midticomponent Solutions
samples between absorbance (A) and concentration (C) for
analyzing the concentration in unknown samples. In addi- For solutions, samples should be diluted and placed in cells
tion, the Law is helpful in choosing the optimum sample path of appropriate path length (typically 0.2-1.0 mm). It is pre-
length for accurate eincJysis, as will be further discussed [43]. ferred to use lower concentrations in longer path length cell
rather than higher concentrations in shorter path length cell.
The desired absorbance is in the reinge of 0.3-0.8. Lower con-
Dispersive-Type Infrared Spectrometers centrations will minimize nonlinear effects due to dispersion
In this design, zin infrared source of energy is usually pro- (that is, change of refractive index with wavenumber). Where
vided by a Nemst glower, which is composed of rare earth ox- freedom from intermolecular effects is uncertcdn or where in-
ides (zirconium, cerium, etc.) formed into a cylinder. On termolecular effects are known to be present, calibration
electrically heating to approximately 1500°C, this filament must be based on measurements taken from S5rnthetic mix-
material produces the needed infrared radiation. The beam tures of all components. The procedure is described in ASTM
of radiation is split into a reference and sample beam by mir- E 168 [44].
rors. The reference beam is passed through air or a beam at- Calibration is achieved by dissolving a known weight of a
tenuator and the sample beam is passed through the sample pure component in a suitable infrared solvent. Next, the ab-
where selective radiation absorption occurs [42]. sprbcmce is measured at all analjîceJ wavenumbers and cor-
rected for baselines as further discussed. The procedure is re- curacy than is possible on superimposed bands. The general
peated for a range of concentrations covering the expected procedure involves the removal of spectral contributions of
concentrations. From this, absorbance is plotted against con- specific and known components from a spectrum containing
centration. Analytical curves can also be constructed for each multiple components in order to assess the unique spectral
of the wavenumbers or bands where the target component is characteristics of the remaining target component [44].
represented. So too, the procedure is repeated for each of the
components to be analyzed in the solution [44].
Band Area Methods
Band shape changes can cause peak-height data to be non-
Analysis of Gases linear. Band area, however, may remain essentially unaf-
For gases, all calibration measurements for a given analysis fected by the changes in shape of the band because band area
must be made at a fixed total pressure. This pressure must be is a function of the total number of absorbing centers in the
equal to the total pressure employed in the analysis. Low sample. If the shape change is caused by changes in inter-
molecular weight gases frequently produce very strong, sharp molecular forces, even band area may be linear [44].
absorption features. Addition of a diluent gas and use of pres- Band area is calculated by integrating across bandwidth.
sure below atmospheric may be necessary. Absorbances cire Band area is advantageous when band shape undergoes
measured for each of the standard wavenumbers selected for change as a function of increasing concentration. Frequently,
analysis. Where possible, integrated absorbances are pre- band area is found to be more accurate than peak-height
ferred to offset the effect of small pressure vetriations. The ab- measurements because one is, in effect, averaging multipoint
sorbances Eire plotted against the partial pressures (or mole data. When integrated area is used for quantitative analyses,
fractions) to produce analytical curves [44]. the reliability of the results frequently depends on the base-
line treatment selected. The accuracy by band area is often
improved by limiting the range of absorbances. The wings
Achieving Reproducible Baselines contribute very little signal while contributing substantial
uncertainties to the totEil Eirea. A useful guideline is to limit
Any quantitative method depends on the choice of a repro- the integration limits to absorbance values, which are no
ducible baseline. The correction of raw data for baseline ab- smaller than 20-30% of the peak absorbance [44].
sorbance is important in some methods. The guiding factor
in baseline selection is the reproducibility of the results.
Methods used for drawing baselines with computerized in-
struments are similar in most ways to those for data recorded Hydrocarbon Analysis
on chart paper [44]. Hydrocarbon analysis using infrared spectroscopy must be-
A technique known as the cell-in-cell-out method is often gin at the parent backbone structure. The simple aliphatic hy-
used in single-beam infrared work. In this method, a blank drocarbon is the root of most Ediphatic compounds and con-
(that is, solvent in cell, potassium bromide (KBr) pellet, or sists of simple linear chains, branched chains, and cyclic
other substrate) is measured at a fixed wavenumber and then structures. Aliphatic compounds can consist of one or more
the analyte readings are recorded. One variation involves the of these structures. The infrared spectrum is useful in provid-
subtraction of the absorbance minimum from the absorbance ing specific information on the existence of most of these
maximum at the chosen baseline point. The point of mini- structures, by inference or directly. The spectrEd contributions
mum absorbance is adjacent to or at least near the band un- are characterized by C—H and C—C stretching and bending
der evaluation. Alternatively, two points may be needed if the vibrations, which are generally unique for each molecule. For
band of interest is superimposed on a sloping background. In aromatic compounds, ring C=C-—C stretching and bending
such case, a line is drawn from one side to the other and ab- vibrations are distinctly characteristic as are carbon-carbon
sorbance is calculated as the value at the peak maximum mi- multiple bonding in alkene and alkjrne structures [45].
nus the baseline absorbance minimum. An inappropriate In terms of recognizing a compound as having an organic
choice of baseline in this situation may have deleterious ef- structure with aliphatic constituents, the C—H stretch vibra-
fects on the accuracy of the final calculation [44]. tions for methyl and methylene are the most characteristic.
The baseline correction described above should be per- In Fig. 22, methylene/methyl bands can be seen at 1470 and
formed only if the spectrum is plotted in absorbance units. 720 cm"^ An important methylene rocking vibration occurs
When the spectrum is plotted in transmittance, the two-base- at 725-720 cm~'. As C—H stretching absorptions all occur
line transmittances and the transmittance at the analytical below 3000 cm"', bands between 3150 and 3000 cm~' and
wavenumber Eire converted to absorbance. Conversion to ab- are almost always associated with unsaturation, for example,
sorbance is required because a sloping linear baseline in C=C—H and/or aromatic rings. Figure 23 shows examples of
transmittance becomes curved in absorbance [44]. either single or pair absorbancies of unsaturated hydrocar-
bons featuring C=C with attached hydrocarbons. The num-
ber of bands and their associated positions point to the dou-
Employing the Difference Method ble bond location Emd spacing around the double bond [45].
Spectral subtraction using a computer is a common practice One or more aromatic rings can tjîcally be recognized by
in qualitative infrared analysis. This technique is also used to the C=C—C and C—-H ring-related vibrations/bending. Typi-
perform quantitative infrared analyses. The advantage of cally, the C—H stretching occurs about 3000 cm~\ revealing
spectral subtraction (the difference method) is that small a number of weak-moderate bands compared with the
concentration differences can be measured with greater ac- aliphatic C—H stretch. The number and locations of the C—H
tinctive spectral contribution. T5T3ically, a unique group fre-

Saturated Aliphatic (ajlcane/allcyl) Group Frequencies quency associated with halogen-carbon stretching is as-
Functional group/assignment
signed to the C—^X bond (Fig. 24). If more than one halogen
Group frequency (cm')
is present, the identification of the group frequency is some-
Methyl (-CHj> what more complex. It is largely influenced by whether the
2970-2950/2880-2860 Methyl C-H asym./sym. stretch halogens are on the same or different CcU"bon atoms, and if
1470-1430/1380-1370 Methyl C-H asym./sym. bend different, their relative proximity is important.
1385-1380/1370-1365 gem-Dimethyl or "iso" - (doublet)
1395-1385/1365 Trimethyl or "tert-butyl" (mlltiplet)
Relating to alcohols and hydroxy c o m p o u n d s , the 0—H
Methylene (>CH2) stretch is probably one of the most pronounced and charac-
2935-2915/2865-2845 Methylene C-H asym./gym. stretch teristic of all the infrared group frequencies. There is typi-
1485-1445 Methylene C-H bend Ccdly a high degree of association coming from hydrogen
750-720 Methylene - (CH2)-rocklng bonding with other hydroxy groups. And, in cases, these may
(n>3) come from hydroxy groups from within the same molecule
1055-1000/1005-925 Cyclohexane ring vibrations (intramolecular bonding). Alternatively, they may associate
Methyne (>CH-) with nearby molecules (intermolecular bonding). Collec-
2900-2880 Methyne C-H stretch
tively, the effects of hydrogen bonding result in the produc-
1350-1330 Methyne C-H bend
1300-700 Skeletal C-C vibrations tion of a well-defined but broad band cuid the lowering of
Special methyl (-CHj) frequencies mean absorption frequency. This is exhibited in compounds
2850-2815 Methoxy methyl ether O-CH3 such as carboxylic acids, which produce strong hydrogen
C-H stretch bonding. See Fig. 25 for alcohol a n d hydroxy c o m p o u n d
2820-2780 Methylamino, N-CH3, C-H stretch group frequencies [45].
Because alcohols exist as three distinct classes, primary,
FIG. 22—Saturated aliphatic (alkane/alkyl) group frequen- secondcury, and tertiary, they are identified by the extent of
cies. Courtesy Coates Consulting. carbon substitution on the central hydroxy-substituted car-
bon. The infrared characterization of these alcohols is re-
flected in the position of the OH stretch absorption but also
Olefinic (alkene) Group Frequencies by other absorptions including the C—O— stretching fre-
quency. These can be observed in the primary and secondary
Origin Group frequency Assignment
alcohols shown in the spectra shown in Fig. 26. Ethers are
wavenumber (cm')
somewhat related to edcohol and hydroxy compounds where
0=0 1680-1620 Alkenyl 0 = 0 stretch the hydrogen of the hydroxy group is substituted by an aro-
1625 Aryl-substituted C=C matic (aryl) or aliphatic (alkyl) molecular fragment. Other-
1600 Conjugated 0 = 0 wise, the overall appearance of an ether spectrum is sharply
C-H 3095-3075 Tenninal (vinyl) C-H stretch
different from any associated alcohol due to the impact of the
+3040-3010
3095-3075 Pendant (vinylldene) C-H hydrogen bonding on the hydroxy group [45].
stretch In amines, the terms primary, secondary, and tertisiry are
3040-3010 Medial, cis- or frans-C-H used to describe the substituted nitrogen as opposed to car-
stretch bon as with alcohols. As with alcohols, these structural dif-
0-H 1420-1410 Vinyl C-H in-plane bend ferences are significant and distinctly influence the infrared
1310-1290 Vinylidene C-H in plane
bend
C-H 995-985+915-890 Vinyl C-H out-of-plane bend
895-885 Vinylidene 0-H out-of-plane
bend
C-H 970-960 trans 0-H out-of-plane bend
Aliphatic Organohalogen Compound Group Frequencies
700 (broad) cis C-H out-of-plane bend
wavenumber (cm"')
FIG. 23—Olefinic (alkene) group frequencies. Courtesy
Coates Consulting. C-F 1150-1000 Aliphatic fluoro compounds,
C-F stretch
C-CI 800-700 Aliphatic chtoro compounds,
C-CI stretch
C-Br 700-600 Aliphatic bromo compounds,
bonds around the aromatic ring is defined by the structure of C-Br stretch
the bands in the spectrum. Other important bcuids for aro- 0-1 600-500 Aliphatic iodo compounds,
matic ring vibrations are positioned around 1600 and 1500 C-l stretch
c m ~ \ which are exhibited as pairs with some splitting. The Note that the ranges quoted serve as a guide only; the
nature and structure of these two bands are largely influenced actual ranges are influenced by carbon chain length, the
by the position and nature of substituents on the ring [45]. actual number of halogen substituents, and the molecular
On the surface, the interpretation of halogenated com- conformations present.
p o u n d s contained in infrared spectra is functionally very
simple. While not always true, the polar nature of the group FIG. 24—Aliphatic organohalogen compound group frequen-
consisting of a single atom linked to carbon produces a dis- cies. Courtesy Coates Consulting.
Alcohol and Hydroxy Compound Group Frequencies

wavenumber (cm-1)
0-H 3570-3200 (broad) Hydroxy group, H-bonded OH stretcti
3400-3200 Normal "polymeric" OH stretch
3550-3450 Dimeric OH stretch
3570-3600 Internally bonded OH stretch
0-H 3645-3630 Nonbonded hydroxy group, OH stretch
3635-3620 Primary alcohol, OH stretch
3620-3540 Secondary alcohol, OH stretch
3640-3530' Tertiary alcohol, OH stretch
0-H 1350-1260 Phenols, OH stretch
1410-1310 Primary or secondary, OH in-plane bend
720-590 Phenol or tertiary alcohol, OH bend
C-0 -1050' Alcohol, OH out-of-piane bend
-1100° Primary alcohol, C-0 stretch
-1150' Secondary alcohol, C-0 stretch
-1200' Tertiary alcohol, C-0 stretch
Phenol, C-0 stretch
'Frequency influenced by nature and position of other ring substituents.

"Approximate center of range for tlie group frequency.
Courtesy Coates Consulting.
FIG. 25—Alcohol and hydroxy compound group frequencies. Cour-

tesy Coates Consulting.
spectra. It is possible to readily describe functional group

structures, especially for the primary and secondary amino
compounds. Although somewhat weaker than hydroxy com-
pounds, the hydrogen bonds play an important role in the se-
lective identification of the various amino compounds. In the
case of ammonium and amino salts, strong hydrogen bond-
ing is observed. Primary and secondary amines are largely
characterized by the N—H bond group frequencies. The ter-
tiary amines, like esters, produce vibrations associated with
the C—^N bond, see Fig. 27 for group frequencies for Amino
Compounds [45].
I I I I I I I I I I I I I The carbonyl group, C = 0 absorption, is often the most
o o o o o o o o o
characteristic and intense of the entire infrared spectrum.
Common group frequencies for carbonyl compounds can be
Wavenumber (cm') seen in Figure 28. With the exception of the aldehyde, all
other carbonyl compounds can be generedly considered to be
100 derived from the base structure of ketone. This occurs as one
or both alky (or aryl) substituents are replaced by a single hy-
droxy group (carboxylic acids) or two ether groups (organic
Cctrbonate). Commonly, the group frequencies for the various
classes of carbonyl compounds overlap and the carbonyl
band alone is insufficient to identify the specific functional
group. Common examples include carboxylic acids where
C—O, C—O—H, and O—H vibrations are characteristic, as
are esters CÔ—C and amides, C—N and N—H. So too, a
o e o
characteristic broad feature in the range 3300-2500 cm"'
<o M eo . that overlaps the C—H stretching region is observed for hy-
<o n CM M
drogen-bonded O—H in most carboxylic acids [45].
Wavenumber (cm'')
ATR spectra of (a) primary (1-octanol) and (b) secondary

(2-octanol) alcohols. Courtesy poates Consulting.
Characterization of Inorganics
Infrared spectroscopy can be used very effectively to charac-
FIG. 26—ATR spectra of (a) primary (1-octanol) and (b) sec- terize inorganic molecular species that often co-occupy space
ondary (2-octanol) alcohols. Courtesy Coates Consulting. with various hydrocarbon compounds found in fuels and lu-
bricating oils. Essentially any compound that forms covalent

Amine and Amino Compound Group Frequencies bonds within a molecular ion fragment will produce a char-
Origin Group frequency Assignment acteristic absorption spectrum with unique group frequen-
wavenumber (cm"^) cies. The metal complexes and chemical fragments associ-
ated with heteroxy groups such as nitrates, sulfates,
Primary amino phosphates, silicates, etc. and transition metal carbonyl com-
N-H 3400-3380 Aliphatic primary amine, pounds have already been generally discussed as related to
+3345-3325 NH stretch the salts of carboxyllc acids, amino, and ammonium com-
N-H 3510-3460 Aromatic primary amine, pounds [45].
+3415-3380 NH stretch
N-H 1650-1590 Primary amine, NH bend
C-N 1090-1020 Primary amine, CN stretch
Secondary amino ASTM Petroleum Products and Lubricants IR Test
>N-H 3360-3310 Aliphatic secondary amine, Standards w i d e r Subcommittee D02.04
NH stretch
>N-H -3450 Aromatic secondary amine, Aromatics in Finished Gasoline by GC-FTIR:
NH stretch ASTM D 5986
>N-H 3490-3430 Heterocyclic amine,
NH stretch
This method can be used for determining aromatic content in
=N-H 3350-3320 Imino compounds, gasolines that contain oxygenates such as alcohols emd ethers
NH stretch as additives. It can be used for both, and does not interfere
>N-H 1650-1550 Secondary amino, NH bend with benzene and other aromatics by this method. The sam-
C-N 1190-1130 Secondary amine, ple is injected through a cool on-column injector into a gas
CN stretch
Tertiary amino
chromatograph equipped with a methylsilicone WCOT col-
C-N 1210-1150 Tertiary amine, CN stretch umn interfaced to a FT-IR instrument.
Aromatic amino
C-N 1340-1250 Aromatic primary amine, Benzene/Toluene in Gasoline by Infrared (Ir)
CN stretch Spectroscopy: ASTM D 4053
C-N 1350-1280 Aromatic secondary amine,
CN stretch A gasoline sample is examined by infrared spectroscopy and
C-N 1360-1310 Aromatic tertiary amine, following a correction for interference is compared with cal-
CN stretch ibration blends of known benzene concentration.
Benzene/Toluene in Engine Fuels using Mid-IR

FIG. 27—Amine and amino compound group frequencies.
Courtesy Coates Consulting. Spectroscopy: ASTM D 6277
A beam of infrared light is imaged through a liquid sample
cell onto a detector, and the detector response is determined.
Wavelengths of the spectrum that correlate highly with ben-
zene or interferences are selected for analysis using selective
bandpass filters or mathematically by selecting areas of the
Example Carbonyl Compound Group Frequencies whole spectrum.
Group frequency (cm-1) Functional group Methyl Tert-Butyl Ether in Gasoline by Infrared
Spectroscopy: ASTM D 5845
1610-1550/1420-1300 Carboxylate (carboxyllc acid salt) This infrared method measures MTBE and other oxygenates
1680-1630 Amide in the concentration ranges from about 0.1 to about 20 mass
1690-1675/(1650-1600)' Quinone or conjugated ketone percent. A sample of gasoline is analyzed by infrared spec-
1725-1700 Carboxyllc add
1725-1705 Ketone troscopy.
1740-1725/(2800-2700)' Aldehydle
1750-1725 Ester
1735 SIx-membered ring lactone ASTM STANDARDS
1760-1740 Alkyl carbonate
1815-1770 Add (acyl) hallde No. Title
1820-1775 Aryl carbonate
1850-1800/1790-1740 Open-chain add anhydride D 1319 Hydrocarbon Types by Fluorescent Indicator Ad-
1870-1820/1800-1775 Five-membered ring anhydride sorption
2100-1800 Transition metal carbonyls D 1840 Naphthalene Hydrocarbons in Aviation Turbine Fu-
els by Ultraviolet (UV) Spectrophotometry
' Lower frequency band is from the conjugated double bond.
D 2427 Hydrocarbon Types in Gasoline by Gas Chromatog-
"Higher frequency band characteristic of aldehydes.
associated with the termlhal aldehydic C-H stretch.
raphy
D 2789 Hydrocarbon Types in Gasoline by Mass Spectrom-
etry
FIG. 28—Carbonyl compound group frequencies. Courtesy
Coates Consulting. D 2887 Boiling Range Distribution of Petroleum Fractions
by Gas Chromatography
D 3524 Diesel Fuel Diluent in Used Diesel Engine Oils by
Gas Chromatography
D 3525 Gasoline Diluent in Used Engine Oils Gas Chro- [4] NMR Spectral Archive, National Institute of Advanced Indus-
matography Method trial Science and Technology. Tsukuba, Ibaraki, Japsin. SDB-
D 3606 Benzene/Toluene in Gasoline by Gas Chromatogra- SWeb: http://www.aist.go.jp/RIODB/SDBS/.
[5] Denis, J., Briant, J., and Hipeaux, J., Lubricant Properties Analy-
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Gas Chromatography Products Using Low Resolution Pulsed NMR Spectrometry,"
D 4053 Benzene/Toluene in Gasoline by Infrared (IR) Spec- Fuel, Vol. 64, 1985, pp. 226-228.
troscopy [7] Gauthier, S. and Quignard, A., "Accurate Determination of Hy-
D 4291 Ethylene Glycol in Used Engine Oil drogen Content in Petroleum Products by Low Resolution," '//
D 4420 Aromatics in Finished Gasoline by Gas Chromatog- NMR Revue IFF. Vol. 50, No. 2, 1995, pp. 249-282.
raphy [8] Willis, J., Lubrication Fundamentals, Marcel-Dekker, Inc., NY,
D 4815 Methyl Tert-Butyl Ether in Gasoline by Gas Chro- 1980, pp. 1-25.
matography [9] ASTM D 5292-93: Aromatic Carbon Contents of Hydrocarbon
D 5186 Aromatics and Polynuclear Aromatics in Diesel and Oils by High Resolution Nuclear Magnetic Resonance Spec-
troscopy, Annual Book of ASTM Standards, ASTM International,
Aviation Turbine Fuels by SFC
West Conshohocken, PA, 1993.
D 5480 Engine Oil Volatility by Gas Chromatography
[10] Shugar, G. and BaUinger, J., Chemical Technicians' Ready Refer-
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D 5580 Aromatics in Finished Gasoline by Gas Chromatog- [11] Norris, T. A., "Chromatography II," Lubrication, Vol. 65, No. 2,
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D 5599 Oxygenates in Gasoline by Gas Chromatography [12] ASTM D 5307: Determination of Boiling Range Distribution of
D 5623 Sulfrir Determination by GC-Sulfrir Detector Crude Petroleum by Gas Chromatography, Annual Book of
D 5769 Aromatics in Gasoline by Gas Chromatography- ASTM Standards, ASTM International, West Conshohocken, PA.
Mass Spectrometry (GC-MS) [13] Altgelt, K. and Gouw, T., Chromatography in Petroleum Analysis,
D 5845 Methyl Tert-Butyl Ether in Gasoline by Infrared Marcel-Dekker, Inc., NY, 1979, pp. 41-73.
Spectroscopy [14] Troyer, D. and Fitch, J., Oil Analysis Basics, Nona Corporation,
Tulsa, OK, 1999.
D 5986 Aromatics in Finished Gasoline by GC-FTIR
[15] Fitch, J., "Oil and Water Don't Mix," Practicing Oil Analysis Mag-
D 6277 Benzene/Toluene in Engine Fuels Using Mid-IR
azine, July/August 2001, p. 20.
Spectroscopy [16] Denis, J., Briant, J., and Hipeaux, J., Lubricant Properties Analy-
D 6293 Oxygenates O-PONA Hydrocarbons in Fuels by Gas sis and Testing Editions Technip, Paris, p. 53.
Chromatography [17] "Gas Chromatography with Atomic Emission Detector for Tur-
D 6296 Olefins in Engine Fuels by Gas Chromatography bine Engine Lubricant Analysis," JOAP Conference Proceedings,
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D 6379 Hydrocarbon Types Aromatic Hydrocarbon Types [18] Norris, T. A., "Chromatography II," Lubrication, Vol. 65, No. 2,
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D 6417 Estimation of Engine Oil Volatility by Capillary Gas [19] Li, Z., "Separation Techniques with Liquid Chromatography,"
The FRH Journal, 1984, pp. 69-76.
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[20] Stevenson, R., "Rapid Separation of Petroleum Fuels by Hydro-
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[34] Norris, T. A., "Chromatography II," Lubrication, Vol. 68, No. 3, [42] Shugar, G. and Ballinger, J., Chemical Technicians' Ready Refer-
1979, pp. 25-40. ence Handbook, Fourth Edition, McGraw-Hill, Inc., NY, 1996,
[35] Silverstein, R., Bassler, G., and Morrill, T., Spectrometric Identi- pp. 761-775.
fication of Organic Compounds, Fifth Edition, John Wiley and [43] Anonymous, Chapter 10.9, Infrared Analyzers.
Sons, Inc., NY, 1991, pp. 3-39. [44] ASTM E 168: Standard Practices for General Techniques of In-
[36] Denis, J., Briant, J., and Hipeaux, J., Lubricant Properties Analy- frared Quantitative Analysis, Annual Book of ASTM Standards,
sis and Testing, Editions Technip, Paris, 2000, pp. 24-28. ASTM International, West Conshohocken, PA, 1999.
[37] ASTM D 2786-91: S t a n d a r d Test Method for H y d r o c a r b o n [45] Coates, J., Infrared Spectra, A Practical Approach to the Interpre-
Types Analysis of Gas-Oil S a t u r a t e s Fractions by High tation of Coates Consulting, Marcel Dekker, NY, 1985.
MNL37-EB/Jun. 2003
Volatility
Rey G. Montemayor^
VOLATILITY, IN ITS SIMPLEST DEFINITION, IS THE TENDENCY OF A DISCUSSION

LIQUID TO CHANGE INTO VAPOR. For fuels, lubricants, and other
petroleum products, this tendency is measured in a variety Distillation
of ways. Volatility parameters are related to the perfor-
m a n c e characteristics and/or safety of these materials. Distillation parameters are importcuit volatility characteris-
Among the various ways of determining the volatility prop- tics of motor and other automotive spark-ignition fuels, avi-
erties of materials are: distillation, rate of evaporation mea- ation gasoline, aviation turbine fuels, diesel and other non-
surement, flash point test, and vapor pressure determina- aviation gas turbine fuels, solvents, and other petroleum
tion. Distillation determines the temperatures required to products. Gasolines and gasoline blends are used in a variety
evaporate known portions of the material, as well as the of engines operating u n d e r various atmospheric and me-
temperatures at which distillation begins and ends. Distilla- chanical conditions. In order to provide satisfactory perfor-
tion also determines the boiling range of the materials. A mance, gasoline must have the optimum distillation charac-
volatility property particularly important in solvents and teristics. Gasoline that vaporizes too readily in pumps, fuel
coating materials is the rate of evaporation. The flash point lines, and carburetors will cause decreased fuel flow to the
of a liquid is the lowest temperature, corrected for bciro- engine resulting in rough engine operation or stoppage. If the
metric pressure, at which application of an ignition source gasoline does not vaporize easily, difficulty in start-up, poor
causes the vapor above the specimen to ignite. Vapor pres- warm-up and acceleration, as well as unequal distribution of
sure is the force per unit area exerted on the walls of a fuel to the combustion cylinders may result. The distillation
closed container by the vaporized portion of the liquid ma- temperatures of various petroleum products can be deter-
terial in the container. mined at atmospheric pressure using ASTM D 86, Standard
Test Method for Distillation of Petroleum Products [1] or at
The significance of the different volatility properties reduced pressure using ASTM D 1160, Standard Test Method
varies from one material to another. For crude oil, distilla- for Distillation of Petroleum Products at Reduced Pressure
tion data are critical assay information. For solvents distil- [2]. The 10%, 50%, and 90% (recovered) distillation points
lation, flash point and evaporation rate are important pa- are important control points in the production of fuel blends.
rameters. For motor and aviation gasoline, distillation and In the mid-1980s the use of automatic distillation equip-
vapor pressure data are paramount since these properties ment gained popularity because of increased ability to con-
are related to the performance characteristics of these ma- trol the rate of distillation, emd efficiency in operation. Figure
terials. Distillation characteristics of diesel and other non- 1 [3] shows the classical manucJ D86 distillation set-up using
aviation fuels exert a great influence on their performance. a gas burner. Figure 2 [4] shows the manual D86 distillation
Flash points and fire points for distillates and residual fuels, apparatus assembly using electric heater. The use of an elec-
as well as lubricants, are significant from the perspective of tric heater improved the ability to control the rate of distilla-
safety in handling, storage, and transportation of these mation. However, it was still difficult to m a i n t a i n the 4 - 5
terials. mL/min distillation rate required by the method. The advent
This chapter will deal with the different test methods deal- of automatic distillation apparatus allowed the distillation
ing with the volatility characteristics of fuels and lubricants. parameters specified in the method to be controlled accu-
A summary of the test methods, scope, significance, preci- rately without operator intervention. The distillation flask
sion, and results will be given. Other internationcd standards and the receiving cylinder in an automatic D86 distillation
dealing with volatility properties determination and their unit are essentially the same as the manual unit. Although
corresponding ASTM standards will be referenced. Distilla- electric heaters eire used, the use of microprocessors to con-
tion for materials other than crude oils is discussed under the trol the rate of distillation provided precise temperature con-
section on Distillation. Flash point eind fire point determina- trol and allowed conformance to the method requirements.
tions are discussed in the Flammability section. Distillation Platinum resistance temperature probes or thermocouples
test methods applicable to crude oils are dealt with in the replaced the mercuiy-in-glass thermometers to allow unat-
Crude Distillation section. Vapor pressure measurements are tended operation. Automatic level followers using optical
covered in the Vapor Pressure section. sensors removed the necessity of manually observing and
measuring recovered distillation volumes. Data obtained by
automatic distillation units are very similar to those obtained
' Imperial Oil Ltd., Products and Chemicals Division, Sarnia, On- by manual instruments. However, the data are not statisti-
tario Canada
675

Thermometer has been in use for such an extended period, a tremendous

amount of historical databases exist for estimating end-use
Distilling sensitivity on products and processes. The distillation char-
Flask Bath Cover acteristics of hydrocarbons often have an important effect on
their safety and performance, especially in the case of fuels
Heat and solvents. Volatility is the major determinant of the ten-
Resistant dency of a hydrocarbon to produce potentially explosive va-
Boards pors. It is also critically important for both automotive and
aviation gasolines, affecting starting, warm-up, and tendency
to vapor lock at high operating temperature or at high alti-
tude, or both. The presence of high boiling point components
in these and other fuels can significantly affect the degree of
solid combustion deposit formation. Distillation limits are
often included in petroleum product specifications, in com-
mercial contract agreements, process refinery/control appli-
cations, and for compliance to regulatory requirements.
The precision of manual and automatic D86 distillation for
Air Vents group 1 materials is given in Table 6 [11]; Table 7 [12] for
groups 2,3,and 4 using manual distillation; and Table 8 [13]
Support- for groups 2,3, and 4 using automatic distillation.
Generally, the distillation temperatures corrected for baro-
metric pressure, corresponding to IBP, 5%, 10%, 20%, 30%,
FIG. 1—Manual D 86 distillation unit with gas burner.
40%, 50%), 60%), 70%), 80%, 90%, 95%, and FBP are reported.
The initial boiling point (IBP) is the corrected temperature
reading that is observed at the instant the first drop of con-
densate falls from the lower end of the condenser tube. The
cally equivalent. Data are available for users to compare 5-95% distillation temperature is the corrected temperature
manual and automatic D 86 results (Tables lA and IB) [5,6]. reading corresponding to each 5-95% volume distilled or re-
Similar improvements have occurred with D 1160.The rela- covered. The final boiling point (FBP) or end point (EP) is the
tive bias between manual and automatic D 1160 are given in maximum corrected temperature reading obtained during
Table 2 [7]. the test. Sometimes, the dry point (DP) is required. DP is the
ASTM D 86, Standard Test Method for Distillation corrected temperature reading that is observed or detected at
of Petroleum Products at Atmospheric Pressure the instant the last drop of liquid evaporates from the lowest
point in the distillation flask. The corrections to be applied to
This test method is under the jurisdiction of ASTM Commit- the observed temperature readings are obtained by means of
tee D-02 on Petroleum and Lubricants, and is the direct re- the Sydney Young equation given in Eqs 1,2, and 3, as ap-
sponsibility of Subcommittee D02.08 on Volatility. This stan- propriate, or by the use of Table 9 [14]:
dard was originally published in 1921. The latest edition is D
86-OOa and incorporates a major rewrite of the standard, Cc = 0.0009 (101.3 - Pk) (273 -I- t^) (1)
which was started in 1996.
G = 0.00012 (760 - P) (273 + tc) (2)
This test method covers the distillation at atmospheric
pressure of natureil gasolines, motor gasolines, aviation gaso- Cf = 0.00012 (760 - P) (460 + tf) (3)
lines, aviation turbine fuels, special boiling point spirits,
naphthas, white spirit, kerosines, gas oils, distillate fuel oils, where:
and similar petroleum products, utilizing either manual or Cc and Cf = corrections to be added algebraically to the tem-
automatic equipment. perature reading in Celsius or Fahrenheit
In a D86 distillation, a 100 mL specimen is distilled under tc = observed temperature reading in Celsius
prescribed conditions that are appropriate to its nature. tf = observed temperature reading in Fahrenheit
Table 3 [8] shows the distillation group characteristics of var- Pk — barometric pressure prevailing at the time of the
ious materials tested to provide D86 distillation data. Table 4 test in kPa
[9] and Table 5 [10] indicate the various test parameters re- P = barometric pressure prevailing at the time of the
quired for each distillation group. Systematic observation of test in mm Hg.
temperature readings and volumes of condensate are made, After applying the corrections, the corrected temperature
and from these data, the results of the test are calculated and readings are rounded and reported to the nearest 0.5°C
reported. (1.0°F) or 0.1 °C (0.2°F), as appropriate to the apparatus used.
The basic method of determining the boiling range of a However, other calculated values can be reported from D86
petroleum product by performing a simple batch distillation distillation data, such as percent recovery and percentages
has been in use as long as the petroleum industry has existed. evaporated at prescribed temperature readings.
It is one of the oldest test methods under the jurisdiction of Typical D86 results for motor gasoline, reformulated gaso-
ASTM Committee D 02, dating from the time when it was still line, diesel, and jet fuel are given in Table 10 [15], Table 11
referred to as the Engler distillation. Since the test method [16], Table 12 [17], and Table 13 [18].
CHAPTER 25: VOLATILITY 677
25 min.
Length of part
' bath
approx. 390
Front View
NOTE 1—^Legend:
l-Condenser bath 11-Distillation flask
2-Bath cover 12-Temperature sensor
3-Bath temperature sensor 13-Flasl< support board
4-Bath overflow 14-Flasl« support platform
5-Bath drain 15-GrDund connection
6-Condenser tube 16-Electric heater
7-Shield 17-Knob for adjusting level
8-Viewing window of support platform
9a-Voifage regulator 18-Power source cord
9b-Voltmeter or ammeter 19-Reoeiver cylinder
9o-Power switch 20-Receiver cooling bath
9d-Power light indicator 21-Receiver cover
10-Vent
FIG. 2—Manual D 86 distillation unit with electric heater.

TABLE lA—Relative bias between manual and automatic D86 distillation.
Sample IBP 5% 10% 20% 30% 40% 50% 60% 70% 80% 90% 95% FBP Sample
1 + 1.1 + 1.9 +2.2 + 1.6 + 1.4 +0.7 +0.8 +0.7 +0.7 +0.1 +0.4 0.7 -0.4 1
2 (+0.9) (0.0) +0.8 +0.5 +0.4 +0.6 +0.2 +0.1 +0.1 +0.4 (+4.7)" ( + 1.3)" (-1.2)° 2
3 +0.7 + 1.4 + 1.6 + 1.0 +0.8 +0.6 +0.3 +0.1 +0.2 +0.9 +0.5 +0.1 -0.8 3
4 +0.3 +0.6 +0.8 +0.8 0.3 0.7 +0.6 +0.8 + 1.1 + 1.2 +0.8 +0.5 -0.9 4
5 +0.5 + 1.3 + 1.3 + 1.3 + 1.2 + 1.0 +0.9 +0.6 +0.8 + 1.0 +0.4 +0.4 -0.9 5
6 + 1.2 + 1.2 + 1.6 + 1.2 + 1.2 + 1.1 +0.8 + 1.1 + 1.2 +0.2 -0.1 +0.2 -0.3 6
7 +0.3 +0.8 +0.8 +0.7 +0.8 +0.8 + 1.0 + 1.5 + 1.6 + 1.6 + 1.5 + 1.7 -0.7 7
8 +0.3 +0.5 +0.7 +0.6 +0.7 + 1.2 + 1.2 + 1.1 + 1.3 + 1.9 + 1.1 + 1.2 -0.8 8
9 + 1.7 +2.0 + 1.8 + 1.5 + 1.5 + 1.5 + 1.2 +0.9 + 1.3 +0.6 -0.4 +0.4 -1.2 9
10 + 1.5 + 11.5 + 1.2 +0.7 +0.4 +0.6 +0.9 + 1.0 + 1.4 + 1.9 +0.9 +0.1 -2.1 10
11 +0.9 + 1.1 + 1.2 +0.8 +0.7 +0.6 + 1.1 + 1.0 +0.4 +0.5 -0.4 +0.1 -0.8 11
12 + 1.0 (+2.4)" +2.3 + 1.2 + 1.2 + 1.2 + 1.2 +0.9 + 1.1 +0.2 -0.7 (-0.8) -0.9 12
13* +0.3 +0.3 +0.4 +0.3 +0.2 +0.9 + 1.4 + 1.0 +0.1 + 1.1 + 1.2 + 1.0 -1.2 13*
14* +0.5 +0.4 +0.7 +0.5 +0.8 + 1.1 + 1.7 + 1.7 + 1.0 +0.5 +0.3 0.0 -0.8 14*
''Points between parentheses have not been included in the precision analysis.
'Gasoline-alcohol blends.
NOTE—1. Data reported are based on averages of ASTM and IP data.
2. Fourteen samples of gasoline were analyzed in 26 laboratories.
3. The bias reported below is (average of automated results)—(average of manual results).
TABLE IB—Relative bias between manual and automatic d 86 distillation, various samples [6]
(currently under review in ASTM Subcommittee D02.08).
Summary of Average Relative Bias in °C (auto—manual)
ASTM Interlaboratory Crosscheck Data from 1994 to 1998
Sample #Lab A #Lab M IBP 5% 10% 20% 30% 40% 50% 60% 70% 80% 90% 95% FBP
Jet A 12 99 26 -0.7 1.9 1.1 0.8 0.6 0.7 0.7 0.8 0.9 0.8 0.6 0.3 -0.6
Diesel 14 129 43 -1.9 2.7 2.1 1.2 1.2 1.1 1.0 0.7 0.7 0.6 0.5 0.3 0.4
Mogas 13 76 17 -1.1 0.2 -0.1 -0.5 0.1 -0.7 -0.3 -0.3 -0.4 -0.5 -1.9 -3.4 -1.0
Refor 36 86 8 -1.1 0.7 0.3 0.2 -0.1 -0.1 -0.2 0.4 0.5 0.1 -0.5 -2.1 0.4
Summary of Average Relative Bias in °F (auto—manual)
ASTM Interlaboratory Crosscheck Data from 1994 to 1998
Sample N #Lab A #Lab M IBP 5% 10% 20% 30% 40% 50%) 60% 70% 80% 90% 95% FBP
Jet A 12 99 26 -1.3 3.3 2.1 1.3 1,1 1.2 1.3 1.4 1.6 1.5 1.0 0.5 -1.1
Diesel 14 129 43 -3.4 4.9 3.8 2.2 2.1 2.0 1.9 1.2 1.2 1.1 0.8 0.5 0.8
Mogas 13 76 17 -1.9 0.3 -0.2 -0.9 0.1 -1.2 -0.5 -0.5 -0.7 -0.9 -3.5 -5.2 -1.7
Refor 36 86 8 -2.0 1.4 0.6 0.3 -0.2 -0.2 -0.4 0.8 0.9 0.2 -0.9 -3.8 -0.7
TABLE 2—Relative bias between m a n u a l and automatic D 1160 [7].

1 mm Hg Pressure (All AET Values in °C)
Sample 1 Sample 2 Sample 3
Boiling
Point Automatic Manual Automatic Manual Automatic Manual
IBP 225.1 239.7 342.6 338.4 321.3 330.8
5% 268.2 270.1 371.3 373.5 363.7 364.4
10% 288.9 290.1 380.7 380.7 378.7 379.0
20% 321.0 324.0 388.7 388.4 397.5 397.2
30% 347.1 349.5 394.4 394.3 412.1 411.8
40% 370.1 373.4 400.9 400.0 426.6 425.9
50% 392.1 395.7 407.2 405.9 439.9 439.6
60% 416.0 420.0 414.0 412.8 453.2 452.4
70% 440.8 443.5 422.6 421.7 467.7 467.8
80% 472.1 472.5 433.1 433.1 486.0 485.6
90% 518.5 514.1 452.6 452.0 511.5 514.1
FBP 547.5 544.8 493.9 488.1 547.4 538.7
10 m m Hg Pressure (All AET Values in °C)
Sample 1 Sample 2 Sample 3
Boiling
Point Automatic Manual Automatic Manual Automatic Manual
IBP 203.2 199.6 343.0 342.7 319.0 319.0
5% 252.3 254.5 370.2 370.3 360.7 359.9
10% 274.7 280.7 376.9 378.1 374.6 374.2
20% 313.5 316.5 383.3 384.8 392.7 392.5
30% 340.6 342.2 391.0 391.1 408.0 407.4
40% 363.1 366.4 397.0 396.9 422.4 421.2
50% 385.6 388.9 402.9 403.3 436.4 434.1
60% 408.4 411.5 409.1 410.2 450.7 448.1
70% 433.0 436.5 419.4 419.0 465.3 462.9
80% 461.3 465.5 430.3 430.9 483.3 480.3
90% 507.5 506.9 450.5 451.2 509.1 504.8
FBP 538.5 536.3 492.8 482.7 544.0 536.3
TABLE 3—Group characteristics.
Group 0 Group 1 Group 2 Group 3 Group 4
Sample
characteristics
Distillate tj^pe natural
gasoline
Vapor pressure at
37.8°C, kPa a65.5 <65.5 <65.5 <65.5
100°F, psi >9.5 <9.5 <9.5 <9.5
(Test Methods
D 323, D 4953,
D 5190, D 5191,
D 5482, IP 69 or
IP 394)
Distillation, IBP "C slOO >100
"F <212 >212
EP°C £250 S250 >250 >250
°F £482 <482 >482 >482
TABLE 4—Preparation of apparatus.

Flask, mL 100 125 125 125 125
ASTM distillation thermometer 7C (7F) 7C (7F) 7C (7F) 7C (7F) 8C (8F)
IP distillation thermometer range low low low low high
Flask support board A B B C C
diameter of hole, m m 32 38 38 50 50
Temperature at start of test
Flask
°C 0-5 13-18 13-18 13-18 not above
°F 32-^0 55-65 55-65 55-65 ambient
Flask support and shield not above not above not above not above
ambient ambient ambient ambient
Receiving cylinder and 100 ml charge
°C 0-5 13-18 13-18 13-18" 13-ambient"
°F 32^0 55-65 55-65 55-65" 55-ambient''
"See 10.3.1.1 for exceptions.
TABLE 5—Conditions during test procedure.

Temperature of cooling bath" cF 0-1 0-1 0-5 0-5 0-60
32-34 32-34 32-40 32-40 32-140
Temperature of bath around C 0-4 13-18 13-18 13-18 ±3
receiving cylinder 'F 32-40 55-65 55-65 55-65 ±5
of charge
temperature
Time from first application of heat to 2-5 5-10 5-10 5-10 5-15
initial boiling point, m i n
Time from initial boiling point
to 6% recovered, s 60-100 60-100
to 10% recovered, min 3^
Uniform average rate of condensation 4-5 4-5 4-5 4-5 4-5
from 5% recovered to 5 mL
in flask, mL/min
Time recorded from 5 mL residue to 5 max 5 max 5 max 5 max 5 max
end point, m i n
''The proper condenser bath temperature will depend upon the wax content of the sample and its distillation fractions. The test is generally performed using one
single condenser temperature. Wax formation in the condenser can be deduced from (a) the presence of wax particles in the distillate coming off the drip tip, (b)
a higher distillation loss than what would be expected base on the initial boiling point of the specimen, (c) an erratic recovery rate and (d) the presence of wax par-
ticles during the removal of residual liquid by swabbing with a lint-free cloth (see 8.3). The minimum temperature that permits satisfactory operation shall be used.
In general, a bath temperature in the 0 to 4°C range is suitable for kerosine, Grade No 1 fuel oil and Grade No. 1-D diesel fuel oil. In some cases involving Grade
No. 2 fuel oil. Grade No. 2-D diesel fuel oil; gas oils and similar distillates, it may be necessary to hold the condenser bath temperature in the 38 to 60°C range.
TABLE 6—Repeatability and reproducibility for group.

Manual Manual Automated Automated
Repeatability'^ Reproducibility" Repeatability" Reproducibility"
Point, % °C op °C °F °C -F °C -F
IBP 3.3 6 5.6 10 3.9 7 7.2 13
5 1.9 + 0.86Sc 3.4 + 0.86SF 3.1 + 1.74Sc 5.6 + 1.74SF 2.1 + 0.67Sc 3.8 + 0.67SF 4.4 + 2.0Sc 7.9 + 2.0SF
20 1.2 + 0.86Sc 2.2 + 0.86SF 2 . 0 + 1.74Sc 3.6 + 1.74SF 1.1 +0.67Sc 2.0 + 0.67SF 3.3 + 2.0Sc 6.0 + 2.0SF
30-70 1.2 + 0.86Sc 2.2 + 0.86SF 2.0 + 1.74Sc 3.6 + 1.74SF 1.1 +0.67Sc 2.0 + 0.67SF 2.6 + 2.0Sc 4.7 + 2.0SF
80 1.2 + 0.86Sc 2.2 + 0.86SF 2.0 + 1.74Sc 3.6 + 1.74SF 1.1 +0.67Sc 2.0 + 0.67SF 1.7 + 2.0Sc 3.0 + 2.0SF
90 1.2 + 0.86Sc 2.2 + 0.86SF 0.8 + 1.74Sc 1.4 + 1.74SF 1.1 +0.67Sc 2.0 + 0.67SF 0.7 + 2.0Sc 1.2 + 2.0SF
FBP 3.9 7 7.2 13 4.4 8 8.9 16
"Sc or SF is the average slope (or rate of change) calculated in accordance with 13.2.
TABLE 7—Repeatability and reproducibility for groups 2, 3, and 4 (manual method).

Repeatability" Reproducibility"
"F
IBP 1.0 + 0.35Sc 1.9 + 0.35SF 2.8 + 0.93Sc 5.0 + 0.93SF
5-95% l.O + 0.41Sc 1.8 + 0.41SF 1.8 + 1.33Sc 3.3 + 1.33SF
FBP 0.7 + 0.36Sc 1.3 +0.36SF 3.1 +0.42Sc 5.7 + 0.42SF
% volume at 0.7 + 1.92/SC 0.7 + 1.66/SF 1.5 + 1.78/Sc 1.53 + 3.20/SF
temperature reading
"Calculate Sc or Sp from 13.2.
TABLE 8—Repeatability and reproducibility for groups 2, 3 and 4 (automated).

Repeatability" Reproducibility"
Collected, % "C op "C °F
IBP 3.5 6.3 8.5 15.3
2% 3.5 6.3 2.6 + 1.92Sc 4.7 + 1.92SF
5% 1.1 + 1.08Sc 2.0 + I.OSSF 2.0 + 2.53Sc 3.6 + 2.53SF
10% 1.2 + 1.42Sc 2.2 + 1.42SF 3.0 + 2.64Sc 5.4 + 2.64SF
20-70% 1.2 + 1.42Sc 2.2 + 1.42SF 2.9 + 3.97Sc 5.2 + 3.97SF
80% 1.2 + 1.42Sc 2.2 + 1.42SF 3.0 + 2.64Sc 5.4 + 2.64SF
90-95% 1.1 + 1.08Sc 2.0 + 1.08SF 2.0 + 2.53Sc 3.6 + 2.53SF
FBP 3.5 6.3 10.5 18.9
"Sc or SF is the average slope (or rate of change) calculated in accordance with 13.5.
TABLE 9—Approximate thermometer reading correction. ASTM D 1160, Standard Test Method for Distillation of
Correction per 1.3kPa(10mmHg) Petroleum Products at Reduced Pressure
Temperature Range Difference in Pressure
This test method is under the jurisdiction of ASTM Commit-
°C °F °C °F
tee D-02 and is the direct responsibility of Subcommittee
10-30 50-86 0.35 0.63 D2.08 on VolatiHty. This standeird was originally published in
30-50 86-122 0.38 0.68
50-70 122-158 0.40 0.72 1951. The latest edition is D 1160-99.
70-90 158-194 0.42 0.78 This test method covers the determination, at reduced
90-110 194-230 0.45 0.81 pressures, of the boiling range of petroleum products that
110-130 230-266 0.47 0.85 can be partially or completely vaporized at a m a x i m u m liquid
130-150 266-302 0.50 0.89
temperature of 400°C. The reduced pressure inside the appa-
150-170 302-338 0.52 0.94
170-190 338-374 0.54 0.98 ratus during the test is measured by a Mcleod vacuum gage
190-210 374^10 0.57 1.02 or a n appropriately calibrated electronic gage such as the
210-230 410-446 0.59 1.07 Baratron. Both manual and automatic methods are specified.
230-250 446-482 0.62 1.11 The schematic diagram of a vacuum distillation apparatus is
250-270 482-518 0.64 1.15
indicated in Fig. 3 [19]. Both manual and automatic D 1160
270-290 518-554 0.66 1.20
290-310 554-590 0.69 1.24 distillation units use platinum resistance temperature probes
310-330 590-626 0.71 1.28 or thermocouples.
330-350 626-662 0.74 1.33 The specimen is distilled at an accurately controlled pres-
350-370 662-698 0.76 1.37
698-734 1.41
sure between 0.13 and 6.7 kPa (1 and 50 m m Hg) under con-
370-390 0.78
390-410 734-770 0.81 1.46 ditions that are designed to provide approximately one theo-
"Values to be added when barometric pressure is below 101.3 kPa (760 mm retical plate fractionation. The distillation pressure is
Hg) and to be subtracted when barometric pressure is above 101.3 kPa. controlled by a pressure regulating system consisting of a low
TABLE 10—ASTM D-2 interlaboratory cross check program—auto D 86 distillation for motor gasoline.
Lab Code IBP 5% 10% 20% 30% 40% 50% 60% 70% 80% 90% 95% FBP %REC
1 34.6 51.7 62.0 79.1 94.8 105.7 112.9 119.4 127.4 141.7 167.2 184.2 215.8 97.5
2 30.6 52.2 62.8 81.7 96.1 106.1 112.7 119.4 128.9 146.1 172.2 198.4 214.4 96.6
3 38 54 64 83 98 107 114 121 131 149 176 217 223 95.8
4 34.0 44.5 56.1 75.7 92.8 104.6 112.3 118.7 127.3 141.4 166.7 183.8 223.1 96.5
5 33.8 53.0 62.7 79.7 95.1 105.7 112.5 118.7 126.5 142.1 166.8 185.5 222.2 97.9
6 31.7 49.7 60.0 78.9 95.0 106.2 112.7 119.2 127.4 142.0 164.8 182.2 218.8 97.4
7 34.8 55.1 64.1 82.3 96.8 106.6 113.1 120.2 129.4 146.5 171.1 200.6 214.1 96.2
8 37.1 56.4 65.8 83.9 99.1 108.8 115.6 122.4 131.8 149.0 174.5 208.3 225.0 96.9
10 35.4 47.0 57.8 76.5 94.1 105.7 113.1 119.6 127.7 142.2 166.8 183.4 225.5 97.0
TABLE 11—ASTM D-2 interlaboratory cross check program—auto D 86 distillation for reformulated gasoline.
Lab Code IBP 5% 10% 20% 30% 40% 50% 60% 70% 80% 90% 95% FBP %REC %LOSS E200 E300
1 103.1 132.5 141.6 153.3 165.6 180.5 199.2 222.5 250.2 279.1 318.1 351.8 391.1 97.4 1.3 50.4 85.7
2 108.8 124.7 134.7 147.7 160.8 175.1 195.0 218.1 246.5 276.6 316.9 347.7 395.6 97.3 0.9 52.8 86.8
4 100.2 130.5 140.2 151.9 164.1 178.3 198.0 220.7 247.8 276.4 313.5 346.2 396.9 97.8 1.2 50.9 86.4
5 104 134 137 150 162 177 196 220 248 278 317 349 400 96.9 3.1 51.8 86.1
6 105.3 120.1 133.5 147.6 160.1 175.2 195.2 219.5 247.6 395.3 319.1 353.5 395.3 96.9 1.9 53 87
7 94.1 129.2 138.0 150.0 161.0 175.3 193.5 217.4 245.5 274.7 311.5 341.4 393.2 99.1 0.5 52.9 87.3
8 107.6 124.5 135.5 148.1 160.3 175.1 193.6 217.7 244.7 273.7 311.7 340.3 394.7 97.7 52.9 87.2
10 109.8 132.5 142.5 159.1 170.1 183.8 202.6 222.4 244.3 278.2 319.0 353.3 394.2 98.1 0.9 48.7 85.7
TABLE 12—ÂSTM D-2 interlaboratory cross check program—Âuto D 86 distillation for diesel fuel.
1 177.4 203.2 209.4 228.8 243.2 253.8 263.3 271.2 281.6 293.0 309.0 323.9 341.3 98.3
3 182.8 205.2 214.1 230.7 244.4 255.2 264.6 273.4 282.8 294.3 311.8 330.4 343.5 97.5
4 176.3 201.7 210.5 226.5 240.1 251.3 260.6 269.1 278.2 289.2 305.2 319.3 336.0 98.7
5 177.1 202.0 210.0 228.6 243.4 254.9 264.1 273.1 282.0 293.8 310.4 335.2
8 183.7 210.5 228.7 243.9 254.9 264.7 274.1 283.3 294.8 311.9 329.9 340.0
9 179.7 203.8 212.9 227.5 241.7 253.4 261.9 270.8 280.4 291.9 308.0 323.1 339.5 98.3
10 178.8 204.4 212.8 227.8 242.2 253.3 262.8 271.1 280.6 291.7 308.9 325.6 340.6 98.3
11 179.5 203.7 216.4 232.6 247 257.4 266.9 276.3 285.4 297.1 315.0 332.9 343.5 97.8
13 182.0 200.5 211.9 231.4 245.9 256.6 **268.3 274.9 283.9 296.1 313.4 333.4 341.1 97.6
14 169.5 201.0 212.5 229.0 244.0 255.0 265.0 273.5 283.0 293.5 309.5
TABLE 13—ASTM interlaboratory cross check program—auto D 86 distillation for jet fuel.
1 158.6 175.0 180.3 187.0 194.4 202.0 210.0 219.3 230.0 239.4 254.7 261.6 273.3 99.0
2 159.7 175.2 179.2 186.1 192.8 199.5 207.7 216.3 226.2 238 253.3 266.1 274 97.5
3 163.0 178.6 183.0 190.7 197.6 205.1 213.0 221.8 232.5 244.4 259.6 269.9 290.8 98.9
4 160.0 174.1 180.1 186.6 193.0 200.3 207.9 216.6 227.0 239.0 254.1 265.0 275.2 98.1
5 161 175 179 187 193 200 208 216 227 238 253 264 277 98
6 159.9 172.4 177.3 184.7 191.3 198.9 206.1 214.3 224.1 235.4 249.5 259.8 272.6 99.7
8 161.4 175.0 180.2 187.3 193.9 200.8 208.0 210.6 226.9 238.8 253.3 263.8 277.3 98.4
9 160.1 176.1 180.4 186.8 194.1 201.3 209.1 217.7 227.9 239.8 255.6 267.3 281.2 98.0
10 161.8 175.9 180.1 186.8 192.5 199.8 207.6 216.2 225.9 237.3 251.5 261.8 277.3 98.4
efficiency, high capacity vacuum p u m p connected to one of was n o decomposition. The equations [20] used to convert the
two surge tanks, each having a capacity of 10-20 L and ar- observed distillation temperature to AET are:
ranged in series. A solenoid vsJve or other type of regulator is
installed in the connection between the tanks so that the first 748.1 X A
tank is maintained at p u m p pressure and the second one at the AET = - 273.1 (4)
[1/(VT,K] + (0.3861 X A) - 0.00051606
pressure of the distillation apparatus. Data are obtained dur-
ing the distillation, from which the initieJ boiling point, the fi- 5.143222 - (0.972546 X logp)
nal boiling point, and a distillation curve relating volume per- (5)
2 5 7 9 . 3 2 9 - ( 9 5 . 7 6 X log p)
cent distilled and Atmospheric Equivalent Temperature
(AET) can be obtained. Atmospheric Equivalent Temperature or
is the temperature converted from the observed temperature
during the test, to the expected distillate temperature if the 5.994295 - (0.972546 X log P)
distillation was performed at atmospheric pressure and there A = (6)
2 6 6 3 . 1 2 9 - ( 9 5 . 7 6 X log P)
Digital Temperature Indicator

[• J_ PRT Sensor IvjcimoiGHel Option # 2 Pressure
Reguiating System
.L
Repressi/ring
(ColdTrap tft^Connec
Option # 1
Surge Tanks Vacuum Pump

Vacuum Source
Thermowell
Circulating •
^—^ ._S2?'' I
XTCooiant F i o w ^ ^ = > ~ * / U
Thermo-RegulaW Immersion Heater
Coolant Circulating System
FIG. 3—D 1160 vacuum distillation apparatus.
where: the nearest degree Celsius corresponding to the volumetric

AET = atmospheric equivalent temperature in °C percentages of liquid recovered in the receiver. The sample
A= value obtained from Eqs 5 and 6 identity, density, and total amount of distillate recovered in
VT,K = observed vapor temperature, °K the receiver and the cold trap are also reported.
p= pressure of the system in pKa, observed when the va-
por temperature was read Other International Standard Test Methods for
P = pressure of the system in m m Hg, observed when the Distillation
vapor temperature was read. All the aforementioned distillation test methods are ASTM
standard test methods. Although ASTM standard test meth-
Alternatively, the AET corresponding to the observed vapor ods are used extensively t h r o u g h o u t the world, there are
temperature can be obtained from a set of Tables given in the other international distillation standards that are used and
method (Tables 14-19) [21]. are applicable to specific geographiceJ eireas. Table 22 gives a
This test method is used for the determination of the dis- cross reference for a n u m b e r of international distillation
tillation characteristics of petroleum products and fractions standards and their corresponding ASTM designation.
that may decompose if distilled at atmospheric pressure. The
boiling range, obtained at conditions designed to obtain ap-
Flaitimability
proximately one theoretical plate fractionation, can be used
in engineering calculations to design distillation equipment, From a safety point of view, a critical volatility property of fu-
to prepare appropriate blends for industrial purposes, to de- els and lubricants is flash point. The flash point of a liquid is
termine compliance with regulatory rules, to determine the the lowest temperature corrected to a pressure of 101.3 kPa
suitability of the material as feed to a refining process, or for (760 m m Hg) at w h i c h application of an ignition source
a host of other purposes. The boiling range is directly related causes the vapors of a specimen of the sample to ignite u n d e r
to viscosity, vapor pressure, heating value, average molecular specified test conditions. Flash point measures the tendency
weight, and many other chemical, physical, and mechanical of the specimen to form a flammable mixture with air under
properties. Petroleum product specifications often include controlled laboratory conditions. It is only one of a n u m b e r
distillation limits based on data by this test method. Many en- of properties that must be considered in assessing the overall
gineering design correlations have been developed on data by flammability hazard of a material. Flash point is used in ship-
this test method. These correlative methods are used exten- ping and safety regulations to define flammable and com-
sively in current engineering practice. bustible materials. Flash point can indicate the possible pres-
The precision for manual D 1160 distillation is given in ence of highly volatile and flammable materials in a relatively
Table 20 [22]. Table 21 gives the precision for automatic D nonvolatile Eind nonflammable material.
1160 as obtained from Research Report RR:D2-1206 [7]. Various regulatory organizations use flash point to define
The observed vapor temperature readings are converted to flammable and combustible materieds as it relates to trans-
Atmospheric Equivalent Temperature (AET) using the tables porting, shipping, and safety regulations. Prior to 1990, the
and/or equations mentioned earlier. The AET is reported to Federal Register of the U.S. Department of Transport defined
TABLE 14—AET conversion table at 0.13 kPa (1 mm Hg) pressure °C.
P (mm Hg) T 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
1 35 195.2 195.9 196.6 197.3 198.0 198.6 199.3 200.0 200.7 201.4
40 202.1 202.7 203.4 204.1 204.8 205.5 206.2 206.8 207.5 208.2
45 208.9 209.6 210.2 210.9 211.6 212.3 213.0 213.6 214.3 215.0
50 215.7 216.4 217.0 217.7 218.4 219.1 219.7 220.4 221.1 221.8
55 222.5 223.1 223.8 224.5 225.2 225.8 226.5 227.2 227.9 228.5
60 229.2 229.9 230.6 231.2 231.9 232.6 233.3 233.9 234.6 235.3
G5 235.9 236.6 237.3 238.0 238.6 239.3 240.0 240.6 241.3 242.0
70 242.7 243.3 244.0 244.7 245.3 246.0 246.7 247.3 248.0 248.7
75 249.3 250.0 250.7 251.4 252.0 252.7 253.4 254.0 254.7 255.4
80 256.0 256.7 257.4 258.0 258.7 259.3 260.0 260.7 261.3 262.0
85 262.7 263.3 264.0 264.7 265.3 266.0 266.6 267.3 268.0 268.6
90 269.3 270.0 270.6 271.3 271.9 272.6 273.3 273.9 274.6 275.2
95 275.9 276.6 277.2 277.9 278.5 279.2 279.9 280.5 281.2 281.8
100 282.5 283.2 283.8 284.5 285.1 285.8 286.4 287.1 287.7 288.4
105 289.1 289.7 290.4 291.0 291.7 292.3 293.0 293.6 294.3 295.0
110 295.6 296.3 296.9 297.6 298.2 298.9 299.5 300.2 300.8 301.5
115 302.1 302.8 303.4 304.1 304.7 305.4 306.0 306.7 307.3 308.0
120 308.6 309.3 309.9 310.6 311.2 311.9 312.5 313.2 313.8 314.5
125 315.1 315.8 316.4 317.1 317.7 318.4 319.0 319.7 320.3 320.9
130 321.6 322.2 322.9 323.5 324.2 324.8 325.5 326.1 326.7 327.4
135 328.0 328.7 329.3 330.0 330.6 331.2 331.9 332.5 333.2 333.8
140 334.5 335.1 335.7 336.4 337.0 337.7 338.3 338.9 339.6 340.2
145 340.9 341.5 342.1 342.8 343.4 344.1 344.7 345.3 346.0 346.6
150 347.3 347.9 348.5 349.2 349.8 350.4 351.1 351.7 K2.3 353.0
155 353.6 354.3 354.9 355.5 356.2 356.8 ^7.4 358.1 358.7 359.3
160 360.0 360.6 361.2 361.9 3625 363.1 363.8 364.4' 3^.0 365.7
165 366.3 366.9 367.6 368.2 368.8 369.4 370.1 370.7 371.3 372.0
170 372.6 373.2 373.9 374.5 375.1 375.7 376.4 377.0 377.6 378.3
175 378.9 379.5 380.1 380.8 381.4 382.0 382.7 383.3 383.9 384.5
180 385.2 385.8 386.4 387.0 387.7 388.3 388.9 389.5 390.2 390.8
185 391.4 392.0 392.7 393.3 393.9 394.5 395; 1 395.8 396.4 397.0
190 397.6 398.3 398.9 399.5 400.1 400.7 401.4 402.0 402.6 403.2
195 403.9 404.5 405.1 405.7 406.3 406.9 407.6 408.2 408.8 409.4
200 410.0 410.7 411.3 411.9 412.5 413.1 413.8 414.4 415.0 415.6
205 416.2 416.8 417.5 418.1 418.7 419.3 419.9 420.5 421.1 421.8
210 422.4 423.0 423.6 424.2 424.8 425.4 426.1 426.7 427.3 427.9
215 428.5 429.1 429.7 430.4 431.0 431.6 432.2 432.8 433.4 434.0
220 434.6 435.2 435.9 436.5 437.1 437.7 438.3 438.9 439.5 440.1
225 440.7 441.3 442.0 442.6 443.2 443.8 444.4 445.0 445.6 446.2
230 446.8 447.4 448.0 448.6 449.2 449.8 450.5 451.1 451.7 452.3
235 452.9 453.5 454.1 454.7 455.3 455.9 456.5 457.1 457.7 458.3
240 458.9 459.5 460.1 460.7 461.3 461.9 462.5 463.1 463.7 464.4
245 465.0 465.6 466.2 466.8 467.4 468.0 468.6 469.2 469.8 470.4
250 471.0 471.6 472.2 472.8 473.4 474.0 474.6 475.2 475.8 476.4
255 477.0 477.6 478.2 478.7 479.3 479.9 480.5 481.1 481.7 482.3
260 482.9 483.5 484.1 484.7 485.3 485.9 486.5 487.1 487.7 488.3
265 488.» 4^.5 490.1 490.7 491.3 491.9 492.4 493.0 493.6 494.2
270 494.8 495.4 496.0 496.6 497.2 497.8 498.4 AS&.Q 499.6 500.2
275 500.7 501.3 501.9 502.5 503.1 503.7 504.3 504.9 505.5 506.1
280 506.6 507.2 507.8 508.4 509.0 509.6 510.2 510.8 511.4 511.9
285 512.5 513.1 513.7 514.3 514.9 515.5 516.1 516.6 517.2 517.8
290 518.4 519.0 519.6^ 520.2 520.7 521.3 521.9 522.5 523.1 523.7
295 524.3 524.8 525.4 526.0 526.6 527.2 527.8 528.3 528.9 529.5
300 530.1 530.7 531.3 531.8 532.4 533.0 533.6 534.2 534.7 535.3
305 535.9 536.5 537.1 537.6 538.2 538.8 539.4 540.0 540.5 541.1
310 541.7 542.3 542.9 543.4 544.0 544.6 545.2 545.8 546.3 546.9
315 547.5 548.1 548.6 549.2 549.8 550.4 550.9 551.5 552.1 552.7
320 553.3 553.8 554.4 555.0 555.6 556.1 556.7 557.3 557.9 558.4
325 559.0 559.6 560.2 560.7 561.3 561.9 562.4 563.0 563.6 564.2
330 564.7 565.3 565.9 566.5 567.0 567.6 568.2 568.7 569.3 569.9
335 570.5 571.0 571.6 572.2 572.7 573.3 573.9 574.4 575.0 575.6
340 576.1 576.7 577.3 577.9 578.4 579.0 579.6 580.1 580.7 581.3
345 581.8 582.4 583.0 583.5 584.1 584.7 585.2 585.8 586.4 586.9
350 587.5 588.1 588.6 589.2 589.8 590.3 590.9 591.5 592.0 %2.6
(mm Hg) T 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
2 36 180.9 181.6 < 182.3 182.9 183.6 184.3 185.0 185.6 186.3 187.0
40 187.6 188.3 189.0 189.6 190.3 191.0 191.6 192.3 193.0 193.6
45 194.3 195.0 195.6 196.3 197.0 197.6 198.3 199.0 199.6 200.3
50 201.0 201.6 202.3 203.0 203.6 204.3 205.0 205.6 206.3 207.0
55 207.6 208.3 208.9 209.6 210.3 210.9 211.6 212.3 212.9 213.6
60 214.2 214.9 215.6 216.2 216.9 217.5 218.2 218.9 219.5 220.2
65 220.8 221.5 222.2 222.8 223.5 224.1 224.8 225.4 226.1 226.8
70 227.4 228.1 228.7 229.4 230.0 230.7 231.4 232.0 232.7 233.3
75 234.0 234.6 235.3 236.0 236.6 237.3 237.9 238.6 239.2 239.9
80 240.5 241.2 241.8 242.5 243.1 243.8 244.5 245.1 245.8 246.4
85 247.1 247.7 248.4 249.0 249.7 250.3 251.0 251.6 252.3 252.9
90 253.6 254.2 254.9 255.5 256.2 256.8 257.5 258.1 258.8 259.4
95 260.1 260.7 261.4 262.0 262.6 263.3 263.9 264.6 2K.2 26S.9
100 266.5 267.2 267.8 268.5 269.1 269.8 270.4 271.0 271.7 272.3
105 273.0 273.6 274.3 274.9 275.6 276.2 276.8 277.5 278.1 278.8
110 279.4 280.1 280.7 281.3 282.0 282.6 283.3 283.9 284.5 285.2
115 285.8 286.5 287.1 287.8 288.4 289.0 289.7 290.3 290.9 291.6
120 292.2 292.9 293.5 294.1 294.8 295.4 296.1 296.7 297.3 298.0
125 298.6 299.2 299.9 300.5 301.2 301.8 302.4 303.1 303.7 304.3
130 305.0 30S.6 306.2 306.9 307.5 308.1 308.8 309.4 310.0 310.7
1^ 311.3 311.9 312.6 313.2 313.8 314.5 315.1 315.7 316.4 317.0
140 317.6 318.3 318.9 319.5 320.2 320.8 321.4 322.1 322.7 323.3
145 323.9 324.6 325.2 325.8 326.5 327.1 327.7 328.4 329.0 329.6
150 330.2 330.9 331.5 332.1 332.7 333.4 334.0 334.6 335.3 335.9
155 336.5 337.1 337.8 338.4 339.0 339.6 340.3 340.9 341.5 342.1
160 342.8 343.4 344.0 344.6 345.3 345.9 346.5 347.1 347.8 348.4
165 349.0 349.6 350.2 350.9 351.5 352.1 ;K2.7 353.4 354.0 354.6
170 355.2 355.8 356.5 357.1 357.7 358.3 358.9 359.6 360.2 360.8
175 361.4 362.0 362.7 363.3 363.9 364.5 3^.1 3K.8 366.4 367.0
180 367.6 368.2 368.8 369.5 370.1 370.7 371.3 371.9 372.5 373.2
185 373.8 374.4 375.0 375.6 376.2 376.9 377.5 378.1 378.7 379.3
190 379.9 380.5 381.2 381.8 382.4 383.0 383.6 384.2 384.8 385.4
195 386.1 386.7 387.3 387.9 388.5 389.1 389.7 390.3 391.0 391.6
200 392.2 392.8 393.4 394.0 394.6 395.2 395.8 396.4 397.1 397.7
205 398.3 398.9 399.5 400.1 400.7 401.3 401.9 402.5 403.1 403.8
210 404.4 405.0 405.6 406.2 406.8 407.4 408.0 408.6 409.2 409.8
215 410.4 411.0 411.6 412.2 412.8 413.5 414.1 414.7 415.3 415.9
220 416.5 417.1 417.7 418.3 418.9 419.5 420.1 420.7 421.3 421.9
225 422.5 423.1 423.7 424.3 424.9 425.5 426.1 426.7 427.3 427.9
230 428.5 429.1 429.7 430.3 430.9 431.5 432.1 432.7 433.3 433.9
235 434.5 435.1 435.7 436.3 436.9 437.5 438.1 438.7 439.3 439.9
240 440.5 441.1 441.7 442.3 442.9 443.5 444.1 444.7 445.3 445.9
245 446.5 447.1 447.7 448.3 448.9 449.5 450.0 450.6 451.2 451.8
250 452.4 453.0 453.6 454.2 454.8 455.4 456.0 456.6 457.2 457.8
255 458.4 459.0 459.5 460.1 460.7 461.3 461.9 462.5 463.1 463.7
260 464.3 464.9 465.5 466.0 466.6 467.2 467.8 468.4 469.0 469.6
265 470.2 470.8 471.4 471.9 472.5 473.1 473.7 474.3 474.9 475.5
270 476.1 476.7 477.2 477.8 478.4 479.0 479.6 480.2 480.8 481.3
275 481.9 482.5 483.1 483.7 484.3 484.9 485.4 486.0 486.6 487.2
280 487.8 488.4 489.0 489.5 490.1 490.7 491.3 491.9 492.5 493.0
285 493.6 494.2 494.8 495.4 496.0 496.5 497.1 497.7 498.3 498.9
290 499.4 500.0 500.6 501.2 501.8 502.4 502.9 503.5 504.1 504.7
295 505.3 505.8 506.4 507.0 507.6 508.2 508.7 509.3 509.9 510.5
300 511.0 511.6 512.2 512.8 513.4 513.9 514.5 515.1 515.7 516.2
305 516.8 517.4 518.0 518.5 519.1 519.7 520.3 520.9 521.4 522.0
310 522.6 523.2 5?3.7 524.3 524.9 525.5 526.0 526.6 527.2 527.7
315 528.3 528.9 529.5 530.0 530.6 531.2 531.8 532.3 532.9 533.5
320 534.1 534.6 535.2 535.8 536.3 536.9 537.5 538.1 538.6 539.2
325 539.8 540.3 540.9 541.5 542.0 542.6 543.2 543.8 544.3 544.9
330 545.5 546.0 546.6 547.2 547.7 548.3 548.9 549.4 550.0 550.6
335 551.1 551.7 552.3 552.8 553.4 554.0 554.5 555.1 555.7 556.2
340 556.8 557.4 557.9 558.5 559.1 559.6 560.2 560.8 5S^.3 561.9
345 562.5 563.0 563.6 564.2 564.7 565.3 565.8 566.4 567.0 567.5
350 568.1 568.7 569.2 569.8 570.4 570.9 571.5 572.0 572.6 573.2
P (mm Hg) T 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 ,
5 35 162.0 1^.6 163.3 163.9 164.6 165.2 165.9 166.5 167.2 167.8
40 168.5 169.1 169.8 170.4 171.1 171.7 172.3 173.0 173.6 174.3
45 174.9 175.6 176.2 176.9 177.5 178.2 178.8 179.5 180.1 180.8
50 181.4 182.1 182.7 183.3 184.0 184.6 185.3 185.9 186.6 187.2
55 187.9 188.5 189.2 189.8 190.4 191.1 191.7 192.4 193.0 193.7
60 194.3 194.9 195.6 196.2 196.9 197.5 198.2 '198.8 199.4 200.1
65 200.7 201.4 202.0 202.6 203.3 203.9 204.6 205.2 205.8 206.5
70 207.1 207.8 208.4 209.0 209.7 210.3 211.0 211.6 212.2 212.9
75 213.5 214.2 214.8 215.4 216.1 216.7 217.3 218.0 218.6 219.2
80 219.9 220.5 221.2 221.8 222.4 223.1 223.7 224.3 225.0 225.6
85 226.2 226.9 227.5 228.1 228.8 229.4 230.0 230.7 231.3 231.9
90 232.6 233.2 233.8 234.5 235.1 235.7 236.4 237.0 237.6 238.3
95 238.9 239.5 240.2 240.8 241.4 242.1 242.7 243.3 244.0 244.6
100 245.2 245.8 246.5 247.1 247.7 248.4 249.0 249.6 250.3 250.9
105 251.5 252.1 252.8 253.4 254.0 254.7 255.3 255.9 256.5 257.2
110 257.8 258.4 259.0 259.7 260.3 160.9 261.5 262.2 262.8 263.4
115 264.0 264.7 265.3 265.9 266.5 267.2 267.8 268.4 269.0 269.7
120 270.3 270.9 271.5 272.2 272.8 273.4 274.0 274.7 275.3 275.9
125 276.5 277.1 277.8 278.4 279.0 279.6 280.3 280.9 281.5 282.1
130 282.7 283.4 284.0 284.6 285.2 285.8 286.5 287.1 287.7 288.3
135 288.9 289.6 290.2 290.8 291.4 292.0 292.7 293.3 293.9 294.5
140 295.1 295.7 296.4 297.0 297.6 298.2 298.8 299.4 300.1 300.7
145 301.3 301.9 302.5 303.1 »}3.8 304.4 305.0 305.6 306.2 306.8
150 307.5 308.1 308.7 309.3 309.9 310.5 311.1 311.8 312.4 313.0
155 313.6 314.2 314.8 315.4 3t'6.0 316.7 317.3 317.9 318.5 319.1
160 319.7 320.3 320.9 321.6 322.2 322.8 323.4 324.0 324.6 325.2
165 325.8 326.4 327.0 327.7 328.3 328.9 329.5 330.1 330.7 331.3
170 331.9 332.5 333.1 333.7 334.4 335.0 335.6 336.2 336.8 337.4
175 338.0 338.6 339.2 ^9.8 340.4 341.0 341.6 342.2 342.9 343.5
180 344.1 344.7 345.3 345.9 346.5 347.1 347.7 348.3 348.9 349.5
185 350.1 350.7 351.3 351.9 352.5 353.1 353.7 354.3 354.9 355.6
190 356.2 356.8 357.4 358.0 358.6 359.2 359.8 360.4 361.0 361.6
195 362.2 362.8 363.4 364.0 .364.6 365.2 365.8 366.4 367.0 367.6
200 368.2 368.8 369.4 370.0 370.6 371.2 371.8 372.4 373.0 373.6
205 374.2 374.8 375.4 376.0 376.6 377.2 377.8 378.4 37ao 379.6
210 380.1 380.7 381.3 381.9 382.5 383.1 383.7 384.3 384.9 385.5
215 386.1 386.7 387.3 387.9 388.5 389.1 389.7 390.3 390.9 391.5
220 392.1 392.7 393.2 ^3.8 394.4 395,0 395.6 396.2 396.8 397.4
225 398.0 398.6 399.2 399.8 400.4 401.0 401.5 402.1 402.7 403.3
230 403.9 404.5 405.1 405.7 406.3 406.9 407.5 408.0 408.6 409.2
235 409.8 410.4 411.0 411.6 412.2 412.8 413.4 413.9 414.5 415.1
240 415.7 416.3 416.9 417.5 418.1 418.7 419.2 419.8 420.4 421.0
245 421.6 422.2 422.8 423.3 423.9 424.5 425.1 425.7 426.3 426.9
250 427.5 428.0 428.6 429.2 429.8 430.4 431.0 431.5 432.1 432.7
255 433.3 433.9 434.5 435.1 435.6 436.2 436.8 437.4 438.0 438.6
260 439.1 439.7 440.3 440.9 441.5 442.0 442.6 443.2 443.8 444.4
265 445.0 445.5 446.1 446.7 447.3 447.9 448.4 449.0 449.6 450.2
270 450.8 451.3 451.9 452.5 453.1 453.7 454.2 454.8 455.4 456.0
275 456.6 457.1 457.7 458.3 458.9 459.4 460.0 460.6 461.2 461.8
280 462.3 462.9 463.5 464.1 464.6 465.2 465.8 466.4 466.9 467.5
285 468.1 "468.7 469.3 469.8 470.4 471.0 471.6 472.1 472.7 473.3
290 473.9 474.4 475.0 475.6 476.1 476.7 477.3 477.9 478.4 479.0
295 479.6 480.2 480.7 481.3 481.9 482.5 483.0 483.6 484.2 484.7
300 485.3 485.9 486.5 487.0 487.6 488.2 488.7 4%.3 489.9 490.5
305 491.0 491.6 492.2 492.7 493.3 493.9 494.4 495.0 495.6 496.2
310 496.7 497.3 497.9 498.4 499.0 499.6 500.1 500.7 501.3 501.8
315 502.4 503.0 503.5 504.1 504.7 505.2 505.8 506.4 506.9 507.5
320 508.1 508.6 509.2 509.i3 510.3 510.9 511.5 512.0 512.6 513.2
325 513.7 514.3 514.9 515.4 516.0 516.6 517.1 517.7 518.3 518.8
330 519.4 519.9 520.5 521.1 521.6 522.2 522.8 523.3 523.9 524.4
335 525.0 525.6 526.1 526.7 527.3 527.8 528.4 528.9 529.5 530.1
340 530.6 531.2 531.8 532.3 532.9 533.4 534.0 534.6 535.1 535.7
345 536.2 536.8 537.4 537.9 538.5 539.0 539.6 540.1 540.7 541.3
350 541.8 542.4 542.9 543.5 544.1 544.6 545.2 545.7 546.3 546.8
P (mm Hg) T 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
10 35 146.8 147.4 148.1 148.7 149.3 150.0 150.6 151.2 151.9 152.5
40 153.1 153.8 154.4 155.0 155.7 156.3 156.9 157.6 158.2 158.8
45 159.5 160.1 160.7 161.4 162.0 162.6 163.3 163.9 164.5 165.1
50 165.8 166.4 167.0 167.7 168.3 168.9 169.6 170.2 170.8 171.4
55 172.1 172.7 173.3 174.0 174.6 175.2 175.8 176.5 177.1 177.7
60 178.4 179.0 179.6 180.2 180.9 181.5 182.1 182.7 183.4 184.0
65 184.6 185.3 185.9 186.5 187.1 187.8 188.4 189.0 189.6 190.3
70 190.9 191.5 192.1 192.8 193.4 194.0 194.6 195.3 195.9 196.5
75 197.1 197.7 198.4 199.0 199.6 200.2 200.9 201.5 202.1 202.7
80 203.3 204.0 204.6 205.2 205.8 206.5 207.1 207.7 208.3 208.9
85 209.6 210.2 210.8 211.4 212.0 212.7 213.3 213.9 214.5 215.1
90 215.8 216.4 217.0 217.6 218.2 218.9 219.5 220.1 220.7 221.3
95 222.0 222.6 223.2 223.8 224.4 225.0 225.7 226.3 226.9 227.5
100 228.1 228.7 229.4 230.0 230.6 231.2 231.8 232.4 233.1 233.7
105 234.3 234.9 235.5 236.1 236.7 237.4 238.0 238.6 239.2 239.8
110 240.4 241.0 241.7 242.3 242.9 243.5 244.1 244.7 245.3 246.0
115 246.6 247.2 247.8 248.4 249.0 249.6 250.2 250.9 251.5 252.1
120 252.7 253.3 253.9 254.5 255.1 255.7 256.4 257.0 257.6 258.2
125 258.8 259.4 260.0 260.6 261.2 261.8 262.4 263.1 263.7 264.3
130 264.9 265.5 266.1 266.7 267.3 267.9 268.5 269.1 269.7 270.4
135 271.0 271.6 272.2 272.8 273.4 274.0 274.6 275.2 275.8 276.4
140 277.0 277.6 278.2 278.8 279.5 280.1 280.7 281.3 281.9 282.5
145 283.1 203.7 284.3 284.9 285.5 286.1 286.7 287.3 287.9 288.5
150 289.1 289.7 290.3 290.9 291.5 292.1 292.7 293.3 293.9 294.5
155 295.2 295.8 296.4 297.0 297.6 298.2 298.8 299.4 300.0 300.6
160 301.2 301.8 302.4 303.0 303.6 304.2 304.8 305.4 306.0 306.6
165 307.2 307.8 308.4 309.0 309.6 310.2 310.8 311.4 312.0 312.6
170 313.2 313.8 314.4 314.9 315.5 316.1 316.7 317.3 317.9 318.5
175 319.1 319.7 320.3 320.9 321.5 322.1 322.7 323.3 323.9 324.5
180 325.1 325.7 326.3 326.9 327.5 328.1 328.7 329.3 329.9 330.4
185 331.0 331.6 332.2 332.8 333.4 334.0 334.6 335.2 335.8 336.4
190 337.0 337.6 338.2 338.8 3^.3 339.9 340.5 341.1 341.7 342.3
195 342.9 343.5 344.1 344.7 345.3 345.9 346.4 347.0 347.6 348.2
200 348.8 349.4 350.0 350.6 351.2 351.8 352.4 352.9 353.5 354.1
205 354.7 355.3 355.9 356.5 357.1 357.7 358.2 358.8 359.4 360.0
210 360.6 361.2 361.8 362.4 362.9 363.5 364.1 364.7 3^.3 365.9
215 366.5 367.1 367.6 368.2 368.8 369.4 370.0 370.6 371.2 371.7
220 372.3 372.9 373.5 374.1 374.7 375.3 375.8 376.4 377.0 377.6
225 378:2 378.8 379.3 379.9 380.5 381.1 381.7 382.3 382.8 3^.4
230 384.0 384.6 385.2 385.8 386.3 386.9 387.5 388.1 388.7 389.3
235 389.8 390.4 391.0 391.6 392.2 392.7 393.3 393.9 394.5 395.1
240 395.6 396.2 396.8 397.4 398.0 398.5 399.1 399.7 400.3 400.9
245 401.4 402.0 402.6 403.2 403.8 404.3 404.9 405.5 406.1 406.7
250 407.2 407.8 408.4 409.0 409.5 410.1 410.7 411.3 411.9 412.4
255 413.0 413.6 414.2 414.7 415.3 415.9 416.5 417.0 417.6 418.2
260 418.8 419.3 419.9 420.5 421.1 421.6 422.2 422.8 423.4 423.9
265 424.5 425.1 425.7 426.2 426.8 427.4 428.0 428.5 429.1 429,7
270 430.3 430.8 431.4 432.0 432.5 433.1 433.7 434.3 434.8 435.4
275 436.0 436.5 437.1 437.7 438.3 438.8 439.4 440.0 440.5 441.1
280 441.7 442.3 442.8 443.4 444.0 444.5 445.1 445.7 446.3 446^8
285 447.4 448.0 448.5 449.1 449.7 450.2 450.8 451.4 451.9 452.5
290 453.1 4S3.6 454.2 454.8 455.4 455.9 456.5 457.1 457.6 458.2
295 458.8 459.3 459.9 460.5 461.0 461.6 462.2 462.7 463.3 463.9
300 464.4 465.0 465.6 466.1 466.7 467.3 467.8 468.4 468.9 469.5
305 470.1 470.6 471.2 471.8 472.3 472.9 473.5 474.0 474.6 475.2
310 475.7 476.3 476.8 477.4 478.0 478.5 479.1 479.7 480.2 480.8
315 481.3 481.9 482.5 483.0 483.6 484.2 484.7 485.3 485.8 486.4
320 487.0 487.5 488.1 488.6 489.2 489.8 490.3 490.9 491.4 492.0
325 492.6 493.1 433.7 ^4.2 494.8 495.4 495.9 496.5 497.0 497.6
330 498.2 498.7 499.3 499.8 500.4 501.0 501.5 502.1 502.6 503.2
335 503.7 504.3 504.9 505.4 506.0 506.5 507.1 507.6 508.2 508.8
340 509.3 509.9 510.4 511.0 511.5 512.1 512.7 513.2 513.8 514.3
345 514.9 515.4 516.0 516.5 517.1 517.7 518.2 518.8 519.3 519.9
350 520.4 521.0 521.5 522.1 522.6 523.2 523.7 524.3 524.9 525.4
TABLE 18—AEl conversion table at 2.67 kPa (20 mm Hg) pressure °C.
P (mm Hg) T 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
20 35 131.0 131.6 132.2 132.8 133.4 134.1 134.7 135.3 135.9 136.5
40 137.1 137.8 138.4 139.0 139.6 140.2 140.8 141.5 142.1 142.7
45 143.3 143.9 144.5 145.1 145.8 146.4 147.0 147.6 148.2 148.8
50 149.4 150.1 150.7 151.3 151.9 152.5 153.1 153.7 154.3 155.0
55 155.6 156.2 156.8 157.4 158.0 158.6 159.2 159.9 160.5 161.1
60 161.7 162.3 162.9 163.5 164.1 164.7 165.4 166.0 166.6 167.2
65 167.8 168.4 169.0 169.6 170.2 170.8 171.5 172.1 172.7 173.3
70 173.9 174.5 175.1 175.7 176.3 176.9 177.5 178.1 178.8 179.4
75 180.0 180.6 181.2 181.8 182.4 183.0 183.6 184.2 184.8 185.4
80 186.0 186.6 187.3 187.9 188.5 189.1 189.7 190.3 190.9 191.5
85 192.1 192.7 193.3 193.9 194.5 195.1 195.7 196.3 196.9 197.5
90 198.2 198.8 199.4 200.0 200.6 201.2 201.8 202.4 203.0 203.6
95 204.2 204.8 205.4 206.0 206.6 207.2 207.8 208.4 209.0 209.6
100 210.2 210.8 211.4 212.0 212.6 213.2 213.8 214.4 215.0 215.6
105 216.2 216.8 217.4 218.0 218.6 219.2 219.8 220.4 221.0 221.6
110 222.2 222.8 223.4 224.0 224.6 225.2 225.8 226.4 227.0 227.6
115 228.2 228.8 229.4 230.0 230.6 231.2 231.8 232.4 233.0 233.6
120 234.2 234.8 235.4 236.0 236.6 237.2 237.8 238.4 239.0 239.6
125 240.2 240.8 241.4 242.0 242.6 243.2 243.8 244^4 244.9 245.5
130 246.1 246.7 247.3 247.9 248.5 249.1 249.7 250.3 250.9 251.5
135 252.1 252.7 253.3 253.9 254.5 255.1 255.6 256.2 256.8 257.4
140 258.0 258.6 259.2 259.8 260.4 261.0 261.6 262.2 262.8 263.4
145 263.9 264.5 265.1 265.7 266.3 266.9 267.5 268.1 268.7 269.3
150 269.9 270.5 271.0 271.6 272.2 272.8 273.4 274.0 274.6 275.2
155 275.8 276.4 276.9 277.5 278.1 278.7 279.3 279.9 280.5 281.1
160 281.7 282.2 282.8 283.4 284.0 284.6 285.2 285.8 286.4 286.9
165 287.5 288.1 288.7 289.3 289.9 290.5 291.1 291.6 292.2 292.8
170 293.4 294.0 294.6 295.2 295.8 296.3 296.9 297.5 298.1 298.7
175 299.3 299.8 300.4 301.0 301.6 302.2 302.8 303.4 303.9 304.5
180 305.1 305.7 306.3 306.9 307.4 308.0 308.6 309.2 309.8 310.4
185 310.9 311.5 312.1 312.7 313.3 313.9 314.4 315.0 315.6 316.2
190 316.8 317.4 317.9 318.5 319.1 319.7 320.3 320.8 321.4 322.0
195 322.6 323.2 323.8 324.3 324.9 325.5 326.1 326.7 327.2 327.8
200 328.4 329.0 329.6 330.1 330.7 331.3 331.9 332.5 333.0 333.6
205 334.2 334.8 335.3 335.9 336.5 337.1 337.7 338.2 338.8 3^.4
210 340.0 340.6 341.1 341.7 342.3 342.9 343.4 344.0 344.6 345.2
215 345.7 346.3 346.9 347.5 348.1 348.6 349.2 349.8 350.4 350.9
220 351.5 352.1 352.7 353.2 353.8 354.4 355.0 355.5 356.1 356.7
225 357.3 357.8 aSb.A 359.0 359.6 360.1 360.7 361.3 361.9 362.4
230 363.0 363.6 364.1 364.7 365.3 365.9 366.4 367.0 367.6 368.2
235 368.7 369.3 369.9 370.4 371.0 371.6 372.2 372.7 373.3 373.9
240 374.5 375.0 375.6 376.2 376.7 377.3 377.9 378.4 379.0 379.6
245 380.2 380.7 381.3 381.9 382.4 383.0 383.6 384.2 384.7 385.3
250 385.9 386.4 387.0 387.6 388.1 388.7 389.3 389.8 %0.4 391.0
255 391.5 392.1 392.7 393.3 393.8 394.4 395.0 395.5 396.1 396.7
260 397.2 397.8 398.4 %8.9 399.5 400.1 400.6 401.2 401.8 402.3
265 402.9 403.5 404.0 404.6 405.2 405.7 406.3 406.9 407.4 Afy&.Q
270 408.5 409.1 409.7 410.2 410.8 411.4 411.9 412.5 413.1 413.6
275 414.2 414.8 415.3 415.9 416.5 417.0 417.6 418.1 418.7 419.3
280 419.8 420.4 421.0 421.5 422.1 422.6 423.2 423.8 424.3 424.9
285 425.5 426.0 426.6 427.1 427.7 428.3 428.8 429.4 430.0 430.5
290 431.1 431.6 432.2 432.8 433.3 433.9 434.4 435.0 435.6 436.1
295 436.7 437.2 437.8 438.4 438.9 439.5 440.0 440.6 441.2 441.7
300 442.3 442.8 443.4 444.0 444.5 445.1 445.6 446.2 446.7 447.3
305 447.9 448.4 449.0 449.5 450.1 450.6 451.2 451.8 452.3 452.9
310 453.4 454.0 454.5 455.1 455.7 456.2 456.8 457.3 457.9 458.4
315 459.0 459.6 460.1 460.7 461.2 461.8 462.3 462.9 463.4 464.0
320 464.6 465.1 AIS5.7 466.2 466.8 467.3 467.9 468.4 469.0 469.5
325 470.1 470.7 471.2 471.8 472.3 472.9 473.4 474.0 474.5 475.1
330 475.6 476.2 476.7 477.3 477.8 478.4 479.0 479.5 480.1 480.6
335 481.2 481.7 482.3 482.8 483.4 483.9 484.5 485.0 485.6 486.1
340 486.7 487.2 487.8 488.3 488.9 489.4 490.0 490.5 491.1 491.6
345 492.2 492.7 493.3 493.8 494.4 494.9 495.5 496.0 496.6 497.1
350 497.7 498.2 498.8 499.3 499.9 500.4 501.0 501.5 502.1 502.6
=> (mm Hg) T 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
50 35 109.0 109.6 110.2 110.7 111.3 111.9 112.5 113.1 113.7 114.3
40 114.9 115.5 116.1 116.7 117.2 117.8 118.4 119.0 119.6 1202
45 120.8 121.4 122.0 122.6 123.1 123.7 124.3 124.9 125.5 126.1
50 126.7 127.3 127.9 128.5 129.0 129.6 130.2 130.8 131.4 132.0
55 132.6 133.2 133.7 134.3 134.9 135.5 136.1 136.7 137.3 137.9
60 138.5 139.0 139.6 140.2 140.8 141.4 142,0 142.6 143.1 143.7
65 144.3 144.9 145.5 146.1 146.7 147.3 147.8 148.4 149.0 149.6
70 150.2 150.8 151.4 151.9 152.5 153.1 153,7 154.3 154.9 155.5
75 156.0 156.6 157.2 157.8 158.4 159.0 159,5 160.1 160.7 161.3
80 161.9 162.5 163.1 163.6 164.2 164.8 165,4 166.0 166.6 167.1
85 167.7 168.3 168:9 169.5 1701 170.6 171,2 17f.8 172.4 173.0
90 173.6 174.1 174.7 175.3 175.9 176.5 177.0 177.6 178.2 178.8
95 179.4 180.0 180.5 181.1 181.7 182.3 182.9 183.4 184.0 184.6
100 185.2 185.8 186.3 186.9 187.5 188.1 188,7 189.2 189.8 190.4
105 191.0 191.6 192.1 192.7 193.3 193.9 194,5 195.0 195.6 196.2
110 196.8 197.4 197.9 198.5 199.1 199.7 200,3 200.8 201.4 202.0
115 202.6 203.1 203.7 204.3 204.9 205.5 206,0 206.6 207.2 207.8
120 208.3 208.9 209.5 210.1 210.7 211.2 211.8 212.4 213.0 213.5
125 214.1 214.7 215.3 215.8 216.4 217.0 217.6 218.1 218.7 219.3
130 219.9 220.4 221.0 221.6 222.2 222.7 223.3 223.9 224.5 225.0
135 225.6 226.2 226.8 227.3 227.9 228.5 229.1 229.6 230.2 230.8
140 231.4 231.9 232.5 233.1 233.7 234.2 234.8 235.4 236.0 236.5
145 237.1 237.7 238.2 238.8 239.4 240.0 240.5 241.1 241.7 242.3
150 242.8 243.4 244.0 244.5 245.1 245.7 246.3 246,8 247.4 248.0
IK 248.5 249.1 249.7 250.3 250.8 251.4 252.0 252.5 253.1 253.7
160 254.3 254.8 255.4 256.0 256.5 257.1 257.7 258.3 258.8 259.4
165 260.0 260.5 261.1 261.7 262.2 262.8 263.4 263.d 264.5 265.1
170 2K.7 266.2 266.8 267.4 267.9 268.5 269.1 269.6 270.2 270.8
175 271.3 271.9 272.5 273.0 273.6 274.2 274.8 275.3 275.9 276.5
180 277.0 277.6 278.2 278.7 279.3 279.9 280.4 281.0 281.6 282.1
185 282.7 283.3 283.8 284.4 285.0 285.5 286.1 286.7 287.2 287.8
190 288.4 288.9 289.5 290.0 290.6 291.2 291.7 292.3 292.9 293.4
195 294.0 294.6 295.1 295.7 296.3 296.8 297.4 298.0 298.5 299.1
200 299.7 300.2 300.8 301.3 301.9^ 302.5 303.0 303.6 304.2 304.7
205 305.3 305.9 306.4 307.0 307.5 308.1 308.7 309.2 309.8 310.4
210 310.9 311.5 312.0 312.6 313.2 313.7 314.3 314.9 315.4 316.0
215 316.5 317.1 317.7 318.2 318.8 319.3 319.9 320.5 321.0 321.6
220 322.2 322.7 323.3 323.8 324.4 325.0 325.5 326.1 326.6 327.2
225 327.8 328.3 328.9 329.4 330.0 330.6 331.1 331.7 332.2 332.8
230 333.4 333.9 334.5 335.0 335.6 336.1 336.7 337.3 337.8 338.4
235 338.9 339.5 340.1 340.6 341.2 341.7 342.3 342,8 343.4 344.0
240 344.5 345.1 345.6 346.2 346.8 347.3 347.9 348,4 349.0 349.5
245 350.1 350.7 351.2 351.8 352.3 352.9 353.4 354,0 354.5 355.1
250 355.7 356.2 356.8 357.3 357.9 358.4 359.0 359,5 360.1 360.7
255 361.2 361.8 362.3 362.9 363.4 364.0 364.5 365.1 3K.7 366.2
260 366.8 367.3 367.9 368.4 369.0 369.5 370.1 370.6 371.2 371.8
2^ 372.3 372.9 373.4 374.0 374.5 375.1 375.6 376.2 376.7 377.3
270 377.8 378.4 378.9 379.5 380.0 380.6 381.2 381.7 382.3 382.8
275 383.4 383.9 384.5 385.0 385.6 386.1 386.7 387.2 387.8 388.3
280 388.9 389.4 390.0 390.5 391.1 391.6 392.2 392.7 393.3 393.8
285 394.4 394.9 395.5 396.0 396.6 397.1 397.7 398.2 398.8 399.3
290 399.9 400.4 401.0 401.5 402.1 4(^.6 403.2 403.7 404.3 404.8
295 405.4 405.9 406.5 407.0 407.6 408.1 408.7 409.2 409.8 410.3
300 410.9 411.4 412.0 412.5 413.1 413.6 414.2 414.7 415.3 415.8
305 416.4 416.9 417.4 418.0 418.5 419.1 419.6 420.2 420.7 421.3
310 421.8 422.4 422.9 423.5 424.0 424.6 425.1 425.6 426.2 426,7
315 427.3 427.8 428.4 428.9 429.5 430.0 430.6 431.1 431.6 432,2
320 432.7 433.3 433.8 434.4 434.9 435.5 436.0 436.6 437.1 437,6
325 438.2 438.7 439.3 439.8 440.4 440.9 441.5 442.0 442.5 443,1
330 443.6 444.2 444.7 445.3 445.8 446.3 446.9 447.4 448.0 448,5
335 449.1 449.6 450.1 450.7 451.2 451.8 452.3 452.9 453.4 453,9
340 454.5 455.0 «5.6 A56A 456.7 457.2 457.7 458.3 458.8 459,4
345 459.9 460.4 461.0 461.5 462.1 482.6 463.1 463.7 464.2 464.8
350 465.3 4^.8 466.4 466.9 467.5 468.0 468.6 469.1 4^.6 470,2
TABLE 20—Precision of manual D 1160.

Repeatability Reproducibility
Pressure 0.13kPa(l mmHg) 1.3 kPa (10 mmHg) 0.13 kPa(l mmHg) 1.3 kPa (10 mmHg)
IBP 17 15 56 49
FBP 3.3 7.1 31 27
Volume
Recovered 5-50% 60-90% 5-50% 60-90% 5-50% 60-90%. 5-50% 60-90%
C/V%
0.5 2.4 2.5 1.9 2.0 6.5 3.9 7.0 5.4
1.0 2.9 3.0 2.4 2.5 10 6.0 9.3 7.2
1.5 3.2 3.3 2.8 2.9 13 7.6 11 8.5
2.0 3.4 3.5 3.1 3.2 16 9.4 12 9.8
2.5 3.6 3.7 3.3 3.5 16 11 14 11
3.0 3.8 3.9 3.6 3.7 21 12 15 11
3.5 3.9 4.0 3.8 3.9 23 13 16 12
4.0 4.0 4.2 3.9 4.1 25 15 16 13
4.5 4.1 4.3 4.1 4.3 27 16 17 13
5.0 4.2 4.4 4.3 4.4 29 17 18 14
5.5 4.3 4.5 4.4 4.6 30 18 19 15
6.0 4.4 4.6 4.5 4.7 32 19 19 15
6.5 4.5 4.7 4.7 4.8 34 20 20 16
7.0 4.6 4.8 4.8 5.0 35 23 21 16
7.5 4.7 4.8 4.9 5.1 37 22 21 16
8.0 4.8 4.9 5.0 5.2 38 23 22 17
8.5 4.8 5.0 5.1 5.3 40 24 22 17
9.0 4.9 5.1 5.2 5.4 41 25 23 18
9.5 5.0 5.1 5.3 5.5 43 25 23 18
10.0 5.0 5.2 5.4 5.6 44 26 24 19
10.5 5.1 5.2 5.5 5.7 46 27 24 19
11.0 5.1 5.3 5.6 5.8 47 28 25 19
11.5 5.2 5.4 5.7 5.9 48 29 25 20
12.0 5.2 5.4 5.8 6.0 50 30 26 20
12.5 5.3 5.5 5.9 6.1 51 30 26 20
13.0 5.3 5.5 6.0 6.2 52 31 27 21
13.5 5.4 5.6 6.0 5.3 54 32 27 21
14.0 5.4 5.6 6.1 6.3 55 33 27 21
14.5 5.5 5.7 6.2 6.4 56 33 28 22
15.0 5.5 5.7 6.3 6.5 57 34 28 22
TABLE 21—Precision of automatic D 1160 distillation in °C [7].

1 mm Hg Pressure 10 mm Hg Pressure
Boiling
Point Repeatability Reproducibility Repeatability Reproducibility
IBP 15.9 29.9 16.7 35.4
5% 8.0 17.5 6.8 11.1
10% 5.5 16 3.7 8.0
20% 3.8 12.2 4.3 10.4
30% 3.8 12 3.2 7.1
40% 5.2 9.6 2.9 8.6
50% 4.7 8.8 3.1 10.2
60% 6.5 9.5 3.7 12.8
70% 4.4 11.1 3.4 11.3
80% 7.3 13.1 3.8 14.1
90% 6.5 24.8 5.0 25.5
FBP 9.5 37.4 6.4 19.7
TABLE 22—Cross reference of international distillation standards relative to ASTM distillation test methods.
ASTM Distillation
Designation Pressure ISO IP BS AFNOR DIN FTM JIS
U.S. Europe U.K. U.K. France Germany Japan
D86 Atmospheric 3405 123 7392 M07-002 51 751 791-1001 K2254
D 1160 Vacuum 6616 51 356 K2258
D2892 Vacuum 8708 51567
D5236 Vacuum 51 567
flammable liquids as those having flash points below 37.8°C temperature probes or thermocouples are used to measure
and combustible liquids as those having flash points between the temperature of the specimen during the test, and changes
37.8°C and 93.3°C using specified ASTM flash point test in the ionization current, thermal conductivity, or pressure
methods. In 1990, the U.S. decided to align its definition of are used to detect the occurrence of the flash point. Table 24
flammable and combustible material with the United Na- gives a summary of the applicable scope, temperature range,
tion's definition, and now defines [23] flammable liquid as repeatability, and reproducibility for these various flash
having a flash point below 60.5°C and a combustible liquid point methods.
with flash point between 60.5°C and 93.3°C. Gasoline and All reported flash point values are corrected for the ambi-
aviation fuels are obviously flammable liquids. Flash point ent barometric pressure at the time of the test. The observed
specifications have been established for aviation turbine fu- flash point is corrected for barometric pressure by using the
els, kerosines, diesel fuels, fuel oils, hydrocarbon solvents, lu- equations [32]:
bricants, and other petroleum products.
There are a number of ASTM flash point test methods: D Corrected flash point = C + 0.25 (101.3 - p) (7)
56, Flash Point by Tag Closed Tester [24]; D 92, Flash and = C + 0.033 (760 - P) (8)
Fire Points by Cleveland Open Cup [25]; D 93, Flash Point by
Pensky-Martens Closed Cup Tester [26]; D 1310, Flash Point where: p = ambient barometric pressure in kPa
and Fire Points of Liquids by Tag Open Cup Apparatus [27]; P - ambient barometric pressure in mm Hg.
D 3278, Flash Point by Setaflash Closed Cup Apparatus [28];
D 3828, Flash Point by Small Scale Closed Tester [29]; and D Historically, the proper operation of flash point testers was
3941, Flash Point by the Equilibrium Method With a Closed verified by determining the flash point of 1,4-dimethyl ben-
Cup Apparatus [30]. A new flash point method, D 6450, Flash zene (p-xylene). However, due to its toxicity and its relatively
Point by Continuously Closed Cup (CCCFP) Tester [31] that low flash point (27°C), eiltemative flash point verification flu-
was recently approved as an ASTM standard is included in ids were studied. The results of an interlaboratory study con-
this work. ducted in 1993 by the ASTM S-15 Coordinating Committee
Table 23 gives the comparison of the different ASTM test on Flash Point in cooperation with the NationsJ Institute of
methods of determining the flash point of a material. These Standards and Technology led to the establishment of con-
flash point test methods all require a given specimen size, a sensus reference flash point values for n-decane, n-undecane,
prescribed rate of heating, temperature measuring device, in- n-tetradecane, and n-hexadecane to be used as flash point
troduction of a heating source at specific stage during the verification fluids for the different flash point test methods.
test, some mechanism of detecting the flash point, and baro- Table 25 summarizes the method specific flash points of
metric pressure correction. In manual flash point equipment, these reference standards [33,34]. The study also attempted
the ignition source is a gas test flame, and the mechanism of to determine the relative bias of the different flash point test
detecting the flash point is the visual observation of a flame method as shown in Table 26 [33]. However, the report of the
that instantaneously propagates itself over the entire surface study stressed that the observed relative bias among the dif-
of the fluid. When the ignition source is a gas flame, the ap- ferent flash point test methods are only applicable to the pure
plication of the test flame may cause a blue halo or an en- hydrocctrbon liquids used in the study, and may not be appli-
larged flame prior to the actual flash point. Such a phe- cable to mixtures. The observed D 56/D 93 of 0.97 for n-de-
nomenon is not a flash and should be ignored. In the cane and 0.98 for n-undecane was not unexpected since the
automated equipment, the specimen size and equipment di- rate of heating for D 56 is much slower than D 93 thus allow-
mensions are the same as those of the manual apparatus. ing thermal equilibrium between the bulk of the specimen
However, the rate of heating, temperature measurements, and the vapors above it. Open cup flash point methods like D
and detection of the flash point are done automatically ac- 92 are expected to give higher flash points than closed cup
cording to the meinual procedure requirements. Resistance flash point methods. This is because sufficient volatile vapor
TABLE 23—Comparison of the test parameters of different ASTMflashpoint test methods.

Repeat
Expected Flash Pt. FP
ASTM Cup Sample Flash Stirring Heating (FP) Test Test Report to
Designation Apparatus Type Size Point Rate Rate Initiation Every Nearest
D56 Tag Closed 50 mL <60°C N/A rC/min 5°C below FP 0 . 5 X rise 0.5''C
aeox N/A 3°C/mln 5°C below FF 1.0°Crise 0.5°C
D92 Cleveland Open 70 mL N/A N/A 14-17°C/min 28°C below FF 1.0°C rise 1.0°C
D 93 Free. A Pensky-Martens Closed 75 mL slice 90-120 r p m 5-6°C/min 23 ± 5 ^ 1.0°C rise 0.5°C
below FF
D 93 Proc. B Pensky-Martens Closed 75 mL >110X 250 r p m l-1.5°C/min 23 ± 5 ^ 2.0°C rise 0.5°C
below FF
D 1310 Tag Open 50 mL All ranges N/A rC/min 10°C below FF 1.0°C rise 0.5^
D3278 Setaflash Closed 2 mL All ranges N/A N/A Target FF N/A 0.5°C
D3828 Small Scale Closed 2mL All ranges N/A N/A Target FF N/A 0.5°C
D3941 Equilibrium Closed 50 mL All ranges N/A N/A Target FP N/A 0.5°C
Method Closed 75 m L All ranges 90-120 r p m N/A Target FF N/A 0.5°C
D6450 Continuously Closed ImL All ranges 5.5 ± 0.5° 18°C below FF l.O-Crise 0.5-0
Closed Cup C/min
TABLE 24—Comparison of the scope and precision of the different ASTM flash point test methods.
ASTM Temperature Expected (95% (95%
Designation Apparatus Scope Range Flash Point Confidence) Confidence)
D56 Tag Liquids, viscosity Below 93°C <60°C 1.2''C 4.3°C
<5.5 mm^/s at 40°C >60-C 1.6°C 5.8°C
or 9.5 mm^/s at
25°C.
D92 Cleveland Petroleum products 79-400''C 8°C 18°C
D 93 Proc. A Pensky-Martens Distillate fuels 40-360°C All ranges 0.035 X °C 0.078 X °C
(diesel, kerosene, X = reported X = reported
heating oil, turbine result in°C result in °C
fuels, new
lubricating oils, and
other homogeneous
petroleum liquids
not covered by
Proc. B
D 93 Proc. B Pensky-Martens Residual fuel oils. 40-360''C Residual 2°C 6°C
cutback residua. fuels 5°C 10°C
used lube oils. Others
mixtures of
petroleum liquids
with solids, liquids
that form surface
films, viscous
liquids.
D1310 Tag Liquids - 1 8 to 165°C -18to93°C 2°C 4°C
93 to 165°C 5°C 7°C
D3278 Setaflash Paints, enamels, 0-110°C Solvents 1.7°C 3.3X
lacquers, varnishes. Resins/paints 3.3''C 5.0°C
and related
products with
viscosity, 150 St at
25°C
D3828 Small Scale Petroleum products Ambient to 20-70°C O.S'C 0.03(M + 29) "C
300°C above TCC 0.022 M"-^ °C 0.083 M"^ °C
M = mean of M = mean of
two results two results
D3941 Equilibrium Liquids with 0-1 l O X All ranges 2°C 3°C

method specimen and vapor
temperature
approximately in
equilibrium
D6450 Continuously Fuel oils, 10-250°C All ranges 1.9°C 3.rc
Closed Cup lubricating oils,
other solvents, and
liquids
TABLE 25—Flash point verification fluids.

Reference Reference Value Expanded # of Independent
Material Test Method °C Uncertainty (°C) Observations
RM8517 D56 50.9 ±0.8 17
n-Decane D93 52.8 ± 1.0 21
D 3278/D 3828 49.7 ± 1.2 6
RM8518 D56 67.1 ±0.7 17
n-Undecane D92 73.2 ±2.5 14
D93 68.7 ± 1.4 21
D 3278/D 3828 65.9 ± 1.6 6
RM8519 D92 115.5 ±2.6 13
n-Tetradecane D93 109.3 ±2.7 17
RM 8520 D92 138.8 ±2.4 13
n- Hexadecane D93 133.9 ±2.8 16
Uncertainty: The uncertainty of each value in this Report is the numerical value of an expanded uncertainty V = kuc, with U determined from a
combined standard uncertainty Uc, and a coverage factor k equal to a t-factor from the ^distribution with degrees of freedom equal to the number
of independent observations minus 1. This expanded uncertainty defines a range of values for the certified value within which the true value is be-
lieved to lie, at a confidence level of 95%.
TABLE 26—Relative bias among various flash point test methods.

Verification Fluid D 56/ D 93 D 92/D 93 D 3278/D 93 D 3828/D 93
n-Decane 0.964 0.941
n-Undecane 0.977 1.065 0.982
n-Tetradecane 1.057
n-Hexadecane 1.036
the oldest D-2 standard test method in publication. The latest

edition is D 56-OOa. The term "Tag" in this standard is a con-
Both traction of Tagliabue, who invented the original small closed
y \ Thermometer ThermomeJer
tester for flash point determination in 1861 [35]. The Tag
closed tester is a modification of the Tagliabue closed tester
Flome Size Flome Tip and was first tried in 1916. The modified closed cup tester
\ Bead was the subject of full comparison series of tests conducted
Oil by ASTM in 1917. Figure 4 shows a schematic diagram of a
Chomber
manual Tag Closed Cup tester [24].
ASTM D 92, Standard Test Method for Flash and Fire

Points by Cleveland Open Cup
D2.08 on Volatility. It was originally published in 1921. The
latest edition is D 92-98b.This open cup tester has been used
in the United States since 1908. In early models, testing was
conducted by passing a small test flame across the top of the
cup by hand. Later on, this was converted to the use of a
swinging arm, which controlled the movement of the test
flame at a defined height above the top of the cup. Figure 5
[25] shows the schematic diagram of a manual Cleveland
Open Cup Apparatus.
In addition to determining the flash point of a liquid mate-
rial, D 92 EJSO determines the fire point. Fire point is defined
as the lowest temperature corrected to a barometric pressure
of 101.3 kPa (760 m m Hg) at which application of an ignition
source causes the vapors of the test specimen to ignite and
sustain burning for a m i n i m u m of 5 s under specified condi-
tions of test. The fire point determination is an extension of
the flash point test. After the flash point is determined, heat-
ing of the specimen is continued at a rate of 5-6°C/min. The
test flame is applied at 2°C intervals until the test specimen
ignites and sustains burning for a minimum of 5 s. Just like
flash point, the fire point is also corrected for barometric
pressure using the same equation utilized for flash point.
ASTM D 93, Standard Test Method for Flash Points by

Pensky-Martens Closed Cup Tester
FIG. 4—D 56 tag closed cup tester (manual). This test method is under the jurisdiction of ASTM Commit-
D2.08 on Volatility. It was originally published in 1921. The
concentration above the liquid will tcike longer in an open latest edition is D 93-00. It was developed in Germany in 1870
test cup relative to a closed test cup. D 92 flash point results by Meirtens, and was based on the original tester by Pensky.
were indeed higher than D 93. D 3278 and D 3828, which also Its development in 1870 was for flash points well above 100°C
allow thermeJ equilibrium between specimen and vapor tem- to test lubricating oils and other similar materieds such as bi-
perature, gave lower flash points when compared to D 93 for tumen products. A schematic diagram of a manual Pensky-
n-decane a n d n-undecane. Martens Closed Cup Flash Tester is given in Fig. 6 [26].
Test Method D 93 Procedure A covers the determination of
ASTM D56, Standard Test Method for Flash Point by flash points of relatively non-viscous, homogeneous materi-
Tag Closed Tester als. Test Method D 93 Procedure B, on the other hand, is
This test method is under the jurisdiction of ASTM Commit- meant to measure viscous, nonhomogeneous materials like
tee D-02 and is the direct responsibility of Subcommittee residual oils, materials that tend to form surface film when
D2.08 on Volatility. It was originally published in 1918 and is heated, and liquids that contain suspended solids. A 1994 in-
THCRMOMETEII
A8TM NO. l i e
IP > • C
TEST FLAMC
APPLICATOR
TEST CUP
HEATIN* PLATE
A ORIFICE
MCTAL aCAO
TO «AS SUPPLY
HEATER PLANE TVPE

OR ELECTRIC RESISTANCE TVPE
millimetres inches
min max min max
A—Diameter 3.2 4.8 0.126 0.189
B—Radius 152 nominal 6 nominal
C—Diameter 1.6 nominal 0.063 nominal
D 2 0.078
E 6 7 0.236 0.276
F—Diameter 0.8 nominal 0.031 nominal
FIG. 5—D 92 Cleveland open cup apparatus (manual).
terlaboratory study [36,37] indicated that samples with kine- cialized by Stanhope-Seta Ltd. during 1967 to 1969, and be-
matic viscosity greater than 13 mm^ls at 40°C gave a lower came known as the Setaflash flash point tester. The Setaflash
observed flash point when tested by Procedure A compcired flash test method differs from the other flash point methods
to the flash point determined by Procedure B. A possible ex- because the temperature equilibrium between the specimen
planation is a lag in the temperature detected by the temper- and the vapor above it is allowed to be established prior to
ature measuring device as the kinematic viscosity of the sam- testing for a flash point. A fresh specimen is used for each test
ple increases, especially when equilibration of the vapor and temperature, unlike D 56, D92, and D 93, where multiple
the bulk of the sample is not established before the flash flash point testing is done on a given specimen at various test
point is detected. Therefore, viscosity effects must be taken temperatures. A schematic diagram of the Setaflash appara-
into account when deciding on the appropriate procedure for tus is shown in Fig. 7 [28].
D 93 flash point determination.
ASTM D 3828, Standard Test Method for Flash Point by
ASTM D 1310, Standard Test Method for Flash Point Small Scale Closed Cup Tester
and Fire Points of Liquids by Tag Open Cup Apparatus This test method is under the jurisdiction of ASTM Commit-
This test method is under the jurisdiction of ASTM Commit- tee D-02 and is the direct responsibility of Subcommittee D
tee D-01 on Paints and Related Coatings, Materials, and Ap- 2.08. It was originally published in 1979. The latest edition is
plications, and is the direct responsibility of Subcommittee D 3828-98. The apparatus used in this test method is the
D1.22 on Health and Safety. It was originally published in same as that described in D 3278. Just like the Setaflash test
1952. The latest edition is D 1310-01. The modem Tag open method, this method allows temperature equilibrium
cup tester was derived from the Tagliabue Open cup Tester between the specimen and the vapor above it to be estab-
patented in 1862. lished prior to testing for a flash point. This test method is
applicable to petroleum products not covered within the
ASTM D 3278, Standard Test Method for Flash Point by scope of D 3278.
Setaflash Closed Cup Apparatus
This test method is under the jurisdiction of ASTM Commit- ASTM D 3941, Standard Test Method for Flash Point by
tee D-1 and is the direct responsibility of Subcommittee the Equilibrium Method with a Closed Cup Apparatus
D1.22. It was originally published in 1973. The latest edition This test method is under the jurisdiction of ASTM Com-
is D 3278-96. The original closed cup miniflash point tester mittee D-01 and is the direct responsibility of Subcommit-
was invented by T. Kidd in the early 1960s. It was commer- tee D 1.22. It was originEdly published in 1980. The latest
SHUTTER
HANDLE (OPTIONAL)
(MUST NOT TIP EMPTY CUP)
STIRRER DRIVE FLEXIBLE SHAFT

(PULLEY DRIVE OPTIONAL)
SHUTTER OPERATING KNOB
FLAME EXPOSURE DEVICE
THERMOMETER
DISTANCE PIECE
TEST CUP
mm in.
n* max min max
A 4.37 5.16 0.172 0.203
B 41,94 42.06 1.651 1.6S6
F MIN THICKNESS
C 1.58 3.18 0.062 0.125
OVER CUP AREA
0 9.52 0.375
lE.METAL SURROUNDING
THE CUP e Sr.23 57.86 2.253 2.278
F 6.35 0.25
HEATER FLAME-TYPE
OR ELECTRIC RESISTANCE
TYPE (FLAME TYPE SHOWN)
NOTE 1—Lid assembly can be positioned either right or left-handed.
FIG. 6—D 93 Pensky-Martens closed cup apparatus (manual).
edition is D 3941-96. The apparatus used in this test method lar results to those obtained by D 93. However, the results are
is the same as that described in D 56 and D 93. However, not equivalent [38].
similar to the Setaflash or Small Scale test method, this
method allows temperature equilibrium between the speci- Other International Flash Point Test Methods
men and the vapor above to be established prior to testing All the aforementioned flash point test methods Eire ASTM
for a flash point. standard test methods. Although ASTM standard test meth-
ods are used extensively throughout the world, there are
ASTM D 6450, New Standard Test Method for Flash other international flash point standards that are used and
Point by the Continuously Closed Cup (CCCFP) Tester are applicable to specific geographical jireas. Table 27 gives a
This test method is under the jurisdiction of ASTM Commit- cross reference for a number of international flash point
tee D-02 and is the direct responsibility of Subcommittee D standards and their corresponding ASTM designations.
2.08. The first pubUshed edition will be the 1999 edition. The There are flash point test methods used mainly in Europe,
apparatus is continuously closed during the test but a prede- which do not have an equivalent ASTM standard. The Abel
termined amount of air is injected into the test chamber after flash point tester is a closed cup tester developed originally in
each introduction of the ignition source. This test method is 1876. It is currently used in parts of the United Kingdom. It
different than the other flash point methods because a preset is similar to the D 56 Tag closed-cup tester but with provision
change in the pressure inside the test chamber is used to defor stirring the specimen. The Abel-Pensky closed cup tester
tect when the flash point has been reached. In addition, an was developed in Germany in 1879 and adopted as the Ger-
electric arc is used as the source of ignition when testing for man standard for testing petroleum product in 1882. It is still
a flash point occurrence. This flash point method gives simi- used widely use in Europe.
A—Hinge
B—Ud
C—Pilot flame jet
D—Test flame jet
E—Filing orifice
F—Test flane gas control screw
G—Shutter guide
H—Shutter knob
J—Shutter
K—Udlock
L—Ud sealing 0-ring
M—Thermometer
N—Sample cup
P—^Thermometer well
R—Test flame gage
BORE OF TEST JET

12.65 30.45 7.65
12.60 30/W 7.60
12.47
m^
5.10
12.42 5.05
Li|:W SHUTTER
(1.22 THICK NOM.)
48.42
BORE OF FILLtNO ORIFICE
46.37
1.60/1.85 DIA.
4.00 10.00
7.65
7.60
ITîZZZ^^
16.00
T
10.18
p IO.I3
7.00 OIA.
NOM. 42.00
41.00
49.70
49.40 12.47 5.10
TYP.
12.42 5.05
SPECIMEN CUP AND LID LID ( 2 . 0 0 THICK NOM.)
NOTE 1—All dimensions are in millimetres.
FIG. 7—D 3278 and D 3828 small scale (Setaflash) apparatus.
TABLE 27—Cross reference of international flash point methods versus ASTM flash point test methods.
ASTM ISO IP DIN AFNOR FTM EN SIS
ns
u.s Europe U.K. Germany France Europe Japan
D56 304 791-1101 K2265-1996
D92 2592 36 51 376 791-1103 K2265-1996
D93 2719 34 51 758 M07-019 K2265-1996
D 1310
D3278 3679 303 55 680 K2265-1996
D3828 3679 303 55 680 456 K2265-1996
D3941 1523 K2265-1996
D6450
170 (Abel)
304 51 755 M07-036 150 223
(Abel-Pensky)
Crude Distillation ASTM D 5236, Standard Test Method for Distillation of

Heavy Hydrocarbon Mixtures (Vacuum Potstill
Crude oil is a complex mixture of mostly organic molecules Method)
with minute quantities of inorganic materials. The organic
molecules are mostly hydrocarbons, with minor sulphur, ni- This test method is under the jurisdiction of ASTM Commit-
trogen, and oxygen components, and trace quantities of met- tee D-02 and is the direct responsibility of Subcommittee
als such as vanadium and nickel. In the assay or preliminary D02.08. It was originally published in 1992. The latest edition
characterization of crude oil, atmospheric and reduce pres- is D 5236-99. It describes the procedure for the distillation of
sure distillations are performed in order to determine the
yields of various boiling ranges.
Two test methods are used in the distillation of crude oils,
ASTM D 2892, Standard Test Method for Distillation of CONOENSOR
Crude Petroleum (15-Theroetical Plate Column) [39], and
ASTM D 5236, Standard Test Method for Distillation of
Heavy Hydrocarbon Mixtures (Vacuum Potstill Method)
[40]. Crude oil distillation is one of a number of tests con-
ducted on a crude oil to determine its market value. The frac-
tions produced during crude oil distillation can be used alone SOI.ENOID li
or in combination with other fractions to produce samples
for analytical studies, engineering, and product quEility eval-
uations. The precision values for these two methods are sum-
COLUMN.WIT
marized in Table 28. MANTLE
VACUUM CONNECTION
(WHEN USED)
ASTM D 2892, Standard Test Method for Distillation of
Crude Petroleum (15-Theoretical Plate Column) A P SENSOR
PRODUCT
This test method is under the jurisdiction of ASTM Com- : COOLER
mittee D-02 and is the direct responsibility of Subcommit-
tee D02.08. It was originally published in 1970. The latest
edition is D 2892-99a. It describes the procedure for the dis-
tillation of stabilized crude petroleum to a final cut temper- RECEIVER w
ature of 400°C AET (Atmospheric Equivalent Temperature). TEMPERATURE

AET is the atmospheric equivalent temperature converted stTirri--'
I-
PROBE
from the observed vapor temperatures and was previously N 2 BUBBLER
discussed in the ASTM D1160 section. Equations 4, 5, and
6, as well as Tables 14-19, are applicable for D 2892 also.
This test method employs a fractionating column having an DISTILLING FLASK WITH MANTL'ES
efficiency of 14-18 theoretical plates operated at a reflux ra-
tio of 5:1., thus corresponding to the standard laboratory
distillation efficiency referred to as 15/5. Figure 8 [37]
shows the schematic diagram of the apparatus used for this
test method. Distillation yields by mass or volume are cal-
culated from the data and reported to the nearest 0.1%. Va-
por temperatures are reported to the neeirest 0.5°C. TypiceJ STIRRING MOTOR
D2892 distillation results for two different crude oils are
given in Tables 29 [41] and 30 [42].
FIG. 8—D 2892 test apparatus.
TABLE 28—Precision values for crude distillation methods.

ASTM
Designation iWethod Procedure or Cuts Repeatability Reproducibility
D2892 15/5 Distillation Atmospheric Pressure Under determination 1.2 mass % 1.2 vol %
Reduced Pressure Under determination 1.4 mass % 1.5 vol %
D5236 Vacuum Potstill 10 vol % 6.rc 16.9°C
20 vol % 4.5°C 12.8°C
30 vol % 6.rc 13.5X
40 vol % 4.9°C 11.2''C
50 vol % 5.7°C 14.2°C
60 vol % 4.rc 8.4°C
70 vol % 4.8°C 11.4°C
80 vol % 4.9°C 5.rc
90 vol % 4.4°C 4.4''C
TABLE 29—D 2892 crude distillation results for a new grade oil.
Weight
Boiling Range in No Loss LV % Cum Mid API Density at
(AET, °C) Grams Wt% Volume (mL) Charge Crude LV% LV% Gravity 15°C
Init. to 20 88 2.6 146.6 3.7 3.7 3.7 1.8 104.3 0.6001
21-50 91 2.7 144.1 3.6 3.6 7.3 5.5 92.5 0.6315
93 212 6.4 300.9 7.5 7.5 14.8 11.1 69.3 0.7046
163 452 13.6 593.3 14.9 14.9 29.7 22.3 54.2 0.7618
200 199 6.0 247.5 6.2 6.2 35.9 32.8 44.4 0.8039
250 260 7.8 312.6 7.8 7.8 43.8 39.8 38.5 0.8317
280 188 5.6 221.3 5.5 5.5 49.3 46.5 34.9 0.8479
316 278 8.3 323.0 8.1 8.1 57.4 53.4 32.8 0.8608
330 208 6.2 237.0 6.0 6.0 63.4 60.4 29.8 0.8765
343 90 2.7 102.0 2.6 2.6 65.9 64.7 28.8 0.8820
343 + 1266 38.0 1358.4 34.1 34.1 100.0 82.0 20.2 0.9320
Recov 3332 3987 37.7 0.8357
Loss 6 0.2
Charge Density == 0.8406 Charge Weight = 3345
API = 36.7 Weight of Water = 7
T A B L E 3 0 — D 2 8 9 2 C r u d e d i s t i l l a t i o n r e s u l t s for l i g h t s o u r b l e n d oil
Weight
Boiling Range in No Loss LV % Cum Mid API Density at
(AET, ° C) Grams Wt% Volume (mL) Charge Crude LV% LV% Gravity 15°C
Init. to 20 530 1.5 937.1 2.3 2.3 2.3 1.2 118.7 0.5656
21-50 1709 5.0 2605.2 6.4 6.4 8.7 5.5 84.2 0.6560
100 2063 6.0 2812.9 6.9 6.9 15.7 12.2 61.4 0.7334
125 1077 3.1 1443.3 3.6 3.6 19.2 17.5 58.1 0.7462
150 1559 4.5 2035.2 5.0 5.0 24.3 21.7 53.1 0.7660
175 1289 3.8 1647.7 4.1 4.1 28.3 26.3 49.3 0.7823
205 1896 5.5 2383.1 5.9 5.9 34.2 31.3 46.3 0.7956
220 815 2.4 1009.0 2.5 2.5 36.7 35.4 43.6 0.8077
235 945 2.9 1216.8 3.0 3.0 39.7 38.2 41.6 0.8169
265 1940 5.7 2330.6 5.7 5.7 45.4 42.6 38.4 0.8324
295 1948 5.7 2286.9 5.6 5.6 51.1 48.3 34.5 0.8518
319 1870 5.4 2157.1 5.3 5.3 56.4 53.7 31.6 0.8669
343 1538 4.5 1753.3 4.3 4.3 60.7 58.6 29.7 0.8772
343+ 15105 44.0 15921.8 39.3 39.3 100.0 80.4 17.6 0.9487
Recov 34333 40540.1 35.4 0.8469
Loss 68 0.2
Charge Density = 0.8508 Charge Weight = 33448
heavy hydrocarbon mixtures having an initial boihng point there are other international crude distillation standards that
greater than 150°C such as heavy crude oil, petroleum distil- are used and are applicable to specific geographical areas.
lates, residues, and synthetic mixtures. It employs a potstill Table 22 gives a cross reference for a number of international
with a low pressure drop entrainment separator operated un- crude distillation standards and their corresponding ASTM
der total takeoff conditions. The maximum achievable AET designation.
(see discussion on D 1160 under the distillation section) of
565°C is dependent on the heat tolerance of the chcirge. A
weighed volume of sample is distilled at reduced pressures Vapor Pressure
between 6.6 and 0.013 kPa. at specified distillation rates. Cuts In addition to distillation characteristics, vapor pressure is a
are taken at preselected temperatures. Records of vapor critical volatility parameter of gasoline and other petroleum
temperature, operating pressure, and other variables are fuels. Vapor pressure is the force per unit area exerted by the
made at intervals and each cut point. Figure 9 shows the vapors of the liquid contained in a closed container. Vapor
schematic diagram of the apparatus used for this test method pressure affects the performance chsiracteristics of gasoline
[40]. Distillation yields by mass or volume are calculated and other hydrocarbon fuels, especially during cold starting
from the data and reported to the nearest 0.1%. Vapor tem- and vapor-lock conditions. Vapor- liquid ratio at specified
peratures are reported to the nearest 0.5°C. T3fpical D 5236 temperatures is also an important parameter. For gasoline
distillation results for two different crude oils are given in Ta- and simileir fuels, the vapor pressure is dependent on the va-
bles 31 [43] and 32 [44]. por to liquid ratio in the container, and the temperature. The
vapor pressure of a fuel measured at 37.8°C (100°F) with a 4:1
Other International Test Methods for Crude Distillation vapor to liquid ratio in a designated container, is known as
All the aforementioned test methods are ASTM standard test the Reid Vapor Pressure or RVP. This important fuel charac-
methods for crude oil distillation. Although ASTM standard teristic is measured by ASTM D 323, Vapor Pressure of
test methods are used extensively throughout the world. Petroleum Products (Reid Method) [45].
There are other ASTM test methods related to the measure- Atmospheric) [49]. Vapor-liquid ratio measurements can be
ment of vapor pressure. Among these are: ASTM D 4953, Stan- done by: ASTM D 5188, Standard Test Method for the Vapor-
dard Test Method for the Vapor Pressure of GasoHne and Liquid Ratio Temperature Determination of Fuels (Evacuated
Gasohne-Oxygenate Blends (Dry Method) [46]; ASTM D 5190, Chamber Method) [50] and ASTM D 2533, Standard Test
Standard Test Method for the Vapor Pressure of Petroleum Method for the Vapor - Liquid Ratio of Spark-Ignition Engine
Products (Automatic Method) [47]; ASTM D 5191, Standard Fuels [51]. Two new vapor pressure test methods have been
Test Method for the Vapor Pressure of Petroleum Products approved recently: ASTM D 6377, Standard Test Method for
(Mini Method) [48]; and ASTM D 5482, Standard Test Method Vapor Pressure of Crude Oil: VPCRx (Expansion Method) [52]
for the Vapor Pressure of Petroleum Products (Mini Method- and ASTM D 6378, Standard Test Method for Determination
of Vapor Pressure VPx of Petroleum Products, Hydrocarbons,
and Hydrocarbon-Oxygenate Mixtures (Triple Expansion
TO VACUUM PUKPINO LIME
Method) [53]. The vapor pressure of liquefied petroleum gases
is determined using ASTM D 1267, Standcird Test Method for
the Gage Vapor Pressure of Liquefied Petroleum- (LP) Gases
(LP-Gas Method) [54].
RE*0 TKAP Vapor pressure is critically important for both automotive
and aviation gasolines. It affects starting, warm-up, and ten-
TO VACUUM GAUGE dency to vapor lock at high operating temperatures or eilti-
C080EN8ER—> tudes. M a x i m u m vapor p r e s s u r e limits for gasoline are
legeJly mandated in some etreas as a measure of air pollution
control. Vapor pressure of crude oils is important to the
crude producer and refiner for general heindling jind initial
refinery treatment. Vapor pressure is also used as an indirect
VAPOR THERMOCOUPLE measure of the evaporation rate of volatile petroleum sol-
vents, with higher vapor pressure being associated with a
faster rate of evaporation.
HEAD COHPENSATIMG MANTLE Table 33 summarizes the salient features of these various
VACUUM ADAPTER (not ahown)
vapor pressure and vapor/liquid ratio test methods. The pre-
cision values for the different vapor pressure and V/L test
methods are shown in Table 34.
FLASK THERMOCOUPLE
ASTM D 323, Standard Test Method for the Vapor
Pressure of Petroleum Products (Reid Method)
D02.08. It was originally published in 1930. The latest edition
PLASK MAHTLES is D 323-99.
This test method covers procedures for the determination
of vapor pressure of gasoline, volatile crude oil, and other
OISTILLATIOH FLASK
volatile p e t r o l e u m products. Because the external atmo-
spheric pressure is counteracted by the atmospheric pressure
initially present in the vapor chamber, the Reid vapor pres-
MAGHETIC STIRRER sure is an absolute pressure at 37.8°C. The Reid vapor pres-
sure differs from the true vapor pressure of the sample due to
FIG. 9—D 5236 test apparatus. some small sample vaporization and the presence of water
TABLE 31—D 5236 crude distillation results for a new grade oil bottoms.
Boiling Weight
Range in No Loss LV% Cum Mid API Density at
Init. to 375 28 2.2 31.4 2.3 0.8 66.7 66.3 27.0 0.8921
399 261 20.8 292.2 21.7 7.4 74.1 70.4 26.9 0.8931
450 247 19.7 273.2 20.3 6.9 81.0 77.6 24.9 0.9041
482 130 10.4 141.7 10.5 3.6 84.6 82.8 22.6 0.9175
525 144 11.5 155.5 11.6 3.9 88.6 86.6 21.2 0.9260
550 66 5.3 70.7 5.3 1.8 90.3 89.4 20.0 0.9336
565 36 2.9 38.4 2.9 1.0 91.3 90.8 19.3 0.9375
WETT 5 0.4 5.3 0.4 0.1 91.4 91.4 18.9 0.9402
565 + 338 26.9 337.5 25.1 8.6 100.0 95.7 9.7 1.0015
Recov 1255 1345.9 20.1 0.9324
Loss 2 0.2
Charge Density = 0.9320 Charge Weight = 1253
Weight of Water = 0 API = 20.2
TABLE 32—D 5236 crude distillation results for a light sour blend bottoms.
Weight
Boiling Range in No Loss LV% Cum Mid API Density at
Init. to 399 363 9.7 403.3 10.2 4.1 64.2 62.1 25.6 0.9000
427 635 17.0 702.4 17.8 7.1 71.3 67.7 24.9 0.9041
454 363 9.7 397.0 10.1 4.0 75.3 73.3 23.2 0.9144
482 355 9.5 385.6 9.8 3.9 79.2 77.3 22.1 0.9207
510 305 8.2 328.6 8.3 3.3 82.5 80.9 20.9 0.9282
538 314 8.4 335.1 8.5 3.4 85.9 84.2 19.4 0.9369
565 245 6.6 258.1 6.5 3.6 88.5 87.2 17.5 0.9492
WETT 10 0.3 10.5 0.3 0.1 88.6 88.6 17.0 0.9521
565 + 1150 30.7 1121.8 28.5 11.4 100.0 94.3 6.4 1.0251
Recov 3740 3942.4 17.5 0.9486
Loss 5 0.1
Charge Density == 0.9484 Charge Weight = 3745
TABLE 33—Comparison of ASTM vapor pressure and vapor/liquid ratio test methods.
Vapor Vapor to
ASTM Pressure Test Liquid
Designation Test Method Scope Range Temperature Ratio Resuh
D 323 Proc. A Reid Method Gasoline, volatile crude oil, <180kPa
and other volatile
petroleum products
D 323 Proc. B Reid Method <180kPa All at 37.8°C 4:1 Vapor
rr
D 323 Proc. C Reid Method > 8 0 kPa Pressure
D 323 Proc. D Reid Method Aviation gasoline @ 50 kPa
D 4953 Proc. A Dry Reid Gasoline and gasoline-
D 4953 Proc. B Method oxygenate blends, other air- 35-100 kPa 37.8°C 4:1 Vapor
Dry Reid Semi- containing volatile petroleum Pressure
Automatic products
D5190 Automatic // 7-172 kPa 37.8°C 4:1 DVPE*
Method
D5191 Mini-Method " 7-130 kPa 37.8°C 4:1 DVPE*
D5482 Mini-Method, " 7-llOkPa 37.8^ 4:1 DVPE*
Atmospheric
D6377 Expansion Crude Oils 5-80°C 4:1 to 0.021:1 Vapor
Method Pressure
D6378 Triple Volatile petroleum products, 7-150 kPa 37.8°C 4:1 Vapor
Expansion hydrocarbons, and Pressure
Method hydrocEirbon-
oxygenate mixtures
D5188 Evacuated Gasoline and gasoline 101.3 kPa 36-80°C 8:1 to 75:1 V/L
Chamber oxygenate blends. Temperature
Method
D2533 Evacuated Gasoline 101.3 kPa 36-80°C 20:1 V/L and
Chamber Temperature
Method
D 1267 LP-Gas Liquified Petroleum Products 37.8-70°C Vapor
Method Pressure
*DVPE = dry vapor pressure equivalent (see discussion under individual test method)
vapor £ind air in the confined space. The true vapor pressure served. The pressure reading, suitably corrected for any dif-
of the sample is the pressure exerted only by the molecular ference between the vapor pressure gage and calibration
species in the sample on the walls of the container. The vapor manometer reading, is reported to the nearest 0.25 kPa (0.05
pressure obtained by this method includes the vapor pressure psi) as the Reid vapor pressure.
due to water vapor and air.
Figure 10 [45] shows the schematic diagram of the vapor ASTM D 4953, Standard Test Method for the Vapor
pressure apparatus for Procedure A, C, and D. Figure 11 [45] Pressure of Gasoline and Gasoline-Oxygenate Blends
illustrates the apparatus for Procedure B. The liquid chamber (Dry Method)
of the vapor pressure apparatus is filled with the chilled sam- This test method is under the jurisdiction of ASTM Commit-
ple and connected to the vapor chamber that has been heated tee D-02 and is the direct responsibility of Subcommittee
to 37.8°C in a bath. The assembled apparatus is immersed in D02.08. It was originally published in 1989. The latest edition
a bath maintained at 37.8°C until a constant pressure is ob- is D 4953-99.
TABLE 34—Precision of various vapor pressure and V/L ratio test methods.
ASTM
Designation Metliod Name Procedure/Model Range Repeatability Reproducibility
D323 Reid Method A (Gasohne) 35-100 kPa (5-15 psi) 3.2 kPa (0.46 psi) 5.2 kPa (0.75 psi)
B (Gasoline) 35-100 kPa (5-15 psi) 1.2 kPa (0.17 psi) 4.5 kPa (0.66 psi)
A 0-35 kPa (0-5 psi) 0.7 kPa (0.10 psi) 2.4 kPa (0.35 psi)
A 110-180 kPa (16-26 psi) 2.1 kPa (0.30 psi) 2.8 kPa (0.40 psi)
C 180kPa(>26psi) 2.8 kPa (0.40 psi) 4.9 kPa (0.70 psi)
D 50 kPa (7 psi) 0.7 kPa (0.10 psi) 1.0 kPa (0.15 psi)
D4953 Dry Reid A 3.65 kPa (0.53 psi) 5.52 kPa (0.80 psi)
Method B (Gage) 4.00 kPa (0.58 psi) 5.38 kPa (0.78 psi)
B (Herzog) 2.14 kPa (0.31 psi) 2.90 kPa (0.42 psi)
B (Precision) 3.58 kPa (0.52 psi) 4.27 kPa (0.62 psi)
D5190 Automatic 2.48 kPa (0.36 psi) 3.45 kPa (0.50 psi)
Method
D5191 Mini-Method 0.00807(DVPE + B) 0.0161(DVPE + B)
B = 124 kPa (18.0 psi) B = 124 kPa (18.0 psi)
D5482 Mini-Method, Herzog SC970 1.31 kPa (0.19 psi) 2.69 kPa (0.39 psi)
Atmospheric ABB 4100 1.79 kPa (0.26 psi) 4.14 kPa (0.60 psi)
D6377 VPCRx, Crude V/L = 4 and 37.8°C 0.015 VPCR4 To be determined
Expansion V/L = 0.1 and 37.8° C 0.055 VPCRo 1
Method V/L = 0.02 and 37.8° C 0.065 VPCRo 02
D6378 VPx, Petroleum 0.50 kPa (0.07 psi) 1.63 kPa (0.22 psi)
Expansion Products
Method
D5188 Evacuated V/L 0.6° C 0.9° C
Chamber
D2533 Evacuated V/L Glycerol Mercury 1.0° C 1.3° C
Chamber 1.4° C 1.6° C
D 1267 LP-Gas 12kPa(1.8psi) 18kPa(2.8psi)
Method
'Coupling
C Coupling MUU)G 6ABE VERSION
B \ F
tiquid Choinbtf
(Oni Opening)
Vapor Chambar
DIMENSIONS OF VAPOR PRESSURE APPARATUS

Key Description mm in.
A Vapor chamber, length 254 ± 3 10 ± Ve
B, C, D Vapor and gasoline chambers, 51 ± 3 2 ± Vs
Liquid ID
E Coupling, ID min 4.^ ¥16 non
F, G Coupling, OD 12.7 Vi na
H Coupling, ID 12.7 %
I \felve 12.7 %
J Valve 6.35 Vt "CI —~—or
FIG. 10—D 323 - Procedure A, C, and D apparatus. FIG. 11—D 323 - Procedure B apparatus.
This test method is a modification of D 323, providing two FLOW SYSTEM

procedures to determine the vapor pressure of gasoline and
gasohne-oxygenate blends. Procedure A utilizes the same ap-
paratus and essentially the same procedure as D 323 with the J*-f^*-VENTED ""^
exception that the interior surfaces of the liquid and vapor
40-80 RSI
chambers are maintained completely free of water. Proce-
dure B utilizes a semi-automatic apparatus as shown in Fig-
ure 11 [46] with the liquid and vapor chambers identical in
volume to those in Procedure A. The apparatus is suspended
in a horizontal bath and rotated while attaining equilibrium.
Either a Bourdon gage or pressure transducer can be used
with this procedure. Just like Procedure A, the interior sur-
faces of the liquid and vapor chambers are maintained free of
water. The vapor pressure determined by this method differs L
from the true vapor pressure of the sample due to some small
sample vaporization and includes the vapor pressure of the
air in the confined space.
The liquid c h a m b e r of the vapor pressure a p p a r a t u s is
filled with a chilled sample and connected to the vapor cham-
ber that has been heated to 37.8°C in a bath. The assembled
apparatus is immersed in a bath maintained at 37.8°C until
constant pressure is observed. The pressure reading, suitably
<d. @M®
corrected for any difference between the gage or pressure
transducer and manometer reading, is reported to the near-
est 0.25 kPa (0.05 psi) as the Dry Reid vapor pressure.
Data from a 1991 interlaboratory cooperative program [55] PRESSURE-VAC
indicated a statistically significant bias between Procedure A FOR
CAUBRATION
and Procedure B. The relative bias between procedures can
be corrected by applying the following equation: Z1 13' RING INSAMPLE INLET CONNECTOR
For Procedure B, Gage:
FIG. 12—D 5190 apparatus.
DVPE, Procedure A = 1.029 X (9)
For Procedure B, Transducer (Herzog):
chamber where it is held until thermal equilibrium at 37.8°C
DVPE, Procedure A = 0.984 X (10) is reached. The total vapor pressure is measure by a pressure
trcinsducer. The measured total vapor pressure is converted
where X = observed total vapor pressure using Procedure B. by the instrument to the DVPE value using equation 11. The
DVPE is reported to the nearest 0.1 kPa (0.01 psi) without ref-
ASTM D 5190, Standard Test Method for the Vapor erence to the temperature.
Pressure of Petroleum Products (Automatic Method)
This test method is u n d e r the jurisdiction of ASTM Commit- ASTM D 5191, Standard Test Method for the Vapor
tee D-02 and is the direct responsibility of Subcommittee Pressure of Petroleum Products (Mini-Method)
D02.08. It was originally published in 1991. The latest edition This test method is under the jurisdiction of ASTM Commit-
is D 5190-99. tee D-02 a n d is the direct responsibility of Subcommittee
This test method is suitable for gasoline samples that con- D02.08. It was originally published in 1991. The latest edition
tain oxygenate. This method is suitable for calculation of a is D 5191-99.
dry vapor pressure equivalent (DVPE), i.e., the vapor pres- This test method is suitable for gasoline and gasoline sam-
sure corresponding to that obtained by D 4953, using a n ples that contain oxygenates. This method is suitable for CEJ-
equation derived from a 1991 interlaboratory cooperative culation of a dry vapor pressure equivalent (DVPE) using an
study [55]. equation derived from a 1988 interlaboratory cooperative
study [56].
DVPE, D 5190 = (0.954 X ) - ^ A (11)
DVPE, D 5191 = (0.965 X) - A (12)
where:
X = m e a s u r e d total vapor pressure, in units consistent where:
with A, ctnd X = m e a s u r e d total vapor pressure, in units consistent
A = 1.984 kPa (0.281 psi). with A, and
A = 3.78 kPa (0.548 psi).
The chilled sample cup of the automatic vapor pressure in-
strument (Fig. 12 [47]) is filled with the chilled sample and A similar correlation equation was developed by the U.S.
coupled to the instrument inlet fitting. The sample is auto- Environmental Protection Agency (EPA) using its own data.
matically forced from the sample chamber to the expansion The equation they use to correlate D 5191 results to D 4953,
Procedure B is: sured is converted to a DVPE using Eq 15. The DVPE is re-
ported to the nearest 0.1 kPa (0.01 psi) without reference to
D V P E , D5191 = (0.956 X ) - A (13) the temperature.
where:
ASTM D 6377, Standard Test Method for the Vapor
X = measured total vapor pressure, in units consistent
Pressure of Crude Oil, VPCRx (Expansion Method)
with A, and
A = 2.39 kPa (0.347 psi). This test method is under the jurisdiction of ASTM Commit-
Another correlation equation to correlate D 5191 results to D02.08. It was originally published in 1998. The latest edition
D 323 was developed by the California Air Resources Board is D 6377-98.
(CARB). It is given by the equation: This test method covers the use of automated vapor pres-
sure instruments to determine the vapor pressure exerted by
DVPE, D 5191 = (0.972 X ) - A (14) crude oils at temperatures between 5 and 80°C. Employing
a measuring chamber with a built-in piston, a sample of
where: known volume is drawn from a pressurized sampling sys-
X = measured total vapor pressure, in units consistent tem (floating piston cylinder) into the temperature con-
with A, and trolled chamber at 20°C or higher. After sealing the cham-
A = 4.93 kPa (0.715 psi) ber, the volume is expanded by moving the piston until the
final volume produces the desired V/L value. The tempera-
A known volume of chilled, air-saturated sample is intro- ture of the chamber is then regulated to the measuring tem-
duced into an evacuated, thermostatically controlled test perature. After temperature and pressure equilibrium, the
chamber, the internal volume of which is five times that of measured pressure is recorded as the VPCRx of the sample.
the total specimen introduced into the chamber. After injec- The results are reported to the nearest 0.1 kPa with the test
tion into the test chamber, the test specimen is allowed to temperature and vapor-liquid ratio. For results related to
reach thermal equilibrium at 37.8°C. The resulting rise in ASTM D 323, the final volume of the measuring chamber
pressure in the chamber is measured using a pressure trans- shall be five times the test specimen volume and the mea-
ducer sensor and indicator. The total pressure measured is suring temperature shall be 37.8°C. The relative bias be-
converted to a DVPE using Eq 12. The DVPE is reported to tween the Reid vapor pressure (RVP) obtained by D 323 and
the neeirest 0.1 kPa (0.01 psi) without reference to the tem- the value obtained by this method can be corrected by us-
perature. ing the correlation equation:
ASTM D 5482, Standard Test Method for the RVPE, D323 = A X VPCR4(37.8-(C) + B (16)
Vapor Pressure of Petroleum Products
(Mini-Method-Atmospheric) where:
A = 0.752
B = 6.07 kPa (0.88 psi)
D02.08. It was originally published in 1993. The latest edition ASTM D 6378, Standard Test Method for the Vapor
is D 5482-99. Pressure, VPx, of Petroleum Products, Hydrocarbons,
This test method is a modification of D 5191. In this test and Hydrocarbon-Oxygenate Mixtures
method, the test chamber is not evacuated but rather at at- (Triple-Expansion Method)
mospheric pressure at the start of the test. This test method
is suitable for gasoline samples that contain oxygenates. This This test method is under the jurisdiction of ASTM Commit-
method is suitable for calculation of a dry vapor pressure tee D-02 and is the direct responsibility of Subcommittee
equivalent (DVPE) using an equation derived from a 1991 in- D02.08. It was originally pubhshed in 1998. The latest edition
terlaboratory cooperative study [55]. is D 6378-98.
This test method is similar to D 6377 with the exception
DVPE, D 5482) = (0.965 X ) + A (15) that expansion is done in three steps to a final volume of
(x -I-1) times that of the test specimen. After each expansion,
where: the total pressure is determined. The partial pressure of the
X = measured total vapor pressure, in units consistent dissolved air and the solubility of air in the specimen are cal-
with A, and culated from the three resulting pressures. The temperature
A = 0.538 kPa (0.078 psi) for Herzog Model SC970 of the chamber is then increased to a specified value and to-
A = 1.937 kPa (0.281 psi) for ABB Model 4100 tal pressure is determined. The vapor pressure (VPx) is cal-
culated by subtracting the partial pressure of the dissolved
A known volume of chilled, air-saturated sample is intro- air in the liquid, which has been gas-corrected for tempera-
duced into a thermostatically controlled test chamber at at- ture, from the total pressure. In this test method, air satura-
mospheric pressure, the internal volume of which is five tion prior to the measurement is not required. Results are re-
times that of the total specimen introduced into the chamber. ported to the nearest 0.1 kPa with the test temperature and
After injection into the test chamber, the test specimen is al- vapor-liquid ratio. The vapor pressure determined by this
lowed to reach thermal equilibrium at 37.8° C. The resulting method at a vapor-liquid ratio of 4:1 of gasoline and gasoline-
rise in pressure in the chamber is measured using a pressure oxygenate blends at 37.8°C can be correlated to the DVPE
transducer sensor and indicator. The total pressure mea- value determined by ASTM D 5191. The bias of the results ob-
tained by this test method relative to D 5191 can be corrected cury is also reported.
by using the correlation equation:
ASTM D 1267, Standard Test Method for Gage
D V P E , D 5191 — VP4(37.goc) — A (17) Vapor Pressure of Liquefied Petroleum (LP) Gases
where: (LP-GAS Method)
A = 1.027 kPa (0.15 psi). This test method is under the jurisdiction of ASTM Commit-
ASTM D 5188, Standard Test Method for the D02.H on Liquefied Petroleum Gas. It was originally pub-
Vapor-Liquid Ratio Temperature Determination lished in 1953. The latest edition is D 1267-95.
of Fuels (Evacuated Chamber Method) The test apparatus (see Fig. 13 [54]) consisting of two inter-
This test method is under the jurisdiction of ASTM Commit- connected chambers and equipped with a suitable pressure
tee D-02 and is the direct responsibility of Subcommittee gage, is purged with a portion of the sample, which is then dis-
D02.08. It was originally published in 1991. The latest edition carded. The apparatus is then filled completely with the por-
is D 5188-99. tion of the sample to be tested. Thirty-three and one third to
This test method covers the determination of the tempera- forty volume percent of the sample content of the apparatus
ture at which the vapor formed from a selected volume of is immediately withdrawn to provide adequate free space for
volatile petroleum products saturated with air at 0-1 °C pro- product expansion. The apparatus is then immersed in a wa-
duces a pressure of one atmosphere in an evacuated chamber ter bath at the standard test temperature of 37.8°C or, option-
of fixed volume. This test method is suitable for gasoline ally, at some higher temperature up to and including 70°C.
samples that contain oxygenate. A known volume of chilled, The observed gage pressure after temperature equilibration,
air-saturated sample is introduced into an evacuated, ther- corrected for gage error and barometric pressure, is reported
mostatically controlled test chamber of known volume. The to the nearest 5 kPa (0.5 psi) as the LPG Vapor Pressure at the
sample volume is ceJculated to give the desired vapor-liquid selected test temperature. The observed gage vapor pressure
ratio for the chamber in use. After injection, the chamber is corrected by adding any gage correction to obtain the cor-
temperature is adjusted until a stable chamber pressure of rected vapor pressure. The corrected vapor pressure is then
101.3 kPa is achieved. corrected to a barometric pressure of 760 mm (29.9 in) Hg by
use of the following equations:
The tendency of a fuel to vaporize in automotive engine
fuel systems is indicated by the vapor-liquid ratio of that fuel. LPGVPcorr = observed gage pressure
Automotive fuel specifications generally include T(V/L =20) (18)
limits to ensure products of suitable volatility performance. + gage correction
For high ambient temperature, a fuel with a high value of LPGVPeorr to 760 mm Hg LPGVPcorr, kPa
T(v/L =20) indicating a fuel with a low tendency to vaporize, is (19)
- ( 7 6 0 - P i ) 0.1333
generally specified. Conversely, for low ambient tempera-
tures, a fuel with a low T(V/L =20) value is specified. LPGVPcorr, psi - (760 - Pi) 0.0193 (20)
ASTM D 2533, Standard Test Method for the

Vapor-Liquid Ratio of Spark-Ignition Engine Fuels A (CAGE)
(Evacuated Chamber Method)
C (STRAIGHT-THROUGH VALVE)
D02.08. It was originally published in 1966. The latest edition
is D 2533-99.
This test method covers a procedure for measuring the vol-
ume of vapor formed at atmospheric pressure from a given
volume of gasoline. The ratio of these volumes is expressed as
the vapor-liquid (V/L) ratio of the gasoline at the temperature
of the test.
A measured volume of liquid fuel at 34-40°F (0-4°C) is B (LOWER
(BLEEDER CHAMBER)
introduced through a rubber septum into a glycerol or mer- VALVE
COUPLING)
cury filled burette. The charged burette is placed in a tem- F (INLET VALVE)
perature-controlled water bath. The volume of the vapor in
equilibrium with liquid fuel is measured at the desired tem-
perature or temperatures and the specified pressure (usually
760 mm Hg). The vapor-liquid (V/L) is then calculated. If it
is desired to know the temperature corresponding to a given
V/L, the vapor-liquid ratio is determined at several temper-
atures, and the selected pressure. The results are plotted C (UPPER C H A M B E R )
and the temperature read at the given V/L. The vapor-liquid
ratio is reported to the nearest 0.1 unit and the correspond-
ing temperature reading to the nearest 0.1 °C (0.2°F). If
other than 760 mm Hg the pressure in millimeters of mer- FIG. 13—D 1267 apparatus.
TABLE 35—Cross reference of international vapor pressure standards relative to ASTM distillation test methods.
ASTM
Designation ISO IP BS AFNOR DIN FTM JIS
U.S. Europe U.K. U.K. France Germany Japan
D323 3007 69 2000 M07-007 51754 791-1201 K2258
D4953
D5190
D5191
D5482
D6377
D6378
D5188
D2533
D 1267 4256 161 51 616
where P] = observed barometric pressure in m m Hg. por/Liquid ratios cem be determined using a variety of tech-
niques a n d instrumentation. For safety in handling and
L P G V P c o r r to 750 mm Hg = L P G V P c o r r , k P a transporting veirious fuels cmd lubiicemts, a variety of flash
(21) point test methods are available.
- (29.92 - Pz) 3.3864 For the most part, this chapter on volatility characteristics
= LPGVPcorr, psi - (29.92 - P2) 0.4912 (22) of fuels and lubricants has dealt mainly with ASTM standard
test methods that are used worldwide. However, there are
where P2 = observed barometric pressure, in. Hg. other international standards that correspond to the ASTM
standards described herein that are used and are applicable
Information on the vapor pressure of hquefied petroleum in other parts of the world. The discussions on the different
gas (LPG) products under temperature conditions of 37.8-70° ASTM test methods mentioned in this chapter are fairly brief,
C is pertinent to the selection of properly designed storage ves- by design a n d space constraints. For m o r e details, it is
sels, shipping containers, and customer utilization equipment strongly recommended that the readers refer to the actual
to ensure safe handling of these products. Determination of ASTM test methods themselves.
the vapor pressure of LPG is important for safety reasons to
ensure that the maximum operating design pressures of stor-
age, handling, and fuel systems will not be exceeded under
normal operating temperature conditions. For LPG, vapor ASTM STANDARDS
pressure is an indirect measure of the most extreme low tem-
perature conditions under which initial vaporization can be No. Title
expected to occur. It can be considered a semi-quantitative D 0056 Standard Test Method for Flash Point by Tag Closed
measure of the amount of the most volatile material present Cup Tester
in the product. D 0086 Standard Test Method for Distillation of Petroleum
Products
Other International Test Methods for Vapor Pressure D 0092 Standard Test Method for Flash and Fire Points by
Determination Cleveland Open Cup Tester
D 0093 Standard Test Method for Flash Point by Pensky-
All the aforementioned test methods are ASTM standcird test Martens Closed Cup Tester
methods for vapor pressure determination. Although ASTM D 0323 S t a n d a r d Test Method for Vapor Pressure of
standard test methods are used extensively throughout the
Petroleum Products (Reid Method)
world, there are other international vapor pressure standards
D 1160 Standard Test Method for Distillation of Petroleum
that are used and are applicable to specific geographical area.
Products at Reduced Pressure
Table 35 gives a cross reference for a n u m b e r of international
D 1310 S t a n d a r d Test Method for Flash Point and Fire
vapor pressure s t a n d a r d s a n d their corresponding ASTM
Points by Tag Open Cup Apparatus
designations.
D 2533 Standard Test Method for the Vapor-Liquid Ratio of
Spark-Ignition Engine Fuels
D 2892 S t a n d a r d Test Method for Distillation of Crude
CONCLUSION Petroleum (15-Theoretical Plate Column)
D 3278 Standard Test Method for Flash Point by SetaFlash
Volatility parameters of petroleum products and lubricants Closed Cup Apparatus
are important parameters that are related to the performance D 3828 S t a n d a r d Test M e t h o d for Flash Point by Small
characteristics and safety in handling and transporting these Scale Closed Cup Tester
materials. Optimum distillation and vapor pressure veJues D 3941 Standard Test Method for Flash Point by the Equi-
are paramount in the proper and efficient operation of vari- librium Method with a Closed Cup Apparatus
ous engines fueled by different petroleum products u n d e r D 4953 S t a n d a r d Test Method for the Vapor Pressure of
different conditions. Distillation can be carried out either at Gasoline and Gasoline-Oxygenate Blends (Dry
atmospheric or reduced pressures. Vapor pressure and Va- Method)
D 5188 Standard Test Method for the Vapor-Liquid Ratio FTM 791-1101 Flash Point, Tag, Closed Cup
Determination of Fuels (Evacuated C h a m b e r FTM 791-1103 Flash Point, Cleveland Open Cup
Method) FTM 791-1201 Reid Vapor Pressure
D 5190 Standard Test Method for the Vapor Pressure of
Petroleum Product (Automatic Method)
D 5191 Standard Test Method for the Vapor Pressure of REFERENCES
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D 5482 Standard Test Method for the Vapor Pressure of [2] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
West Conshohocken, PA, 1999, pp. 416^33
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[3] Annual Book of ASTM Standards, Vol. 5.01, ASTM International,
D 6377 Standard Test Method for Vapor Pressure of Cude West Conshohocken, PA, 1999, p. 18
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D 6378 Standard Test Method Determination of Vapor West Conshohocken, PA, 1999, p. 19
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No. Title shohocken, PA, 1995.
[8] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
ISO 1523 Flash Point, Equilibrium Method, Close
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[9] Annual Book of ASTM Standards,Vol. 5.01, ASTM International,
ISO 2592 Flash Point, Cleveland Open Cup
West Conshohocken, PA, 1999, p. 21.
ISO 2719 Flash Point, Pensky-Martens, Closed Cup [10] Annual Book ofASTM Standards,Vol. 5.01, ASTM International,
ISO 3007 Reid Vapor Pressure West Conshohocken, PA, 1999, p. 22.
ISO 3405 Distillation, Atmospheric Pressure [11] Annual Book of ASTM Standards, Vol. 5.01, ASTM International,
ISO 3679 Flash Point, SetaFlash, Closed Cup West Conshohocken, PA, 1999, p. 26.
ISO 4256 Vapor Pressure, LPG [12] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
ISO 6616 Distillation, Reduced Pressure West Conshohocken, PA, 1999, p. 27.
ISO 8708 Crude Distillation, 15/5 [13] Annual Book ofASTM Standards,Vol. 5.01, ASTM International,
AFNOR M07-002 Distillation, Atmospheric Pressure West Conshohocken, PA, 1999, p. 28.
AFNOR M07-007 Reid Vapor Pressure [14] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
AFNOR M07-019 West Conshohocken, PA, 1999, p. 24.
Flash Point, Pensky-Martens, Closed Cup
AFNOR M07-036 [15] ASTM D-2 Interlaboratory Crosscheck Program, Motor Gaso-
Flash Point, Abel-Pensky line, ASTM International, West Conshohocken, PA, June 1999,
DIN 51 356 Distillation, Reduced Pressure p. 35.
DIN 51 376 Flash Point, Cleveland Open Cup [16] ASTM D-2 Interlaboratory Crosscheck Program, Reformulated
DIN 51 567 Crude Distillation, 15/5 Gasoline, ASTM InternationeJ, West Conshohocken, PA, June
DIN 51 616 Vapor Pressure, LPG 1999, p. 57.
DIN 51 680 Flash Point, SetaFlash, Closed Cup [17] ASTM D-2 Interlaboratory Crosscheck Program, Diesel Fuel,
DIN 51 751 Distillation, Atmospheric Pressure ASTM International, West Conshohocken, PA, June 1999, p. 57.
DIN 51 754 Reid Vapor Pressure [18] ASTM D-2 Interlaboratory Crosscheck Program, Jet Fuel, ASTM
DIN 51 755 International, West Conshohocken, PA, June 1999, p. 37.
Flash Point, Abel-Pensky
DIN 51 758 [19] Annual Book of ASTM Standards, Vol. 5.01, ASTM International,
JIS K2254 West Conshohocken, PA, 1999, p. 423.
Distillation, Atmospheric Pressure [20] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
JIS K2258
Distillation, Reduced Pressure West Conshohocken, PA, 1999, p. 431.
JIS K2265
Flash Point, Tag, Closed Cup [21] Annual Book of ASTM Standards,Vol. 5.01, ASTMlntemational,
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Flash Point, Abel-Pensky West Conshohocken, PA, 1999, p. 417^22.
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Reid Vapor Pressure [22] Annual Book ofASTM Standards, Vol. 5.01, ASTM International,
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Distillation, Atmospheric Pressure West Conshohocken, PA, 1999, p. 427.
IP 034 [23] Section 173.120, Ch. 1, 49 CFR, (10-1-97 edition). Codes of Fed-
IP 036 eral Register, Washington DC, p. 446.
Flash Point, Cleveland Open Cup
IP 123 [24] Annual Book of ASTM Standards, Vol. 5.01, West Con-
IP 303 Distillation, Atmospheric Pressure
shohocken, PA, 1999, pp. 1-10.
IP 304 Flash Point, SetaFlash, Closed Cup
[25] Annual Book of ASTM Standards, Vol. 5.01, West Con-
IP 069 Flash Point, Tag, Closed Cup shohocken, PA, 1999, pp. 44-51.
IP 161 Reid Vapor Pressure [26] Annual Book of ASTM Standards, Vol. 5.01, West Con-
Vapor Pressure, LPG shohocken, PA, 1999, pp. 52-61.
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FTM 791-1001 Distillation, Atmospheric Pressure shohocken, PA, 1997, pp. 126-132.
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[37] Montemayor, R. G., "The EiSect of Kinematic Viscosity on the [52] Annual book of ASTM Standards, Vol. 5.03, ASTM International,
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MNL37-EB/Jun. 2003
Elemental Analysis
R. Kishore Nadkami ^
A MAJORITY OF ELEMENTS IN THE PERIODIC TABLE ARE PRESENT IN Analysis of Petroleum Products
PETROLEUM PRODUCTS Tcinging in concentration from percent
levels of C—H—O—S to parts per billion levels of trace ele- All well-established elemental analytical techniques have
ments. The metals in crude oils originate from marine ani- been used for the analysis of petroleum products. Several
mals and plants. Additives and lubricating oils have metals m o n o g r a p h s are available on this subject although all of
purposely added to them to affect their performance in inter- them are at least two decades old. A more recent monograph
nal combustion engines. has been published by ASTM, which contains papers from
several authors covering a wide variety of techniques [5].
Except for carbon and hydrogen, sulfur, oxygen, and to a
Most prominent among these techniques are atomic spec-
lesser extent nitrogen, are the most abundant elements typi-
troscopy (atomic absorption spectroscopy, AAS, and induc-
cally found in crude oils. Some specific crude oils may also
tively coupled plasma atomic emission spectroscopy, IC-
contain significant amounts of vanadium and nickel, such as
PAES), X-ray fluorescence (XRF), a n d micro-elemental
those from Venezuela. Generally, it is agreed that vanadium,
techniques.
nickel, and iron occur as metallo-porphyrins; mercury, anti-
mony, and arsenic as organometallic compounds; mercury Sample Preparation
can also occur as dissolved element mercury; molybdenum
and germanium as carboxylic acid salts, and silica and salt as Sample preparation techniques can vary from none to quite
colloidal minerals [1]. Extensive data on crude oil composi- elaborate depending on the final measurement step. Micro-
tion are available. The so-called crude assay analysis of oils elemental analysis and, for some matrices, atomic spec-
carried out by many oil companies includes elemental analy- troscopy and XRF techniques need n o sample preparation at
sis of sulfur, nitrogen, vanadium, nickel, and iron among all. For others, it can be as simple as dilution in an organic
other parameters. There are probably millions of such data solvent for m e a s u r e m e n t by AAS, ICP-AES, or XRF. For
points in the oil companies' proprietary databases. some specific analyses, a sample may be ashed (D 482 and D
874) and then brought into an aqueous acidic solution before
being analyzed by a n atomic spectroscopic technique. In
Significance of Metals in Petroleum Products such cases, dry ashing (D 482) may not be preferred due to
the potential for the loss of volatile elements. Wet ashing us-
The reason for interest in elemental analysis of petroleum ing various acids or their mixtures can minimize volatiliza-
products is two-fold. First, many metals and nonmetals pre- tion losses. The D 874 procedure uses sulfuric acid for this
sent in crude oils have a deleterious effect on the refinery and work. This method is well-suited for bringing the organic
processing operations, generally acting as catalyst poisons. samples into inorganic solutions, however, as a stand-alone
The sulfur and nitrogen compounds generated during pro- method for estimating the total meted oxides/sulfates in the
cessing are also potential environmental concerns. Second, sample, it has several drawbacks due to the formation of in-
the lube additives and oils contain deliberately added termetallic compounds during oxidation and sulfation. Gen-
organometallic compounds to enhance their performance. erally, this results in significantly underestimating the
Though m u c h of this chemistry is proprietary, certain aspects amount of total metal oxides using the residual weight from
are universally known. Generally, the presence of sulfur, D 874 compared to the ICP-AES or XRF sum of oxide results.
phosphorus, alkaline earth metal, zinc, copper, etc. com- This means that the residual mass is less than the ICP-AES or
pounds define the composition of the additives and lubricat- XRF sum of oxides [6].
ing oils. A summary of additive elements generally used and
their effects on engine performance is given in Table 1. Two
Wear Metals in Used Oils
documents published by ASTM are useful in understanding
the significance of tests carried out on petroleum products Trace metals in used lubricating oils come from the mechan-
[3,4]. In this chapter, the elemental analysis of petroleum ical wear from oil-wetted components of an engine or as a
products will be discussed. Particulcir focus will be on the contaminant from air, fuel, and liquid coolant. Generally, the
most commonly used methods, although many other methods metals are present as particulate materials rather than as true
may also be available. solutions. The presence of specific metals in used lubricating
oils can be associated with specific metal components of an
engine. In a normally running engine, weeir metal content
' Millennium Analytics, Inc., 47 Helena Street, East Brunswick, NJ of the oil slowly increases due to normal wear. However, a
08816. sudden increase in one or more metal concentrations in oil
707

TABLE 1—Presence and role of specific elements in lubricants [2].

Element Compounds Performance
B Borax and esters Antiwear agents, antioxidant, deodorant cutting

oils, greases, brake fluids
Ba Sulfonates, phenates, Diorganodiphosphates, Detergent inhibitors, corrosion inhibitors, deter-
phosphonates, Thiophosphonates gents, rust inhibitors, ATF, greases
Ca Sulfonates, phenates Detergent inhibitors, dispersants
Cd Dithiophosphates Stream turbine oils
Cr Salts Grease additive
Hg Organic Compounds Bactericide in cutting oil emulsions
Mg Sulfonates, phenates Detergent inhibitors
Mo M0S2, dibutyldithicarbamate, phosphate Greases, extreme pressure additives
Ni Cyclopentadienyl complexes Antiwear agents, carbon deposit reduction, im-
proved lubrication and combustion
P Metaldialkyldithiophosphates Detergents, antirusting agents
Pb Naphthenate Extreme pressure additive, greases, gear oils
Sb Dialkyldithiocarbamates. Antiwear, extreme pressure, antioxidant
Dialkylphosphorodithionates
Se Selenides Oxidation and bear corrosion inhibitors
Si Silicone Polymers Foam inhibitors
Sn Organo Compounds Antiscuffing additives, metal deactivators
Zn Dialkyldithiophosphates, dithiocarbamates, Antioxidant, corrosion inhibitors, antiwear addi-
phenolates tives, detergents, extreme pressure additives,
crankcase oils, hypoid gear lubricants, greases,
aircraft piston engine oils, turbine oils, ATF, rail-
road diesel engine oils, brake lubricants
TABLE 2—Wear metals (elements) in used lubricating oils [2]. of years conducted this kind of analysis on their jet engine
Elements Wear Indication oils under the acronym "SOAP" (Spectrometric Oil Analysis
Ag Wrist pin bearings in railroad and auto engines, silver Program) [7]. As a result of the success of this program, the
plotted spline lubricating pump U.S. Air Force, Army, and Navy established a Joint Oil Anal-
Al Piston and bearings wear, push rods, air cooler, pump ysis Program (JOAP) in 1976. Over 100 laboratories through-
hosings, oil pumps, gear castings, box castings out the world are involved in these analyses using AAS, ICP-
B Coolant leakage in system AES, and rotating disk electrode emission spectrometry. To
Cd Bearings
Cr Ring wear, cooling system leakage, Cr-plated parts in expedite in-field analysis, a portable graphite furnace multi-
aircraft engines, cylinder liners, seal rings element AAS instrument has been developed that is capable
Cu Wear in bushings, injector shields, coolant core tubes, of analyzing nine wear metals in undiluted oil samples [8]. By
thrust washers, valve guides, connecting rods, use of a rapid sequential analysis mode, u p to 24 elements in
piston rings, bearings, sleeves, bearing cages a single aspiration have been determined using a multi-
Fe Wear from engine block, cylinder, gears, cylinder
liners, valuve guides, wrist pins, rings, camshaft, oil element AAS spectrometer [9].
pump, crankshaft, ball and roller bearings, rust Rotating disk electrode emission spectrometry either by a
Mg Cylinder liner, gear box housings in aircraft engines single spark technique or ashing rotrode technique has been
Mo Wear in bearing alloys and in oil coolers; various Mo-
alloyed components in aircraft engines, piston rings shown to rapidly provide multielement analysis of used oils.
Na Antifreeze leakage By anailyzing two aliquots, one directly and one after acid dis-
Ni Bearings, valves, gear platings solution, differentiation can be m a d e between large and
Pb Bearings, fuel blowby, thrust bearings, bearing cages, small wear particles [10]. A correlation has been shown to ex-
bearing retainers ist between ICP-AES and rotrode emission techniques. Re-
Sb Crankshaft and camshaft bearings
Si Dirt intrusion from improper air cleaner, seal sults suggest that rotrode is somewhat more effective in sam-
materials pling particulates than ICP-AES [11]. ICP-mass spectrometry
Sn Bearings and coatings of connecting rods and iron has been proposed as a sensitive tool for the determination of
pistons environmentally important elements in used oils. The tech-
Ti Various Ti-alloyed components in aircraft engines nique has detection limits of parts per billion and needs no
W Bearings
Zn Neoprene seals, galvanized piping sample preparation other than solvent dilution. However, be-
cause of the matrix interference and formation of polyatomic
species, it lacks the precision and accuracy of other atomic
spectroscopy techniques [12],
indicates failure or excessive wear of a specific engine com- Inhomogeneous sampling, due to the effect of particle size
ponent. Table 2 summarizes the typical wear metals and the of wear metals, continues to be a big concern in atomic spec-
t3rpe of engine wear they may indicate, since in some cases, troscopic analysis. Severely worn engines produce large par-
more than one source may exist for certain elements. ticulates. It is more important to euialyze large particles t h a n
Elemental analysis of used oils is generally performed us- small ones in such cases. An appreciable fraction of sus-
ing atomic spectroscopy techniques, particularly ICP-AES in p e n d e d metallic particles, especially large ones, may not
recent years, because of its capability of simultaneous deter- reach the atomization source; r a t h e r they collect on the
mination of multielements. The U.S. Air Force for a n u m b e r chamber walls and are washed down the drain, resulting in
CHAPTER 26: ELEMENTAL ANALYSIS 709
low biased results. Also, particulates that reach the source Atomic Spectroscopic Methods
may not be "totally" atomized. To overcome this particle size
The most widely used techniques for metal analysis in
effect, the so-called particle size independent methods have
petroleum products are atomic absorption (AAS) and induc-
been developed, which consist of heating the oil in a small
tively coupled p l a s m a atomic emission (ICP-AES) spec-
amount of minerad acids and then diluting with an appropri-
troscopy methods. Other related techniques such as flame
ate organic solvent [13].
emission spectroscopy, graphite furnace AAS, and hydride
At present, in the D2 committee, the only available method
generation AAS, although still viable, do not appear to be pop-
for the determination of wear metals in used oils is D 5185, ular at least in the petrochemical analysis area, perhaps be-
which is a n ICP-AES method. Two methods based on the cause of the adequate sensitivity offered by AAS and ICP-AES.
rotrode technology have also been recently published: D 6595
and D 6728. Atomic Absorption Spectrometry (AAS)
This widely used metal determination technique, not only in
D02 Test Methods petrochemicals, but in all industrial application areas, has
evolved into a "cookbook" type of analysis. Many m o d e m in-
There are about 80 test methods under the jurisdiction of struments are fully automated. The technique is applicable to
Subcommittee 3 on Elemental Analysis (see Table 3). These nearly 70 elements with precision and accuracy of 1-3%
m e t h o d s could be roughly classified according to their achievable u n d e r optimal conditions. Once the material is in
principle chemical/physical technique that is utilized in the solution, the analysis time is less than a minute per sample al-
analysis of samples. though time depends on n u m b e r of elements/sample. Other
than refractory oxide-forming elements, detectability by AAS
Classical Wet Chemistry Methods is less than p p m for most metals. Although mostly free from
These methods are based on the gravimetric-titrimetric fin- atomic spectral interferences, AAS does suffer from molecu-
ish for the final determination of the species of interest. Al- lar spectral, ionization, chemical, and matrix interferences.
though at one time widely used, they have been largely dis- However, most of these are well documented and are taken
placed by spectrometric techniques particularly for metals in care of during routine analyses.
most m o d e m laboratories. Many times these methods are In AAS, a sample solution is vaporized and the elements at-
considered as the referee methods; however, the expertise in omized at high temperatures. The element concentration is
conducting these tests is hard to find today. These methods determined by absorption of light of a characteristic wave-
include: length emitted by a primary source. The light source is typi-
cally a hollow cathode lamp, which consists of a tungsten an-
ode and a cylindrical hollow cathode enclosed in a gas-tight
Analysis ASTM Technique
chamber. The cathode contains the analyte metal; usually in-
Phosphorus D1091 Photometry and Gravimetry
dividual lamps are needed for each element, although some
D3231 Photometry
D4047 Titrimetry multielement lamps are available. The detector is usually a
Vanadium D 1548 Photometry photomultiplier tube. A monochromator is used to isolate the
Nitrogen D3228 Kjeldahl Titration spectral line, and the light source is modulated to discrimi-
Lithium/Sodium D3340 Flame Photometry nate against continuum radiation from atomization source.
Chlorine D 4929A Potentiometry
Usually the AAS instruments use a flame as the atomization
D5384 Titrimetry
Lead D3341 Titrimetry source. The fuel/oxidant composition and ratio determine the
D3348 Colorimetry temperature of the flame. An air-acetylene flame is used for
Sulfur, active D4952 Colorimetry most elements. The NaO-acetylene flame is used for elements
Sulfur, mercaptan D3227 Potentiometry that form stable monoxides in air-acetylene flame.
There are literally hundreds of papers published using AAS
Bomb Combustion Methods for industrial products including petrochemicals. An exhaus-
tive review on this subject is available, although somewhat
These methods utilize combustion in a b o m b (a sealed metal dated [14]. There are several standard test methods based on
container pressurized with oxygen and an ignition source) or this technique in the D2 committee; these include:
an enclosed flame to concentrate the species of interest—
generally a gaseous element—in a n aqueous solution fol-
Analysis ASTM
lowed by a final determination such as gravimetry or titrime-
Aluminum/silicon in fuel oils by ashing, fusion and AAS D 5184B
try. Similar to the classical wet chemistry methods cited Lead in gasoline by complexation and AAS D 3237
above, many of these methods are also considered as referee Manganese in gasoline by AAS D 3831
methods, but have been increasingly replaced by m o d e m in- Trace metals in gas turbine fuels D 3605
strumental methods of analyses. These methods include: Additive metals in oils by AAS D 4628
Trace metals in coke by ashing, fusion, and AAS D 5056
Ni, V, Fe, and Na in crude oils and residual fuels by AAS D 5863
Analysis ASTM Detection Technique direct or after ashing
Chlorine D808 Gravimetry
Hydrogen D 1018 Gravimetry
Graphite Furnace Atomic Absorption Spectrometry
Sulfur D 129 Gravimetry
D 1266 Gravimetry or Titrimetry (GFAAS)
D1552 Titrimetry or IR Detection This technique uses graphite furnace rather than a flame as
D2784 Titrimetry or Turbidimetry
an atomization source, a n d it improves the sensitivity of
TABLE 3—D02.SC3 Elemental analysis subcommittee test methods.

Method Designation Current Year of Publication Subject
D 129 2000 Sulfur in Petroleum Products (Bomb Method)
D482 2000 Ash from Petroleum Products
D808 2000 Chlorine in Petroleum Products (Bomb Method)
D874 2000 Sulfated Ash
D 1018 2000 Hydrogen in Petroleum Fractions
D 1091 2000 Phosphorus in Oils and Additives
D1266 1998 Sulfur in Petroleum Products (Lamp Method)
D 1317 1989 (WD) Chlorine Na-Alcoholate Method
D 1368 1989 (WD) Lead in Reference Fuels
D 1548 1992 (WD) Vanadium in Heavy Fuel Oil
D1552 2001 Sulfur in Petroleum Products (High Temp. Method)
D 1839 1991 (00) Amyl Nitrate in Diesel Fuels
D2622 1998 Sulfur by X-ray Spectroscopy
D2784 1998 Sulfur in LPG
D3116 1989 (WD) Trace Lead in Gasoline
D3120 1996 Sulfur in LPG by |x coulometry
D3227 2000 Mercaptan Sulfur by Potentiometry
D3228 2001 Modified Kjeldahl Method for Nitrogen
D3229 1988 (WD) Low Level Lead in Gasoline
D3230 1999 Salts in Crude Oil
D3231 1999 Phosphorus in Gasoline
D3237 1997 Lead in Gasoline by AAS
D3340 1998 Li and Na in Lubricating Greases
D3341 2000 Lead in Gasoline (I CI method)
D3348 1998 Field Test Method for Pb in gasoline
D3431 1987 (WD) Nitrogen by Microcoulometiy
D3605 2000 Metals in Gas Turbine Fuels
D3701 2001 Hydrogen by NMR
D3831 1998 Mn in Gasoline by AAS
D4045 1999 Sulfur by Hydrogenolysis
D4046 1991 (00) Alkyl Nitrate in Diesel Fuels
D4047 2000 Phosphorus by Wet Chemistry
D4294 1998 Sulfur by EDXRF
D4628 1997 Additive Metals by AAS
D4629 1996 Nitrogen by Chemiluminescence
2001 Hydrogen by NMR
D4808 2001
D4927 1999 Additive Metals by XRF
D4929 2000 Organic Chloride in Crude Oil
D4951 1997 Additive Metals by ICPAES
D4952 1996 Active Sulfur Species
D5056 1998 Metals in Petroleum Coke by AAS
D5059 2000 Lead in Gasoline by XRS
D5184 1997 Al and Si by ICPAES
D5185 2001 Metals by ICPAES
D5291 1995 Instrumental CHN
D5384 2000 (00) Field Test Kit for Chlorine
D5453 1998 Sulfur by UV Fluorescence
D5600 1995 Metals in Petroleum Coke by ICPAES
D5622 2000 (00) Oxygen by Reductive Pyrolysis
D5708 1996 Ni, V, Fe in Oils by ICPAES
D5761 2001 Practice for Emulsification
D5762 2000 Nitrogen by Boat Chemiluminescence
D5863 1998 Ni, V, Fe, Na in Oils and Fuels
D6334 1999 Sulfurs in GasoUne by WDXRF
D6443 1999 Metals in Lubes by WDXRF
D6445 1999 Sulfur in Gasoline by EDXRF
D6470 1999 Salt in Crude
D6481 2000 Metals in Lubes by EDXRF
D6595 2001 Wear Metals in Lubes by Rotrode
D6667 2001 Sulfur in LPG by UV-Fluorescence
D6728 2001 Contaminants in Fuels by Rotrode
D6732 Copper in Jet Fuels by GFAAS
(WD): Standard is withdrawn from publication.
flame AAS by several orders of magnitude. Even though tration of the metals in this matrix necessitates very large di-
GFAAS covers all elements which can be determined by AAS, lutions. The technique uses m u c h smaller sample than that
the strength of GFAAS lies in the determination of elements required for flame AAS, but it takes longer time for analysis.
at sub-ppm levels, and those that are somewhat difficult to do Matrix interferences are also m o r e significant t h a n with
by AAS, e.g., V, Ni, Pb, Sb, As, and Cd. It is not an ideal tech- flame AAS, and this translates into poorer precision (and ac-
nique for additive metals in lube oils since the high concen- curacy).
Most applications of GFAAS in the petroleum products TABLE 4—ICPAES Analytics for oil analysis [2].
area have been in research. Recently, a method to measure Element Wavelength, nm Detection and Upper Limits, ppm
copper in jet fiiels by GFAAS has been published (D 6732). Ag 328.07 0.005-100
Al 308.22; 309.27; 396.15 0.02-100
Inductively Coupled Plasma-Atomic Emission B 249.77 0.05-100
Ba 455.40; 233.53; 493.41 0.0003-50
Spectrometry (ICP-AES)
Ca 393.37; 317.93; 315.88 0.001-20
The most significant development in atomic spectroscopy in Cd 214.44; 226.50; 228.80 0.007-100
the last two decades has been the development and wide pop- Co 228.62 0.007-100
Cr 276.65; 283.56; 267.71 0.001-100
ularity of the ICP-AES technique. It is increasingly replacing Cu 324.75; 327.40 0.002-50
AAS instruments in the laboratories worldwide as a reliable, Fe 259.94 0.004-100
accurate, precise, and rapid technique that is sensitive to ppb K 766.49 0.2-50
levels for multielement aneJysis of petroleum products. It is Mg 279.55; 285.21; 279.08 0.0004-20
second only to graphite furnace AAS in its low detection lim- Mn 257.61; 357.60; 293.30 0.001-50
Mo 202.03; 204.60; 281.62 0.014-100
its for most elements. However, its wide dynamic range Na 589.00 0.015-100
(10''-10*) makes it unique among other atomic spectroscopic Ni 341.47; 231.60; 216.56 0.02-100
techniques. This permits the measurement of percent levels P 214.91; 178.29; 177.51 0.10-200
of some elements Eind p p m levels of others in the same solu- Pb 220.35; 283.31 0.05-100
tion with one aspiration without multiple dilutions. Because S 190.00; 180.73; 182.04 0.05-100
Sb 231.15; 206.84 0.05-100
of the high temperature of the plasma, chemical and matrix Si 288.16; 251.61 0.02-100
interferences c o m m o n in flame AAS are not seen in ICP-AES. Sn 283.99; 189.99; 242.95 0.05-100
In ICP-AES, the liquid sample sprayed into the argon Ti 334.94; 337.28; 350.50 0.001-100
V 292.40; 309.31; 311.07 0.005-100
plasma through a nebulizer is vaporized, atomized, ionized,
Zn 206.20; 213.86; 202.55 0.005-20
and electronically excited. The excited state ions and atoms,
in returning to their ground states, emit photons of wave- NOTE: Other suitable interference-iree wavelengths may also be used.
lengths characteristic of an element. The emitted light is
5185 test methods for the determination of metals in addi-
measured by a polychromator in a simultaneous spectrome-
tive, lube oils, base oils, and used oils have been modified to
ter or by a single photomultiplier in a scanning or sequential
include the mandatory addition of an internal standard and
spectrometer. Nebulizers are a critical pEirt of the instrument
increasing the dilution factor.
and a n u m b e r of models have been devised to overcome the
Numerous applications of ICP-AES in the petroleum prod-
physical interferences encountered in nebulizers of earlier
ucts area have been published. Memy of these were reviewed
yecirs. Commonly used nebulizers are glass concentric pneu-
in Ref. 2. Some of the work published since then is reviewed
matic, cross flow or grid pneumatic, more advanced ultra-
here.
sonic, and Babington high solids nebulizers. See Ref. 15 for a
good review of ICP-AES instrumentation. Robotics can be used for sample dilutions in ICP-AES a n d
XRF. Generally, the precision of XRF was found to be slighdy
A major drawback of the ICP-AES technique is the spectral better than that of ICP-AES [18]. Use of an internal standard
interference that makes accurate trace element determination and kerosene as a preferred solvent has been shown to offer
difficult in complex matrices. High-resolution spectrometers superior precision for a n u m b e r of elements in crude oils [19].
are used to separate the overlapping spectral lines and correct Hausler and Carlson have reviewed vEirious sample prepara-
for background interferences. However, usually the atomic tion techniques used for petroleum products before ICP-AES
emission lines and their associated interfering wavelengths measurements were made at the Phillips Petroleum Company
are well characterized, and normEdly interference-free lines [20]. Similar work performed in Exxon has been reviewed by
can be selected for the elements of interest. Many sensitive Botto [21]. Applications of more advanced ultrasonic nebu-
lines are "ion" lines, also. Some typically used wavelengths lizers in ICP-AES have been described by Botto [22,23].
a n d their detection limits for oil aneJysis are given in Table 4.
Although at present, there are only five test methods utiliz-
The sample preparation is usually simple in ICP-AES in- ing this technique in D2 committee, it is expected that this
volving 10- to 100-fold dilution in an organic solvent such as will increase in the future. In many laboratories, ICP-AES in-
kerosene, xylene, methyl ethyl ketone, methyl iso-butyl ke- struments are replacing AAS instruments because of the for-
tone, etc. The organometallic standards ctre used for instru- mer's superior capabilities discussed earlier in this chapter.
ment calibration. Generally, these methods are used in the petrochemical lab-
The viscosity of oil samples plays em important role in ac- oratories for the determination of a n u m b e r of elements in a
curate ICP-AES measurements. Usually, base oil is added to wide concentration range in a variety of petrochemiccJ ma-
samples and calibration standards, to approximately equate trices. These methods include:
the viscosity. In an important piece of research, Banscd and
McElroy [16] showed that viscosity modifiers can produce
severe biases in ICP-AES measurements due to the changes Analysis ASTM
in the nebulizer aerosol formation affecting the ICP-AES Additive elements in lubricating oils D 4951
torch temperatures. The biases are largest for low excitation Additive and trace elements in fresh and used lubricating D 5185
oils and base oils
potential elements. This problem can be solved by using both Aluminum and silicon in fuel oils after ashing £ind fusion D 5184A
an internal standard (e.g., Cobalt) and adequate sample dilu- Trace metals in petroleum coke after ashing and fusion D 5600
tion (e.g. 100-fold). This work was independently confirmed Ni, V, and Fe in crude oils and residual fuels sifter ashing D 5708
by Jansen et al [17]. In light of this work, both D 4951 and D or dissolution in a solvent
Although not ICP-AES, two methods based on atomic reviewed in Ref. 2. There are, however, no test methods avail-
emission spectroscopy (D 6595 and D 6728) have been pub- able in Subcommittee 3 jurisdiction at present that utilize ion
Hshed using rotrode to determine contaminants and wear chromatography for the elemental analysis.
metals in lube oils and fuels, respectively.
MicroElemental Analysis Methods
Inductively Coupled Plasma-Mass Spectrometry
(ICP-MS) The micro- in this category of methods usually refers to the
presence of these non-metals in minor quantities in the
This technique combines the power of ICP for atomizing and petroleum products. It may also reflect on the fact that usu-
ionizing the samples with the sensitivity and the selectivity of ally a very small quantity of sample is used in the analysis. In
mass spectrometric detection. By combining ICP-MS with all of these cases, the sample is combusted and the element
solution separation techniques such as high-pressure liquid
of interest in the gases produced is detected by a variety of
chromatography (HPLC) or ion chromatography (IC), the
techniques. These methods are widely used in the petro-
technique can be used for metal speciation studies. The tech-
chemical industry for the analyses of a variety of different
nique can simultaneously determine nearly 70 elements in a
products. Essentially all these methods are based on the com-
sample with detection limits down to parts per trillion for
most elements. However, often these low detection limits mercially available instruments. This list continues to grow
cannot be achieved in complex matrices. The matrix effects as more commercial instruments become available. These
are common to ICP-MS just as they are in ICP-AES. Many in- methods include:
ternal standards are required to cover the entire mass range
because of mass bias. A serious concern in ICP-MS measure- Analysis ASTM Technique
ment is the sample preparation step. Extreme care must be Carbon-Hydrogen- D5291 IR or GC
exercised in controlling the blank contamination because of Nitrogen
the generally ultra-low levels of trace elements being deter- Chlorine, Organic D 4929B Microcoulometry
Nitrogen D4629 Chemiluminescence
mined. D5762 Chemiluminescence
In spite of the versatility of this technique, the applications Oxygen D5622 Reductive Pyrolysis
in the petrochemicals field are limited. Al-Swaidan [24] used Sulfur D3120 Oxidative Microcoulometry
D4045 Hydrogenolysis and
dilution of samples in xylene followed by nitric acid extrac- Rateometric Colorimetry
tion to determine low levels of several elements in Saudi Ara- D5453 UV Fluorescence
bian crude oil and gasoline samples. Williams [12] has used D6667 UV Fluorescence
ICP-MS to analyze diluted waste oils for the determination of
several trace elements as a screening tool to decide whether
the used oils can be recycled or must be disposed of as haz- Generally, these methods eire free from interference from
ardous wastes. McElroy et al. [25] have demonstrated the use other constituents of the sample, are capable of rapid and
of this technique, using cobalt as the internal standard, in de- many time automated analyses, and have precisions of about
termining vanadium, phosphorus, nickel, and calcium in a 2-5% dependent on the concentration level of the analyte
number of crude oils. More interestingly, they have com- (Table 5).
bined HPLC with ICP-MS to identify selenium, nickel, and
vanadium species in crude oils. Neutron Activation Analysis (NAA)
The D02.SC3 subcommittee has not published any ICP-MS A large body of data exists on the applications of this tech-
test methods so far. An informal survey did not indicate that nique to crude oil and petroleum products. However, because
ICP-MS was being widely used in the petrochemical labora- of the difficulty of access to a nuclear reactor and associated
tories, perhaps because of the high cost of the instrumenta- radiation hazards, it has found little use in petrochemical or
tion, as well as ICP-AES offering adequate sensitivity in most oil company laboratories.
cases. Since the petroleum products contain essentially a
C—H—O matrix that does not get activated during thermal
neutron irradiation, there is very little background interfer-
Ion Chromatrography ence. However, there could be interference from other trace
This technique has revolutionized the determination of an- element nuclei present in the sample. Generally, these iso-
ionic species from individual wet chemistry techniques to
one simultaneous multi-anion instrumental method. The TABLE 5—Precision of MicroElemental test methods.
technique is a combination of ion exchange chromatography, Analysis Test Method Repeatability Reproducibility
eluent suppression, and conductometric, amperometric, or
Carbon D5291 (X + 48.48) 0.0072 (X +48.48) 0.018
UV-visible detection. It needs only microliters of a sample Chlorine D 4929B 0.7 (X)O-* 1.0 (X)"-^'
and can rapidly determine several anions in a large dynamic Hydrogen D5291 (X''-^) 0.1162 (X°-5) 0.2314
range in a single sample. The analysis, however, is aqueous Nitrogen D4629 0.15 (X)''-^'' 0.85 iXf-^'*
based which means petrochemical samples must be brought D5291 0.1670 0.4456
into aqueous solution generally by combustion in an oxygen D5762 0.009 (X) 0.291 (X)
Oxygen D5622 0.06 - 0.81% 0.26 - 0.81%
atmosphere in a closed vessel. Sulfur D3120 28% 38%
The technique has been used to determine halogens, sulfur, D4045 0.16 V ^ 0.26 VJ
phosphorus, and nitrogen in samples such as fuel oil, gaso- D5453 0.1867(X)°"^ 0.2217(X)0-^
line, diesel fuel, waste oil, coke, etc. The literature has been X: Average value of two results.
topic interferences are well-known and suitable alternate change proportional in magnitude to energy of the incident
interference-free g a m m a rays can be used for quantitative X-ray. The series of changes are sorted and counted by a
analysis. The literature until the late '80s has been reviewed multi-channel analyzer. Simultaneous determination of all
earlier [2]. elements (with atomic numbers greater than Mg) is possible.
Optimization of specific elements is accomplished through
the use of secondary targets and filters. Radioisotope sources
X-Ray Fluorescence Spectrometry (XRF) can be used in place of X-ray tubes in instruments designed
for limited element applications.
Similar to AAS and ICP-AES, XRF is a technique widely used
Sensitivity in X-ray fluorescence analysis is highly depen-
in the petroleum products testing laboratories mainly for the
dent on the sample matrix. Detection limits are typically in
analyses of sulfur, chlorine, and additive metals. The tech-
the p p m range, with the highest sensitivity observed for the
nique is non-destructive, has multi-element capability, and
transition metals. Sensitivity declines significantly for the
high level of precision combined with low (ppm level) detec-
lower atomic n u m b e r elements. Resolution and sensitivity of
tion limits. The cost of the instrumentation, particularly a
EDXRF is typically a n order of magnitude worse t h a n for
wavelength dispersive XRF, is quite high, typically greater
WDXRF. However, the cost of an EDXRF spectrometer, es-
than that of ICP-AES. However, many dedicated inexpensive
pecially the single-element models, can be ten times less than
single element instruments are available.
for a WDXRF spectrometer.
In the XRF technique, a sample is bombarded with X-rays
XRF is a well-established technique with numerous appli-
resulting in ejection of electrons from the inner shells of the
cations in most petrochemical testing laboratories. The pre-
target atoms. In the process, X-rays of discrete characteristic
1990 literature in this area was reviewed in Ref. 2. See Ref. 26
energy are emitted as electrons from the outer shells replace
for a review of currently available instrumentation in both
the ejected electrons. Every element produces a unique sec-
small and large WD- and ED-XRF instruments. Sieber et al.
ondary X-ray spectrum whose intensity is proportional to the
have described the use of XRF in complementary fashion to
element concentration in the sample. XRF has been typically
other spectroscopy techniques for the determination of lu-
applied to all elements above the atomic n u m b e r 10 (neon).
bricant additive elements [27]. EDXRF has been applied to
The basic components of X-ray spectrometers are a source of
the determination of vanadium, nickel, and iron in petroleum
excitation consisting of a high p o w e r X-ray tube (usually
and petroleum residua [28], and Mg, P, CI, K, Zn, Ca, and Mo
comprised of a tungsten, molybdenum, chromium, rhodium,
in crude oils and lubricating oils [29]. Both qualitative and
or scandium target), a wavelength or an energy dispersive
quantitative analysis of low atomic n u m b e r elements (e.g.,
spectrometer for selecting the characteristic fluorescent sig-
magnesium) have recently become feasible due to the use of
nals, and integrating or counting circuits for measurements.
synthetic multilayer crystals and improvement in detector
Due to n u m e r o u s interelement matrix effects, standards windows and associated electronics [30].
with compositions similar to the samples need to be used and
Several ASTM m e t h o d s use a n XRF technique a n d are
corrections m a d e for matrix element absorption and en-
complementary to other methods using AAS or ICP-AES
hancement of the analyte element. For solids, particle size
listed earlier. All three techniques should produce equivalent
and shape can affect accuracy.
results when properly followed. The XRF methods include:
Many of these interferences and matrix effects can be com-
pensated by corrective techniques such as standard addition,
internal standards, matrix dilution, thin film method, and Analysis ASTM
mathematical corrections, provided interference and matrix Lead in gasoline with Bi internal standard or direct D 5059
effects are accounted for. comparison
Metals in lubricant and additive components D 4927
Speed, convenience, minimal sample preparation, and its Sulfur in gasoline and methanol fuels D 2622
nondestructive nature are the main advantages of the XRF Sulfur in petroleum products D 4294
technique. Inherently very precise, XRF rivals the accuracy of Metals in lube oils D 6443
wet chemistry techniques in the analysis of major con- Metals in lube oils D 6481
stituents, provided interferences and matrix effects are ac- Sulfer in gasoline D 6334
Sulfer in gasoline D 6445
counted for.
The two main types of XRF instrumentation available can
be divided into wavelength (WDXRF) and energy dispersive In general, AAS, ICP-AES, and XRF have similar precision
(EDXRF) instruments. In WDXRF, primary X-rays irradiate for the most commonly determined elements in petroleum
the sample and generate fluorescent X-rays. These are then products. Table 6 illustrates this by comparing the repeata-
diffracted by a crystal. A goniometer selects the geometry be- bility and reproducibility of D 4628 AAS, D 4927 XRF, and D
tween the crystal and detector. The geometry controls the de- 4951/D 5185 ICP-AES methods for selected additive elements
tection of X-rays from the element of interest. Different crys- in lube oils.
tals can have different sensitivities a n d cover different
wavelength ranges, and are used depending on the X-ray Miscellaneous Methods
wavelength of the analyte element. Many commercial There are two methods available for the determination of hy-
WDXRF instruments have two detectors and u p to six crystals drogen content of aviation turbine fuels, and of light and
to optimize the instrumental conditions for each element. middle distillates, gas oils and residua (D 3701 and D 4808,
The EDXRF instrument generally uses a lower power X-ray respectively), based on nuclear magnetic resonance.
tube. The emitted X-ray radiation from the sample impinges Perhaps the oldest methods used in the elemental analysis
directly on a detector, typically a Si(Li), which generates a of petroleum products are those for the determination of ash
TABLE 6—Precision of alternate methods for elemental analysis of lubricating oils.

D 4927 (XRF) ICP-AES D 4927 (XRF) ICP-AES
Element*^ D 4628 (AAS) A B D4951 D5185 D 4628 (AAS) A B D4951 D5185
Barium 0.011 0.0027 0.0015 0.011 0.0023 0.04 0.006 0.016 0.019 0.034
Calcium 0.0050 0.0047 0.0034 0.0058 0.0032 0.017 0.018 0.016 0.0083 0.0119
Magnesium 0.0037 0.0032 0.0061 0.015 0.012 0.0147
Phosphorus 0.0065 0.0042 0.0026 0.0071 0.011 0.018 0.010 0.0136
Sulfur 0.0047 0.0042 0.016 0.0132 0.020 0.019 0.061 0.021
Zinc 0.0054 0.002 0.0019 0.0022 0.0066 0.012 0.0051 0.012 0.0072 0.0166
[ mass percent elemental concentration.
and sulfated ash (D 482 and D 874, respectively). The meth- TABLE 7—Standard reference materials for elemental analysis of
ods need a minimal a m o u n t of apparatus, perhaps available petroleum products available from NIST.
in any laboratory. Because of their apparent simplicity, the Sample Type NIST Designation Certification
tests, however, may give an erroneous impression about the Crude oil 8505 Vanadium
composition of complex products. The sulfated ash method Diesel fuel oil 2723; 2724a Sulfur
(D 874), in particular, is fraught with drawbacks resulting in Fuel oil, Distillate 1624c Sulfur
extremely erroneous d a t a inconsistent with the chemical Fuel oil. Residual 1618 Vanadium and Nickel
1634c Trace elements
composition of the additive products. This happens because 1619a; 1620b; 162Ie; Sulfur
of the formation of a n u m b e r of nonstoichiometric com- 1622e; 1623c; 2717
pounds rather than only sulfates during sulfation and com- Kerosene 1616a; 1617a Sulfur
bustion [6]. It has been suggested that this empirical test be Lube additive 1848 Additive Elements
replaced by m o d e m instrumented analysis, such as AAS, ICP- Lubricating oil 1818a Chlorine
1819a Sulfur
AES, or XRF, which give m u c h more precise information on 1836 Nitrogen
the metal content of the petroleum additive products. 1083; 1084a; 1085a Wear Metals
Petroleum coke 2718; 2719 Trace Elements
Reference Fuel 2712-2715 Lead
Standard Reference Materials
Standard reference materials (SRM) play a vital role in eval- these aneJyzed samples as reference materials need to be con-
uating new anal3?tical test methods, assessing the laboratory sidered with caution. These are consensus values and not cer-
capability for performing the tests with required precision tified values. Experience in these programs has shown that a
and accuracy, and for routine quality assurance of the data large degree of uncertainty is associated with the calculated
generated in the laboratories. Often SRMs are also used as mccin vjJues. Hence, such materials are better suited EIS quality
the calibrating materieds. control materials rather than as primary reference standards.
National Institute of Standards and Technology (NIST) is
perhaps the leading source of extremely reliable SRMs in a
ASTM Proficiency Testing
variety of matrices. NIST certifies each SRM based on repli-
cate analysis values obtained by at least two independently A n u m b e r of cross-checks Eire conducted by the coordinating
based methods. There are other national bodies in the U.K., Subcommittee 92 on a four-month cycle. This program has
Germany, etc. which also produce similar SRMs. There are been extremely popular worldwide providing the participat-
also some commercial companies that supply reference ma- ing laboratories with a measure as to how well they are per-
terials, although their certified values do not undergo the rig- forming against their counterparts in the oil industry as well
orous scrutiny that NIST undertakes. as against the precision stated in the ASTM test methods. A
The NIST SRMs useful for elementzJ aneJysis Eire listed in large n u m b e r of Subcommittee 3 test methods are utilized in
Table 7. As can clearly be seen, it would be highly desirable these exercises (Table 8). The reproducibilities obtained in
to have additioneJ SRMs available for other analyses, partic- these programs have genercdly been poorer than those speci-
ularly for additive elements in adpacks and lubricating oils. fied in the ASTM test methods. With recent changes in the
NIST is currently engaged in preparing several other materi- statistical calculations to delete the outliers, the precisions
als for certification. have improved and are somewhat consistent with the pub-
Another source for reference materials is from the industry lished reproducibilities. To help the laboratories improve
round robins such as the Inter-Laboratory Cross-Check Pro- their test precision, Subcommittee 3 is adding non-manda-
grams (ILCP) conducted by Committee D2. About 1800 labo- tory "helpful hints to the analyst" sections a n d mandatory
ratories worldwide take part in these thrice-a-year cross- quality control sections to the test methods under its juris-
checks. At present, 16 materials are used in these cross-checks: diction.
engine oil lubricants, #2 diesel fuel, aviation turbine fuel, mo-
tor gasoline, #6 fuel oil, automatic transmission fluid, gear oil,
International Test M e t h o d s Harmonization
automotive lubricants additives, industrial gear oil, turbine oil,
reformulated gcisoline, base oil, petroleum wcix, crude oil, in- With the increasing globalization of commerce in the petro-
service diesel oil, and lubricating grccise. However, the use of chemicals industry, many national standeirds bodies are heir-
monizing the test methods usage in different countries. Many Future Developments
companies use alternate test methods in their product speci-
fications to ensure that the best methods quoted are viable in A n u m b e r of new test methods for elemental analyses are be-
the countries where the products are sold. In such instances, ing developed in the D02 Subcommittee 3. Many are for the
it is vital that the a h e m a t e method designations quoted pro- determination of trace elements and some for specific analy-
duce equivalent results. Table 9 lists the test methods for ele- sis in a specific matrix. Some of the work underway at the in-
mental analysis issued by six leading national standards or- dustry request includes:
ganizations: ASTM for U.S.A., IP for U.K., DIN for Germany, • lead, m a n g a n e s e , p h o s p h o r u s , and silicon in n a p h t h a ,
ISO, JIS for Japan, and AFNOR for France. This table is ex- gasoline, and light petroleum products by ICP-AES;
cerpted from a m u c h larger table of equivalent test methods • phosphorus in reformulated gasoline by WDXRF;
available in Ref. 32 by Nadkami. Clearly, m u c h more work • sulfur and trace metals in petroleum coke by XRF;
on test method harmonization is necessary when Tables 3 • chlorine in gasohol;
emd 9 Eire compared. • hydrogen by pulsed NMR;
TABLE 8—Subcommittee 3 test methods used in ASTM D2 Interlaboratory Cross-check programs.

Product Analysis (Test Method)
Engine Oil Lubricants Additive elements (D 4628; D 4927; D 4951; D 5185); Ash (D 482);
Ash, sulfated (D 874); nitrogen (D 3228, D 4629; D 5291, D 5762);
sulfur (D 129, D 1552, D 5453).
#2 Diesel Fuel Ash (D 482); sulfiir (D 129, D 2622, D 4294, D 5453); C-H-N (D 5291)
Aviation Turbine Jet A Mercaptan sulfur (D 3227); sulfur (D 1266, D 1552, D 2622, D 4045,
D 4294, D 5453)
Motor Gasoline Lead (D 3237); phosphorus (D 3231); sulfur (D 1266, D 2622, D 3120,
D 4294, D 5453)
#6 Fuel Oil Al and Si (D 5184); Ash (D 482); Nitrogen (D 3228, D 4629, D 5291,
D 5762); sulfur (D 1552, D 2622, D 4294, D 5453); V, Ni, Fe, Na
(D 1548, D 5708, D 5863)
ATF Additive Elements (D 4628, D 4927, D 4951, D 5185); Nitrogen
(D3228, D 4629, D 5291, D 5762); Sulhxr (D 1552)
Automotive Lubricant Additives Additive Elements (D 4628, D 4927, D 4951, D 5185); Ash (D 482);
Ash sulfated (D 874); Nitrogen (D 3228, D 4629, D 5291, D 5762);
sulhir(D1552)
Reformulated Gasoline Sulhir (D 2622, D 3120, D 4294, D 5453)
Gear Oil Additive Elements (D 4628, D 4951, D5185); Ash sulfated (D 874);
sulfur (D 4294).
Base Oil Nitrogen (D 4629, D 5291); Sulfur (D 2622, D 4294).
Crude Oil Ni-V-Fe (D 5708, D 5863); Nitrogen (D 4629, D 5762); Sulfur (D2622,
D 4294)
In-service Diesel Engine Lubricating Oil Additive Elements (D 5185, D 6595)
TABLE 9 --International equivalent test methods for elemental analysis of petroleum products."
Analysis ASTM (D) IP DIN (51-) ISO JIS (K-) AFNOR
Ash 482 4 575 6245 2272 M07-045
Lead-AAS 3237 428
ICl 3341 270 EN 237 EN 237 EN 237
Volumetric 2547 248 2083 M07-014
WDX 2599 228 769T2 3830 2255 M07-082
Metals-AAS 4628 308 391
ICP 4951 437
XRF 4927 407 391
Nitrogen-Kjeldahl 3228 2609
Chemilum 4629 379 2609 M07-058
Phosphorus in Lubes 4047 149 4265
Si/Al in Fuels 5184 377 790 10478
Sulfated Ash 874 163 575 3987 2272 T60-143
Sulfur-Bomb 129 61 T60-109
EDX 4294 336 577
High Temp. 1552 M07-025
Lamp 1266 107 8754 M07-031
Mercaptan 3227 342 3012 2276 M07-022
Microculometry 3120 16591
Oxidative microculometry 3246 373 M07-052
WDX 2622 400T6 14596 T060-142
Wickbold 2785 243 4260
Vanadium 1548 2541 M07-027
V, Ni by AAS 3605 413 790T3 8691
" Excerpted from Ref. 32.
• mercury in crude oil; Lubricants, ASTM STP 1109, R. A. Nadkami, Ed., ASTM Inter-
• silicon on gasoline-naptha by by ICP-AES; national, West Conshohocken, PA, 1991, p. 70.
[10] Lukas, M., and Anderson, D. P., Modem Instrumental Methods of
• metals in middle distillate fuels by ICP-AES;
Elemental Analysis of Petroleum. Products and Lubricants, ASTM
• on-line sulfur determination in gasoline and diesel by XRF. STP 1109, R. A. Nadkarni, Ed., ASTM Intemational, West Con-
shohocken, PA, 1991, p. 83.
Quality Control [11] Nygaard, D., Bulman, P., and Alavosus, T., Modem Instrumental
A good quality control or quality assurance program is es- Methods of Elemental Analysis of Petroleum Products and Lubri-
sential in obtaining reliable data. It has, however, been seen cants, ASTM STP 1109, R. A. Nadkarni, Ed., ASTM Interna-
that many laboratories do not incorporate this step in their tional, West Conshohocken, PA, 1991, p. 77.
analytical sequence. To help the laboratories improve their [12] Williams, M. C, Modem Instrumental Methods of Elemental
performance, a nonmandatory section on quality control is Analysis of Petroleum Products and Lubricants, ASTM STP 1109,
being added to most of the applicable Subcommittee 3 test R. A. Nadkami, Ed., ASTM Intemational, West Conshohocken,
PA, 1991, p. 96.
methods. It is hoped that this will encourage the laboratories
[13] Kauffman, R. E., Saba, C. S., Rhine, W. E., and Eisentraut, K. J.,
to institute quality control practices as an integral and pivotal Analytical Chemistry, Vol. 54, 1982, p. 975.
part of their testing protocols. [14] Sychra, V., Lang, I., and Sebor, G., Progress in Analytical Atomic
Spectroscopy, Vol. 4, 1981, p. 341.
[15] Noble, D., Analytical Chemistry, Vol. 66, No. 2, 1994, p. 105A.
Concluding Remarks [16] Bansal, J. G. and McElroy, F. C, "Accurate Elemental Analysis
Most of the test methods used for the elemental analysis of of Multigrade Lubricating Oils by ICP Method: Effect of Viscos-
petroleum products are based on m a t u r e analytical tech- ity Modifiers," SAE Technical Series Paper 932694, Society for
Automotive Engineers, Warrendale, PA, 1993.
niques a n d i n s t r u m e n t a t i o n . No one technique can be a
[17] Jansen, E. B. M., Knipscheer, J. H., and Nagtegaal, M., Journal
panacea for analyzing all elements in all materials. An ideal
of Analytical Atomic Spectroscopy, Vol. 7, 1992, p. 127.
analytical technique should have high sensitivity, broad lin- [18] Mackey, J. R., Watt, S. T., Cardy, C. A., Smith, S. I., and Meu-
ear dynamic range, high precision, no matrix interferences, nier, C. A., Modem Instrumental Methods of Elemental Analysis
m i n i m u m sample preparation, and be inexpensive to acquire of Petroleum Products and Lubricants, ASTM STP 1109, R. A.
and operate, useful for all elements, simple to operate, rapid, Nadkami, Ed., ASTM Intemational, West Conshohocken, PA,
nondestructive, etc. [31]. Few, if any, of the methods can 1991, p. 62.
meet all these criteria. The analyst has to make a wise choice [19] Gonzales, M., and Lynch, A. W., Modem Instrumental Methods
as to the best available technique for a specific analysis in a of Elemental Analysis of Petroleum Products and Lubricants,
particular matrix. ASTM STP 1109, R. A. Nadkami, Ed., ASTM Intemational, West
Conshohocken, PA, 1991, pp. 62.
[20] Hausler, D. and Carlson, R., Spectrochemica Acta Reviews, Vol.
14, 1991, p. 125.
REFERENCES [21] Botto, R. I., Spectrochimica Acta Reviews, Vol. 14, 1991, p. 141.
[22] Botto, R. I., Journal of Analytical Atomic Spectrometry, Vol. 8,
[1] Role of Trace Metals in Petroleum, T. F. Yen, Ed., Ann Arbor Sci- 1993, p. 51.
ence Publishers, Ann Arbor, MI, 1975. [23] Botto, R. I. and Zhu, J. J., Journal of Analytical Atomic Spec-
[2] Nadkami, R. A., "Overview," Modem Instrumental Methods of trometry, Vol. 11, 1996, p. 675.
Elemental Analysis of Petroleum Products and Lubricants, ASTM [24] Al-Swaidan, H. M., Analytical Letters. Vol. 21, 1988, p. 1487.
STP 1109, R. A. Nadkami, Ed., ASTM International, West Con- [25] McElroy, F. C, Mennito, A., Debrah, E., and Thomas, R., Spec-
siiohocken, PA, 1991, p. 1. troscopy, Vol. 13, No. 2, 1998, p. 42.
[3] Significance of Tests for Petroleum Products, ASTM STP 7C, K. [26] Newman, A., Analytical Chemistry, Vol. 69, 1997, p. 493A.
Boldt, and B. R. Hall, Eds. ASTM International, West Con- [27] Sieber, J. R., Salmon, S. G., and Williams, M. C, Modem In-
shohocken, PA, 1977. strumental Methods of Elemental Analysis of Petroleum Products
[4] Manual on Significance of Tests for Petroleum Products, ASTM and Lubricants, ASTM STP 1109, R. A. Nadkami, Ed., ASTM In-
MNLl, G. V. Dyroff, Ed. ASTM International, West Con- temational, West Conshohocken, PA, 1991, p. 118.
shohocken, PA, 1989. [28] Shay, J. Y. and Woodward, P. W., Modem Instrumental Methods
[5] Modern Instrumental Methods ofElemental Analysis of Petroleum of Elemental Analysis of Petroleum Products and Lubricants,
Products and Lubricants, ASTM STP 1109, R. A. Nadkami, Ed., ASTM STP 1109, R. A. Nadkami, Ed., ASTM Intemational, West
ASTM International, West Conshohocken, PA, 1991, p. 19. Conshohocken, PA, 1991, pp. 128.
[6] Nadkami, R. A., Ledesma, R. R., and Via, G. H., "Sulfated Ash [29] Wheeler, B. D., Modem Instrumental Methods of Elemental Anal-
Test Method: Limitations of Reliability and Reproducibility," ysis of Petroleum Products and Lubricants, ASTM STP 1109, R. A.
SAE Technical Paper No. 952548, Society of Automotive Engi- Nadkami, Ed., ASTM Intemational, West Conshohocken, PA,
neers, Warrendale, PA, 1995. 1991, p. 136.
[7] Eisentraut, K. J., Newman, R. W., Saba, C. S., Kauffman, R. E., [30] Vrebos, B., Spectroscopy, Vol. 12, No. 6, 1997, p. 54.
and Rhine, W. E., Analytical Chemistry, Vol. 56, 1984, p. 1086A. [31] Hieftje, G. M., Journal of Analytical and Atomic Spectrometry,
[8] Niu, W., Haring, R., and Newman, R., American Laboratory, Vol.4, 1989, p. 117.
Vol. 19, No. 11, 1987, pp. 40. [32] Nadkami, R. A., Guide to ASTM Test Methods for the Analysis of
[9] Carter, J. M., Batie, W., and Bemhard, A. E., Modem Instru- Petroleum Products and Lubricants, Manual 44, ASTM Intema-
mental Methods of Elemental Analysis of Petroleum Products and tional, West Conshohocken, PA, 2000.
MNL37-EB/Jun. 2003
Diesel Fuel Combustion

Characteristics
Thomas W. Ryan III^
HISTORICALLY, FUELS HAVE BEEN MADE TO MEET THE REQUIRE- the current procedures are needed. An alternative to the cur-
MENTS of specific engine tjês. This tailoring of the fuels has rent method for rating the ignition quality of diesel fuel is
been accomplished in an iterative process, in which problems presented and described.
are uncovered in the field and efforts are made to resolve the
problems through a process of specification and qualifica-
tion. An example of this process is the development of the ENGINE COMBUSTION AND EMISSIONS
currently used "cetane number"(CN). Cetane n u m b e r is the
measured parameter defined to provide a rating of the igni- Combustion in any heat engine can be divided into three pri-
tion quality of fuels for diesel engines. As refinery processes mary phases: (1) Formation of the appropriate mixture of
became more complex and focused on the production of fuel and air, (2) ignition, and (3) completion of combustion.
gasoline in the 1920s, and as the diesel engine gained accep- In a diesel engine, the fuel is injected into air that has been
tance, the quantities of high quality, straight run diesel fuel
compressed to high pressure and temperature. Some of the
became limited. The fuels that were available in that time pe-
fuel from the incoming spray jet vaporizes and mixes prior to
riod demonstrated problems with cold starting and low tem-
ignition, forming a pre-mixed fraction of the fuel that ignites
perature white smoke.
and b u m s as a premixed flame. The remaining fuel is ignited
As will be described in more detail in the next section, in- in the jet and b u m s as a diffusion flame, ideally at the same
dustry groups were formed to address these and other fuel re- rate as it is injected. The three processes are described in
lated issues. The mechanism for defining specifications for fu- more detail in the following subsections.
els has evolved through the efforts of organizations such as
the Coordinating Research Council (CRC), the American
Petroleum Institute (API), the Society of Automotive Engi-
neers (SAE), the American Society of MechaniccJ Engineers FUEL INJECTION
(ASME), and ASTM International (ASTM). In more recent
Combustion in a diesel engine occurs when fuel is injected at
times, government environmental regulatory agencies have
very high pressure (up to 200 MPa) through a small orifice or
taken a very active role in defining limits on the fuel proper-
multiple orifices in the injection nozzle into the combustion
ties that affect the exhaust emissions. The basic mechanism
chamber, that contains air that has been compressed to high
consists of the definition of standard fuel rating test proce-
pressure and temperature. The high-pressure injection pro-
dures and the compilation of fuel specifications, which define
cess results in a break-up of the fuel injection jets into small
the allowable limits of the variety of fuel properties controlled
droplets due to the shear forces induced between the high ve-
by the specifications. The development of specifications has
locity jets and the relatively quiescent air in the combustion
been based on a wealth of empirical data and, as indicated
chamber. The fuel droplets, consisting of drops in sizes rang-
above, usually in response to specific problems.
ing from approximately ten micrometers to several hundred
The specifications of the fuels for the various types of heat micrometers, traverse the combustion chamber at high ve-
engines caji generally be considered in terms of those proper- locity. The droplets go through a process of heating and evap-
ties, which affect, or reflect, fuel stability and handling, con- oration due to heat transfer from the hot air, and decelera-
tamination, c o m b u s t i o n characteristics, and emissions. tion due to aerodynamic drag. The evaporation process leads
ASTM D 975 is an example of a standard established for diesel to a preferential disappearance of the small droplets and
fuel. This specification is summarized in Table 1 and gener- rapid mixing of the vaporized fuel with the air resulting in the
ally reflects concerns for fuel stability, and engine durability formation of a very fuel-rich mixture in the tip of the fuel jets.
and performance. Those properties that impact the engine The challenge for diesel engine designers is to match the
emissions are discussed in another section of this manual. combustion chamber size and shape with the characteristics
The focus of this chapter is identification and discussion of of the fuel injection spray jets. The fuel jets must traverse the
the issues related to the fuel properties that affect the ignition combustion chamber in order to reach the air in all parts of
and combustion characteristics of fuels for diesel engines. It the combustion chamber. At the same time, the fuel must va-
will become clear from the discussion that modifications of porize, mix with the air, and start to react. If the fuel jet pen-
etrates too far, the fuel interacts with the wall, resulting in de-
graded mixing, low temperature combustion on the walls,
' Institute Engineer, Southwest Research Institute, 6220 Culebra and high u n b u m e d hydrocarbon and smoke emissions. If the
Road, San Antonio, TX 78228.
717
TABLE 1—Specification properties for various fuel oils.

Low S Low
Property Method No. 1 SNo.2 No. 1 No. 2 No. 4
Flash, C, min D93 38 52 38 52 55
Water, v% D1796 0.05 0.05 0.05 0.05 0.05
T90, C m a x D86 288 338 288 338
K. Vis.,(min) mm^/s@40C D445 1.3 1.9 1.3 1.9 5.5
K.Vis.,(max) mm^/s@40C D445 2.4 4.1 2.4 4.1 24.0
Ash, %inass,inax D482 0.01 0.01 0.01 0.01 0.01
Copper Corrosion D130 3 3 3 3
Cetane Number, m i n D613 40 40 40 40 30
Cetane Index D976 40 40
Aromatics, % vol, max D1319 35 35
Cloud Pt, C, max D2500 6 6 6 6 6
Sulfur, % mass, max D2622 0.05 0.05
Ramsbottom Carbon on 10% D524 0.15 0.35 0.15 0.35
residue, mass %
fuel vaporizes and mixes too close to the nozzle, the mixture ing to ignition. In reality, these processes are occurring si-
will be overly rich, leading to high unbumed hydrocarbons multaneously.
and smoke emissions. Likewise, a very simplistic view of chemical aspects of ig-
The fuel properties that have the greatest effect on injec- nition is based on achievement of the fuel's autoignition tem-
tion include viscosity, density, and surface tension. Viscosity, perature. This can be measured following ASTM E 659, as de-
a measure of the fuel's resistance to flow shear, impacts the scribed in Chapter 37. In reality, ignition is a very complex
fuel spray characteristics through flow resistance inside the chemical process that involves pyrolysis and oxidation reac-
injection system and in the nozzle holes. Higher viscosity tions that are kinetically controlled, with an exponential de-
generally results in reduced flow rates for equal injection pendence on the local temperatures and a nonlinear rela-
pressure and degraded atomization. tionship with pressure.
Diesel fuel injection systems are designed to precisely me- Diesel fuel ignition characteristics are very important for
ter the required volume of fuel into the combustion chamber several reasons. First, they affect the ability of the fuel to ig-
during each appropriate part of the compression portion of nite during cold-start. In the limiting case, if the fuel resists
the combustion cycle of the engine operation. All diesel in- autoignition at the highest achievable compression tempera-
jection systems meter the fuel on a volume basis, so that fuel ture it is impossible to start the engine. Second, the ignition
density affects the mass of fuel injected. Increased density be- characteristics are important because they affect the quantity
yond specification results in higher than designed fuel injec- of fuel injected during the ignition delay time. If the ignition
tion rates due to the direct relationship between mass, vol- delay time is long, a large quantity of injected fuel becomes
ume, and density. premixed prior to the start of combustion. When combustion
Surface tension, or the tendency of the fuel to adhere to it- does occur, however, most of the premixed fuel ignites at the
self at the fuel-air interface, affects the tendency of the fuel to same time, leading to very high rates of combustion, high
form drops at the jet-air interface. Increased surface tension rates of pressure rise, and "diesel knock." Third, if the igni-
tends to degrade atomization rates. It should be noted, how- tion delay time is long, the resulting premixed burning leads
ever, that the surface tension of most hydrocarbons is very to higher combustion temperatures and increased oxides of
similar one to another. Based on this fact, surface tension nitrogen (NOx) exhaust emissions. The mechanism for this
does not play a first order role in the jet break-up and atom- NOx formation process is described below.
ization process, at least on a comparative basis.
COMBUSTION
IGNITION
The combustion process in diesel engines can be monitored
by measuring the pressure in the combustion chamber dur-
Dec [1] theorizes that ignition occurs in the rich region at
ing the compression and combustion processes. It is possible
the tip of the fuel jet, when the fuel's vapors achieve tem-
to apply the First Law of Thermodynamics to the diesel en-
peratures sufficient for decomposition and oxidation. In a
gine in order to obtain an estimate of the instantaneous rates
diesel engine, the fuel does not ignite instantaneously. The
of heat release during combustion. The First Law for a
time elapsed from injection to ignition is known as the ig-
closed, constant mass system is
nition delay time. The ignition delay time occurs because a
certain amount of time is required for the fuel to vaporize dQ/dt + dW/dt = dU/dt (1)
and ignite. A very simplistic view of the ignition process
separates the physical and chemical aspects of the ignition where.
process. The time necessary for the fuel to vaporize and mix Q = heat transfer
is known as the physical delay, while the chemical delay is W = work
the time required for the onset of chemical reactions lead- U = internal energy
CHAPTER 27: DIESEL FUEL COMBUSTION CHARACTERISTICS 719
If it is assumed that the combustion process can be treated as Figure 1 is a heat release rate diagram for an engine condi-
a heat transfer into the system, then Eq 1 can be rearranged tion in which there is a fairly large premixed b u m fraction.
Also plotted in Fig. 1 is the injection pressure as it was mea-
dQ/dt = dU/dt - dW/dt (2) sured simultaneously with the cylinder pressure. The inflec-
and, tion in the injection pressure at 178° indicates the point in
time when the injection nozzle valve opens and fuel starts to
dU/dt = m Cv dT/dt (3) be injected into the cylinder. This is noted as the start of in-
where, jection. Also indicated are the premixed and the diffusion
b u r n phases, or fractions. The time from the start of injection
m = mass trapped in the cyUnder (air + fuel mass) to the start of the premixed b u m phase is called the ignition
Cv = specific heat at constant volume of mixture delay time. Note that during this delay period a significant
T = temperature in the combustion chamber. quantity of fuel is injected, vaporized, and mixed with the hot
Also it is assumed that, air in the cylinder. When ignition does occur, this premixed
fuel ignites spontaneously.
dW/dt = P dV (4)
As shown in Fig. 1, the premixed b u m fraction typically
where. has a very high heat release rate. As indicated above, this
rapid release of energy results in an increase in the engine
P = instantaneous pressure in the cylinder noise called "diesel knock." It is this almost instantaneous re-
V = instantaneous volume in the cylinder. lease of energy that raises the temperature in the cylinder
Assuming Ideal Gas behavior, early in the combustion process and leads to high combus-
tion temperature throughout the rest of the combustion pro-
PV=mRT cess. While this increase in the combustion t e m p e r a t u r e
might be assumed to increase the overall cycle efficiency due
or,
to Camot consideration, it can also increase the heat transfer
dT/dt = (1/mR) (p dV/dt + V dp/dt) and it almost always increases the NOx emissions.
where.
R = Gas Constant. EMISSIONS
With appropriate substitution, Eq 2 becomes,
Combustion temperatures are important because they domi-
dQ/dt = (Cv/R - 1) P dV/dt + (C^/R) V dP/dt (5) nate the rate of formation of NOx emissions. NOx is impor-
tant because it reacts with the unburned hydrocarbons in the
It can be seen that the apparent heat release rate during com-
atmosphere to form smog. Most of the NOx emissions result
bustion, dQ/dt, can be computed using Eq 5, the measured
from a chemical kinetic process, known as the Zeldovich [3]
cylinder pressure, and using the geometric relationship be-
Thermal NOx emissions mechanism, where,
tween cylinder volume and crankangle. The computation is
performed using cylinder pressure data that is resolved based N2 + O = NO -h N
on crankangle [3]. The pressure is measured using a high (6)
N + O2 = NO -h O
speed piezoelectric pressure transducer installed in one of
the engine's cylinders. The pressure data is recorded simulta- The rate constants for the two reactions are exponential func-
neously with a record of the crankangle position. tions of the temperatures in the combustion chamber. These
0.20 20000
Heat release rate

u> Injection pressure
0.15 - 15000 .S
a
I< 0.10 10000

lU
oc
tu
s
X v>
0) UJ
3 a
O 0.
lU 0.05 - 5000
z
<
I- o
z
< "N .
111
0.00
Premixed
Start of Injection •^-Diffusion-^
-0.05 1 1 n- r 1 1 *T*—*—i 1 r -5000
90 105 120 135 150 165 180 195 210 225 240 255 270 285
CRANK ANGLE [degrees; TDC=180]
FIG. 1—Heat release rate diagram.

temperatures depend on the thermodjrnamic processes that which was measured in a 1994 Caterpillar 3176 engine. Note
occur during compression and combustion, as well as on the the very small premixed b u m phase for this engine and the
adiabatic flame temperature of the fuel-air mixture. fact that the injection pressure and the heat release rates have
The adiabatic flame temperature is a fundamental prop- similar shapes. The correspondence of the injection and heat
erty of the fuel air mixture, depending on the initial pressure release rates indicates that the fuel is being burned as it is in-
and temperature, the air-fuel ratio, and the fuel properties, jected.
including hydrogen, carbon, and oxygen content, and heat of In addition to NOx, the u n b u m e d hydrocarbons (HC) and
combustion. The highest adiabatic flame temperature occurs particulate emissions (PM) from diesel engines are impor-
in stoichiometric, or chemically balanced mixtures, using fu- tant, not only for their role in reducing efficiency and con-
els with high carbon contents. The adiabatic flame tempera- tributing to smog formation, but also from the direct health
ture can be computed based on the above parameters using risk associated with these pollutants. The U.S. Environmen-
a n equilibrium calculation [3]. tal Protection Agency (EPA) and the California Air Resources
In a diesel engine, the pressure and temperature at the start Board [4] have defined diesel PM as an air toxin, recognizing
of reaction are defined by the engine design and the operat- the potential health risks associated with h u m a n exposure to
ing condition. If the temperatures are high, the ignition delay diesel PM.
times tend to be short, leading to a smaller premixed b u m Diesel PM is defined by regulatory bodies as anything col-
phase and lower initial temperatures for the diffusion b u m lected on a specified filter that is maintained at 125°F. The
phase. If the ignition delay times are long, a large quantity of collection procedure involves dilution of the exhaust sample
fuel is injected during the delay time and the premixed b u m with fresh air. The method has been defined by EPA to simu-
phase is larger, leading to higher temperatures at the start of late what occurs when diesel exhaust is emitted into the at-
the diffusion b u m phase. In a diffusion flame, the fuel actu- mosphere. Diesel PM is a complex mixture of soot, u n b u m e d
ally b u m s at the location where the fuel and air mix to the fuel, and partially reacted fuel.
chemically correct (stoichiometric) fuel-air ratio. The fuel The formation of u n b u m e d HC and PM is a result of the
b u m s at the stoichiometric adiabatic flame temperature. If heterogeneous n a t u r e of the diesel c o m b u s t i o n process
there is a large quantity of fuel in the premixed b u m phase, where fuel injection, vaporization, mixing, ignition, and com-
the initial temperature for the diffusion b u m phase is high, bustion are all occurring nearly simultaneously in the engine.
leading to higher temperatures during the diffusion b u r n The HC emissions result from a combination of sources in-
phase. cluding fuel that is deposited on the combustion chamber
M o d e m practice in diesel engine design is to minimize the walls and does not react, or only partially reacts. It also in-
premixed b u m fraction by controlling the initial rate of fuel cludes fuel that has mixed and is either too lean or too cold
injection and thereby minimizing the a m o u n t of fuel injected to react. It should be noted that the mass of HC emissions per
during the ignition delay time. Figure 2 is a plot of the heat BHP/hr from diesel engines are typically an order of magni-
release rate and injection pressure for an engine and associ- tude lower than the engine out HC emissions from spark ig-
ated operating condition in which the initial injection rate is nition engines.
controlled in order to minimize the amount of fuel injected Soot is the product of diffusion burning where some of the
during the ignition delay time. This is done by designing the fuel partially reacts, forming compounds that ultimately re-
injection system to provide a slow initial rate of injection, fol- sult in the growth of high molecular weight compounds that
lowed by a rapidly increasing rate once ignition occurs. This are very rich in carbon. Soot formation is a very complex
is demonstrated by the increasing injection pressure in Fig. 2, chemical process that is affected by the physical processes
0.30 25000
0) 0.25
20000
0)
•a Heat release rate V
B Injection pressure "5
ID 0.20 a.
15000
1-
3
0.15 OT
X V)
If) 10000 Ui
3
O 0.10 a.
UJ z
z O
< 5000 H
1-
z 0.05 U
lU
<
1-
-5
Z
(/z> 0.00 _-^\- 0
-0.05 -5000
90 105 120 135 150 165 180 195 210 225 240 255 270 285
CRANK ANGLE [degrees; TDC=180]
FIG. 2—Heat release rate diagram-small premixed burn phase.

that occur during the fuel mixing and combustion processes.

A simplistic view of the diesel diffusion burning process in-
volves a relatively thin flame front formed at the interface be-
tween the fuel and air. In this view, the fuel is on one side of
the flame and air on the other. The initial soot formation re-
actions include thermal break down (pyrolysis) of the fuel be-
fore it enters the flame. Under these conditions, the soot pre-
cursor reactions (leading to greater soot formation potential)
favor high temperature and long residence times. More soot
precursors are formed if the mixing rates are slow and the
temperatures are high. Higher temperatures also lead to
higher soot oxidation rates. The level of PM emissions from a
given diesel engine is the result of the difference between the
formation rate and the oxidation rate. In general, higher tem-
peratures tend to lead to lower soot and PM emissions, due
primarily to the effect of the increased temperature on the
PM oxidation rate.
The diesel engine designer faces a conflict between PM and
NOx emissions. High temperatures are desirable for PM
emission control, but they also lead to high NOx emissions. It
is this trade-off that constitutes one of the primary concerns
of modem diesel engine design. In general, current practice
is to reduce the combustion temperatures to the highest level 2 3 4 5
possible consistent with achievement of the NOx emissions
H/C (Atomic Ratio)
standard. The PM emissions are controlled through engine
combustion chamber and injection system design to prevent FIG. 4—Adiabatic flame temperature and
interactions of the fuel and combustion chamber wall. In ad- NOx versus fuel hydrogen to carbon ratio.
dition, higher injection pressures are used to produce higher
mixing rates that lead to lower residence times in the pyroly-
sis zone and thus lower soot formation rates. D I E S E L F U E L I G N I T I O N QUALITY
The effects of fuel properties and composition on soot for-
mation were studied extensively by Naegeli and Moses [5]. Current Practice (Cetane Number)
They concluded that the primary controUing fuel property is
Diesel fuel specifications currently include only two specified
the hydrogen content. This is demonstrated in Fig. 3 where the
properties that are related directly to combustion. Heat of
soot emissions from a diffusion flame are plotted versus the
Combustion, and cetane number. Heat of Combustion is a
fuel hydrogen to carbon ratio. Fuel hydrogen and carbon con-
fundamental property of the fuel, based on the Heat of For-
tents are determined in the laboratory using ASTM D 5291.
mation of the individual molecules. Its determination is fairly
It is interesting to note that the fuel hydrogen content is the straightforward following ASTM D 240, which employs a
primary fuel variable affecting both NOx and PM. High hy- bomb calorimeter. The procedure consists of completely
drogen content (as H atoms) fuels have lower adiabatic flame burning a weighed sample of the unknown fuel in a combus-
temperatures and thus lower NOx formation tendencies. The tion bomb that is contained in a controlled temperature bath.
NOx relationship to fuel hydrogen to carbon ratio is pre- The Heat of Combustion is determined by measuring the
sented in Fig. 4, where the adiabatic flame temperatures and temperature increase of the bath.
the predicted NOx emissions (Zeldovich Mechanism) are
plotted versus fuel hydrogen to carbon ratio [6]. Higher hy- Cetane number, on the other hand, as determined follow-
drogen content fuels also tend to form less soot, and thus ing ASTM D 613, is not a fundamental property of the fuel.
lower PM emissions. Cetane number is a defined parameter designed to provide an
indication of the ignition quality of diesel engine fuels.
Higher cetane number means that the fuel has better ignition
qUcJity than fuels with lower cetane numbers. Cetane num-
ber is determined in an engine test in which the ignition qual-
ity is rated versus those of blends of two reference fuels. The
history and method of ASTM D 613 and cetane numbers are
described in the following paragraphs.
In 1932, Boerlage and Broeze [7] proposed that the ignition
quality of a fuel be based on a comparison of its ignition de-
lay time in a diesel engine to that of a blend of two reference
fuels. They developed the "cetene scale" in which a fuel was
1.5 1.75 1.85
assigned a "cetene number." The reference fuels were two
Fuel H/C Ratio pure hydrocarbons, cetene (C16H32) and mesitylene. Cetene
FIG. 3—Soot concentration versus fuel H/C burned readily in conventional engine, while mesitylene did
ratio. not bum at all.
problem with the cetane procedure is related to the fact that

neither the engine nor the test conditions are representative
nil 11 u of current engine design or typical operating conditions.
The current procedure, developed over 50 years ago, in-
7//////1 volves the use of the Waukesha engine. The prechamber has
a movable end plate, which is used to change the volume of
1 PRE-CHAMBER
the prechamber and, thus, the compression ratio, as shown
in Fig. 5. The specified operating conditions of the test are
equivalent to a high-speed idle test, with the speed set at 900
w/rr/rrz/rm rpm and the fuel flow set at 13 ml/min (equivalent to an
air/fuel ratio of approximately 30:1).
One of the more frequent complaints is the fact that the
CFR engine design is not representative of current diesel en-
gines. The engine design includes a cylindrical precombus-
tion chamber. The fuel injector is located in one end of the
prechamber and the other end is moveable and is used to
vary the compression ratio. The motion of the prechamber
end plate not only changes the compression ratio, but also
changes the distance from the injection nozzle to the com-
bustion chamber wall. Modern diesel engines, both light-
duty and heavy-duty, utilize direct in-cylinder fuel injection.
These engines have mixture preparation, surface condition,
combustion chamber geometry, and thermodynamic condi-
FIG. 5—Cross section of the CFR engine. tion effects that are significantly different than the precham-
ber CFR engine. This means the current cetane test engine
In 1935, ASTM adopted this form of diesel fuel rating sys- and test method expose the fuel to temperature history, air-
tem using hexadecane (C16H34) and alpha-methylnaphtha- fuel ratio, and surface effects that are different than those en-
lene ( d iH]o) as the reference fuels. The former was assigned countered in most actual engines in the field.
a cetane number of 100, while the latter was given a cetane Another complaint is that the test condition used in the test
number of 0 [8]. In 1962, ASTM added heptamethylnonane, method is effectively a moderate load at very low speed. The
(C16H34) to the cetane scale as an intermediate, low ignition test speed is 900 rpm and the air-fuel ratio is 30:1. This speed
quality fuel with a defined cetane number of 15 [9]. is much higher than cranking speed and thus does not repre-
The standard apparatus for determining and comparing ig- sent cold start conditions. The speed is also much lower than
nition delay times is a Coordinated Fuels Research (CFR) normal operating speeds in most high-speed diesel engines,
diesel engine developed by the Waukesha Motor Company. It so that it is not representative of hot running conditions, and
is a one-cylinder, four-stroke cycle engine with a cylindrical thus it is not a good indicator of the hot running characteris-
prechamber chamber design (see Fig. 5) and a compression tics of the fuel. The moderate load, represented by the 30:1
ratio capability ranging from 6:1 to 28:1. air/fuel ratio, does not incorporate intake pressures above
The ASTM D 613 test procedure consists of running the test ambient (not boosted) so that compression pressure histories
fuel at specified conditions of speed, load, and intake tem- are different than in modem turbocharged diesel engines.
perature. The injection timing is adjusted so that the start of Some of the other reported problems are related to the cost
injection is 13° Before Top Dead Center (BTDC). The com- and time required for the measurement [11]. Other problems
pression ratio is adjusted until ignition occurs at TDC. The are associated with the repeatability and reproducibility
test fuel is then replaced with blends of the reference fuels [11-13]. Accurate and repeatable determination of the cetane
until one is determined to have a slightly higher compression number of alternative and ignition-improved fuels, and fuels
ratio and one with a slightly lower compression ratio than the at the lower end of the cetane scale, are all problematic
test fuel. The cetane number of the test fuel is determined by [12-15]. Many researchers are even questioning the validity
linear interpolation of the cetane numbers of the reference of the cetane scale as an indicator of ignition quality
fuels. As an example, typical U.S. diesel fuel has a cetane [9,12,14,16-18].
number of 45. The 45 cetane number reference fuel is a blend The current test method has poor repeatability and repro-
consisting of 64.7 vol.% hexadecane and 35.3 vol.% hep- ducibility. LeBreton [12] conducted tests on the repeatability
tamethylnonane . of the CFR engine results and found the standard deviation
Unfortunately, a number of problems are associated with for the data to be 0.8 cetane numbers. However, the sample
using the CFR engine for evaluating ignition delay time and only contained fuels with cetane numbers between 45 and 50.
thus cetane number. It has been criticized for a variety of sig- Glavinceveski et al. [13] reported repeatability results for a
nificant shortcomings. The primary complaint is a failure of set of 48 fuels as being 1.57 cetane numbers. The test resuks
cetane number to consistently provide an accurate measure- for these same fuels, performed in a number of engines, was
ment of ignition quality. The specific shortcomings of the cur- calculated to be 4 cetane numbers. Once again, the majority
rent cetane procedure were extensively discussed during a of the fuels had cetane number ratings between 40 and 50,
CRC-hosted workshop, Diesel Fuel Combustion Performance, and none had cetane number below 37. Glavinceveski et al.
held in Atlanta, Georgia in 1984 [10]. It appears that the main [13] showed that the scatter of the cetane number rating
CHAPTER 2 7: DIESEL FUEL COMBUSTION CHARACTERISTICS 723
method increases dramatically as the rating drops below 40 Elliott [25] noticed the ignition delay time decreased with
cetane number. lower fuel/air ratio. In a more comprehensive study of physi-
The standard test method (ASTM D 613) is reported to have Ccil delay time, Wakil et al. [26] drew the same conclusion and
a repeatability of ± 1 CN. Indritz [19] examined data for a showed that it was caused by the relative spacing of the fuel
large n u m b e r of reference and test fuels, tested in a n u m b e r of droplets. They also found that physical delay times increased
test engines. The results of his comparisons are presented in with droplet size a n d fuel boiling point due to vaporization
Fig. 6, where the cetane numbers are plotted versus compres- characteristics. Rao a n d Lefebvre [27] also determined that
sion ratio. Two observations can be made regarding the re- the physical delay time is always a significant pEirt of ignition
sults. First, it is clear that there is not a universal relationship delay. In a study of chemiccd delay times, Chang et al. [28]
between the cetctne n u m b e r and the compression ratio. It is found that the rate of reaction of high-cetane-number fuels
likely that the lack of a universal relationship between cetcine increases faster after ignition t h a n t h a t of low-cetane-
n u m b e r a n d compression ratio results from day-to-day and n u m b e r fuels. Cox a n d Cole [29] studied the chemical kinet-
engine-to-engine differences in the combustion. Injection ics involved in chemical delay time and demonstrated a large
nozzle performance, combustion chamber deposits, variation increase in delay time with decreasing oxygen concentration
in compression ratio calibration, a n d variations in the injec- of the air/fuel mixture.
tion p u m p pressure and calibration all contribute to the dif- There have been a n u m b e r of studies concerning the effects
ferences. Second, the variation in the measurements is on the on cetane number caused by blending alternative fuels with
order of +/— 5 CN. An error of 5 CN Ccin mean the difference diesel fuel ASTM #2 (DF-2). Saeed a n d Henein [30] found
between starting or not starting in cold weather, depending that the addition of 10 vol% ethanol in diesel fuel caused only
u p o n the specifics of the engine design. a slight decrease in cetane number. However, they noted a
Much of the research into ignition quality has centered on drastic decrease in cetane n u m b e r as the amount of ethanol
how the ignition delay time a n d cetane n u m b e r relate to the in t h e blend increased from 20-70 vol%. Henein a n d
conditions under which the tests are conducted. Yu et al. [20], Fragoulis [9] studied the effects of blending a number of al-
in experiments performed in a specifically designed research ternative fuels with DF-2. They found that blends containing
engine, conducted duplicate tests in which combustion oc- indolene, unleaded gasoline, and No. 6 fuel oil each produced
curred every other cycle. They found that the peak of the dif- a drastic d r o p i n cetane n u m b e r . Blends of DF-2 with
ference in the pressure traces of the fired a n d unfired cycles m e d i u m n a p h t h a a n d Jet A fuel p r o d u c e d very small de-
increased with decreasing ignition delay time. Tsao et cd. [21] creases in cetane number, while a blend with No. 4 fuel oil
found that delay times increased with decreasing air temper- caused the cetcine n u m b e r to increase slightly.
ature and engine speed. Hardenberg and Hase [22] reported Dabovisek and Savery [31] concluded that the ignition de-
the delay times decreased with increasing compression pres- lay a n d therefore cetane n u m b e r of a blend of two fuels is
sure a n d air temperature. Finally, Parker et al. [23] and Walsh controlled by the component with the greatest autoignition
and Cheng [24] showed the ignition delay time can be de- resistance, or lowest cetane number. Needham a n d Doyle
creased by increasing the fuel temperature at injection. [14] determined cetane number for synthetic and alternative
Other studies of the ignition delay time have focused on fuels. They conducted studies of the cetane number of blends
differentiating the physical and chemical aspects of the igni- containing naphtha, sunflower oil, sunflower oil ester, shale
tion delay time. The physical aspects include the atomiza- oil, coal synthetic liquids, and tar sands. They found that
tion, mixing rates, a n d vaporization rates of the fuel. These ASTM D 613 for the vegetable oil Eind the blends of naphtha
physical aspects are related to the fuel properties of viscosity, and methanol with DF-2 did not accurately predict the igni-
density, and distillation characteristics. The chemical aspects tion delay. Finally, Siebers [18] conducted constant volume
relate mostly to the chemical composition of the fuel and the combustion b o m b tests on blends of naphtha Etnd coal de-
corresponding impacts on the chemical kinetics of the ther- rived liquids with DF-2, and on a degummed sunflower oil, a
mal decomposition and free radical generation mechanisms. sunflower oil monoester, and methanol to determine how the
delay times varied with temperature in the bomb. All fuels be-
820 880 WOO t040 1080
haved similarly t o reference fuels w i t h the exception of
•80
methanol, for which the delay time increased dramaticcdly as
CAtCULATB) ISENTROPIC TEMPERATURE - K the temperature decreased, presumably due to the unique
chemical structure of methanol.
fS
• P r o p o s e d Alternatives to ASTM D 6 1 3
Due to the issues discussed above, including the time Eind ex-
I R • Rvtaranca FtMl
0 " Unknown Furt
pense required to conduct D 613 cetane n u m b e r determina-
tions, a n u m b e r of edtemative methods have been proposed.
The proposed methods have included numerous correlations
"^n^^ with other physical a n d chemical properties, constant-
-1HU_^, volume combustion b o m b based methods, and correlative
techniques based on NMR and FTIR analysis of the test fuel.
•I
12 13 M W It 17 Hardenberg and Hase [22] tried to use activation energy as
COMPRESSION RATIO an indicator of cetane number. Collins a n d Unzelman [32]
FIG. 6—Scatter plot of Cetane measurements. used API gravity a n d mid-point temperature. Klopfenstein
[33] correlated density and mid-boiling point temperature by Ryan et al. [41], however, indicate that cetane number is
with cetane number, while Murphy [34] included percent hy- not related to emissions from modem heavy-duty diesel en-
drogen. Glavincevski et al. [13] tried to use aromatics to pre- gines operating at standard ambient conditions. Analysis of
dict cetane number, and Steere [35] developed a correlation the heat release rates indicate that the combustion process in
between cetane number, aniline point, viscosity, density, and these modem diesel engines is dominated by diffusion burn-
D 86 distillation. Cetane index (ASTM D 976) involves corre- ing, with the combustion rate controlled by the rate of fuel in-
lations that are modified periodically, and that incorporate a jection. Under these circumstances, cetane number, as a
number of different properties. While all of the correlations measure of the ignition delay time, is not important for typi-
provide reasonable predictions of the CN of fuels that are cal diesel fuels because the start of combustion is controlled
similcir to those used to develop the correlations, they are not by the conditions in the engine and the design of the injection
reliable for prediction of cetane numbers of fuels that are dif- system. Injection system designs that allow for control of the
ferent than the fuels used to develop the coirelations. Typi- rate of fuel injection can reduce the amount of fuel injected
cally, these correlations must be modified periodically to ac- during the ignition delay time, and thus reduce the depen-
commodate changes in feedstock source and refinery dence on the ignition quality of the fuel, as discussed previ-
processing technology. In addition, the accuracy of the cor- ously.
relation is limited to the precision of ASTM D 613 test It is clear that the current procedure for rating the ignition
method and the number of engine tests used to obtain an av- quality of diesel fuel is no longer adequate. First, it probably
erage cetane number for an individual fuel sample. does not represent the sensitivity of current and future en-
Nuclear magnetic resonance (NMR) has been used to pre- gines as indicated by the work of Ryan et al. [41], and second,
dict cetane number [10,36,37]. Bailey et al. [37] used the rel- because it is not as repeatable or reproducible as it needs to
ative quantities of methine and methylene hydrogen to pre- be for use in current emd older engines. If the results of In-
dict the cetane numbers of non-aromatics. They also dritz [19] are accepted, a variation of +/— 5 cetane numbers
developed a model for aromatic hydrocarbon fuels, based on is possible. Using the results of Ullman et al. [39,40] a 5
the relative quantity of alpha hydrogen and relative squared cetane number variation can produce as much as a 4% dif-
sum of alkyl hydrogen along with the methine and methylene ference in the NOx emissions and as much as a 13% variation
hydrogen. It was reported that the deviations from perfect in the PM emissions from older and current engines.
correlation with D 613 cetane number were most likely due Ryan et al. [42-45] developed a constant volume combus-
to scatter in the D 613 results. tion bomb based technique (CVCA) for rating the ignition
Fodor [38] reported some promising results using Fourier quality of fuels for diesel engines. The primary objective of
Transform Infrared (FTIR) analysis of the fuel. In these tech- these efforts was to develop a technique that is based on mea-
niques the fuel sample is analyzed using FTIR and the result- surement of the ignition delay time, a fundamental combus-
ing spectra are used to develop correlations with the cetane tion property of the fuel. The goal was to eliminate the engine
number. While the techniques are generally very fast and re- sensitivity inherent in the ASTM D 613 technique. A great
quire very small fuel samples, the methods are based on cor- deal of effort was devoted to developing a technique based on
relations and are unstable when used outside the range of a calibration using the defining reference fuel rather than a
properties/specifications of the fuels used to develop the cor- correlation. Several hundred fuels were examined using this
relation. Again, as stated above, the accuracy of the correla- technique. The test fuels included petroleum based diesel fu-
tion is related to the accuracy and number of ASTM D 613 en- els, various refinery products, coal slurries, various oxy-
gine tests. genated fuels, blends of various fuels and fuel components, a
Another significant issue with the current cetane rating wide range of cetane improver additives, and a large number
scale is related to a concern over whether cetane number proof alternative fuels. The apparatus and technique, now called
vides an accurate and representative indication of the igni- the IQT (Ignition Quality Tester), has been further refined
tion quality of all diesel fuels. Ignition quality in a diesel en- and developed by Allard et al. (45-47) and is currently being
gine is important for cold start, for engine noise, and can be examined for approval as an ASTM test method.
related to both NOx and PM. Tavacha and Cliffe [17] noted Based upon the above discussion, it appears that the en-
that cetane number is a measure of the ignition temperature, gine-based technique for diesel-fuel ignition quality rating is
not ignition quality. Needham and Doyle [14] found that ig- not acceptable for the numerous reasons listed. It is also clear
nition delay is not the controlling factor in determining over- that the other noncombustion-based techniques (FTIR,
all performance. They recommended development of a new NMR, Property Correlation) are also not acceptable because
rating method. Sieber's [18] results showed that cetane num- they involve correlations that are valid only for the type of fu-
ber does not provide an accurate measure of ignition quality els used to develop the correlations. It appears that the best
of fuels whose ignition delay dependence on temperature, or approach is one in which a fundamental combustion prop-
compression ratio, or the type of ignition (single two stage) erty, such as ignition delay measured in a well-defined ex-
differs from the reference fuels. periment, is used as the basis for the rating. It appeeirs that it
Oilman et al. [39-40] studied the effects of fuel properties is also desirable to use a technique that is based on a calibra-
on engine emissions. The tests, performed in a 1988 Detroit tion rather than one based on a correlation.
Diesel Series 60 engine calibrated to near 1991 emissions lev-
els, indicated that both the NOx and the PM were related to
CVCA/IQT Method
the cetane number. The Series 60 is a direct injection, tur-
bocharged, intercooled diesel engine. The CFR engine is an As indicated above, the IQT method is based on the use of the
indirect injection, naturally aspirated engine. Recent results CVCA technique developed by Ryan et al. [42-45]. This tech-
nique was originally suggested by Hum et al. [ 15] and Yu et al. The test method consists of setting the initial conditions in
[14]. In this method, the fuel sample is injected into a constant- the bomb, followed by injection of the fuel sample and
volume combustion chamber, which contains air at a pre-se- recording of the pressure history during injection, ignition,
lected elevated temperature and pressure. The constant-vol- and combustion. The needle lift trace, using the output of the
ume combustion chamber is equipped with a pressure proximeter on the injection nozzle, is used to document the
transducer at one end and an inward opening pintle nozzle at start of injection. The needle lift data and the pressure varia-
the other end. A proximeter is installed on the injection nozzle tion in the vessel are recorded and used to determine the time
for recording the start of injection. The injection nozzle is sup- from the start of injection to the start of combustion. This
plied with fuel from a pneumatically driven, single-plunger time has been defined as the ignition delay time. Figure 9 is
fuel injection pump. The initial conditions in the bomb, the a pressure trace showing actual data generated during a test
quantity of fuel injected, and the fuel injection characteristics in the IQT.
are all precisely controlled. Figure 7 is a schematic showing the As can be seen in the figure, the pressure in the bomb ini-
internal geometry of the constant-volume combustion cham- tially drops due to evaporative cooling of the injected fuel.
ber. Figure 8 is a photograph of the IQT. The pressure then rises rapidly due to combustion. The igni-
Inlet
Tc Chamber Surface
Tc High Temperature
Policeman
Injection Nozzle
Body
Tc Nozzle Tip
Exhaust
FIG. 7—Schematic of the bomb geometry used in the IQT.
3 4 5 6 7 9 10
Ignition Delay (mS)
FIG. 9—Pressure versus time in the IQT during ignition and

FIG. 8—Photograph of the IQT. combustion.
tion delay time is precisely defined by the initial rise of the for the IQT, where the cetane n u m b e r is plotted versus the ig-
needle lift trace and the point at which the pressure recovers nition delay time.
back to the initial pressure. The test method consists of charging the fuel reservoir on
The IQT is a calibrated technique, meaning that the cetane the injection p u m p with the unknown fuel. This requires ap-
number-ignition delay time relationship is defined by cali- proximately 50 mL sample of fuel to accomplish both the sys-
bration with a large n u m b e r of reference fuel blends. Ini- tem flush as well as fuel charge for testing. The system is then
tially, the calibration curves were developed using blends of set for initiation a n d the test sequence is automatically
the secondctry reference fuels, but recent results [48] indicate started. The sequence consists of venting the vessel and pres-
that the use of ASTM D 613 National Exchange Group (NEG) surizing to the initial pressure. After a short stabilization
checks fuels provide for a more consistent and cost effective time the test fuel is injected and the pressure and needle lift
calibration. Figure 10 is a plot showing the calibration curve histories are recorded and used to define the ignition delay
N-cetane: 100 CN
E
3
O
c
ffi
Heptamethylnonane: 15 CN
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
Ignition Delay (mS)
FIG. 10—IQT calibration curve [48].
70
\ r
• iqtvscl-613
A IQTCNvsColH
65 ^ Col22vsd613
• Col17vsCol16
0) — ^ Col 25 vs Col 24
• •
Ji 60
E ^•k.
3
Z 55
•
c •
w^
0) 50
O
CO
(D 45
a
40 ^"^^
35
35 40 45 50 55 60 65 70
IQT Predicted Cetane Number
FIG. 11—Results of recent round robin testing of the IQT.
time. The vessel is then vented and the process repeated. This REFERENCES
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850087, Society of Automotive Engineers, Wsirrendale, PA, 1985. Engineers, Warrendale, PA, 1994.
[24] Walsh, G. J. and Cheng, W. K., "Effects of Highly Heated Fuel [39] UUman, T., "Investigation of the Effects of Fuel Composition o n
on Diesel Combustion," SAE Paper 850088, Society of Automo- Heavy-Duty Diesel Engine Emissions," SAE Paper 892072, So-
tive Engineers, Warrendale, PA, 1985. ciety of Automotive Engineers, Warrendale, PA, 1989.
[25] Elliot, M. A., "Combustion of Diesel Fuel," SAE Transactions, [40] UUman, T., Mason, R. L., and Montalvo, D. A., "Effects of Fuel
Vol. 3, No. 3, p. 490. Aromatics, Cetane Number, and Cetane Improver on Emissions
[26] El Wakil, M. M., Myers, P. S., and Uyehara, O. A., "Fuel Vapor- from a 1991 Prototype Heavy-Duty Diesel Engine," SAE Paper
ization and Ignition Lag in Diesel Combustion," SAE Transac- 9072171, Society of Automotive Engineers, Warrendale, PA,
tions, Vol. 64, 1956, p . 712. 1990.
[27] Rao, K. V. L. and Lefebvre, A. H., "Spontaneous Ignition Delay [41] Ryan, T. W., Olikara, C , Buckingham, J., and Dodge, L. G., "The
Times of Hydrocarbon Fuel/Air Mixtures," ASME Transactions, Effects of Fuel Properties on Emissions from a 2.5 gm NOx
Vol. 70, 1985. Heavy-Duty Diesel Engine," SAE Paper 982491, Society of Au-
[28] Chiang, C. W., Myers, P. S., and Uyehara, O. E., "Physical and tomotive Engineers, Warrendale, PA, Oct., 1998.
Chemical Ignition Delay in an Operating Diesel Engine Using [42] Ryan, T. W., "Correlation of Physical and Chemical Ignition De-
the Hot-Motored Technique-Part II," SAS Transactions, Vol. 68, lay to Cetane Number," SAE Paper 852103, Society of Automo-
1960, p. 562. tive Engineers, Warrendale, PA, 1985.
[29] Cox, R. A. and Cole, J. A., "Chemical Aspects of the Autoignition [43] Ryan, T. W. and Stapper, B., "Diesel Fuel Ignition Quality as De-
of Hydrocarbon/Air Mixtures," Combustion and Flame, Vol. 60, termined in a Constant Volume Combustion Bomb," SAE Paper
1985, p. 109. 870586, Society of Automotive Engineers, Warrendale, PA,
[30] Saeed, M. N. and Henein, N. A., "Ignition Delay Correlations for 1987.
Neat Ethanol DF-2 Blends in a DI Diesel Engine," SAE Paper [44] Ryan, T. W. and Callahan, T. J., "Engine and Constant Volume
841343,Societyof Automotive Engineers, Warrendale, PA, 1884. B o m b Studies of Diesel Ignition and Combustion," SAE Paper
[31] Dobovisek, Z. and Savery, C. W., "Ignition Delay of Selected Al- 881626, Society of Automotive Engineers, Warrendale, PA,
ternative Fuels in IC Engines," SAE Paper 859225, Society of 1988.
Automotive Engineers, Warrendale, PA, 1985. [45] Ryan, T. W., "Development of a Portable Fuel Cetane Quality
[32] Collins, J. M. and Unzelman, G. H., "Diesel Trends Emphasize Monitor," Belvoir Fuels and Lubricants Research Report No.
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API 47th Midyear Refining Meeting, May 1982. [46] AUard, L. N., et al., "Diesel Fuel Ignition Quality as Determined
[33] Kloptenstein, W. E., "Estimation of Cetane Index for Esters of in the Ignition Quality Tester (IQT)," SAE Paper 961182, Soci-
Fatty Acids," JAOCS Vol. 59, No. 12, Dec. 1982, p. 531. ety of Automotive Engineers, Warrendale, PA, 1996.
[34] Murphy, M. J., "An Improved Cetane Number Predictor for Al- [47] AUard, L. N., et al., "Diesel Fuel Ignition Quality as Determined
ternative Fuels," SAE Paper 831746, Society of Automotive En- in the Ignition Quality Tester (IQT)-Part II," SAE Paper 971636,
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[35] Steere, D. E., "Development of the Canadian General Standards [48] AUard, L. N., et al., "Diesel Fuel Ignition Quality as Determined
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tomotive Engineers, Warrendale, PA, 1984. 010, Society of Automotive Engineers, Warrendale, PA, 1999.
MNL37-EB/Jun. 2003
Engineering Sciences of
Aerospace Fuels
Eric M. Goodger^
NOMENCLATURE RFNA red fuming nitric acid

RP-1 rocket propellant narrow-cut kerosine
A/F air-fuel ratio o n volume basis SAE SOCIETY OF AUTOMOTIVE ENGINEERS
a/f air-fuel ratio on mass basis SIT spontaneous ignition temperature
ARP Aerospace Recommended Practice (SAE) S entropy
BOCLE ball-on-cylinder lubricity evaluator Sa air specific impulse
C velocity of air Sf fuel specific impulse
CI/LIA corrosion inhibitor/lubricity improving additive s.f.e.e steady flow energy equation
CNG compressed natural gas syngas synthetic, or synthesis, gas, (CO -I- H2)
CU conductivity unit (microsiemens/meter) AT flame temperature rise in luminometer
D(X-Y) dissociation enthalpy between a particular X—Y J"* m a x i m u m adiabatic reaction temperature at con-
bond stant pressure
E overall energy TAFLE Thornton aviation fuel lubricity evaluation
E activation energy TLV threshold limit value
E(X-Y) m e a n empirical dissociation enthalpy between U,u internal energy, specific internal energy
many X-Y bonds UDMH unsymmetrical dimethylhydrazine
FBP final boiling point UHC u n b u m t hydrocarbons
FSII fuel system icing inhibitor V,v volume, specific volume
H, h enthalpy, specific enthalpy VM molar volume
\Ha standard enthalpy of atomization VP vapour pressure
AHf standard enthalpy of formation W , w work transfer, specific work transfer
AH° standard enthalpy of reaction WSIM water separation index modified
Hi total thermochemical enthalpy at temperature T P fuel density
based on standard initial temperature of 298.15 K r ratio of specific heat capacities {cp/c^
HFRR high frequency reciprocating wear rig
HiTTS high temperature thermally stable
lATA INTERNATIONAL AIR TRANSPORT ASSOCIA-
TION
IBP initial boiling point IN AEROSPACE APPLICATIONS, PROPULSION SETS THE MOST STRIN-
Id density impulse GENT requirements in terms of the levels of energy to be pro-
Is specific impulse vided for the purpose, subject to the constraints of mass and
JFTOT jet fuel thermal oxidation tester volume available for carriage of the fuel within the vehicle. In
K partial pressure equilibrium constant this study, the following definitions are employed, with the
K' concentration equilibrium constant maximum levels of net specific energy shown in parentheses:
LNG liquefied natural gas Conventional fuels - aviation fuel mixtures of a hydrocar-
M molar mass, g/mol bon nature invariably derived from petroleum
MTBE methyl tertiary butyl ether (44 MJ/kg)
m mass, kg
NG natural gas High-performance fuels—hydrogen, and individual hydro-
NIR near infrared spectroscopy carbon materials of particularly high energy content
n.f.e.e. non-flow energy equation (120 MJ/kg)
p pressure
Q, q heat transfer, specific heat transfer Substitute high-performance fuels—materials based on
R gas constant non-cryogenic compounds of C, H, O, N, boron, etc.
Ro universal gas constant (68 MJ/kg)
The performance of a bulk fuel in practice is a function of
' Managing Editor, Landfall Press, 28E Jessopp Road, Norwich, Nor- both the properties of the fuel in question and the conditions
folk, NR2 3QB, UK.
729
under which it is used. The former in turn are dependent on 2. Stirling, & Ericsson—Camot efficiency; approximated by
the nature and properties of the fuel components, whereas the small-scale non-flow units employing continuous external
latter influence the extent of intrinsic energy released and its combustion.
conversion to produce vehicular thrust. This is particularly 3. Otto—Efficiency lower t h a n C a m o t ; broadly similar to
true with ramjet and rocket engine fuels since the chemiccJ property changes in spark-ignition reciprocating piston
behavior of the combustion products within the duct between engine.
the combustion chamber and the thrust nozzle outlet can ex- 4. Diesel—Efficiency lower than Camot; broadly similar to
ert an overriding influence on the level of resultant thrust. property changes in compression- ignition reciprocating
This chapter provides a concise overview of the heat input piston engine.
requirements of high performance engines together with the 5. Bray ton—Efficiency lower than Camot; broadly similar to
heat release available from candidate fuels. It also includes property changes in continuous-flow gas turbine, ramjet
brief comment on the handling characteristics of these fuels and rocket engines.
in order to ensure that the most attractive candidates are not A major advantage of continuous-flow over reciprocating
precluded from use by insurmountable problems within the engines is that power is being generated continuously rather
distribution, storage, and vehicular fuel systems. t h a n intermittently, hence the power-volume ratios are
higher. The particular theoretical cycle of interest as a yard-
stick for assessing high-performance jet propulsion is there-
ENGINE THERMODYNAMICS fore the Bra5?ton Cycle (known in Europe as the Joule cycle).
This comprises em initial compression without heat rejection
The strength of the bonds between individual atoms com- through the walls (i.e., "adiabatic," and in fact "isentropic"
prising a fuel molecule represents stored chemical energy, since it is also reversible), followed respectively by heat addi-
and this energy is required to be released and transformed in tion at constcint pressure (isobaric), work output by isentropic
some way to produce propulsive thrust, the customary chain expansion, and finally an isobciric heat rejection returning to
of conversions following the energy route from chemical to the initial state (Fig. 1). Thermodynamic expressions are
heat to mechanical. These events take place in a heat engine, available for the heat and work transfers applying to the vari-
and the b r a n c h of engineering science that includes such ous components of this cycle and, on completing an overall
heat-to-work conversions is known as Thermodynamics. energy book-keeping exercise, the thermcil efficiency of the
Brayton cycle appears as follows:
Although the actual processes involved throughout a prac-
tical heat engine are quite complex, a simplified overview is work output I Ur-D/r
adopted by providing a thermodynamic basis of gases associ- ''Brayton = 1
heat input
ated with idealized conditions and processes, then incorpo-
rating the necessary effects of reality since reeil gases do not where rp is the pressure ratio of the cycle, equal to p^max'/'mm;
x/Pl
follow exactly these idealized processes. The science of ther- and
modynamics is built on the concept of a perfect gas that fol- the index y is the ratio of
lows certain laws absolutely during changes in its major
properties of pressure (p), temperature (T), and volume (V) / specific heat capacity of gas at constant pressure \
[Appendix 1]. Fortuitously, the complete range of properties I specific heat capacity of gas at constant volume j
of such a gas at any given state can be fixed by specifying two and equals 1.4 approximately for air.
(unrelated) properties only. This makes it possible to repre-
sent the complete state of the gas by means of a unique point
on a two-dimensional graph of one property plotted against
another (e.g., p against V). Furthermore, when the state of the
gas changes in etn ideal (reversible) manner, this process of
change can be represented by a unique line on the graph.
E}4}ansion
Even further, when a n u m b e r of different changes follow
each other in such a m a n n e r as to return to the original state,
they form a closed loop, which represents a cycle that could
Compression
be repeated indefinitely. Careful selection of the cyclic loop
processes can therefore provide a heat transfer into the gas
Heat rejection
together with a work transfer outwards, thus giving the basis
of an ideal cyclic heat engine [Appendix 2]. Such a cycle, even
though idccJ, is subject to the fundamental laws of thermo-
djTiamics which stipulate that, although energy cannot be
created or destroyed, not all the heat input can be converted Heat
in
to work because part of the heat must be rejected at a lower addition
temperature. Hence, the net heat input must equal the work
output, but the word net must be included or implied. Z 3to4
Ideal gas cycles conceived by sequencing various processes -• • 4to1

rejection
include the following:
1. Camot—Meiximum efficiency between given temperature FIG. 1—^The Brayton cycle shown
limits, but insufficiently practical since work output low. on a non-flow basis.
CHAPTER 28: ENGINEERING SCIENCES OF AEROSPACE FUELS 731
Heat Hence, the higher the pressure ratio, the better the effi-
addition
ciency of heat-work conversion. AppHcations of the Brajôn
cycle to gas turbine engines are shown schematically in Fig. 2.
2»
• ^ ^
The Brayton and other ideal cycles were conceived as hav-
ing the heat transfers effected across the boundary wall sep-
arating the working gas (usually air, hence the expression
"air standard cycle") and the surrounding atmosphere. This
is a practical possibility and is used, in fact, in Stirling and
Compressor Turbine
Ericsson type engines; however such heat transfers tend to
take time. Since the chemical energy of a fuel cem be released
readily by reaction with oxygen (as shown later under Oxida-
tion Heat Release) combustion with atmospheric air is the
most convenient and effective approach to oxidation (al-
though not necessarily the most efficient or desirable, but
Heat
rejection electrochemical oxidation as in a fuel cell does not appear
a) Closed circuit (industrial)
likely to suit the high-performance r e q u i r e m e n t s of
aerospace propulsion). The alternative oxidants required in
the case of rocket engines operating beyond the Earth's at-
Heat
mosphere are included in Table 1.
addition
Fortuitously, under most conditions the behavior of real
gases, such as air upstream of the combustor and burnt prod-
^3 ucts downstream, approximates very closely to that of perfect
• ^ ^
gases, and ideal cycles can thus be used for comparative pur-
/| poses with the actual changes of events in practical engines.
In practice, also, it is customary to fit a diffuser (a duct of in-
creasing cross sectional area) upstream of the compressor so
that the reduced air velocity promotes an initial part of the
compression. The corresponding fitment of a nozzle (a duct
of decreasing cross sectional area) downstream of the turbine
1/ reduces the pressure with a corresponding increase in exit
Propulsive gases gas velocity and thus in thrust. Once the exit velocity reaches
1
the sonic level, (= V ( g RT) = 331.45 m/s in dry air at 0°C),
b) Open circuit (propulsion) the exit area chokes, with n o possibility of the effects of
chEmges in conditions being transferred back to the nozzle in-
FIG. 2—Schematic of gas turbine engines utilizing the Bray- let. Consequently, further acceleration of the gas requires ex-
ton cycle on a steady-flow basis. pansion of the nozzle, as shown in Fig. 3.
Thus, the key thermodjTiamic requirement of high perfor-
mance fuels is an ability to b u m readily and completely within
high-pressure air or other oxidant flowing at high speed, with
minimal radiation so that the bulk of the released heat re-
mains within the working gas. The next step, therefore, is to
TABLE 1—Relative performance of rocket fuels and oxidants.

Merit order
Formula Id
Fuels
Liquid hydrogen LH2
Hydrazine N2H4
UDMH (CH3)2N2H4 Unsymmetrical dimethylhydrazine
Hydyne 60/40 mass mixture of UDMH and
diethylenetriamine (NH2CH2CH2)2NH
RP-1 rocket propellant narrow-cut kerosine
Liquid a m m o n i a LNH3
Ethanol C2H50H
Liquid diborane LB2H6
Oxidants
Liquid fluorine LF2
Liquid oxygen L02
Nitrogen tetroxide N204
HTP H202 High test peroxide with cone. H2O2 > 80%
RFNA HN03 Red fuming nitric acid containing 7% or
more of dissolved oxides of nitrogen
Chlorine trifluoride CIF4
identify the candidate fuels available, examining their prop- carbon structures are feasible, most of them categorized into
erties with a view to their meeting this requirement. a n u m b e r of "series" depending on their general formulae, as
shown in Table 2.
The main properties of the first members of these hydro-
FUEL MOLECULAR STRUCTURE carbon series are shown in Table 3. ICnowledge of the molec-
ular structure of a hydrocarbon in terms of size, shape, and
The majority of conventional fuels, and also some alternative carbon-carbon bonding together permit prediction of a num-
high performance variants, are based on compounds of hy- ber of physical a n d chemical characteristics that transfer
drogen and carbon (hydrocarbons). The structure of these across to fuel in bulk, as shown in the following analysis:
molecules is determined largely by the valency (chemical
combining power) of the two basic elements. Since hydrogen
Storage Stability
is monovalent, and carbon tetravalent, the simplest hydro-
carbon s t r u c t u r e possible is clearly CH4 (Fig. 4). This is The saturated hydrocarbons contain their maximum content
named methane, and forms the main constituent of the many of hydrogen and are, therefore, stable since they do not need
natural gases (NG) found around the world, invariably incor- to react to seek further hydrogen. On the other hand, the un-
porating small amounts of heavier hydrocarbons, nitrogen, saturated hydrocarbons incorporate multi-bonding between
carbon dioxide, etc. depending on the location and the geo- adjacent carbon atoms, which imparts instability as these
logical history. As the standard domestic/industrial fuel, this bonds open relatively easily to admit additional hydrogen or
is one of the exceptions of using an individual hydrocarbon to permit inter-bonding of like molecules (polymerization),
fuel commercially. As a gas, it does not lend itself easily to leading to self-contamination by the formation of gums and
t r a n s p o r t applications unless stored u n d e r compression other deposits. Nevertheless, these unsaturated hydrocar-
(CNG) or cryogenically liquefied (LNG). Many other hydro- bons do exist because although they are energetically unsta-
ble to elemental decomposition, they are reasonably stable
Fuel kinetically in that the rates of reaction are very slow below
SOO^C at low pressure in the absence of catalysts—compara-
Diffuser Nozzle
ble to a stone remaining stationary resting on a hillside rather
than sliding down the slope.
Air- — > Exhaust jet
# B u o y a n c y i n Air
Since the atom of hydrogen is the lightest of all the elements,
Fuel
its mass was taken as unity, cind the masses of all other atoms
assessed relative to it. With the subsequent adoption of the
a) Open circuit gas turbine with
Internal heat release plus C''^ isotope as the mass basis with a value of 12 exactly, ad-
diffuser and subsonic nozzle
justment to other elemental values gives a value just exceed-
Fuel
t- ing unity for naturally-occurring hydrogen, but approximate

rounded integers generally give sufficient accuracy in prac-
tice. Hence, the molar mass (M) of a hydrocarbon CaHb for
Air- -—Exhaust jet
example would be given by:
Fuel
f M = 12 a + b g/mol (not kg/mol)
Note that "mole" is the n a m e of the physical quantity,
(1)
b) Ramjet with supersonic nozzle

Fuel whereas "mol" is the symbol. As a n example, the molar mass
Oxidant
t- of methane, CH4, is derived as follows:
12.01115 + 4 (1.00797) = 16.04303 g/mol exactly, or
-—Exhaust jet 12 + 4 ( 1 ) = 1 6 g/mol approximately.
Comparison of the molar mass levels with the value of 28.96
Oxidant ^ g/mol for atmospheric air shows that any leaks of methane or
Fuel
ethene (plus, of course, hydrogen) would disperse upwards
b) Rocl<et
into the atmosphere rather than sink and accumulate as po-
FIG. 3—Schematic of continuous flow jet engines. tentially explosive mixtures with air.
CH4 H-c-H (XTJD:)

S^-
Condensed Plane Electron bond Spatial structural Ball and stick Stuart
molecular structural plane structural (Tetrahedral) model model
FIG. 4—Representations of the structure of methane [1].
TABLE 2—General features of the major hydrocarbon series.

Series name Series Description Cg example General properties
molecular
Petroleum Organic formula Condensed Plane structural
technology chemistry formula formula
HHHHHH
I I I I II
Paraffins Alkanes CjjH2n+2 Open-chain saturated C5H14 H-C-C-C-C-C-C-H Stable
I I I I I I Hydrogen-rich
HHHHHH (high specific
energy)
Spontaneously
ignitable (imless
isomerized)
Hexane
HHHHHH
I I I I II
Olefins Alkenes CjjH2u Open-chain unsaturated CgH22 C=C-C-C-C-C-H Unstable
I I I II
H HHHH
Hex-1-ene
Naphthenes Cyclanes (CH2)jj Closed-chain saturated C5HJ2 H2 H2 Stable
Aromatics Aromatics CjjH2ii.6 Closed-chain resonance CgHg

etc. stabilized
Stable but attacks
elastomers
Carbon-rich
(smoke, deposits,
Benzene radiant flame)
Physical State apply to the molecules of the other hydrocarbon series. Liq-
uid density also increases progressively with molecular size.
The variations in boiling and freezing points show that in-
crease in molecular size incurs a progressive change from gas
to liquid to solid. Although hydrocarbon molecules are gen- Spontaneous Ignitability
erally not polar, in that they do not tend to have their centers Molecules will commence oxidation only when sufficient en-
of negative and positive charges so displaced as to give a per- ergy is supplied to rupture one of the internal bonds, permit-
manent electrostatic field around them, they do exhibit weak ting a combination with an oxygen atom (see the section on
forces of inter-molecular attraction because of the orbital Oxidation Heat Release and its Appendix). This preliminary
movements of the myriad of electrons surrounding the host product is liable to be unstable, so initiate a chain of reac-
of atomic nuclei. With small molecules (e.g., the paraffins tions until eventually full combustion occurs with the forma-
CH4 to CaHg) these attractions are so small that the molecules tion of CO2 and H2O. This initial energy may be supplied as
are free to move independently, and the bulk material exists heat, leading to thermal agitation of the molecules and con-
as a gas at normal temperature and pressure. With larger sequent bond rupture. The minimum temperature at which
molecules (e.g., C4H10 to C16H34), the attractions are suffi- this chain process leads to ignition is known as the sponta-
cient to hold the molecules together to give bulk liquids. The neous ignition temperature, SIT (sometimes described as au-
even larger molecules (C17H36 plus) are so strongly attracted toignition temperature, AIT). The larger molecules, being
as to be firmly locked together as solids. Similar arguments more unwieldy, are less able to withstand thermal agitation
TABLE 3—Properties of first members of the major hydrocarbon series.
Series Member Formula H/C Molar Liquid bp fp SIT Stoic a/f Net calorific values Maximum
name name molar mass density °C °C mass kj/mol kJ/mol Specific Energy combution
g/raol energy density temperature
20°C MJ/kg MJ/L °C
Paraffins methane CH4 4 16.04 0.415'' -161.5 -184.0 540 17.19 -74.90 -0.80 50.05 20.77 1974
ethane C2H6 3 30.07 0.561'' -88.3 -172.0 515 16.05 -84.72 -1.43 47.52 26.66 2009
propane C3H8 2.67 44.10 0.585'' -44.5 -190.0 450 15.63 -102.92 -2.05 46.39 27.14 2016
butane C4H10 2.5 58.12 O.6OO'' -0.6 -135.0 405 15.42 -124.82 -2.66 45.77 27.46 2020
pentane C5H12 2.4 72.15 0.626 36.2 -131.5 260 15.29 -146.54 -3.27 45.38 28.41 2022
hexane ^6^14 2.3 86.18 0.660 69.0 -94.3 255 15.14 -167.30 -3.89 45.13 29.79 2023
Olefins ethene C2H4 2.0 28.05 0.384'' -103.8 -169.4 490 14.75 52.32 -1.32 47.19 18.20 2147
propene C3H6 2.0 42.08 0.610'' -47.0 -185.2 460 14.75 20.43 -1.93 45.81 27.94 2089
but-1-ene C4H8 2.0 56.11 0.631'' -6.3 -185.4 385 14.75 1.17 -2.54 45.35 28.62 2075
pent-1-ene C5H10 2.0 70.14 0.641 34.0 -139.0 275 14.75 -20.93 -3.16 45.03 28.86 2066
Naphthenes cyclopentane C5H10 2.0 70.14 0.751 49.5 -93.9 14.75 -77.29 -3.10 44.23 23.22 2037
cyclohexane C6H12 2.0 84.16 0.778 80.7 6.6 280 14.75 -123.22 -3.69 43.86 34.12 2032
Aromatics benzene C6H6 1.0 78.11. 0.878 80.1 5.5 577 13.24 82.98 -3.17 40.61 35.66 2093
toluene C7H8 1.14 92.14 0.866 110.5 -95.0 592 13.47 50.03 -3.77 40.97 35.48 2075
xylenes (avg) C9H10 1.25 106.17 0.868 140.2 -31.3 563 13.64 18.06 -4.38 41.25 35.82 2069
Parent hydrogen H2 00 2.02 0.070'' -252:7 -259 574 34.19 0 -0.24 120.24 8.42 2171
elements carbon C(gr) 0 12.01 2.2IS 3667 sublimes 11.48 0 -0.3 32.76 72.4S 2036
b = at boiling point
s = solid
without rupture, and thus exhibit lower levels of SIT. Fur- Stoichiometry
thermore, molecules that are m a d e more compact by iso-
The stoichiometric mixture is chemically correct in that the
merization (rearrangement geometrically with n o loss or
proportions of fuel and oxidant leave no excess or deficiency
gain of any atoms) show higher levels. These two p h e n o m e n a
of either material on reaction. With atmospheric air adopted
are illustrated by the following examples:
as the standard oxidant, it is noted that nitrogen and oxygen
Methane Normal Octane exist in ratios of 3.76 by volume, aind 3.31 by mass. Conse-
CH4 n-CgHig quently m moles of oxygen are contained in 4.76 m moles of
air, representing 32 m grams of oxygen and (4.31 X 32 m) or
H H H H H
H H H H
137.9 m grams of air. The stoichiometric equation with air
H—C—H 1 1 1 11
H—C—C—C—C—C-
1 1
-C—C—H for a hydrocarbon fuel of known formula, CaHb, becomes:
1
1 CaHb + ms (O2 + 3.76 N2) = nj CO2 + n2 H2O + n^ N2 (2)
H H H H H H H H H
SIT 540 230 where nis = stoichiometric moles of O2 per mole of fuel.
Molar balances of the four elements individually give the
Isooctane vEilues of the unknown molar quantities, and permit expan-
i-CgHig sion of E q 2 to the following:
(2,2,4-trimethylpentcine) CaHb + (a + 0.25 b) (O2 + 3.76 N2)
(3)
H H a CO2 + 0.5b H2O + (3.76 a + 0.94 b) N2
H—C—H H—C—H Hence,

H H H stoichiometric air-fuel molar ratio = (A/F)s
(4)
H—C C C C C—H = 4.76 m J l = 4.76 a + 1.19 b
H H H H and.
H—C—H
stoichiometric air-fuel mass ratio = (ci/f)s
H
28.96 _ 137.85 a + 34.46 b
(A/F)s (5)
467 "C 12a+ b 12a+ b
Since hydrogen, in comparison with carbon, needs more [Appendix 4]. By trial and error, a value of T* is found where
air for combustion, the stoichiometric air-fuel ratios are the total thermochemical enthalpy absorbed by the products
higher with the hydrogen-rich fuels, as in Table 3. arising at that temperature is equal to the value of AH" [Ap-
pendix 5].
Oxidation Heat Release The combustion temperatures shown in Table 3 do not in-
dicate any marked variation. This follows because any higher
Since the events of interest here relate to flowing, rather than hydrogen content, despite giving a higher specific energy,
non-flowing, mixtures, changes of energy are expressed in would also generate larger quantities of H2O product. The
terms of enthalpy rather than internal energy. Thermodynam- particularly high heat capacity of this product absorbs the
ically, the standard enthalpy of formation (AHf) of a com- additional heat release and so permits little change in the re-
pound is the net enthalpy change occurring when the compo- sulting temperature.
nent elements are first raised to a gaseous atomic state and As a general rule, hydrogen is preferable to carbon in view
then permitted to release the 'dissociation enthalpy' in forming of its high specific energy, its clean burning capability with
the compound in question. The resulting vEilue is commonly minimsJ emissions, its wide range of flammability, and its
negative, indicating an enthalpy loss of the system material due relatively high flame velocity. Consequently, the hydrogen-
to a net outwards flow, and showing the resultant compound rich paraffins tend to be preferable to the carbon-rich aro-
to be more stable than its parent elements. Similarly, when matics. However, other requirements sometimes pertain.
both the compound and its stoichiometric proportion of O2 are
energised to gaseous atoms by provision of the dissociation en-
thalpy, and then permitted to react, the net enthalpy output is
known as the standard enthalpy of reaction (Af/°) and, again,
COMMERCIAL FUELS PROPERTIES
is negative when flowing outwards. (In petroleum technology
AND TESTS
terms, on the other hand, heat released by combustion is
shown as positive since this is the desired objective.) These To date, the most common source of liquid fuels for high per-
standard enthalpies involve equal initial and final tempera- formance engines is crude oil, which evolves from decayed
tures, the standard value being 25°C (298.15 K) and denoted by marine matter and collects within the strata of porous rocks
the superscript o [Appendix 3]. The molar enthalpies of reac- (hence rock oil, or "petr"-"oleum"). Crude oil consists mainly
tion in Table 3 are seen to increase with molecular size. of hydrocarbons with traces of other materials depending on
the nature of the source and reservoir rocks. Individual frac-
tions are derived by continuous distillation (fractionation)
Maximum Combustion Temperature followed by various methods of treatment to ensure the spec-
The maximum temperature realized by combustion occurs ified quality. Commercial fuels invariably comprise mixtures
when no heat is lost through the combustor walls (adiabatic). of many different compounds with properties that either rep-
Since the conditions of interest in this study relate to mix- resent a m e a n of the c o m p o n e n t values (e.g., density) or
tures flowing at constant pressure (isobaric), the relevant range over a m i n i m u m to a m a x i m u m (e.g., distillation tem-
m a x i m u m temperature is described here as the isobaric adi- peratures). Exceptions occur in some cases where perfor-
abatic reaction temperature, and denoted by T*. The method m a n c e is overriding the making of individual materials,
of computation is based on the concept of equating the en- rather than mixtures, essential (e.g., hydrogen).
thalpy released by the reactants, in generating the dissociated The quality of aviation fuels is maintained by detailed spec-
products at the initial temperature, with that which would ifications devised under the auspices of national authorita-
have been required to heat these products from the initial tive bodies such as ASTM International in the U.S.A., the
temperature to the final temperature T*. Hence, Ministry of Defence in the U.K., and other organizations else-
where. As well as the properties, the test methods by which
AHr = physical enthalpy absorbed by products they are assessed are also specified, as with ASTM (civil) and
heated from 25°C (298.15 K) to T* Department of Defense (military) in the U.S.A., the Institute
of Petroleum in the U.K. and other national bodies elsewhere.
The first step in computation, therefore, is to derive the sto- Typical properties of representative fuels are shown in Table
ichiometric combustion equation, taking into account that at 4. ASTM and IP now adopt an increasing number of tests
a level of about 1800°C the products of reaction become so jointiy.
agitated thermally as to start dissociating back to their reac-
tant form. The extent of this dissociation is dependent on the A convenient technique for presenting an overview of the
level of temperature, and expressed in terms of an equilib- major properties of petroleum-derived fuels is to select den-
rium constant, which is the ratio of the partial pressures of sity as a basis for comparison, and to plot all other major
the products and reactants. Since carbon burns in a two- properties against it, as shown for petroleum fuels in Fig. 5.
stage process through CO to CO2, the combustion reactions The following discussion deals with the properties in an or-
at high temperature are written reversibly as follows: der comparable to that presented in Table 4, including values
for substitute high performance fuels and the composite plot
H2 + 0.5 O2 ^ H2O, and CO + 0.5 O2 CO2 against density.
The stoichiometric equation at high temperature therefore
appears in the following form: Density
CaHb + m, (O2 + 3.76 N2) The standard ASTM method of measuring the density (p) of a
(6)
ni CO2 + n2 H2O + ns CO -F n4 H2 + nj O2 + n^ N2 liquid fuel is by means of a hydrometer floating in the fuel
TABLE 4—Typical properties of conventional and substitute high-performance fuels.
Fuel Density Boiling range fp Kinematic Flash SIT Stoic a/f Flamm. Net calorific values Maximum
kg/L@ °C °C viscosity point °C mass limits Specific Energy combustion
15°C cSt@ °C a/f mass energy density temperature
15°C MJ/kg MJ/L °C
Aviation
gasoline 0.72 46 - 145 -70 0.5 -40 470 14.9 26-4 44.2 31.8 2025
Wide cut
ftiel 0.78 73 - 235 -62 1.5 -10 270 14.5 24-4 43.6 34.0
Aviation
kerosine 0.80 152 - 256 -52 1.8 43 254 14.8 22-4 43.4 34.7 2022
High flash
fuel 0.82 185-244 -51 2.3 63 250 14.7 22-4 43.2 35.4
Gas oil 0.84 180-360 -30 6.0 70 247 14.6 21-3 42.9 36.0 2027
Methanol
CH3OH 0.79 64.8 -95.5 0.8 11 385 6.5 12.6- 1.6 19.9 16.0 1969
MTBE
CH3OC4H9 0.75 55.0 -109 ? 435 11.7 20.2 - 3.6 35.1 26.0 2002
Nitfomethane
CH3NO2 1.14 101 -17 0.6 35 419 1.7 10.9 12.5 2412
Hydrazine
N9H4 1.01 113.5 2 1.0 52 270 4.3 18.3 - 0 16.7 16.9 2219
Pentaborane
B5H9 0.63 58.4 -46.6 0.6 13.1 45-? 67.8 42.7 2527
Triethyl
borane
(^2^5)36 0.68 95 -134 0.5 14.8 47.1 32.0
NOTE: Lamina flame speeds:
most hydrocarbon fuels = 0.5 m/s approximately,
hydrocarbon = 35 m/s
boranes = 45 m/s
sample, correcting the results to the standard temperature of tion temperature/recoveries, vapor pressure, and flash point.
15°C by meajis of international standard tables. Details are These data can be supported by experimental examination of
given in ASTM D 1298, Density, Relative Density (Specific equilibrium air distillation (usually confined to piston-engine
Gravity) or API Gravity of Crude Petroleum and Liquid gasolines), vapor-liquid ratio, and the direct laboratory mea-
Petroleum Products by Hydrometer Method. The data in surement of the evaporation rates of individual droplets.
Table 4 show that the densities of the hydrocarbon oxy- In the standard test ASTM D 86, Distillation of Petroleum
genates (methanol and MTBE) differ little from those of Products at Atmospheric Pressure, the apparatus comprises
petroleum fuels, whereas nitrogen compounds are heavier. a controlled heat source, a flask equipped with a thermome-
Liquid hydrogen, of course, has been seen to be very much ter, and a side arm leading into a cooled condenser tube, plus
lighter, although a 50% liquid/solid slush mode increases a measuring cylinder. The 100 mL test sample is progres-
density by about 18%. The droplet size resulting in fuel sively vaporized in the flask, and the condensed droplets col-
sprays bears a direct relationship to density, typically show- lected in the cylinder. The corresponding readings of tem-
ing an increase of about 20% with a doubling of density. perature and (percentage) volume recovery are plotted as a
distillation curve. The initieJ boiling point (IBP) is taken as
the temperature at the fall of the first condensed droplet, and
Volatility the final boiling point (FBP) as the highest vapor tempera-
The volatility characteristics of a commercial fuel mixture ture reached during the test, both temperatures being cor-
can be assessed by standard methods of measuring distilla- rected for barometric pressure. The data in Table 4 show that
the boiling points of the substitute fuels generally lie within sample, based on the inverse relationship between viscosity
the range of gasoline and light kerosine. and sphere terminal velocity. Kinematic viscosity is generally
Volatility can also be assessed by measurement of vapor determined from the time taken for a given volume of sample
pressure, but this test applies mainly to wide-cut and the to flow under gravity through a U-shaped capillary-tube vis-
more volatile fuels. Similarly, the vapor-liquid ratios at given cometer, usually vertically disposed, at a specified tempera-
temperatures indicate volatility. For gasoline, the standard ture, as in ASTM D445, Kinematic Viscosity of Transparent
test ASTM D 2533, Vapor-Liquid Ratio of Spark-Ignition En- and Opaque Liquids (The Calculation of Dynamic Viscosity).
gine Fuels is undertciken under static conditions, whereas the In this test, the hydraulic head of the sample, which is den-
SAE ARP492, Aircraft Engine Fuel P u m p Cavitation E n - sity dependent, promotes the flow by gravity, whereas the dy-
durance Test relating to pumping applications with wide-cut namic viscosity resists the flow, hence the result is dependent
fuels is undertaken dynamically. In the latter test, the "vapor" on the quotient of these two effects. The test involves a low
volume measured incorporates the air released during the rate of shear, the kinematic viscosity of the sample being de-
pumping process, and is dependent on the air solubility of termined by multiplying the measured flow time with the cal-
the fuel. ibration constant for the instrument used.
Another s t a n d a r d test concerns flash point. For the An increase in fuel density is associated with increases in
petroleum fuel range, this is an assessment of volatility rather molecular size and inter-molecular forces, and also in kine-
than flammability since the m i n i m u m fuel concentration to matic viscosity. Raising the temperature of a fuel promotes
sustain combustion (the weak mixture limit), which exhibits expansion, and the increase in molecular spacing weakens
a value of about 1% by volume in the mixture with air, is the molecular attraction. Typical of action-at-a-distance
c o m m o n over the whole range of petroleum fuels from gaso- forces, this attraction follows an inverse power law, and plots
lines to residual fuel oils. ASTM D 93, Flash Point By Pensky- as a hyperbolic curve against temperature. For convenience,
Martens Closed Cup Tester is based on heating the fuel sam- these curved relationships have been converted to straight
ple progressively, and repeatedly inserting a standard-sized lines by plotting on the following empirical logarithmic basis:
flame into the vapor-air mixture above the liquid free surface
until a temperature is reached where the flame promotes mo- log log (u + a) = n log r -I- b
mentary combustion. The flash point (the weak temperature where a, n, and b are constants. On such axes printed on spe-
limit), in contrast to the weak mixture limit, varies directly cially designed charts (e.g. ASTM D341, Standard Viscosity-
with density, reflecting the change in volatility. The substi- Temperature Charts for Liquid Petroleum Products), two
tute fuels in Table 4 show slightly lower values of flash point points only need be determined by experiment, the remain-
than the conventionals. (Note that the fire point relates to the der being found graphically on the straight line passing
slightly higher temperature where combustion is continuous through them, limited at the high-temperature end by vapor-
rather than momentary.) ization and/or ignition, and at the low temperature end by
freezing.
Viscosity In fuel technology, dynamic viscosity is of interest in rela-
tion to the setding rate of contaminants during storage, but
Viscosity arises in a bulk fuel from the weak electrostatic the m o r e generally-used kinematic viscosity provides an
forces acting between the molecules. These permit many hy- indication of the power required for p u m p i n g , filtration,
drocarbon fuels to exist in the liquid phase under ambient and spraying, bearing a direct relationship to spray droplet
conditions but, at the same time, promote resistance to the size. Such data available in Table 4 show that the viscosities
internal displacement involved in flow. This resistance is of the substitute fuels lie between those of gasoline and wide
termed dynamic viscosity, and is defined as the tangential cut fuel.
force on unit Eirea of either of two peirallel planes within the
fuel sample located at unit distance apart when one plane
moves with unit velocity in its own plane relative to the other Solidification
plane. Thus, dynamic viscosity is the ratio of the applied
shear stress and the rate of shear, such that: Comparable with the range of boiling points resulting from
progressive heating of a commercial fuel mixture as the sev-
force length . . .^ . eral components distill in turn, a range of solidification tem-
Dynamic viscosity = 17 = X —^—r— in units of Poise
peratures can be expected from progressive cooling as each
•^ area velocity component crystallizes as wax. Eventually a temperature is
The smaller unit, centipoise (cP), is more convenient, where reached where the viscosity approaches infinity as the fuel so-
lidifies completely. The relevant solidification temperatures
1 cP = 0.01 P = 1 mN s/m^ can be determined and expressed in several ways. Generally,
Division with density provides the kinematic viscosity, as the sample is cooled until the first appearance of wax crystals
follows then, in order to avoid spurious results from supercooling, it
Kinematic viscosity = v = ri/p in units of Stokes is allowed to warm until the wax just disappears. (Thermody-
Here again, it is more convenient to use the smaller unit, cen- namically, the temperatures of appearance and disappear-
tistokes (cSt), where ance of wax must be different.) In ASTM D 2386, Freezing
Point of Aviation Fuels, the sample is stirred and the result
1 cSt = 0.01 St = 1 mm^/s designated as the freezing point. D3rnamic methods are also
Dynamic viscosity can be determined by measuring the ter- available, as in ASTM D 4305, Filter Flow of Aviation Fuels at
minal velocity of a small sphere falling under gravity in the Low Temperatures, in which the sample is cooled under pre-
scribed conditions and repeatedly subjected to a low pressure reflected from the ends of the tube, and in extreme cases may
pulse directing it through a fine wire mesh filter until a tem- even experience detonation involving a combination of shock
perature is reached at which the filter plugs. Other suggested wave a n d flame. These tests are not standardized, b u t
methods for assessing fiiel fi-eezing include a system for opti- adopted in combustion laboratories and on chamber rigs by
cally sensing the presence of wax crystals in the sample, and engine manufacturers.
a chemical analysis method based on the relationship of freez- The data in Table 4 show certain differences in flammable
ing to the concentrations of aromatics and saturates as deter- mixture limits, with those for hydrogen and pentaborane be-
mined by near-infrared (NIR) spectroscopy. An alternative ing particularly wide. Also, the maximum flame velocity for
"Phase Technology" method incorporates freezing, cloud, and hydrogen is relatively high.
pour points based on a light scattering technique [10].
The freezing points of most of the substitute fuels shown S p o n t a n e o u s Ignitability
are relatively low, with the exception of hydrazine.
In the standard ASTM E 659, Autoignition Temperature of
Surface Tension Liquid Chemicals, a small charge of liquid fuel is delivered as
a droplet by means of a syringe into a heated open flask, and
This property helps to determine the size of fuel droplets in a the delay noted before the onset of ignition. The method com-
spray. It can be assessed in a laboratory by measuring the prises repeated tests at progressively lower temperatures un-
force required to free some flat object (e.g., a glass slide or til the m i n i m u m level is found to promote ignition (the spon-
wire ring) vertically upwards from the surface of the fuel, and taneous ignition temperature, or SIT). The associated delay
then dividing this force by the length of periphery of the ob- period is a maximum, and usually comprises several seconds
ject. Values for both conventional and substitute fuels reduce under the test condition of atmospheric pressure. The levels
with increasing temperature but vary little from a range of of SIT for the conventional hydrocarbons vary inversely with
20-40 mN/m, the exception being hydrazine with values density but tend to be higher for the substitute fuels.
ranging from 60-80 mN/m. ASTM D 3825 can be used, but
for liquid gases only.
Stoichiometry
Flammability As an extension of the treatment of hydrocarbons in the sec-

tion on Stoichiometry, the stoichiometric combustion equa-
The flammable nature of a fuel can be assessed in various tion for the substitute fuels provides the following general ex-
ways. In the case of the petroleum fuels, the weak mixture pression:
limit was seen to be approximately c o m m o n (at about 1% va-
por in the mixture with air), consequently the weak tempera- CaHbOcNd + ms (O2 + 3.76 N2) = nj CO2 + Uz H2O + Us N2
ture limit at which this mixture pertains, that is, the flash From molar balances of the four elements,
point, depends on the volatility of the fuel. With different
types of fuel, however, the weak mixture limits differ, hence m . = a + 0.25 b - 0.5 c
flash point then gives a direct indication of fire safety. The Hence, stoichiometric air-fuel molar ratio
flash points for the substitute fuels in Table 5 are seen to be = (A/F), = 4.76 a 1.19 b - 2 . 3 8 c
slightly lower than those of the conventionals.
Mixture limits of flammability can be determined in a lab- and, stoichiometric air-fuel mass ratio
oratory tube apparatus by seeking the particular air-fuel ra- 137.85 a -I- 34.46 b 68.92 c
(a/f)s =
tios at which the flame fails to propagate following ignition. 12 a-H b + 16 c + 14 d
A similar rig can be employed to determine the rate of flame The values in Table 4 show, in comparison with the hydro-
propagation during the uniform movement over the first few carbons, the reductions in stoichiometric air-fuel ratios ex-
centimeters after ignition. When the flame progresses further pected in view of the presence of oxygen and/or nitrogen in the
cdong the tube, it becomes subjected to the pressure waves fuel. Hydrogen, of course, is the exception on a mass basis.
TABLE 5—Relative stoichiometric calorific and specific impulse values of elements, non-carbon hydrides and organometsdlics [5].
Rel. Fuel Rel. Fuel Rel. Fuel Rel. Air

Density Specific Specific
Material Symbol Sp. En. En. Dens. Impulse (Sfd) Impulse (Sf) Impulse (So)
Av. kero. 100 100 100 100 100
(43.4 MJ/kg) (34.7 MJ/L) (l.OSkNs/L) (25.5 kN s/kg) (1.76 kN s/kg)
Hydrogen H2 276 24 19 254 105
Beryllium Be 153 353 119 54 116
Boron B 133 400 193 65 105
Magnesium Mg 57 124 48 25 122
Aluminum Al 72 241 96 29 122
Ammonia NH3 43 33 63 83 88
Hydrazine N2H4 38 48 67 53 93
Dlborane B2H6 168 90 58 108 107
Pentaborane B5H9 156 123 73 92 106
TEA A1(C2H5)3 98 103 69 66 108
Aluminum borohydrlde A1(BH4)3 125 86 60 89 107
When boron is present in the fuel, the resuking product of necessity, still be hot, following the second law of thermody-
combustion is B2O3, and the same principles of molar bal- namics that permits partial conversion only of heat to work.
ance apply to derive the stoichiometric air-fuel ratios. Hence the combustion water leaves in the vapor phase, and
the "net" value of specific energy is more meaningful in engine
practice. This is routinely derived by subtracting the latent en-
Calorific Values thalpy of the combustion water using the following expres-
sion, which also converts the non-flow constant-volume result
Whereas the oxidation heat release was treated thermochem-
to steady-flow constant-pressure:
ically in the Oxidation Heat Release section leading to the
derivation of AHr°, the thermodynamic approach permits an Net specific energy @ 25°C and constant pressure, in units
application to practical test methods in the laboratory. The of MJ/kg = gross specific energy @ 25°C & constant volume
thermodynamic laws of gases (Appendix 6) give rise to the — 0.2122 (mass % hydrogen in sample)
following energy equation:
These experimental results, of course, will not tally exactly
Q — W = At/ in non flow case, and
with values of AHr° because initial and final temperatures dif-
Q - W = AH in steady flow case with negligible fer in the former case, and are c o m m o n in the latter (Table 3).
changes in potential and kinetic In order to improve accuracy, n u m e r o u s corrections are
energies. made to allow for the enthalpies of formation of nitric and
sulfuric acids produced on combustion, and for the heat in-
where
put from the burnt firing wire. Further refinements to correct
Q = heat transfer
for heat transfers into and out of the CcJorimeter during the
W = work transfer
test are represented by the adiabatic method and the isoperi-
At/ = change in internal energy bol method, both of which incorporate an outer water bath.
AH = change in enthalpy, where H = U +pV, andp V = flow In the former method, the temperature of the outer bath au-
energy. tomatically matches that of the calorimeter water, so mini-
mizing any heat interchange. In the latter method, the outer
Since it is far easier to measure heat transfer than work bath is maintained at some selected constant temperature so
transfer, conditions are selected where work transfer is zero that heat interchange may be c o m p u t e d accurately, the
so that these expressions simplify to whole instrument being heavily insulated. In this latter case,
Q = AC/ in non flow case at constant volume, and the local environment (the outer bath) is isothermal but the
external environment (the laboratory) is not, hence the use of
Q = AH in steady flow case at constant pressure. the term isoperibol rather than isothermal.
With gaseous fuels, the enthalpy released on combustion is Because of the requirements of test time and practiced ex-
determined as the energy density (MJ/L) by burning at con- pertise in the above methods, attention has turned towards
stant pressure through a steady flow calorimeter. The heat so methods of estimating specific energy based on statistical
released is measured from the rise in temperature of the flow- correlation between accurate values of related properties.
ing cooling water. The test result is corrected for the stan- ASTM D 3338, Estimation of Net Heat of Combustion of Avi-
dardized volume of fuel gas burnt, together with the expan- ation Fuels, involves correlation between aromatic content,
sion of both the cooling water and the flue gases. density, and averages of distillation temperatures at stated
With liquid fuels, specific energy is determined by burning recoveries, whereas alternative methods are based on den-
a known mass of fuel in a stainless steel b o m b located in a sity, aniline point, and/or sulfur content. Such methods are
water-filled calorimeter u n d e r non-flow constant volume dependent on the combined accuracies of the test results in-
conditions, as in ASTM D 4809, Heat of Combustion of Liq- volved, and are therefore less precise than those obtained by
uid H y d r o c a r b o n Fuels by B o m b Calorimeter (Precision direct calorimetric determination.
Method). The b o m b is pressurized to 3.0 MPa (30 atm) with The results presented in Table 4 for the petroleum fuels re-
water-saturated oxygen gas to ensure complete combustion. flect the density effect of reducing specific energy and in-
The combustion heat so produced raises the temperature of creasing energy density shown for the individual hydrocar-
the caJorimeter water by about 3K, as measured by a plat- bons in Table 3. The former effect, again, is understandable
inum resistance or thermistor instrument. The mathematical from the reducing level of hydrogen content, whereas the lat-
product of this temperature rise and the thermal capacity of ter is underscored by the fact that energy density is the direct
the calorimeter—determined previously using benzoic acid arithmetical product of specific energy and density, and
of known specific energy—provides a value of the quantity whereas the former falls by a mere 20% over the density range,
of heat absorbed. Division by the initial mass of the sample the latter rises by about 50% and is therefore the dominant
thus gives the specific energy of the sample fuel at constant term in the product, as seen in Fig. 5. A special requirement
volume. arises in the case of ramjet powered aircraft. These are essen-
Because the final temperature of this test is only marginally tially high-speed vehicles, hence fuel storage volume is at a
above ambient, the water produced by combustion of the hy- p r e m i u m to minimize drag, and energy density becomes the
drogen content of the fuel condenses to the liquid phase, criterion. The customary rise with increasing density is shown
adding its latent enthalpy of vaporization to the combustion in Fig. 6 for some specially selected high-performance fuels
energy. Consequently, the resulting specific energy is de- indicating the expected need for high density.
scribed as the "gross" value. In contrast, the combustion prod- Substitute fuels of higher energy density can be achieved
ucts leaving the working section of any heat engine must, of by replacing the c a r b o n in the h y d r o c a r b o n with some
Hydrogen 15
content 14 -
%Mass IS 1=
- 45 Specific
- 44 energy
43 MJ/kgnet
Energy 35
density
density
MJ/Lnet ^^ •= =-^
- 4
. Viscosity
0 est @ 40°C
Temperature °C
Density, Icg/L @ 15°C

FiG. 5—Basic properties of jet fueis [1]. Properties in braclcets represent limits to
distiiiation ranges.
An interesting conclusion concerns the level of specific en-

ergy available from unit masses of stoichiometric fuel-air
>i H-cot d
mixtures. Although hydrogen enrichment of a fuel tends to a
Shelldyne M
higher specific energy on a fuel mass basis, the stoichiomet-
Adamantines ric air-fuel mass ratio also rises, consequently more air is
_ Pertiydrofluoranthene
^ 40- Energy-dense cyclics icalin 4 ^ '* l-Methyipertiyfluorene available to share the energy output. Hence, the stoichiomet-
Cyciododecarres ric mixture values of specific energy vary little from about 2.9
XT Conventional petroleum fuels
MJ/kg (net). This means that, in general, whereas the fuel car-
Normal and monocyclic
hydrocarbons C^
7^ rying capacity of a vehicle is largely affected by specific en-
ergy of the fuel, the performance of the engine is not.
Maximum Comibustion Temperature

The isobaric adiabatic reaction temperature for a commer-
HaW cial fuel mixture cannot be calculated without knowledge of
the individual chemical constituents and their proportions.
0.4
T 1 I 1.2
"7
1.6
However, a broad assessment can be made on the assump-
0.8
Density kg/L at 15°C
tion of an average molecular formula in each case.
The combustion temperature values included in Table 4
FiG. 6—Energy densities of candidate high-performance fu- have been computed on the following basis:
els [1,2].
Fuel Assumed Average Formula
Aviation gasoline C7.3H15.3

element contributing more calorific value to the resultant liq- Aviation kerosine Cl2.5H24.4
uid hydride. Examples of such fuels include hydrides of Gas oil C15H27.3
boron, beryllium, lithium, magnesium, aluminium, and tita-
nium, plus compounds of hydrogen, carbon, and boron as in- The calculated vEilues for the petroleum fuels are seen to
cluded in Table 4. vary little from 2025°C. On the other hand, methanol is lower
at 1969°C, while nitromethane and pentaborane are higher at FUEL COMBUSTION PERFORMANCE IN
2412 and 2527°C, respectively. CONTINUOUS FLOW
Smoke Tendency Fuel Preparation and Mixing
Within fuel-rich regions of a flame, hot fuel molecules can Fuels b u m only in the vapor/gas phase, consequently the
become so agitated thermally that they crack into portions, first stage in satisfactory combustion is to vaporize the fuel
involving the release of free atoms of carbon in the form of and mix it thoroughly with the oxidant. In an aero gas tur-
smoke. This is undesirable in a heat engine because: bine engine, the low volatility of kerosine is such that car-
buration at ambient air temperatures would be too slow for
• Combustion efficiency is reduced through the loss of the
a satisfactory rate of vapor generation. Vaporization at
calorific value of the free carbon.
flame temperature is practicable, however, and the "walking
• Glowing particles of carbon radiate heat at a relatively high stick" (or T-shaped double walking stick) type of vaporizer
rate and thus overheat the combustor liner so reducing tube fed with air under relatively low pressure receives nar-
its life. row streams of liquid fuel that are vaporized to an extent
• Tendencies to soot deposition within the combustor are in- depending upon the fuel flow rate, and introduced directly
creased, with the possibilities of mechanical damage due to into the flame [1].
t e m p e r a t u r e gradients a n d differential expansion in the
combustor liner. In most o t h e r applications to gas-turbine engines, the
volatility of the fuel is increased substantially to an effective
• Tendencies to exhaust smoke emissions to the environ-
level roughly equivalent to that of a gasoline by subdividing
ment are increased.
into a large n u m b e r of very small droplets. This process of
For jet fuels, ASTM D 1322, Smoke Point of Kerosine and spraying, loosely termed "atomization," gives a massive in-
Aviation Turbine Fuel, is based on determination of the max- crease in surface area per unit volume of fuel, and so aug-
i m u m height to which a diffusion flame, wick-fed from the ments the vaporization rate by several orders of magnitude.
sample, can be adjusted without smoking (Fig. 7). Being The fuel is also distributed in space so that mixing with air is
based on an early design of an illuminating oil lamp bearing effected rapidly.
no resemblance physically to an aero gas-turbine combustor,
Immediately after a fuel droplet is injected into the flame
this method may appear primitive. Nevertheless, it does test
zone, vapor will form and b u m as a premixed flame. As the
the fuel u n d e r diffusion conditions where smoke is m o r e
velocity of the droplet falls, it will become surrounded by a
likely to be generated in the actual combustor operating at
diffusion flame. The proportion of premixed burning may be
high pressure. In ASTM D 1740, Luminometer Numbers of
raised by increasing the relative velocity between the fuel and
Aviation Turbine Fuels, the luminometer n u m b e r is deter-
air, consequently combustion in the gas turbine chamber is
mined with a smoke-point type lamp operating at a fixed level
dictated by the characteristics of the fuel injector as well as
of flame radiation by comparing the flame temperature rise
the geometry of the combustor liner itself. This subdivision of
above the inlet air level for the sample with those for two ref-
a film of fuel into filaments and droplets is achieved by the
erence fuels, tetralin (an aromatic) and zsooctane (a paraf-
shearing action arising from the velocity differences between
fin), as follows:
the spray elements and the air. A number of different pres-
f AT sample - \T tetralin \ sure-jet injection designs are available.
Luminometer Number = 100 U j f-octane - AT tetralin I These practices are not standardized but are adopted in en-
gine manufacturer's development laboratories. An alterna-
Correspondence has been found between smoke point cUid tive approach is to achieve the required shear from velocity
luminometer n u m b e r over a wide range of kerosines. difference by accelerating the air rather than the fuel. This
gives rise to the air-assist a n d air-blast injectors where a
stream of high-velocity air meets a stream of low-velocity
fuel. Droplet sizes tend to be small and, being controlled by
Inclined mirror for ^ Photocell
© ~ viewing smoke in airflow, spatial distribution of fuel is largely unaffected by
flame centre
fuel flow rate [1].
/
Chimney
Ignition
"niemiocouple
Reflecting scale Ignition is initiated by some form of high-energy spark or
Luminometer Configuration
^®''*''" Sample teo-ootane

torch igniter, and the flame then sustains continuous ignition
Flame-height , J ^standard 7 i
of the entering mixture, whereas in rocketry, certain fuel-
adjuster oxidant pairs aire selected because they are hjrpergolic, i.e.,
1
1 ignitable on contact, which eliminates the need for separate
1 /\
U rs'A ignition equipment. In this case, however, it is essential for
1 spontaneous ignition to tak;e place on start-up with the mini-
i \ \
Flame temperature rise, iT m u m of delay, otherwise a "heird start" will ensue, compara-
Smoke Lamp /Ars-AT|.\ ble to the mechanism of diesel knock but with much more
Luminometer No = 100
ÂTU-ATL;
damaging consequences. As there is no standard laboratory
FIG. 7—Smoke point and luminometer number. Schematics method, this refers to the method adopted in continuous-
of apparatus [1]. flow energy practice to effect ignition.
Flame Stabilization peak temperatures that would limit blade life and engine
performance. The temperature traverse qucJity at the outlet
In the aero gas turbine combustor, the flame is required to be of the chamber is known as the pattern factor, defined as
stabiHzed in a defined location against the entry stream of air follows:
over a wide range of conditions, consequently a balcince must
be maintcuned at all times between the velocities of the flame ^ mean.exit
Pattern factor =
and the approaching mixture. The flame velocities of most fu- ' mean.inlet
els in laminar flow eire in the order of 0.5 m/s only and, al-
The m e a n exit temperature values are generally obtained by
though increased markedly by temperature and turbulence,
taking measurements at test points located at the centroids of
the velocity of the incoming mixture, emd thus the eiir, must be
a n u m b e r of equal sub-cireas comprising the total exit area.
reduced by some form of betffle in order to achieve velocity bal-
ance. In the gas turbine chamber, the velocity of the entering Customarily, velocities are also measured at these test points,
air is reduced initially by diffusion. The air then goes through and each temperature weighted on a mass flow basis.
a process of flow reversal by being fed around the outside of the
flame tube before entering through side apertures and en- Specific Impulse
countering a low-pressure region in the core of an air swirl.
The result is a stabilized toroidal vortex of swirling air, the in- In ramjet engines, a higher flame temperature is permitted in
ner surface of which flows upstream. Introduction of the fuel the absence of turbine blades located within the hot pro-
into this surface promotes a region of flame-air velocity bal- pelling gas stream, whereas in rocket engines, even higher
cince. In advanced aero gas turbine engines, a technique of pre- temperatures pertain in the absence of atmospheric diluents.
mixing and prevaporization is used in order to control emis- In both cases, therefore, the extent of dissociation of the com-
sions more effectively. In rocketry, sprays of the liquid fuel Eind bustion products, and of any subsequent part recombination
oxidant may be ctrranged to impinge for thorough mixing. within the propelling nozzle, are usucJly sufficient to influ-
ence substantially the thrust level based on energy density
alone.
Air D i l u t i o n The performance of high speed jet engines is therefore
rated in terms of the stream thrust exerted at the nozzle
In contrast to piston engines where the working surfaces (pis- throat exit plcine where the velocity is sonic, using a parame-
ton crowns) are subjected to combustion temperatures for ter termed specific impulse since it is the impulse (thrust)
only short periods of time, the blades on a gas-turbine disk op- based on unit flow rate of the propelling products. For ram-
erate continuously in a high-temperature environment, and jets, this parameter may be based on the mass flow rate of the
are also subjected to centrifugeJ stresses. Consequentiy, the air alone, or on either the mass of volume flow rates of the
products from the flame must be cooled sufficiently to suit the fuel alone. Thus
metallurgy of the turbine blades. Customarily, some 28% of
the chamber air is used for combustion in the primary zone, ,. .r. . , „ Stream thrust
which gives a flame temperature of about 2050°C. The re- Air specific impulse = bn = ~r- a :~
maining air is introduced progressively downstream, first as f t - " F Air mass flow rate
N s/kg (relates to engine thrust)
secondary Eiir to reduce the temperature of the combustion ma
products to about 1450°C in order to offset the effects of dis- _ , .p. • 1 o Steam thrust
Fuel specific impulse = Sf= -=—5 5 ;—
sociation, and then as dilution air to bring the turbine entry f f T Yuei mass flow rate
temperature (TET) down further to the m a x i m u m level of
N s/kg (relates to mass limitation)
about 1000°C. Higher TET values of 1350°C and above are ac- rrif
ceptable by intemeJ cooling of the nozzle guide vjines and tur- „ , J .^ . , c- Steam thrust
bine blades with air bled from the compressor. Despite fuel Fuel density impulse = Sf^ = Fuel volume flow rate
residence times within the chamber of a few milliseconds only, p
combustion efficiencies under design conditions are high, typ- = -y- ~ Sfpf N s /L (relates to volume limitation)
ically 99.5% or above. Even exhaust smoke that is just visible
represents a combustion inefficiency of no more than 0.01%. where py = fuel density, kg/L.
Relative vsJues of the specific impulse parameters are in-
Turbine Entry Temperatiu-e Distribution cluded in Table 5 for selected elements, non-carbon hydrides,
and organometallies. These show a broad interrelationship
The distribution of entry temperature over the turbine disk with Ccdorific values, but eJso some significant differences.
should be reasonably uniform in order to avoid localized Data for representative monoreactants are shown in Table 6.
TABLE 6—Properties and performance of representative monoreactants [6-8].

Density Reaction
Id* Temp.
Monoreactant Formula (kg/L) (N s/L) (N s/kg) *(K)
UDMH (CH3)2N2H2 0.78 1530 1961 1154
Hydrazine N2H4 1.008 1958 1942 905
Nitromethane CH3NO2 1.12 3126 2491 264
HTP H2O2 1.44 2330 1618 1278
Tetranitromethane C(N02)4 1.638 2907 1775 2170
' Expanding from 68 to 1 atm.
For the rocket engine, the performcince is simiWly based Combustion Emissions
on variants of the specific impulse, as follows:
Aero gas turbine emissions are of concern for their direct ef-
p
Specific impulse = Is = N s/kg, and fects on airport environments, and their cumulative effects at
altitude. The m a i n emissions are CO and UHC at idle/taxiing
Density impulse = /<; = 4 PR N s/L conditions, NOx (= NO + NO2) and smoke at high power dur-
ing take-off and climb, and CO2 a n d H2O throughout.
where rup = mass flow rate of propellants
Some ccirbon monoxide forms in the primary zone of the
= m a s s flow rate of reactant mixture in the gas turbine c h a m b e r but then tends to be oxidized by the sec-
chemiCcJ rocket ondary air. However, u n b u m t hydrocarbons may comprise
PR = density of reactant mixture at storage condi- u n b u m t fuel and also partially reacted fuel in the form of
tions methane and related light hydrocarbons. They normally arise
through over-large spray droplet sizes and/or the chilling ef-
Since the expression for specific impulse [1] contains the fects of mixing with air at low power output.
term V'(Tc/M), where
Nitric oxide occurs in atmospheric air flame-heated to
Tc = combustion temperature, and above 1800 K, a n d also following the three different sources
of thermal NO at high temperatures, prompt NO at fuel-rich
M = m e a n molar m a s s of combustion products low temperatures, and fuel NO from fuel-bound nitrogen
comprising propulsive fluid, at fuel-lean high temperature. Some of the NO oxidizes to
it follows that hydrogen offers the double benefits of high NO2 at full load, and more at low-temperature idle. The ef-
Tc burning to H2O of low molar mass (18) in comparison fects of NOx from subsonic aircraft operating in the tropo-
with a carbon-bearing fuel burning to CO2 of high molar sphere (approximately 6-14 km altitude) are to increase the
mass (44). level of ozone, which acts as a powerful greenhouse gas.
Since combustion characteristics, and resulting thrust lev- With supersonic aircraft operating in the tropopause/strato-
els, vary markedly with fuel-oxidant mixture ratio, the "peak" sphere (approximately 18-23 k m altitude), o n the other
values of specific impulse and density impulse are used for hand, the ozone shield from harmful ultraviolet solar radia-
comparative purposes. Figure 8 shows the variations of peak tion is destroyed by the regeneration reactions of NO2 back
impulse values with densities of the corresponding liquid re- to NO.
actant mixtures. The familiar inverse and direct relationships Smoke comprises finely divided peirticles of carbon-rich
are seen, reflecting earlier variations of specific energy and soot, and forms within fuel-rich regions of the flame such as
energy density with fuel density. Hence, heavy reactants are the core of the fuel spray, but is largely consumed down-
favored for atmospheric operation, and light reactants for stream. ASTM D 1322 and D 1740 are used to measure com-
space flight. The values plotted are for "shifting" equilibrium, bustion emissions.
which allows for changes in product composition along the The fuel parameters likely to improve emissions summa-
length of the propelling duct, a n d are approximately 5% rize as follows:
above corresponding values for "frozen" equilibrium where • PhysiccJ: Low viscosity to generate small droplets in fuel
n o further chemical changes are assumed downstream of the sprays. High volatility to assist rapid vaporization.
combustor.
• Chemical: Low carbon content a n d low aromatics to re-
duce smoke. Addition of organobarium or mcinganese to
reduce smoke.
The most effective hardware methods of reducing emis-
sions appear to center on improvements in fuel prepeiration
a n d aeration in the combustor, plus the use of fuel staging,
variable chamber geometry, and lean premix vaporization.
FUEL HANDLING CHARACTERISTICS
For purposes of delivering fuel through the supply chain,

E loading into aircraft tanks, and then transferring fuel to the
-2
i engine, the liquid phase is the most convenient. Fuels that are
normally gaseous at ambient temperature and pressure can
be liquefied, but this entails either the weight of high-pres-
sure containers or the bulk of a cryogenic system. As indi-
cated earlier, the density of a cryogenic liquid can be in-
—1— — I —
creased moderately by adopting the slush mode in which a
0.2 0.6 1.0 1.4 1.8 significant proportion is frozen. Similarly, particles of solid
Density of peak reactant mixture kg/L fuel may be dispersed throughout a liquid fuel carrier to pro-
mote a high-density slurry. Solid fuels tend to apply to "one-
FIG. 8—Values of peak specific impulse and
density impulse for liquid rocket fuels and oxi- shot" rocket engines only.
dants, with comparative values for mono and In aerospace, the major requirement of calorific value ap-
solid reactants [3,4]. plies on a mass basis, i.e., specific energy, in cases of both
subsonic and extra-atmospheric operation. Supersonic and pumping rates, line velocities, bottom loading (no splash fill-
hypersonic (Mach No. > 5 ) flight within the atmosphere, ing), and settling times have been generally adopted by the
however, is subject to such high levels of drag as to be vol- major fuel suppliers as standard practice for the safe han-
ume-limited, thus requiring optimal energy density. The next dling of such products.
key requirements for handling properties relate to the fol- The electrical conductivity of a fuel is determined by ap-
lowing modes of operation although, of course, some re- plying a voltage across two electrodes immersed in the sam-
quirements apply to more than one mode: ple, and recording the resulting current, as in ASTM D 4308,
1. Preflight fueling—static charge explosion resistance Electrical Conductivity of Liquid Hydrocarbons by Precision
2. During flight—^volatility, viscosity, lubricity, thermal sta- Meter. An alternative method, ASTM D 2624, Electrical Con-
bility ductivity of Aviation a n d Distillate Fuels, applies to fuels
3. After flight—freedom from deposition containing a static dissipator additive. Civil and military re-
4. Between flights—absence of solidification (ice and wax) quirements differ because of the different additives used. For
5. Throughout—freedom from corrosion, insensitivity to example, experience shows a m i n i m u m conductivity of 50
fuel-borne water units to be safe for civil jet fuels, whereas military fuels re-
quire higher conductivity, and this offsets the slight syner-
Since all these requirements are unlikely to be met at once,
gism possible between the additives FSII and CI/LIA. A
it becomes necessary to employ additives.
m a x i m u m limit is also set for jet kerosines (450 CU), all lim-
The characteristics and methods of test for volatility and its applying at the point, time, and temperature of delivery to
viscosity, both of which influence the droplet formation in the user.
sprays and subsequent vaporization in the combustor, have
been dealt with above, plus the appearance of wax. The fol- The conductivity of a fuel in a storage tank may be mea-
lowing properties relate to the overall system of fuel produc- sured directly by portable meters manufactured commer-
tion, distribution, and storage right u p to entry to the engine cially. The Maihak instrument has a conductivity cell on the
bay in the aircraft. end of a cable wound onto a drum. The cell is lowered into
the tank through the sampling hatch, and the direct-reading
meter attached to the drum. With the pocket-sized Emcee in-
F u e l i n g Fire Safety strument, the conductivity cell may be detached from the ca-
ble and fitted directly to the meter to give a laboratory model
During the flow of fuel through pipelines, the presence of
for use with a fuel sample in a beaker. Alternatively, the cell
trace polar contaminants leads to charge separation through
may be attached to the end of a probe and inserted into the
the interchange of electrons, giving rise to ionization.
tank for measurements at a series of levels (e.g., top, middle,
Charges of one sign will tend to drift towetrds and accumulate
and bottom) to check for homogeneity of the contents.
on the walls of the container, whereas those of the opposite
sign will remain in the fuel itself, and thus fuel flow will also An additional measure of safety is the use of static dissipa-
constitute a streaming electrical current. This effect is aug- tor additives (e.g., Stadis 450 for jet fuels). Complex poly-
mented by the presence of droplets of water or particles of meric materials containing nitrogen and sulphur are used to
dirt, and very m u c h so by the extensive contact area of a fil- render the bulk fuel sufficiently conducting to provide rapid
ter medium. Owing to the high state of cleanness of transport dissipation of the charge to an appropriate earthing surface
fuels, the electrical conductivity is very low (e.g., 1-3 CU^ for [1]. Incorporating this additive into an aviation kerosine
aviation kerosine cf. 10 X 10* CU for demineralized water). would raise the conductivity from 1 to about 150 CU, lower-
Consequently, high electrostatic potentials are generated, ing the half-value time from 12-0.08 s.
which cannot be dissipated easily through such an inert fuel
medium. Within the filter-separator or receiver tank, there- Lubricity
fore, an electrostatic gradient develops between fuel and wall
surfaces that can r e a c h a level of breakdown leading to Lubricity, sometimes described as film strength, can be de-
sparks, and to subsequent explosions, if the vapor-air mix- fined as the ability to lubricate with a low tendency to gener-
ture lies within the flammable range. ate friction, wear and/or scuffing. Lubrication takes the three
basic forms:
This dissipation process is known as charge relaxation, and
the time taken for the charge to fall by one half from a given • hydrodynamic (with n o surface contact, as controlled by
value (the half-value time, ti/2) is a n importcint factor indi- viscosity)
cating whether static charges generated in the fuel are haz- • mixed (with limited surface contact)
ardous or not. In practical units. • boundary (with predominantly surface contact).
In the latter instance, lubricity applies particularly to fuel
12
tl/2 = Conductivity seconds pumping equipment operating at high pressure, where poten-
tial surface contact predominates. Although not included in
Typical values of ti/2 are 12 s for aviation turbine fuel of 1 CU, current specifications for jet fuels, the ability to maintain
and 1.2 /as for demineralized water of 10 X 10* CU. Charges boundary lubrication in the close cleEirances between recipro-
can accumulate to an appreciable extent only if ti/2 is high. cating elements or highly-loaded gears in fuel pumps is imper-
The generation of static electrical charges in the handling ative to avoid adhesive wear (surface scuffing or welding) and
of aviation kerosine has long been recognized as a potential oxidative wear (corrosion and abrasion). This was manifested
hazard during aircraft fueling. A n u m b e r of rules covering indirectly in aviation under the following circumstances:
• sticking and hang-up of fuel control systems using wide-
^ 1 CU = 1 Conductivity Unit = IpS/m (picosiemen/meter) cut fuel
• use of corrosion inhibitors (e.g., dilinoleic acid derivatives) sive time available to achieve stability during formation, but
to keep pipelines clean indicated surfactant action which cracking or other refinery processes can be severe enough to
prevented water from coagulating and made removal diffi- promote multi-bonding. With jet fuels, for example, a maxi-
cult. Discontinuation of the inhibitor resulted in problems m u m limit of 5% volume of olefins was set in order to prevent
of fuel p u m p seizure, which were solved on replacement of the incorporation of non-hydrotreated cracked stocks into
the inhibitor, indicating its action as a lubricity enhancer the finished product.
• chemical treatment to convert objectionable mercaptans The combined effects o n a fuel of heat, dissolved oxygen
RSH to innocuous disulphides RSSR' does not appear to and nitrogen, trace sulfur content (particularly disulfides and
affect lubricity, but severe hydrogenation to reduce mer- thiols), and some initiator such as a cataljîc metal result in
captans to paraffins and hydrogen sulphide removes the the formation of small quantities of insoluble products.
polar boundary lubricants and promotes p u m p seizure. These comprise two forms depending on the conditions of
Boundary lubrication is, in fact, dependent more on the flow and temperature, as follows:
trace concentrations of polar compounds than on the nature • Intermediate temperature (<200°C) particulate deposits
of the m a i n h y d r o c a r b o n c o m p o n e n t s of the bulk fuel. from bulk heating accumulating on filter screens causing
These polar compounds most probably comprise high molar blockages.
mass polycyclic aromatics containing sulfur, oxygen, and/or • High temperature (350°C) films of lacquer (varnish) from
nitrogen. localized hot surfaces accumulating in fuel-fed oil coolers,
Lubricity is customarily assessed in practice using a mov- hydromechanical devices, injector feed arms and the fuel
ing specimen rubbing on a stationary specimen under an ap- injectors themselves. These promote loss of heat-transfer
plied load in the presence of the test fuel as, for example, in efficiency, sluggishness and hysteresis with moving parts
the lightly-loaded ASTM D 5001, Measurement of Lubricity involving fine tolerances leading to sticking and eventual
of Aviation Turbine Fuels by Ball-On-Cylinder Evaluator, seizure o n attempts at engine starting. Furthermore, the
BOCLE. This rig is used to measure lubricated mild wear rate higher temperatures within the injector feed arms can lead
of the ball but the results m a y be influenced adversely by cor- to thermal cracking, the resulting carbonaceous material
rosive wear. Wear rates that are high are usually caused by either depositing and reducing the fuel flow, or breaking
scuffing, and a new development is the BOCLE scuffing test. away and blocking the injectors, distorting the spray pat-
terns with consequent thermal damage to combustor liners
The correlation between mild wear and scuffing depends on
and turbine blades.
the composition of the fuel, consequently comparing the
scuffing performance of fuels from their mild wear behavior During flight, the key issues for fuel stability under the ac-
is valid only for fuels of similar composition. The BOCLE is tion of heat are the peak temperature experienced, and the
therefore satisfactory for overall thermal history u p to the point of combustion. For
• p u m p development using a low-lubricity fuel subsonic civil aircraft, for example, the bulk tanks have little
• monitoring supplies of low-sulfur additive-free fuel effect, b u t in some supersonic aircraft, bulk tanks may make
• monitoring changes in additive concentration. some contribution through kinetic heating. In the latter case,
The Dwell test measures friction whereas the more com- the main source of the problem is the use of fuel as a heat
plex Thornton Aviation Fuel Lubricity Evaluation (TAFLE) sink for cooling engine lubricating oil and various items of
rig measures seizure load, friction, and wesir as well as scuff- avionic equipment. The overall result is that fuel approaches
ing. In the High Frequency Reciprocating Wear Rig (HFRR), the injection manifold with a much higher content of sensi-
a hardened steel ball oscillates under load across a hardened ble heat t h a n previously. This situation is exacerbated by fur-
steel plate in the presence of the fuel sample. As before, lu- ther heating in the injector feed arms because of their loca-
bricity rating is based on comparing the wear scar diameter tion within the air stream, which is compression-heated to
with that of a reference fuel, in this case at two test tempera- t e m p e r a t u r e s approaching 600°C. A m a x i m u m operating
tures. A fuel with high lubricity is described as SOFT, and temperature of 163°C is set for the fuel reaching the inlet of
with a low lubricity as HARD. At this time, these are experi- the injectors, but the objective of a currently active research
mental tests derived through industrial research. (For Lu- program is to raise this limit by 100°F (56°C) to 219°C, hence
bricity Improving Additives, see the Water Contamination increasing the heat capacity of the fuel by 50%. Even if the in-
section.) jector fuel should eventually reach 254°C, the SIT level for
aviation kerosine, spontaneous ignition cannot occur in the
absence of adequate oxygen. Nevertheless, hydrocarbon fuels
Stability invariably contain u p to 14% by volume of dissolved atmo-
spheric gases. Furthermore, the concentration of oxygen in
Chemical stability in storage is characterized by hydrocar-
these dissolved gases is raised from the standard atmospheric
bons that are hydrogen-saturated, whereas instability is en-
level of 2 1 % to about 40%. As a result, the application of heat
demic in the presence of double carbon-carbon bonding as in
to such fuels can give rise to slow processes of autoxidation.
the olefins (and even more so in the treble carbon-carbon
bonding in the acetylenes, which renders them unusable for In ASTM D 381, Gum Content in Fuels by Jet Evaporation
aviation). Reactions of the unsaturated hydrocarbons occur for Aviation Fuels, the fuel sample is evaporated under con-
as polymerization of like-to-like molecules, and/or oxidation trolled conditions of temperature and flow of steam (now air),
to H.C.O compounds, the products of both types of reaction and the resulting residue weighed. In Western countries, sta-
taking the form of gums, acids, fuel-borne solid particulates, bility at higher soak temperatures is assessed by ASTM D
and/or surface deposits. Olefins do not occur in crude oils or 3241, Thermal Oxidation Stability of Aviation Turbine Fuels
their straight-run fractions, of course, because of the exten- (JFTOT Procedure), comprising an aluminium tube resis-
tance-heated to 260°C that experiences a skewed normal tem- hindering their coagulation and settlement. Certain soap-like
perature distribution along its length, and downstream a surface-active agents (surfactants) may occur naturally in
heated stainless-steel cloth precision filter of 17/Am nominal fuel, or be introduced either by contamination or in the form
porosity fitted with a differential gauge. The fuel sample flows of otherwise acceptable additives. These inhibit small
at 3 mL/min for 2.5 h along the outer surface of the tube: in droplets of free water from coalescing with each other and
aircraft practice, the fuel flows within the tubing but external settling rapidly. The settlement rates of water droplets can be
flow is used in the test so that any deposits can be examined determined from Stokes' law.
visually. Any pressure drop across the filter indicates the pres-
ence of solid particulates, b u t examination of the upstream
terminEj velocity of spherical peirticle =
heater tube was found to be necessary since tube deposits 18ij
were sometimes evident in the absence of filter blockage. The
where d = diameter of particle (cm),
sample is reported as either a pass or fail, determined jointly
a = density of particle (g/cm^),
by the intensity of tube deposition against set color standards
p = density of fuel (g/cm^), and
(ranging over a ten-step basis from 0, < 1 , 1, < 2 , 2, < 3 , 3, < 4 ,
17 = dynamic viscosity of fuel (g/cm s).
4, >4) and/or level of pressure drop across the filter u p to a
maximum of 25 m m Hg. Among abnormal surface colors is
blue/gray, usually associated with copper contamination. Thus, settling rates are proportional to the square of the di-
ameter of the contaminating particle, emd the density differ-
The JFTOT has also been used at t e m p e r a t u r e s above
ence between the peirticle and the fuel.
260°C in order to find the breakpoint, that is, the temperature
As well as increasing the concentration of free water, cool-
at which the fuel fails both the specified tube rating and mEix-
ing a distillate fuel from 0°C to about —30°C gives rise to the
i m u m pressure drop (25 m m Hg) criteria. The currently de-
progressive formation of ice crystals that tend to remain in
termined brccikpoint for a typical UK aviation turbine fuel
suspension. Supercooling may occur, but impact or contam-
ranges from about 280-310°C, and hydrotreated fuels have
ination promotes instant freezing of both water and some hy-
been found more stable t h a n sweetened fuels in which trace
drocarbon hydrates. A loose network of ice particles builds
contaminants are converted rather than removed. Generally,
u p on filter surfaces, resulting in an increased pressure dif-
breakpoint has also been found to correlate directly with hy-
ferential and, eventually, complete blockage. In general, the
drogen content a n d smoke point. In order to provide a
icing problem in civil aviation is met by the use of fuel-filter
database, the US DOD is collecting information on thermal
heating, whereas military practice is to additize the fuel with
stability results at a test temperature raised from 260-275°C.
a fuel system icing inhibitor, FSII (diethylene glycol-
In the near future, USAF is expected to develop a "JP-8 +
monomethylether) u p to 0.15% by volume.
100" fuel, being a JP-8 fuel with a 100°F (56 K) improvement
in break point by means of a package of anti-oxidant, metcJ Since water, carbon, and nitrogen are essential ingredients
deactivator, detergent, and dispersant additives. These espe- to life, microbiological activity is possible at the water-hy-
cially stable products are now described as High Tempera- drocarbon interface. The most c o m m o n aerobic micro-or-
ture Thermally Stable (HiTTS) fuels. ganism to flourish under these conditions is Cladosporium
resinae (Lindau) de Vries. This is a fungus comprising long
Thermal stability is degraded in the presence of olefins, threads that produce spores too small (approximately 3 ^^m)
copper, and other metcJs, and of sulfur. Copper is a particu- to be filtered out. The threads branch heavily to form a visi-
larly potent oxidation catalyst and, even at the parts per bil- ble tangled greenish-black mat or "mycelium," the mechani-
lion level of concentration, has given rise to a n u m b e r of cal strength of which is sufficient to cause filter blockage cind
problems through carryover when jet fuels were subjected to malfunction of fuel-contents gauges. The fungus is able to ex-
copper sweetening. However, with the adoption of alterna- tract the carbon from a hydrocarbon fuel such as kerosine,
tive methods of treatment, a limit on copper content is no and to generate products which, in association with water,
longer specified, reliance being placed on the results of the corrode through the WEJIS of aluminium fuel systems, pro-
JFTOT. Should a jet fuel contain copper, it can be chelated moting leakage. These tanks are now designed to give free ac-
(neutralized by axi isolating coating) by means of a metal de- cess of all internal water to a drain plug, Eind/or with probes
activating additive such as a propanediamine. However, ex- into the low points to pick up collected water so that it CEin be
cessive use of MDA can passivate the tube surface of the injected into the m a i n fuel delivery system to the engine.
JFTOT and give rise to misleading results.
Biostats are materials that inhibit the growth of bacteria
and fungi, whereas biocides are materials that kill them. In
Water Contamination military aviation practice, the fuel system icing inhibitor to
prevent water freezing problems is also relied upon as a bio-
Even with the strictest housekeeping discipline, traces of wa- stat. In civil aviation, on the other hand, where filter heating
ter invariably collect in liquid fuels during storage smd trans- is used instead, biocidal shock treatment is given every few
fer. Apart from accidental ingress through carry-over from months when the aircraft is out of service, by the addition of
water-washing in the refinery, or defective tank vents or u p to 270 p p m of a boron compound, which is left to act for
seams (pEirticularly in sea-going vessels), the main source is three days.
the humidity of the atmosphere above the fuel surface. Water In addition to the corrosive action of the products of micro-
dissolves in hydrocarbons to a n extent dependent upon tem- organisms discussed above, direct contact of metaJ with wa-
perature, any additional water existing freely as dispersed ter and dissolved air leads to the formation of rust. Materials
droplets. The agitation of fuels by pumping through valves employed as corrosion inhibitors are polcir in nature with hy-
and pipeline systems tends to disintegrate the water droplets. drophilic heads and oleophilic/hydrophobic tails that accu-
m u l a t e as an oil m o n o m o l e c u l a r layer preventing water- The evaluation of atmospheric quality with regard to the
metal contact. As indicated in the earlier section on lubricity, presence of contaminants is commonly expressed in terms of
experience showed these corrosion inhibitors to serve a sec- the threshold limit value (TLV) defined as the acceptable air-
ond purpose in improving lubricity by the same molecular borne concentration of the given c o n t a m i n a n t in occupa-
action, consequently such materials have become known as tional exposures for u p to 8 h daily without adverse effects.
corrosion inhibitor/lubricity improving additives, CI/LIA. However, since the volatility of the contaminant determines
Other problems associated with water during the pumping of its vapor concentration at ambient temperature, it is also cus-
fuels include the augmentation of static charging, as dis- tomary to use the hazard index, defined by (VP/TLV), where
cussed ecirlier, and also foaming in the presence of heat. VP is the vapor pressure.
With aviation kerosines, free water concentrations existing In broad terms, internal effects comprise nausea, dizzi-
as dispersed droplets become visible as a cloud (the specifi- ness, h e a d a c h e , and irritation of the m u c o u s m e m b r a n e ,
cation calling for the fuel to be "clear") at concentrations leading to loss of consciousness with the aromatics, a n d
varying from 30-50 p p m mass depending inversely on blindness with methanol. External contact can cause cold
droplet size. The former figure is recognized by lATA as the b u m s , dermatitis, eye damage, and skin cancers. Reference
m a x i m u m permissible at the time a n d temperature of deliv- to the fuel manufacturers' handbooks is recommended in all
ery, whereas a maximum of 15 p p m is assured by the use of
filter/separators and monitors in the supply system.
The concern with jet fuels is the potential for certain sur-
factants to disarm water separation equipment resulting in FUTURE TRENDS
the unexpected delivery of water to aircraft. A test was needed
initially to guard against the carry-over of powerful surfac- Extrapolation of past experience into the future suggests con-
tants from the refinery, particularly when sulfonation tech- tinuing use of conventional fuels for as long as is practicable,
niques were much in use. ASTM D 2550, Water Separation supplemented by virtually identical fuels derived from
Characteristics of Aviation Turbine Fuels, employs a sepa- sources other than petroleum. Subsequently, recourse will
rometer to determine the efficiency by which a fuel-water need to be made to substitute materials, as discussed below:
emulsion can be separated by a coalescer, assessment being
based on passing a prepared water-fuel emulsion through a Reformulation (Short Term)
standard glass-fiber coalescer and measuring the turbidity of
the effluent by light transmission. An arbitrary scale described In the automotive world, the fuel approach to emission re-
as WSIM (i.e. Water Separation Index Modified) indicates 100 duction is a process of reformulation. This entails tighter
for clear fuel, and less for any remaining water droplets. A controls on vapor pressure, and on the m a x i m u m permitted
small-scale version of this apparatus, D 3948, "Determining concentrations of aromatics, olefins, and sulfur. With jet fu-
Water-Separation Characteristics of Aviation Turbine Fuels els on the other hand, component concentrations are already
by Portable Separometer," comprises a portable micro-sepa- very closely controlled, but the "product giveaway" (the dif-
rometer with a high-speed mechanical stirrer, giving a nu- ference between the actual property and its specified limit)
mericaJ rating designated MSEP. However, the situation is has h a d to be reduced progressively for reasons of eco-
complicated by the fact that certain mandatory fuel additives, nomics. Nevertheless, recent reviews show modest improve-
either singly or in combination, depress WSIM number with- ment in aromatic content a n d smoke point despite small ad-
out, in reality, interfering with the water separator. verse changes in sulfur, freeze point, emd flash point. As the
sources of crude oil change because of shifting markets a n d
Tanks for kerosine usually have fixed roofs, coned to shed
availabilities, the product processes will have to be continu-
rainwater and snow, with free-vents to assist drying. A cone-
ally adjusted t o achieve the necessary specification, and these
d o w n b o t t o m of m i n i m u m slope 1 in 30 leads t o a water
will no doubt involve some form or reformulation to a greater
s u m p a n d drain valve, and a floating suction line ensures
or lesser extent.
freedom from water entrainment during offtake. After filling,
a period of 1 h is usually considered sufficient for water
droplet settlement, irrespective of tank depth. Supplemental Fuels (Medium Term)
Both natural gas and coal can be converted to "syngas" (CO +
Health Issues in Handling H2), which in turn can be synthesized to distillate-type liq-
uids either through WEIX, which is then hydroconverted cat-
The major physiological reactions on exposure to the high- alytically, or via a methanol stage. Alternatively, coal can be
performance transport fuels may have localized and/or sys- de-ashed a n d its molecular components reduced in size suf-
temic (remote) effects, a n d are tabulated under the following ficiently to give liquids directly without the additional energy
headings: required for the more extensive reduction to gaseous dimen-
• Ingestion—swallowing of liquid into the digestive tract sions. Hydrogenation of the aromatic components then gives
• Inhalation—in-breathing of vapor into the lungs the saturates—^paraffins a n d naphthenes.
• Aspiration—introduction of liquid into the lungs either More exotic alternative sources of hydrocarbons include
through inhalation or by vomiting shale oil, tar, coal, peat, and biomatter generally. The first
• External—contact with skin and, particularly, eyes. two have not yet emerged as conventioned fuel sources with
Furthermore, some materials are slow t o eliminate (for ex- established production rates, and therefore cannot be as-
ample, methanol), whereas others are cumulative (for exam- signed meaningful (reserves-production) ratios, but large de-
ple, decaborane). posits are known to exist worldwide.
Substitute Fuels (Long Term) ing either pre-vaporization within the hot flame zone or
relatively fine atomization. They are burnt with minimal
The longer-term approach towards future replacements is to
radiation at virtually constant pressure, with flame stabil-
use alternative fuels that may bear very little similarity to the
ity and temperature distribution across the combustor sec-
c o n v e n t i o n a l . This class may be described as "Substitutes," tion controlled by engine design. Combustion efficiency is
and includes the compounds of carbon with hydrogen, oxy- at a premium, despite the very short residence time of the
gen, and nitrogen. fuel molecules within the combustor, not only for fuel
For aviation, the most promising candidate substitutes ap- economy, but also for minimal emissions. In addition, han-
pear to be liquid methane and liquid hydrogen, but the handling properties are required to meet the wide range of
dling problems with cryogenic fuels are substantial. temperatures and pressures pertaining throughout the sup-
ply system a n d within the aircraft itself during service. All
these requirements combine to comprise a relatively exten-
SUMMARY AND CONCLUSIONS sive specification list of some 28 items or more, as sum-
Current fuels for jet engines are of the petroleum-derived marized in Table 7, yet without precluding either availabil-
mid-distillate kerosine t3'pe with moderate volatility requir- ity or economics.
TABLE 7—Major features of representative U.S. jet fuel specifications (certain variations apply depending on type
and concentrations of additives, etc.).
Wide-cut Kerosine High-flash
Gasoline MIL-T-813133D Kerosine Thermally Low volatility High density
MIL-DTL-5624T ASTM D-1655 MIL-DTL-5624 stable fuel fuel synthetic
JP-4 JetA-l" JP-5 TMIL-DTL-25524E MIL-DTL-38219D MIL-P-87107B
Property NATO F-40 NATO F-35 NATO F-44 JPTS JP-7 JP-10
Color, Saybolt, min Report Report Report -1-24 -1-25
Total acid no. mg KOH /g, 0.015 0.015 0.015 0.015
max
25.0 25.0 23.0-27.0 5.0-20.0 5
Aromatics, % vol., max
Olefins, % vol., max 5.0
Sulfur, total, % mass, max 0.40 0.30 0.40 0.3 0.1
Sulfur, mercaptan, % mass. 0.002 0.002 0.002 0.001 0.001
max
Report Report Report min. 157 min 182
Initial boiling point, °C
10% vol. recovered, °C Report max 205 max 206 max 193 min 196
20% vol. recovered, °C m i n 100 Report Report m i n 206
50% vol. recovered, °C min 125 Report Report max 204 Report
90% vol. recovered, °C Report Report Report max 238 max 260
E n d point °C, max 270 300 300 260 288
Flash point °C, min 38 60 43 60 54.4
Reid vapour pressure @ 14-21 max 20.7 @ 149°C
38.7°C, kPa & 3 3 1 @260°C
Density® 15°C, kg/L 0.751-0.802 0.775-0.840 0.788-0.845 0.767-0.797 0.779-0.806 0.935-0.943
Freezing point, °C, max -58 -47 -46 -53 -43.3 -79
Viscosity @ -20°C, mm^/s, 8.0 8.5 12 @ - 4 0 8.0 40@-54, 10@-18
max
42.8 42.8 42.6 42.8 43.5 42.1 (E.D. 39.4 MJ/L)
Specific energy, net, MJ/kg,
mm
13.5 13.4 13.3-13.5 14.0 14.40
Hydrogen content, % mass.
min
20.0 25.0 18.0-21.0 25.0
Smoke point, m m , m i n
Copper strip corrosion, max 1 1 1 lb lb
Thermal stability (JFTOT)
Change in pres. drop, m m 25.0 25.0 25.0 25 25.0 10
Hg, max
Tube deposit code <3 <3 <3 2
TDR spun mcix 12 12
Existent gum;, mg/100 mL, 7.0 7.0 7.0 5.0 5.0 5.0
max
1.0 1.0 1.0 0.3/0.5 0.3/0.5 1.0
Particulate matter, mg/L,
max
10 15 15
Filtration time, minutes,
max
lb lb lb lb lb
Water reaction interface
rating, max
Microscparator rating, min 70/90 70/85 70/90 Report 85
Electrical conductivity. 150-600 50-450
pS/m,
"Known as F-34 (JP-8) when additized with FSII and CI /LIA. The Jet Fueling System Check List embodies the most stringent requirements of Jet A-1, the British
DEF STAN 91-91, and the lATA Guidance Material for Aviation Turbine Fuels.
NOTE—1. Distillation tests incorporate limits of 1.5% for both residue and loss.
2. Types and concentrations of additives are also specified.
Conventional and some special aviation kerosines are 2] Goodger, E. M. and Vera, R. A., Aviation Fuels Technology,
likely to be available from petroleum sources for the next few Macmillan Publishers Ltd., Basingstoke, UK, 1985.
decades, after which they are likely to be supplemented by 3] Anonymous, "Theoretical Performance of Rocket Propellant
virtually identical materials from other natural sources. For Combinations," Rocketdyne, CA, January 1959.
4] Goodger, E. M., "Property Requirements of Liquid Rocket Pro-
the higher performance applications, attention is likely to
pellants," Journal of the Institute of Petroleum, London, Vol. 46,
turn to the C.H.O.N compounds, and possibly boron. From No. 442, October 1960, pp. 314-27.
emission considerations, molecules with the higher propor- 5] Wilson, W. E. and Berl, W. G., "Fuels," Ch. 6, Ramjet Technology,
tions of hydrogen are attractive, with an eventual elimination TG 610-6, The Johns Hopkins University, Baltimore, MD, July
of carbon by the adoption of liquid hydrogen. Nevertheless, 1965.
the handling problems with cryogenic fuels are substantial, 6] Glassman, I. and Sawyer, R. F., The Performance of Chemical Pro-
and the presence of large quantities of water vapor in the pellants, AGARDOgraph 129, NATO, January 1970.
stratosphere may incur problems. 7] Samer, S. F., Propellant Chemistry, Reinhold Publishing Corpo-
ration, NY, 1966.
8] Sutton, G. P., Rocket Propulsion Elements, John Wiley, NY, 1963.
ASTM STANDARDS 9] StuU, D. R. and Prophet, H., JANAF Thermochemical Tables, Na-
tional Bureau of Standards, Washington, DC, 1971.
No. Title 10] Broadbank, R., "New Technology Revolutionises Fuels Testing,"
D 86 Distillation of Petroleum Products at Atmospheric Petroleum Review, June 1999, pp. 30-31.
Pressure
D 93 Flash-Point by Pensky-Martens Closed Cup Tester
D 341 Standard Viscosity-Temperature Charts for Liquid BIBLIOGRAPHY
Petroleum Products 1] Schobert, H. H., The Chemistry of Hydrocarbon Fuels, Butter-
D 381 Gum Content in Fuels by Jet Evaporation worths, London, UK, 1990.
D 445 Kinematic Viscosity of Transparent a n d Opaque 2] Handbook of Chemistry and Physics, R. C. Weast, Ed., CRC Press,
Liquids (The Calculation of Dynamic Viscosity) Cleveland, OH, republished periodically.
D 1298 Density, Relative Density (Specific Gravity) or API 3] Rogers, G. F. C. and Mayhew, Y. R., Engineering Thermodynam-
Gravity of Crude Petroleum and Liquid Petroleum ics Work and Heat Transfer, Longmans Group Ltd., Harlow, UK,
Products by Hydrometer Method latest edition.
D 1322 Smoke Point of Kerosine and Aviation Turbine Fuel 4] Rose, J. W. and Cooper, J. R., Technical Data on Fuel, The British
D 1740 Luminometer Numbers of Aviation Turbine Fuels National Committee, World Energy Conference, London, 1977.
5] Datschefski, G., Lewis, C, and Walters, M. B., Jet Fuel Specifica-
D 2386 Freezing Point of Aviation Fuels
tion Requirements, Defense Evaluation and Research Agency,
D 2533 Vapor-Liquid Ratio of Spark-Ignition Engine Fuels London, 1997.
D 2550 Water Separation Characteristics of Aviation Tur- 6] Fielding, D. and Topps, J. E. C, Thermodynamic Data for the Cal-
bine Fuels culation of Gas Turbine Performance, Aeronautical Reseach
D 2624 Electrical Conductivity of Aviation and Distillate Council R & M 3099, 1959.
Fuels Containing a Static Dissipator Additive 7] Breitwieser, B., Gordon, S., and Gammon, B., Summary Report
D 3241 Thermal Oxidation Stability of Aviation Turbine on Analytical Evaluation of Air and Fuel Specific-Impulse Charac-
Fuels (JFTOT Procedure) teristics of Several Non-hydrocarbon Jet Engine Fuels, NACA R M
D 3338 Estimation of Net Heat of Combustion of Aviation E52L08, 1952.
Fuels 8] Dukek, W. G., Selected Hydrocarbons as High Performance Fuels,
American Chemistry Society, Symposium on High Energy Fuels,
D 3825 Dynamic Surface Tension by the Fast-Bubble Tech- Philadelphia, 25 Feb. 1960.
nique 9] Brewer, G. D., Hydrogen Aircraft Technology, CRC Press, London,
D 3948 Determining Water-Separating Characteristics of 1991.
Aviation Turbine Fuels by Portable Separometer
D 4305 Filter Flow of Aviation Fuels at Low Temperatures
D 4308 Electrical Conductivity of Liquid Hydrocarbons by APPENDIX 1
Precision Meter
D 4809 Heat of Combustion of Liquid Hydrocarbon Fuels T h e r m o d y n a m i c Properties a n d their Inter-
by B o m b Calorimeter (Precision Method) relationship in Static Gases
D 5001 Measurement of Lubricity of Aviation Turbine Fu- A collection of hot gases suited to act as a working fluid in a
els by the Ball-On-Cylinder Lubricity Evaluator heat-work conversion is known as a thermodynamic system.
(BOCLE) At any instant, this system exists in a particular thermody-
E 659 Autoignition Temperature of Liquid Chemicals namic state as defined by its set of properties, which are con-
sequently described as state functions. Such a property is rec-
ognizable by the fact that it exhibits no change when the
SAE STANDARDS system goes through a complete cycle of events (as discussed
ARP492 Aircraft Engine Fuel P u m p Cavitation Endurance in Appendix 2).
Test In a thermodynamic system:
• an extensive property is dependent on the mass of the sys-
tem, e.g., volume V, internal energy U, enthalpy//, energy£,
REFERENCES entropy S, etc.
[1] Goodger, E. M., Transport Fuels Technology, Landfall Press, Nor- • a specific property is an extensive property expressed on a
wich, UK, October 2000. basis of unit mass of the system, e.g., specific volume v.
specific internal energy u, specific enthalpy h, specific en- • S, the entropy, is a measure of molecular disorder, and is
ergy e, specific entropy s, etc. equal to the ratio of the heat transfer between the system
• and an intensive property is independent of the mass of the and its surroundings to the temperature, hence S = Q/T.
system, e.g., pressure p, temperature T, height z, etc. In engineering thermodynamics, interest generally centers
In the above list, the three properties that can be measured on changes in the above derived properties, hence At/, A//,
physically by means of instrumentation are known as prime AS, etc.
properties. These comprise pressure, volume, and tempera-
ture, the last-named being expressed in absolute terms in
units of kelvin. These three properties can be related by com- APPENDIX 2
bining the following two laws of gases:
1. Boyle's law—Ât constant temperature, p a 1/pv, hence v = The Unique Nature of Thermodynamic
a function of T Parameters
2. Charles' law—Ât constant pressure, v a T, hence v/T = a
function of p Fortuitously, the complete set of properties of a given mass of
a system at any given state is fixed by defining two properties
Consider a mass m of system material at condition 1 going only, provided that these properties are independent of each
through a constant temperature process to condition 3, fol- other, and that the system itself comprises a pure substance,
lowed by a constant pressure process to condition 2. that is, its chemical composition is both homogeneous and
Then, piVi = P2V3, and V3/T1 = V2IT2 constant. This feature is known as the two-property rule. For-
Combination leads to the prime properties being related to tunately, also, mixtures of air and gaseous fuel prior to com-
give the equation of state bustion, and of exhaust gases subsequently, can both be clas-
Pi V/ =P2V2TilTz, sified as pure substances.
hence Pi vilTi = P2 V2IT2 = p v/T = constant = R The Unique Point
and One very valuable consequence of the two-property rule is that
it enables the state of a pure-substance system to be
pV/T = mR represented by a unique state point on conventional graph pa-
where R is the gas constant for the particular material per, which is itself two-dimensional. As an example, the equa-
(= 0.287 kJ/kgK for air). tion of state shows that a system comprising 1.23 kg of air oc-
A material that follows this equation exactly is known as an cupying a volume of 1 m^ at a pressure of 1 atm (101.325 kPa)
ideal gas. (Note that a perfect gas is an ideal gas with values would have to exist at 288 K, all other properties being set by
of specific heat capacity constant at all temperatures.) The these state conditions. The two-property rule provides a most
molar volume, VM, of a gas is the volume occupied by one valuable tool in that the complete thermodynamic state of this
mole of molar mass M, and from Avogadro's law, this is com- air system can be represented by a unique point, X, on the two-
mon for all ideal gases at the same temperature and pressure. dimensional p-V graph shown in Fig. A2.1.
Hence, since
VM = M R T/p and is common, The Unique Process Line
(M R) also is common, and is known as the Universal Gas If the initial thermodynamic state is changed progressively
Constant, Ro, equal to 8.3143 J/mol K at 1 atm and 0°C. through different states, for example by external transfers of
The remaining properties are discussed further below: energy, the various unique points can be connected by a
• U, the internal energy, is the sum of all forms of energy
contained within the internal structure of the system ma-
terial itself. It therefore comprises: the internal potential
energy stored within the atomic and molecular particles
from work done in moving them apart against binding
forces of mutual attraction, and the internal kinetic energy
of the particles moving randomly in translation, rotation,
vibration, and spin.
• H, the enthalpy, is the sum of the internal energy and the
flow energy involved in penetrating the surface of the imag-
inary space of interest (the control region) where condi-
tions and processes Eire being examined. This latter term is
derived simply from the following expression:
Flow energy = work done in penetrating surface
= Force X distance moved
= (force/area) X (distance X area) 0.5 1 1.5
= pV Volume, Vm3
Hence, H =U+pV FIG. A2.1—Representative reversible

• E, the overall energy of the system, incorporates H and {p-V) paths for ideal gas. (Point X repre-
some other parameters (see Appendix 6). sents 1.23 kg air at 288 K) [1].
unique line on the graph representing the process of change. ciency of the Brayton cycle, operating on a steady-flow basis,
Such a hne follows a relationship of the form is shown in Table A2.2, and calculated values are shown plot-
ted in Fig. A2.2.
p y " = constant.
It is interesting to note that, although temperature (T) is a
An infinite n u m b e r of processes is possible depending on the property of a system, whereas an external transfer of heat (Q)
value of the index n, which can vary from 0 to <». The follow-
ing values of n, and the names of the related processes, are TABLE A2.2—Derivation of efficiency of steady-flow
Bra5ôn cycle [1].
shown in the figure, and are listed below:
Process Heat Transfer Work Transfer
n Process Name (1-2) Isentropic 0 -CpiTj - T2)
0 Isobaric (constant pressure) compression
(2-3) Isobaric CpiTs - T,) 0
1 Isothermal (constant temperature)
>1 to<-)' Polytropic heating
(3-4) Isentropic 0 Cp(T3 - T4)
y Adiabatic" (zero heat transfer)
Isochoric* (constant volume) expansion
(94-1) Isobaric -Cp{T, - T4) 0
"Also described as isentropic in the ideal case of a reversible cooling
process since entropy remains constant throughout.
Sometimes described as isometric. -Cp{T, -To)' . {T4 - T,)
Tn = i -
CpiTs --T2) (T3 - T2)
The transfers of heat and work associated with the above From isentropes 1-2 and 3 ^
processes are shown in Table A2.1 T4/T3 = (P4IP3)'-^ -'^"'= U/rpP - '>'^ = (pi/pzf'' ''^'->= T1/T2
Hence-n = 1 -(;/(>)<•>'"-"'^
The Unique Cyclic Process
It is evident that reversible processes can be arranged se- Compression ratio r^
quentially in a variety of ways so that they return to the ini- 10 20 30
tial point and comprise complete cycles. Thus, as outlined L
Typical S-l Typical C-l
earlier, the properties do not change once the cycle is com- may r maX i j .
pleted since the initial and final states coincide. Clearly this
cyclic process encompasses a fixed area (which represents 60
work transfer in the case of pressure-volume axes), and can OTTO
be repeated indefinitely. Each individual component process 2
'o
is related to external transfers of energy (as heat and/or 40 ic
work), which are all calculable from thermodynamic theory. (U
75
Consequently, suitable selection of component processes, E
)_
Typical GT
dD
and of their relationship within the cycle, can result in over- maxrn
20 SI
a . Cut-off ratio
all transfers of heat and work. Traversing the cycle diagram S-l - Spark ignition piston engine
clockwise gives rise to the potential of the continuous con- C-l •" Compression ignition piston engine
GT - Gas turtine engine
version of heat input to work output (as in a heat engine),
provided the second law of thermodynamics is followed in —r "T—
10 20 30
that such a conversion can never be complete, i.e., some of
Pressure ratio Xp
the heat input must be rejected as heat output at a level of
temperature lower than the initial. The derivation of the effi- FIG. A2.2—Variation of engine cycle thermal efficiencies.
TABLE A2.1-- E n e r g y distribution in thermodynamic processes \_p v" = constant, a n d p V = i? r ] .

Work Transfer
Process Heat Transfer Non Flow Steady Flow °
Isobaric Cp (T2 - Ti) R (T2 - Ti) 0
p = k
n = 0
Isothermal RT\n(p,/p2) R T In (p,/p2) RT\n{p,/p2)
r=k RT\n(v2/vt) = RTln(v2/v;) = « r i n (V2 /V,)
n= 1
(7 - n) , ^ ^ ,
Pol3^ropic Cv j^ _ J {T, T2) ^ T ^ (Ti - T2) —I (T, - T2)
pv° = k
n = n
Isentropic 0 Cv {Ti - T2) Cp {T, - T2)
p v"* = k
n = -y
Isochoric Cv {T2 - T,) 0 R {T, - T2)
v = k
n = 00
' Assuming no changes in potential (height) or kinetic (velocity) energies.

is not, the quotient (Q/T) - which is the entropy (S) - does TABLE A3.1—Thermochemlcal bond enthalpies, kj/mol [1].
meet the definition of a property since it does not change over Bond Enthalpy Bond Enthalpy
the complete cycle. A fuller discussion of these thermody- AHa.H2(g) 435.4 D(H—OH) 497.5
namic issues is given in Ref. 1. AHa.02(g) 498.2 E(C—H) 414.5
AH,.N2(g) 946.2 E(C—C) 347.5
AHa.C2(gr) 717.2 E(C=C) 615.5
D (H—O) 428.7 E(C=C) 812.2
APPENDIX 3 E (H—0) 463.1 E(C—0) 351.7
Oxidation Heat Release

The study of heat transfers associated with chemical reac-
tions is termed Thermochemistry. Since the events of interest
which is the mean value for a n u m b e r of such bonds in dif-
here relate to flowing, rather than non-flowing, fluids at con- ferent molecules, and in different locations within them. A
stant pressure, changes of energy Eire expressed in terms of simple physical analogy of the complete formation process is
enthalpy r a t h e r t h a n internal energy (see the section on given by a mass descending from a depression in a hilltop;
Calorific Values). the overall change in potential energy is the net result of the
The formation of a molecule (for example, a fuel) from its climb to the lip of the depression, and the subsequent descent
component elements can be imagined as the following two- from it (Fig. A3.1). Representative values of AHa, D(X—^Y)
stage process: and E(X—Y) are given in Table A3.1
1. Absorption of sufficient enthalpy to release the individual Hence, in the methane example above, the net enthalpy re-
atoms of the c o m p o n e n t molecule into freely gaseous leased, which is described as the standcird enthalpy of forma-
form, as for example; tion, AHf, is given by:
C(gr) ^ C(g), and H2(g) ^ 2 H(g) A//f .CH4 = lAHa - l E ( X - Y ) approximately
where (gr) represents carbon in its standard condition of = [AHa-Cigr) + 2 AHa-H2{g)] - 4 [ E ( C - H ) ]
graphite, and (g) represents gas.
2. Release of excess enthalpy on the combination of these [717.2 + 870.8] - 1658.0 70 kJ/mol
free atoms on the formation of the combined molecule, as (cf. — 74.90 kJ/mol by measurement)
for example;
The term "standard" (superscript "o") indicates that the ini-
C(g) + 4 H(g) -> CH4(g) methane tial and final temperatures are c o m m o n at 25°C. The negative
value above indicates that a net release of entheJpy occurs
The energy involved in the first stage of the process is des-
during formation, hence the resulting methane molecule is
ignated the "enthalpy of atomization," AHa, and is invariably
more stable than its parent elements. Values of AHf for other
directed inwards. In thermochemistry, therefore, this is
hydrocarbon molecules are included in Table 3.
classed as positive since it adds to the total stock of energy of
the elemental material. The second stage involves an energy If now the dissociation enthalpy (but see activation energy
release which, although considered negative on the above ba- below) is applied to a fuel molecule, together with the atom-
sis, is customarily described in the opposite sense as the ization enthalpy of its stoichiometric oxygen molecules, the
"bond dissociation enthalpy," D(X—Y), representing the at- total number of free atoms may rearrange themselves as ox-
omization enthalpy required to dissociate the X—^Y bonds of ide products, and so fall into a m u c h deeper enthalpy trough
the completed molecule back to free atoms. For convenience, as they release their new quantities of bond dissociation en-
use is often made of the empirical bond enthalpy, E(X—Y), thalpy. Hence,
Standard enthalpy of oxidation reaction
= AH?
= 2:(A//;)p - I(A//;?)R
= E(n AHf\ - Km AHf\

where subscripts P cmd R refer to products and reactants re-
spectively,
XD (X-Y)p mi = moles of reactcmt i, and

(AHpP Uj = moles of product j .
As an example, consider the stoichiometric oxidation of
AH? methane to gaseous CO2 and H2O given the following vaJues;
A///-CH4(g) = - 7 4 . 9 0 kJ/mol
Product
molecules AHf •C02(g) = - 3 9 3 . 5 2 kJ/mol, and
A//°-H20(g) = - 2 4 1 . 8 3 kJ/mol
FIG. A3.1—Schematic of standard molar enthalpies of forma-
tion (A H,°) and of reaction (AHr°) [1]. Since CH4(g) + 2 02(g) = C02(g) + 2 H20(g),
it follows that A/:/^°.CH4(g) The Arrhenius plot also gives:

Gradient = E/R^ = 73 100/8.314 3 = 8792 K
= [1 (-393.52) + 2 (-241.83)] - [1 (-74.90) + 0]
= - 3 9 3 , 5 2 - 483.66 + 74.90
APPENDIX 4
= - 8 0 2 . 2 8 kJ/mol
It is noteworthy that the enthalpy of formation of O2, N2, Proportions of Dissociated Combustion Products
C(gr) and other elemental molecules at their standard condi- At temperatures above about 1800 K, the thermal agitation of
tions is zero since AHa and D(X—^Y) are equal and opposite combustion products is such that they begin to dissociate
in sign. It is also of interest to note that the above value is a back towards their reactant materials, giving reversibility to
net quemtity since the product water is in the vapor phase. the combustion reaction, thus
(See the section on Calorific Values.)
combustion.
From the above discussion on enthalpies of formation, it A + B^
dissociation
might appear that the full complement of the dissociation At a sustained high temperature, therefore, a condition of
bond energies would be required in order to dissociate a fuel dynamic equilibrium exists with rates of combustion and dis-
molecule into its component free gaseous atoms of carbon
sociation exactly equal, so t h a t the reactant a n d product
and hydrogen. However, the chain nature of the ignition pro-
materials coexist in proportions that remain constant. These
cess implies that only one bond need be broken to start the
proportions can be determined by using values of parameters
chain. Furthermore, some molecules will have more than the
known as "partial pressure equilibrium constants" at the
average level of energy, and also both bond breaking and re-
given temperature, as shown below.
making are occurring together. All these factors result in an
The rates of such reactions at selected temperatures can be
"activation energy" of a considerably lower level t h a n
determined by experiment, and are found to be proportional
D(C—C) or D(C—H). The actual value can be determined ex-
to the instantaneous concentration of each material raised to
perimentally by plotting ignition temperature (T) against de-
lay (t) on the Arrhenius basis as follows: some power, that is,
forward reaction rate = kp [A]^ [B]'', and
Reaction rate kR [C]'^
dt " ^ reverse reaction rate
where q quantity of heat released per unit mass where [X] instantaneous molar
t •• reaction time concentration of material X,
e = Naperian base = 2.7183
k = rate constant for the reaction,
E = activation energy under the given conditions
and a, b, and c are
Ro = universal gas constant = 8.3143 J/mol K
experimentally-determined
T = absolute temperature
powers.
dq
Since --T- a t -\tae'^''°^: constant e Since the two rates are equal at d5Tiamic equilibrium.
[Cf
It follows that ^ = K'
[A]^ [Bf kR
Int Y + constant + constant = concentration equilibrium constant for the
reversible reaction
which is the equation of a straight line of In t against 1/T. The It follows from Avogadro's law (equal volumes of all gases
value of £ can then be determined by taking two points on the at the same t e m p e r a t u r e a n d pressure contain the same
straight line, as follows: n u m b e r of molecules) that
In (ti/t2) =
E _\_ J_
Rn Ti T2 t, = K = partial pressure equilibrium constant for
^ ^ the reversible reaction,
Ro lniti/t2)
Hence, E
Ti
J_ Furthermore, —^ = -—n r. where p = total pressure.
T2 p total mol ^ ^
For n-octcine the calculations appear as follows: Thus in each case, p^ can be expressed in the following
manner:
8.3143 In (20/1.2)
Px = P, ( 1, where Uj = total moles of product present.
U L\
^^502 598/
8.3143 X 2.8135 Since carbon oxidizes in two stages, first to CO and then to
8.3143 In 16.67
0.001992 - 0.001672 0.00032 CO2, it is the final stage at the high temperature that experi-
ences dissociation, that is
= 73 100 J/mol = 73.1 kJ/mol
CO + O.5O2 ^ CO2
This compares with 347.5 and 414.5 kJ/mol for initially dis-
sociating the C—C and C—H bonds respectively, and with PCO2 ,, _ "CO2
Hence, Kco, — nr>_/n+^0.5
208.59 for AHf. pCO {pOzT "C0(p"02/"t)'
Similarly for the oxidation of hydrogen, Solution for the six unknown values of n requires six equa-
tions, four of which are provided by molar balances of C, H,
H2 + 0.5 O2 ^ H2O
O, and N as for the simple non-dissociated case. The remain-
PH2O "H2O ing two equations are then derived from the published values
Hence, = K,
PH2 ip02)°' '' " " ' " "H2 (p"O2/"t)0-5 of Kco2 and KHJO for the temperature in question, where
(Note; These two equilibrium constants are used for solving ni
Kco2 and
the dissociated general mixture case below). n j {p Us/Ut)"
Since both reactions are occurring together, the half mole
of oxygen produced by dissociation of the mole of carbon n2
K,H20 •
dioxide may be considered as the oxygen required by the n4 {p ns/nt)"
mole of hydrogen. Combination of the two combustion equa- Computer programs exist for the determination of product
tions then gives: concentrations, but the method of solution shown below per-
CO2 + H2 ^ CO + H2O mits derivation from first principles, typical of those o n
which the computer software itself is based.
This is known as the water-gas shift reaction (not to be con- 1. At given temperature, read Kco2 and KHJO from Table A4.1
fused with the water-gas reaction, which is: CO -I- H2 ^ C + 1. Assume value for ns/nt, and evaluate (p ns/nt)"-^
H2O) and leads to:
3. Evaluate ni/ua and n2/n4 from Kco2 and KHJO expressions
Water-gas shift equilibrium constant = KWGS respectively, using Step 2 value.
K,H20 4. Evaluate Ui and ns from carbon balance, and n2 and n4
PCOPHIO
from hydrogen balance using Step 3 value.
KcOj Pco2 Pw.2 5. Evaluate ns from oxygen balance.
(Note: This equilibrium constant is used for solving the imag- 6. Evaluate nj from nitrogen balance.
inary non-dissociated rich mixture case since, although n o 7. Evaluate nt = n5/(assumed ns/ut), and compare with Enj,
dissociation complications arise, the distribution of the lim- with j = 1 to 6.
ited oxygen available to the CO and H2 has to be determined). 8. Repeat from Step 2 until Ut = Xnj.
Selected values of the partial pressure equilibrium con-
stants are given in Table A4.1. Example
Although at the higher temperatures dissociation proceeds
further to promote radicals such as O, H, OH and NOx (that Allowing for dissociation to CO, H2, and O2 only, the stoi-
is, NO + NO2), a first approximation to realistic conditions chiometric combustion equation for methane-air at its iso-
can be made by considering dissociation restricted to CO, H2 baric adiabatic combustion temperature of 2247K (Appendix
and O2 only, giving the following combustion equation for 5) appears as follows:
any general mixture strength;
CH4 + 2 (O2 + 3.76 N2) = 0.903 CO2
CaHb + m (O2 + 3.76 N2)
+ 1.961 H2O + 0.097 CO + 0.038 H2 + 0.068 O2 + 7.52 N2
= ni CO2 + n2 H2O + na CO -I- n4 H2 + Uj O2 + ug N2
Comparison of these product quantities with those for the
where m = moles of 02/mole fuel, as determined from the non-dissociated case below shows clearly the influence of
given air-fuel ratio. dissociation.
Solution follows by iteration on values of ns/nt. It might be
CH4 + 2 (O2 + 3.76 N2) = CO2 + 2 H2O + 7.52 N2
assumed that, as the products cool, the effects of dissociation
would vanish, and the combustion equation then revert to the
complete form in Eq 2 of Stoichiometry. But in fact, the par- APPENDIX 5
tially-burnt products endure on cooling due to freezing of the
reactions when energy is lost through contact with the walls Calculation of M a x i m u m Reaction Temperature
of the containing vessel and any inert molecules present.
The method of solution is based on the concept of equating
TABLE A4.1—Partial pressure equilibrium constants for oxidation the enthalpy released by the reactants, in generating the dis-
reaction, atm~°'^ [9]. sociated products at the initial temperature, with that which
Temperature, K KcOj KH20 KWGS would have been required to heat those products from the
298.15 1.1641 X 10"^ 11.169 X 10^^ 9.5945 X 10"^ initial temperature to the final temperature J*. As in most
300 575.44 X lO''^ 6.1094 X 10^' 10.617 X 10"^ thermochemical work, the standard initial temperature is
500 10.593 X lO^'' 76.913 X 10^' 7.2607 X 10"' taken as 25°C (298.15 K). Hence,
1000 16.634 X 10^ 11.535 X 10' 0.6935
1500 207.01 X 10^ 530.88 X 10^ 2.5645 [Chemical enthalpy released (negative) with reactants at
2000 765.60 3.4670 X 10^ 4.5285 298.15 K oxidized to products at 298.15 K, that is, the stan-
2100 345.94 1.6866 X 10' 4.8754 dard enthalpy of reaction] is equal to
2200 168.27 874.98 5.1999
2300 87.097 480.84 5.5207 [Physical enthalpy absorbed (positive) by products in heating
2400 47.753 277.43 5.8097 from 298.15 K t o r * ]
2500 27.543 167.49 6.0810 that is, - MIr° = (//^*jp algebraically
2700 10.351 68.077 6.5769 But \Hr° = [{^H^)p - (^H^)B.'\
3000 3.0549 22.029 7.2110
Thus, (H^* + A//;)p - (AHf )R = 0
Values of AHf for the products are listed in the literature E. Repeat from step A at new level of T (say 2300 K).
[9], together with values of the physical enthalpies absorbed F. Find T* by interpolation (or minor extrapolation) to give
when heating from 298.15 K to the different levels of T. The zero in equation of step D.
author has found it helpful to sum the two values shown on (All values of n at T* can be found by similar extrapola-
the left-hand side above and designate it as total thermo- tion).
chemical enthalpy at temperature T, ( H i ) , tabulating these
sums for direct use at the temperature levels of interest. The Example
above equation then becomes
All gaseous reaction of stoichiometric methane-air at 1 at-
(AH/)R = 0
mosphere with dissociation pattern as shown;
where H[* CH4(g) + 2 (O2 + 3.76 N2) = ni CO2
= total thermochemical enthalpy at temperature T* based
on initial 298.15 K + n2 H2O -t- n3 CO + n4 H2 -I- ns O2 + 7.52 N2
Expansion gives For methane, a = 1, and b 4.

A. Select T = 2200 K
Euj (Hr*)j - Emi (A//;)i = 0, for reactants i and products j B 1 Kco2 = 168.27, KHJO = 874.98
2 Assume nj/ut = 0.00519, thus (p ns/ut)"-^ = 0.07204
Since AHf-Oz = Mlf-Hz = 0 due to the self-canceling of the
3 ni/nj = 0.07204 (168.27) = 11.936
atomization and bond dissociation enthalpies, (for example
n2/n4 = 0.07204 (874.98) = 61.387
02—i^Ha) -^ 2 O—[D(0—O)] -^ 02), it follows that the pre-
4 n3 = a/(l + ni/ns) = 0.07730
vious expression can be simplified further to
ni = 1 - nj = 0.9227
Euj (fff*)j - mfuei (AH/)fuei = 0, and then to n4 = (b/2)/(l + n2/n4) = 0.03206
n2 = 2 - n4 = 1.9679
EUj ( / / r * ) j - (A///°)fuel
2m - X - (ni + n2) _ 3 - 2.8906
5 ns = 0.05468
= 0, since only one mole of fuel is usually considered.
6 ng = 7.52
Since both linear and non-linear equations require solu-
tion simultaneously here, iteration is necessary on T in the ns ^ 0.05468
7 n, 10.536
non-dissociated case, and on both n and T in the dissociated (assumed nj/ut) 0.00519
case. Suj = (10.52 + ns) = 10.575
As with product concentrations, computer programs exist Since slight difference between Ut and Xuj, repeat from
for the determination of maximum reaction temperature, but step B. 2 using ng/ut = 0.00518
derivation from first principles using the total thermochemi- This gives reasonable equality of 10.57, and all appropri-
cal enthalpy concept is as shown below. ate values of n, as follows:
A. Select some appropriate level of t e m p e r a t u r e T (say, ni = 0.923; uj = 1.968; ns = 0.774; n4 = 0.0321; ns =
2200 K). 0.0547
B. Determine all molar product "n" values; C. Weight each n value with its appropriate Ht^ value at
For the non-dissociated case, from Eq 3 2200 K
For the dissociated case, from the method shown in Ap- e.g., for CO2, ni {Hf) = 0.923 (-289.95) = - 267.6
pendix 4 D. Summation of these weighted values, less formation en-
C. Weight each value of n by its appropriate H[ at the se- thalpy for fuel, gives:
lected T, from Table A5.1 Snj (Hj)i - (A//;)f,ei = - 1 0 2 . 4 4 - (-74.85) = [-27.59]
D. Sum these weighted values, subtract {8Hf)iue\, and check Since this is not zero, repeat from Step A for new temper-
for zero. ature of 2300 K.
TABLE AS. 1—Standard-based total thermochemical enthalpy levels for• gases, kj/mol [9] [1],
H[= (H^ + AH}) Hi = H"-
for Compounds for Elements
Temperature, K CO2 H2O CO H2 O2 N2
298.15 -393.52 -241.83 -110.53 0 0 0
300 -393.46 -241.76 -110.47 0.054 0.054 0.054
500 -385.21 -234.91 -104.60 5.883 6.088 5.912
1000 -360.12 -215.85 -88.843 20.686 22.707 21.460
1500 -331.81 -193.73 -71.680 36.267 40.610 38.405
2000 -302.07 -169.14 -53.790 52.932 59.199 56.141
2100 -296.02 -164.00 -50.154 56.379 62.986 59.748
2200 -289.95 -158.79 -46.509 59.860 66.802 63.371
2300 -283.85 -153.53 -42.853 63.371 70.634 67.007
2400 -277.73 -148.22 -39.183 66.915 74.492 70.651
2500 -271.60 -142.86 -35.505 70.492 78.375 74.312
2700 -259.27 -132.01 -28.121 77.718 86.199 81.659
3000 -240.66 -115.47 -16.987 88.743 98.098 92.738
Similar calculations give ns/iit = 0.00785, hence; In the absence of the effects of gravity or motion, this en-
n , = 0.881; na = 1.953; na = 0.119; n4 = 0.047; nj = 0.083 ergy change is located entirely within the internal energy of
Summation of weighted values gives [ + 3 1 . 6 3 ] the system material, hence:
This also is not zero, but interpolation with value - 27.59
n.f. (q — w) = AM
from Step D gives
r * = 2247 K and n.f. d q z - 1W2) = M2 - Ml (A6.1)
Similar interpolation gives the related vEilues of the prod- This is known as the non-flow energy equation (n.f.e.e.), any
uct moles: change in internal energy leading to changes in temperature
ni = 0.903; nz = 1.961; nj = 0.097; n4 = 0.038; ns = 0.068 or phase.
In the presence of effects of gravity or motion, as in a sys-
tem flowing steadily through a control region, balaxices of
Note
mass cind of energy appear as shown below:
For stoichiometric methane-air, Mass balance: mi = m2 = p A C = Ai Cj/vi = A2 C2/V2
T* = 2327 K, nondissociated where p = density of fluid
= 2247 K, dissociated to CO, H2, and O2 only (as shown A = cross-sectionzJ area of flow
above) C = velocity of flow relative to control region, and
= 2223 K, dissociated to CO, H2, O2, H, O, OH, and NO V = specific volume of fluid = 1/p
For stoichiometric methane-oxygen,
r * = 3045 K, dissociated to CO, H2, O2, H, O, OH, and NO Energy balance: s.f.(iq2 — 1W2)
^2 £2^
= (hi -hi) + g (z2
APPENDIX 6
where z is the height above the Earth's surface, or some other
The Energy Equation datum.
This is known as the steady-flow energy equation (s.f.e.e.),
From the laws of thermodynamics, it is evident that, for a which can also be expressed in various reduced forms de-
system operating in a cycle, the initial and final states are pending on the constancy of certain terms. One useful form
identical, and the net heat input is equal to the work output, concerns negligible changes in both potential and kinetic en-
with some of the heat input being rejected to a lower tem- ergies, applicable to horizontal flow with approximately sim-
perature sink. On a specific basis, therefore: ilcir entry and exit velocities, as shown below:
qnet - W = ( q i n - Qout) " W = 0
Reduced s.f.e.e. = s.f. dqz — 1W2) = h2 — hi (A6. 2)
This is usucJly expressed simply as: q - w = 0
This compares directly with the non-flow case in Eq A6.1.
When the process is not cyclic, the initial and final states
Since this present study concerns steady flow applications to
differ, and the energy equation then becomes:
jet engines, most t h e r m o d y n a m i c considerations deal in
q — w = Ae terms of enthalpy rather thein internal energy.
MNL37-EB/Jun. 2003
Properties of Fuels, Petroleum

Pitch, Petroleum Coke, and
Carbon Materials
Semih Eser^ and John M. Andresen^
THIS CHAPTER PROVIDES AN OVERVIEW ON THE ORIGIN, PROPERTIES, their important properties, including standard methods of
AND APPLICATIONS of fuel oils, petroleum pitch, petroleum coke, measurement and the significance of individual properties in
and some related carbon materials. A c o m m o n thread among industrial applications.
these materials is the line of p r o d u c t i o n that connects
petroleum refining to the manufacture of carbon materials.
S p e c i f i c a t i o n s a n d A p p l i c a t i o n s o f F u e l Oils
Bottom fractions from catalytic cracking of gas oil (FCC de-
cant oil) or from thermal cracking of naphtha (ethylene tar) Fuel oils are burned to generate heat for different purposes
can be used as residual fuel oil, or as feedstocks for producing ranging from home heating to raising steam in utility boilers
carbon black, petroleum pitch, and p r e m i u m petroleum coke to generate electricity. Different types of burners used in
for graphite electrodes. Petroleum pitch is, in turn, used for these applications under various climatic and operating con-
producing carbon fibers and carbon-carbon composite mate- ditions dictate the need for different grades of fuel oils. A
rials, and for densification of graphite electrodes used in elec- standard specification by the ASTM International has di-
tric-arc furnaces to recycle scrap iron and steel. The residua vided fuel oils into five basic grades, designated as Nos. 1, 2,
from vacuum distillation in petroleum refining are subjected 4, 5, and 6 (ASTM D 396). Based on the production methods
to severe thermal cracking in coking processes to produce used in petroleum refining, fuel oils fall into two broad clas-
light and medium distillates and petroleum cokes that are sifications: distillates and residuals. The distillates comprise
used as solid fuel, or as filler for manufacturing carbon anodes overhead or distilled fractions, whereas the residuals consist
for electrochemical production of aluminum. It is important of bottoms remaining from the distillation, or blends of dis-
to recognize that ferrous metals and light metals industries, as tillates with the bottoms from distillation, visbreaking, and
well as manufacturing a n u m b e r of carbon materials, are catalytic cracking processes [2-4]. The six grades of oils can
closely linked with the products of petroleum refining, in- consist of different t5ês according to the refining processes
cluding decant oils, petroleum pitch, and petroleum coke. used in their production, as described in the section on
For each material, production processes, product proper- Petroleum Refining [5]:
ties, and specifications are discussed in the context of re- 1. straight-run distillate;
spective industrial applications. Standard methods used for 2. straight-run residual (i.e., reduced crude);
characterization of these materials are identified with a fo- 3. catalytically cracked distillate;
cused discussion on the interpretation of the results obtained 4. cracked residuals from thermal or catalytic cracking, or
from the standard tests. Literature references are provided hydrocracking;
for further information on each topic. 5. blends of any of the streams listed above.
Cracked oils have rather different composition and proper-
ties from those of the straight-run oils, as discussed later.
FUEL OILS In the ASTM specification. Grades No.l and No.2 are dis-
tillates and Grades No. 4-6 are usually residuals. Some heavy
Petroleum refining processes generate many product streams distillates may, however, be sold as Grade No. 4 fuel oil.
that can be used as fuel oil either in single streams or in Grade Nos. 4 and 5 are subdivided into light and heavy cate-
blends to adjust the desired properties for specific applica- gories. Table 1 summarizes the common uses and some sig-
tions. A broad definition of fuel oils does occasionally include nificant properties of the different grades of fuel oils [6].
diesel fuels since they are closely related to distillate and Grades 1 and 2 are used in domestic and small industrial
heavy fuel oils. In this section, however, diesel fuels are not burners. Grade 1 is a particularly light distillate for use in the
included for discussion, since they are covered separately in vaporizing type burners and under storage conditions that re-
this manual [1]. Industrial use of fuel oil for generating heat quire low pour points. Grades 4-6 are used in pressure atom-
is the principal focus in this section. Specifications and izing-type commercial/industrial b u r n e r s that can handle
applications of fuel oils are introduced with an overview of high viscosity fuels. The viscosity of these residual fuels in-
crease with the increasing number in the grade scale such
that Grade 6 fuel, also called Bunker C, requires preheating
' Department of Energy and Geo-Environmental Engineering and for handling and burning [6].
The Energy Institute, respectively. College of Earth and Mineral Sci-
ences, Pennsylvania State University, 110 Hosier Building, Univer- In general, all grades of fuel oil should be homogeneous hy-
sity Park, PA 16802. drocarbon oils, free from inorganic acid, and free from ex-
757
TABLE 1—Common uses and some significant properties of different grades of fuel oils.
Grade Classification Application Significant Properties
No. 1 Distillate Domestic and small Volatility and pour point
industrial burners of the
vaporizing type
No. 2 Distillate Atomizing type domestic and Volatility and viscosity
small industrial burners
No. 4 (Light) Heavy Distillate Pressure-atomizing type Viscosity and pour point
commercial/industrial
burners
No.4 Heavy Distillate, Pressure-atomizing type Viscosity, flash point, and
Distillate/Residual commercial/industrial sulfur content
blends burners; preheating not
required for handling or
burning
No. 5 (Light) Residual Industrial burners; preheating Viscosity, flash point, and
& No. 5 (Heavy) may be required for sulfur content
handling and burning
No. 6 or Bunker C Residual Industrial burners; Viscosity, flash point, and
preheating required for sulfur content
handling and burning
cessive amounts of solid or fibrous foreign matter. All grades gravity is inversely proportional to specific gravity—the ratio
containing residual components should remain uniform in of the density of oil at 60°F to the density of water at 60°F—
normal storage and not separate by gravity into light and according to the following equation:
heavy oil components outside viscosity limits for the grades.
°API = (141.5/spgr60°F/60°F) - 131.5
Table 2 lists the required specifications for all fuel oil grades
according to the standard designation ASTM D 396. A repre- The API gravity is the most commonly used property to
sentative sample should be taken for testing in accordance classify crude oil and refined petroleum products since the
with ASTM Practice D 4057. Modifications of limiting re- early days of petroleum industry. It has also been used to pre-
quirements agreed upon between the seller and the buyer dict many other characteristics of petroleum oils. Recent
should fall within limits specified for each grade, except as variations in crude oil composition coupled with new pro-
stated in supplementary footnotes for Table 2. The most im- cesses in petroleum refineries have, however, diminished the
portant considerations in selecting a burner and a particular usefulness of API gravity as a descriptor for other properties
grade of oil include the volume of the oil consumed, and a of petroleum oils. Two oils with the same API gravity, for ex-
match between the capabilities of the b u r n e r systems and ample, can have many different characteristics because of
properties of the fuel oils. The heavier grades are less expen- large differences in composition (e.g., different combinations
sive, but they must be handled and burned efficiently to take of paraffinic, naphthenic, and aromatic hydrocarbons). The
advantage of the lower fuel cost, especially in large volume API gravity still remains to be an important property, since it
applications. Sufficient heating in the storage tank and insu- can be measured easily, and used in a number of empirical
lated transfer pipelines are usually necessary to ensure steady correlations for approximate estimation of other properties
flow of heavy oil to the burner. High-viscosity oils require ad- of petroleum fractions [7].
ditional preheating at the burner for proper atomization. The API gravity of fuel oils is measured by using a standard
hydrometer according to ASTM Test Method D 287 or D
1298. Because of the significant volume expansion of oils
I m p o r t a n t F u e l Oil P r o p e r t i e s
upon heating, the API gravity varies strongly with tempera-
Fuel oils are burned to generate heat. The a m o u n t of heat capture. An API gravity of 12 at 60°F, for example, would corre-
tured in combustion systems is the principal concern for the spond to an API gravity of 18 at 180°F (82°C) [4]. Therefore,
fuel user. Important properties of fuel oils must, therefore, the volumetric heating value of oils (Btu/gal) decreases sig-
relate to their combustion characteristics and performance in nificantly with the increasing API gravity. The reasons for
different types of burners and fuel handling systems. Under- this trend are discussed in the next subsection.
standing these properties helps the user to select a fuel best Table 2 shows the gravity limits for the three grades of oil
suited for a specific application. It is also useful to discern the (>35 for No. 1; > 3 0 for No. 2; < 3 0 for No. 4 light). Although
relationships between different properties of fuel oils. All the the differences in gravity between different grades may vary
properties of fuel oils identified in Table 2 are discussed be- depending on the composition of the oils and the refining
low, with reference to standard measurement methods, and processes, typical API gravity ranges for fuel oils are as fol-
the significance of the measured properties. lows: No. 2: 26-39°; No. 4: 24-32°; No. 5: 16-22°; No. 6:
10-15°. As expected, API gravity decreases with the increas-
Gravity ing grade number. The API gravity also changes according to
The density of petroleum oils is often expressed in terms of the fuel types within a given grade. For No.2 fuel, for exam-
API gravity, a scale devised by the American Petroleum ple, the API gravity of straight-run fuel oils range between 36
Institute and National Bureau of Standards (continued as and 39°, while that of thermally, and catalytically cracked oils
National Institute of Standards and Technology). The API would fall in the range 24-28°, and 29-32°, respectively. For
CHAPTER 29: PROPERTIES OF FUELS, PETROLEUM PITCH. PETROLEUM COKE, AND CARBON MATERIALS 759
TABLE 2—Detailed requirements for fuel oils (ASTM D 396).

No. 4 No. 5
Properties No. 1 No. 2 (Light) No. 4 (Light) No. 5 No. 6
Specific Gravity, 60/60°F 0.8499 0.8762 0.8762"
deg API 35 min 30 min
Flash point, °C (°F) min 38 (100) 38 (100) 38 (100) 55 (130) 55 (130) 55 (130) 60 (140)
Pour point, °C (°F) msix 18''(0) - 6 " (20) -6" (20) - 6 " (20)
Kinematic viscosity, mm'^/s
(cSt)''
At38°C(100°F)min 1.4 2.0" 2.0 5.8 >26.4 >65
max 2.2 3.6 5.8 26.4^" 65^ 194^^
At40''C(104''F)min 1.3 1.9 5.5 >24 >58
max 2.1 3.4 24.0' 58^ 168^
At 50°C (100°F) min (42) >92
max (81) 638^^
Saybolt Viscosity
Universal at 38°C (100°F)
min (32.6) (32.6) (45) (>125) (>300) (>900)
max (37.9) (45) (125) (300) (900) (9000)
Furol at 50°C (122°F)
min (23) (>45)
max (40) (300)
Distillation temperature, °C
(°F) 215(420)
10% point max 282'^
90% point min 288 (550) (540)
max 338 (640)
Sulfur content, mass, mcix 0.5 0.5*
Corrosion copper strip, max 3 3
Sulfated ash, % mass, max 0.05 0.10 0.15 0.15
Carbon residue, 10%*; %m, 0.15 0.35
max
Water and sediment, % vol, 0.05 0.05 (0.50)" (0.50)' (1.00)' (1.00)" (2.00)"
max
"It is the intent of these classifications that failure to meet any requirement of a given grade does not automatically place an oil in the next grade unless in fact
it meets all the requirements of the lower grade.
''In countries outside the United States other sulfur limits may apply.
"Lower or higher pour points may be specified whenever required by conditions of storage or use. When pour point less than - 18°C (0°F) is specified, the min-
i m u m viscosity for grade No. 2 shall be L7 cSt (31 SUS) and the m i n i m u m 90% point shall be waived.
'^Viscosity values in parentheses are for information only and not necessarily limiting.
"The amount of water by distillation plus the sediment by extraction shall not exceed the value shown in the table. For Grade No. 6 fuel oil, the amount of sed-
iment by extraction shall not exceed 0.5 weight %, and a deduction in quantity shall be made for all water and sediment in excess of I.O weight %.
^Where low su Ifur fuel oil is required, fuel oil falling in the viscosity range of a lowered numbered grade down to and including No. 4 may be supplied by agree-
ment between purchaser and supplier. The viscosity range of the initial shipment shall be identified and advance notice shall be required when changing from one
viscosity range to another. This notice shall be in sufficient time to permit the user to make the necessary adjustments.
*This limit guarantees a m i n i m u m heating value and also prevents misrepresentation and misapplication of this product as Grade No. 2.
''Where low sulfur fuel is. Grade 6 fuel oil will be classified as low pour -H5°C (60°F) max or high pour (no max). Low pour fuel should be used unless all tanks
and lines are heated.
oils from a single refinery stream, the API gravity can indi- or net (or low) heating values in Btu per gallon. The total
cate w h e t h e r they are straight-run, or cracked oils. For heating value includes the latent heat of evaporation of the
blends, e.g., No. 4 oil, the concentration of different types of water vapor produced during the combustion. For determin-
oils present, would, therefore, determine the API gravity of ing the net heating value, the water from combustion is con-
the blend in the corresponding range. sidered to remain in the gaseous state, and, therefore, the
In general, the API gravity of fuel oils can be qualitatively latent heat of evaporation is not recovered. Although no di-
related to other properties of the oils as shown below [7]: rect reference is made to heating value measurement in the
• The higher the API gravity, the lower the viscosity and car- ASTM classification of fuel oils (there is indirect reference
bon residue. through limiting API gravity. See footnote g in Table 2), heat-
• The higher the API gravity, the lower the volumetric heating value is a n important specification requirement. The
ing value (Btu/gal), and the higher the gravimetric heating heating value, or the heat of combustion of fuel oils, can be
value (Btu/lb). measured by the ASTM D 240. The net heating values of fuel
• The higher the API gravity, the lower the C/H ratio. oil samples can also be measured by the ASTM D 4529, D
3338, or D 4809.
• The higher the API gravity, the higher the rate of combus-
tion, and the shorter the flame length. Depending on the specific gravity and composition of fuel
oils, total heating value ranges typically between 130 000
Heating Value and 160 000 Btu per gallon (36 400-44 800 kJ/liter). The
Heating value is broadly defined as the amount of heat re- net hea-ting value is usually 8400-8500 Btu per gallon
leased by complete combustion of a unit quantity of fuel. Ex- (2350-2380 kJ/liter) lower t h a n the total heating value, de-
perimental measurements can be reported as total (or high). pending on the hydrogen content of the fuel. Figure 1 shows
ture. The kinematic viscosity, expressed in mm^/s (formerly

called centistoke, cSt), is determined as the product of the
.5' 160000 ..... ...-r-:.
5 155000 J^^^/^,'::™ :•
m e a s u r e d flow time a n d the calibration constant of the
" 150000 .:v.;-::=:;.:.;V viscometer.
I 140000
"^^^^feu'
oT 145000 -^sPiRiet^/.f:^***
*îi_ ••••&•
-Total Heating
Value Although the kinematic viscometers are the approved in-
> 135000
•^'-'iftKi^- -Net Heating Value struments, Saybolt viscometers (Universal and Furol) are
^•[^••-T.':--^^^^
o) 130000 •• • ' * ' ' ^ * ^ ; ^ '
also widely used for measuring viscosity. In Saybolt vis-
~ 125000 cometers, the time for the flow of a given volume of liquid
••••; ri^7^:;:\
S 120000 "\r^ ^ î ' ^ I r' f H I". ^ ' i.":—' '1 — r is measured under variable head (as opposed to the con-
^ 0 4 8 1216202428323640 stant head in kinematic viscometers), which decreases as
API Gravity the volume of the oil in the tube decreases. The measured
viscosity is expressed as Saybolt Seconds. The only differ-
FIG. 1—Total and net heating values of fuel oils versus API ence between Universal and Furol viscometers is the larger
gravity. orifice of the Furol tube (3.15 mm) t h a n that of the Univer-
sal (1.77 mm). The Universal is used for testing low-viscos-
ity oils, while the Furol is used for high-viscosity oils to ob-
tain reliable m e a s u r e m e n t s by avoiding the exceedingly
a plot total heating value and net heating value of selected
long, or short, test times depending on the viscosity of oil.
fuel oils as a function of API gravity from the data given in
Most frequently used temperatures for viscosity measure-
reference [8] (1 Btu/gallon = 0.28 kJ/liter). It can be seen
ments are 38°C (100°F) for Saybolt Universal and Kinematic
that the volumetric heating value increases with the de-
viscometers, and 50°C (122°F). Conversion tables can be
creasing API gravity, because of the decreasing hydrogen
used for viscosity conversions between different values [11].
content of the fuels with the decreasing API gravity.
Table 3 gives the Saybolt and kinematic viscosity limits for
In addition to measurement by standard methods and pre- different grades of fuel oils. The grade Nos. 5 and 6 have
diction from the API gravity, there are a number of empirical very broad ranges of viscosity because of the use of many
correlations used to calculate the heating value. Two of the different types of burners that can handle a range of vis-
most commonly used correlations are given below: cosities. In applications, where viscosity needs to be closely
Total Heating Value (Btu/lb) = 14 600C controlled, oils can be purchased on a viscosity basis. Some
suppliers specify their oil as, for example. No. 5-300, indi-
+ 62 000(H-O/8) + 4000S cating No. 5 fuel oil with a viscosity of 300 SSU (Saybolt
where C, H, O, and S are the weight percentages of these ele- Seconds Universal) at 100°F (38°C).
ments in the fuel [8]. The viscosity of fuels depends strongly on temperature; the
Net Heating Value (kJ/kg) = 55 500 - 14 400d - 320S viscosity decreases sharply with the increasing temperature
[11]. This strong temperature dependence is used to control
where d is the density (kg/liter), and S is the sulfur content in the viscosity of residual fuel oils by preheating. When the vis-
wt% [9]. cosity of heavy oils is reduced, pumping becomes easier and
It should be noted that on a weight basis (e.g., Btu/lb, or better atomization is achieved for combustion. Conversely,
kJ/kg), the heating value of a fuel oil decreases with the in- heavy oils become viscous and extremely difficult to handle
creasing density (or decreasing API gravity). However, this at low temperatures. In cold weather applications, the lowest
trend is reversed when reporting the heating value on a vol- operating temperatures must be considered for selecting the
u m e basis (e.g., Btu/gal, or kJ/liter) since the decreasing heat- oil with the adequate viscosity for easy pumping and han-
ing value is more than compensated by the decreasing volume dling. In some applications, the viscosity of heavy fuel oils is
as the density increases. For example, an oil with 14 API grav- controlled by blending with stocks of lower viscosity. Mixing
ity have 290 Btu less per pound (676 kJ/kg) than a 20 API grav- of fuel oils with different chemical characteristics may, how-
ity oil, but one a volume basis the 14 gravity oil will have 3840 ever, cause incompatibility problems leading to deposit and
Btu more per gallon (1075 kJ/liter) than the 20 gravity oil [8]. sludge formation in fuel handling systems [12].
Therefore, oils with a lower API gravity will provide more heat The high viscosity of fuel oil causes the following problems
on a volume basis, but other properties of the fuel oil, such as
[11,13]:
viscosity, pour point, and carbon residue, may be limiting fac-
tors in selecting a given oil, as discussed below. • Difficulty in pumping from storage tank to burner; loss of
p u m p suction
Viscosity
The viscosity of oil measures its resistance to flow [10]. It is
TABLE 3—Summary of ASTM methods for the characterization of
one of the most important properties of especially the resid- petroleum pitch properties.
ual fuel oils that affect handling, heating, pumping, and at-
Property ASTM Designation
omization of heavy residual fuels in combustion. The most
commonly used viscosity term, kinematic viscosity, is deter- Softening point D 3461, D 2319, D 36, D 61, D 3104
Viscosity D5018
mined by measuring the time for a fixed volume of liquid to Solvent Fractionation D 4746, D 2764, D 2318, D 4072, D 4312
flow under gravity through the capillary of a calibrated vis- Coking Value D 4715, D 2416
cometer (ASTM D 445 with specifications given in ASTM D Density D 2320, D 70, D 4892, D 71, D 2962
446). The measurements must be m a d e under a reproducible Ash D2415
driving head and at a closely controlled and known tempera- Sulfur Content D 1266, D 4045, D 2622
CHAPTER 29: PROPERTIES OF FUELS, PETROLEUM PITCH, PETROLEUM COKE, AND CARBON MATERIALS 761
• Insufficient oil flow to the burner causing problems with fuel oils can cause a n u m b e r of operational problems,
starting and erratic combustion including [14],
• Poor atomization causing inefficient combustion and drib- • Plugging of burner tips
bling of oil at the burner nozzle • Erratic and unsteady combustion
The low viscosity of the fuel oil causes, in turn, the follow- • Flame instabilities
ing problems [11,12]: • Erosion of burner tips and mechaniccJ parts.
• Too much oil pumped to the burner causing incomplete The origin of BSW can be traced back to the original
combustion, resulting in smoke, carbonization of burner crude oil, contamination during refinery processes, or ther-
nozzle, and soot formation in the combustion chamber mal degradation a n d oxidation reactions during storage.
• Low heat generation because of the low heating value of Usually heavy oils (No. 5 and No. 6) contain greater
low-viscosity, or high API gravity of the fuel oil amounts of BSW than light oils because of the concentra-
• P u m p slippage, too much oil can slip the cup with rotary tion of BSW of crude oil in the residual fractions due to the
cup burners, resulting in poor atomization. high specific gravity and high viscosity of the residual fuels.
Light oils, such as No. 2 and No. 4, are usually clean, except
Pour Point for some water and small amounts of fine sediment. Table
Pour point represents the temperature at which a fuel oil 1 shows that m a x i m u m BSW is limited to 0.05%vol for oils
stops flowing. This property, measured by ASTM D 97, indi- No. 1 and No. 2, 0.5% vol for No. 4, 1.0% vol for No. 5, and
cates the lowest temperature of the utility of a fuel in flow 2% vol for No. 6.
systems, and it is particularly relevant to waxy heavy oils and Three s t a n d a r d m e t h o d s are used to determine water
heavy oils that require preheating for pumping. Straight-run and bottom sediment either together (ASTM 1796 -by cen-
oils usually have higher p o u r points than cracked oils be- trifugation with added toluene), or separately (ASTM D 95,
cause of the higher concentrations of normal paraffins in Azeotropic distillation for water and ASTM D 473, Extraction
straight-run oils. The usefulness of the pour point test in re- with toluene and weighing the residue). Specific rules apply
lation to residual fuel flow properties is questionable. The to reporting BSW, if water and sediment measurements are
pour point test does not indicate what happens when an oil carried out separately (see footnote in Table 3).
has a considerable head of pressure behind it w h e n it is The occurrence of BSW in fuel oils can be reduced by care-
pumped along a pipeline, or gravitated from a storage tank. ful storage, blending, and transportation practices that re-
Among the tests devised to assess the low-temperature flow duce the formation and/or dispersion of the sediments in the
characteristics of heavy residual fuel oils is ASTM D 3245. fuel oils [14].
ASTM D 3245 is, however, a time-consuming test, and not
suitable for routine control testing, along with its limitations Carbon Residue
in application to very waxy fuels. The term carbon residue is used in several different connota-
tions related to the use of fossil fuels, including carbonaceous
Flash Point particles present in fuel, carbon formed on the burner tips
As fuel oils are heated, they evaporate, and the vapors flash at and furnace walls because of incomplete combustion, and
a certain temperature when ignited by an external flame. carbonaceous residue remaining after pjTolysis of fuels in
This temperature is called the flash point. There are two stan- standard tests. Only the results from standard carbon residue
dard ASTM tests to measure the flash point: ASTM D 92 tests are used in fuel specifications. It is important to distin-
(Cleveland), a n d ASTM D 93 (Pensky-Martens), using an guish between the carbon deposition due to the high carbon
open-cup, and a closed-cup flash tester, respectively. The residue of the fuel oil, and coke or soot formation as a result
closed-cup tester gives lower flash points because of the more of poor combustion [15]. Understanding the difference be-
effective retention of very light vapors that are blown away by tween these two types of deposition helps identify the root
the air flow in the open-cup tester. Therefore, the closed-cup cause of any deposition problem: fuel composition or com-
test is more sensitive in detecting the small amounts of light bustion conditions [16].
vapors in the fuel oil samples. As shown in Table 3, desirable Three standard methods used to determine carbon residue
flash points of fuel oils range from 38°C (Grades N o . l , 2) to are ASTM D 189, Conradson Carbon Residue (CCR), ASTM
60°C (Grade No.6) measured by closed-cup testers. Flash D 524, Ramsbottom Carbon Residue (RCR), and ASTM D
points lower than the desired values may cause fire hazard, 4530, Micro Method. Most specifications are based on CCR,
whereas high flash points can lead to difficulties with start- but correlations exist to convert between CCR and RCR test
ing, especially in a cold furnace. results [ASTM D 189].
Table 3 shows that carbon residue is specified only for light
Distillation fuel oils, No. 1 and No. 2, because small vaporizing-pot and
ASTM D 86 is used to determine the 10% and 90% points of sleeve-t3ê burners used in domestic applications have less
the distillate fuel oils (Grade No. 1 and No. 2) as specified in tolerance for carbon deposition. The carbon tests are con-
Table 3. The distillation characteristics (volatility) of these ducted on 10% bottom residue of the fuel samples remaining
fuels are related to their ignition and combustion properties after distillation.
and the tendency to form solid combustion deposits. The
lower and upper limits to volatility are set to ensure safety Ash
and smooth operation in the use of these fuels. Ash results from the noncombustible organic and inorganic
Water and Sediment (BSW)—The presence of water and species found in fuel oils. Most of the ash can be traced back
sediment, also called bottom sediment and water (BSW), in to the constitution of the crude oil from which the fuel oils
were derived. To a lesser extent, contamination during refin- in the presence of oxygen and moisture to produce sulfurous,
ing and handling may be responsible for the ash content. or sulfuric acid. These acids will cause corrosion of any ex-
Most of the ash-producing materials present in crude oil posed metal surfaces, such as boiler shell and tubes. The
(e.g., water soluble sodium and calcium chlorides, and oil presence of sulfur compounds may also cause problems in
soluble organometallic compounds of nickel and vanadium) various materials applications, such as glass, ceramic, and
tend to concentrate in the heavy products, such as residual metals production [19].
fuel oils. Ash contents of fuel oils can be determined by Total emissions of sulfur oxides from combustion systems
weighing the n o n c o m b u s t i b l e residue after c o m b u s t i o n depend almost entirely on the sulfur content of the fuel with-
using ASTM D 482. out any significant effect of the boiler size, combustor design,
Table 3 shows the permissible ash contents specified for or the fuel grade. Sulfur contents of fuel oils can be reduced
Grades No. 4 (0.05%, 0.10% for light and heavy, respectively), by hydro treatment in petroleum refining [4,5] or by blending
and No.5 (0.15%). No specifications are given for No. 1 and 2 with oils having lower sulfur contents. Flue gas scrubbers are
because ash is seldom found in distillate oils. Also, there is n o used in large installations to remove sulfur from stack gases
ash specification for No. 6 oils (which may contain u p to to comply with SO2 emission limits.
0.2% ash [17]) since the combustion equipment designed for A particular corrosion test, ASTM D 130, Copper Strip
burning heavy residual fuels can handle relatively high ash Corrosion, is used to characterize the corrosive properties
contents. of fuels related mainly to sulfur compounds, such as dis-
Problems encountered with high ash contents depend on solved hydrogen sulfide, mercaptans, active elemental sul-
the application and type of combustion operation, including fur, along with inorganic acids and ammonia. The presence
contamination of products in direct firing applications (e.g., of these compounds in fuels lead to the corrosion of copper
glass and ceramic industry), erosion of p u m p p a r t s and heating lines, cooling coils, and nonferrous metal fittings.
burner tips, and accumulation of ash on boiler tubes. High The copper strip corrosion test measures the extent of dis-
metal contents of heavy oils would also be responsible for coloration of copper strips that came into contact with fuel
producing particulate emissions from combustion with po- samples under specified conditions. Reference strips used to
tentially significant toxicity [18]. measure the extent of discoloration are rated from No. 1
The removal of ash from fuel oils is not practical and very (light-orange) to No. 4 (jet black). The No. 1 and No. 2
costly because most ash-forming compounds are soluble in grades have a m a x i m u m Corrosion Strip specification of
the oil. Problems with high ash contents are usually ad- No. 3, dark tarnish.
dressed by blending with low ash oils and/or by reducing the
impact of ash in combustion operations with fuel additives Instability and Incompatibility
and combustion system treatments [17]. The instability of residual fuel oils refers to the tendency of
a fuel to produce deposit by itself, while incompatibility is
Sulfur Content the tendency of a fuel to produce a deposit when blended
Sulfur is one of the most troublesome elements found in fuel with other fuels [20]. Two oils that are each stable as single
oils. Sulfur is p r e s e n t in a variety of complex chemical fuels may become incompatible when they are mixed. Ma-
compounds in crude oils. Since the molecular chemistry of jor incompatibility problems occur when an oil with an as-
sulfur compounds is extremely complex, sulfur specifications phaltene content of greater t h a n 3 - 5 % is blended with
depend on the measurement of the total sulfur content of paraffinic oils. The incompatibility results in the formation
fuels. Because of the high-boiling points of sulfur-containing of tar-like precipitates that cause problems in handling
compounds, sulfur tends to concentrate in heavy residual and combustion systems. ASTM D 4740 can be used to pre-
fractions obtained from petroleum refining. The sulfur dict the compatibility between a residual fuel oil and a
content of fuel oils generally increases with the increasing specific distillate fuel oils, such as a No. 1 or No. 2 oil. This
grade number. The sulfur range in each grade shows large test is also used for predicting the compatibility of residual
variations because of differences in sulfur contents of crude fuels, although it may not be reliable for residual oil mix-
oils, refining processes, and blending. There are several tures. The asphaltene content of residual oil is believed to
ASTM tests that are used to determine the sulfur contents of affect its stability and compatibility [3,12]. ASTM D 3279
fuel oils, inclu-ding ASTM D 1266, Lamp Method (for No. 1 can be used to determine the asphaltene content of residual
only), ASTM D 1552, High-Temperature Combustion, ASTM fuel oils.
D 129, Oxygen Bomb, and ASTM D 4294, Non-Dispersive
X-ray Fluorescence.
Conclusions
The sulfur limits in fuel oil specifications shown in Table 3
designate the m a x i m u m total sulfur contents for No. 1 and A standard classification of fuel oils according to selected
No. 2 oils as 0.5%. No sulfur specification is listed for grades specifications facilitates the selection of the right fuel oil for
No. 4, 5, and 6. For many applications, however, consumers wide ranging applications in different combustion systems
specify the maximum allowable sulfur limit to comply with that show significant variations in size, combustor design,
the environmental regulations (e.g., Clean Air Act a n d and process needs. A large number of ASTM methods exist to
Amendments in the U.S.) or to limit damage to materials in characterize many properties of fuel oils that are of interest
combustion systems. for a particular application. Understanding the significance
Problems associated with high sulfur contents in fuels are of these tests and careful interpretation of the test results will
related principally to combustion products, namely sulfur help troubleshoot m a n y performance problems in fuel oil
dioxide (SO2) and sulfur trioxide (SO3), which further react handling and combustion systems.
PETROLEUM PITCH The applications of different p e t r o l e u m pitches are

governed by their properties, d e p e n d i n g largely on their
Petroleum pitch has become an important material for a chemical composition. ASTM D 2569 is used to determine
n u m b e r of industrial applications, in particular, for manu- the distillate contents of pitches. A soft pitch, which appears
facturing high-performance c a r b o n fibers and carbon- semi-viscous at ambient temperatures due to its low glass
carbon composites. This section provides an overview of transition temperature (see Softening Point), will produce a
p r o d u c t i o n processes, applications, and properties of relatively large amount of distillate even at low temperatures
petroleum pitch. and weak vacuum (if applied). On the other hand, hard pitch
will yield little distillates even at temperatures up to 360°C.
Accordingly, industrial distillation of pitches is frequently
Production Processes and Applications used to produce carbon-precursors with high softening point
Petroleum pitch is a term used for certain petroleum residues and coking yields [27]. An alternative approach utilizes air-
due to their resemblance to other pitch materials, such as blowing to alter the chemical composition of the pitches to
coal tar pitch, that are thick, dark colored bituminous sub- meet the required specifications [23].
stances obtained from destructive distillation processes. Generally, petroleum pitch is used in the production of pre-
Generally, petroleum pitch is the nonvolatile product ob- m i u m petroleum coke or as an impregnation pitch in the
tained from thermal or catalytic cracking of heavy petroleum manufacture of carbon artifacts for the aluminum and steel
residua [4,21]. It may also be defined as the high boiling industry [28]. The high carbon content and low mineral mat-
point fraction (420-520°C) obtained by vacuum distillation ter content of petroleum pitch makes it an excellent precur-
(0.5-1.0 m m Hg) of catalytic cracking bottoms [22], or as sol- sor for the production of high performance carbon fibers and
vent deasphalted bottoms [23]. Due to its resemblance to coal carbon-carbon composites (see Carbon Fibers from Petroleum
tar pitch, the ASTM methods that are summarized in Table 3 Pitch). Molded in sheets, carbon fibers have higher strength
are often used to test both materials. However, petroleum than steel (227 and 200 GPa, respectively) but only 1/5 of the
and coal tar pitches are substantially different in origin, density, 1720 a n d 7830 kg m~^, respectively [29]. These
structure, and behavior, and, therefore, a ccireful interpreta- impressive properties result from the formation of a discotic
tion of the test results is necessary. liquid crystal phase, carbonaceous mesophase that produces
CoaJ tar pitch is obtained from the distillation of volatile high tensile strength and modulus. Carbonaceous mesophase
by-products, or tar, from coke ovens during the manufacture is formed by alignment of disk-like molecules (see Formation
of metallurgical coke from coal. The differences in the origin of Coke Microtexture in Coking Processes for a description
and processes that lead to the production of petroleum and of carbonaceous mesophase). The a m o u n t of mesophase in
coal tar pitch are apparent in their chemical composition and a p e t r o l e u m pitch can be established following ASTM D
respective industrial applications [24,25]. For instance, the 4616. Although most of the terminology of this method con-
carbon content of petroleum pitch is around 85-90%, which cerns coal tar pitches, the central concept about isotropic
is somewhat lower than that of coal tar pitch (94-96%). This is (non-mesophase) and anisotropic (mesophase) is valid for
linked to the higher hydrogen content of 4-6% for petroleum petroleum pitches. The influence of primary quinoline insol-
pitches, versus 2 - 3 % for coal tar pitches. Hence, petroleum ubles, described in detail in Solvent Fractionation, is minimaJ
pitches contain a relatively high proportion of aliphatic car- or nonexistent in petroleum pitches. Hence, mesophase is
bons compared to coal tar pitches. Both petroleum and coal both readily developed and detected in petroleum pitches,
tar pitches are predominantly aromatic, with the majority of with clear identification of mesophase spheres or anisotropic
alkyl groups being methyl. However, while a tjîcal coal tar texture domains. The a m o u n t of mesophase, as found
pitch has an aromaticity of 98-99%, petroleum pitches have through ASTM D 4616, is generally a function of pitch con-
around 10-20% aliphatic carbon. Coal tar pitches contain rel- densation, heat-treatment temperature, and time. Recently,
atively more condensed aromatic ring structures with a an in-situ ^H NMR technique has been developed to follow
bridgehead aromatic carbon content (i.e., aromatic carbon the mesophase development directly during heat treatment
only bound to other aromatic carbons) of 0.45-0.50. There- [30]. High performance carbon products from mesophase
fore, the volatile compounds in coal tar pitches, as detected by pitches have a wide range of applications, including light-
GC-MS, are mainly three to six aromatic ring compounds, weight components for vehicles, boats, planes and the space
such as phenanthrene, fluoranthene, pyrene, benzo[a]pyrene, industry; high strength and wear parts in brakes and engine
benzo[b]fluroanthene, and a n t h a n t h r e n e , while the non- pistons, and medical artifacts (e.g., in artificial heart, bone
volatile compounds have a much higher condensed structure. plates and ligaments) due to their bio-compatibility with
In contrast, petroleum pitches have a rather open structure, blood, soft tissue, and bones [31,32].
with a bridgehead aromatic carbon content around 0.35-0.40
[26]. The volatile compounds are two-to four-ring compounds
that are heavily alkylated. The non-volatile compounds are Properties of Petroleum Pitch
non-defined entities of larger a r o m a t i c ring structures
The determination of various properties of petroleum pitch is
substituted with long-chain alkyl groups and possibly some
crucial for the establishment of pitch consistency, which can
saturated rings. These differences in structure and com-
be utilized as a strong marketing tool. Pitch buyers often de-
position explain the differences in softening points and
m a n d that the properties described in the Softening Point
viscosity behavior, solubility, density, and coking yields from
through Ash sections meet their specifications, to assure that
the coal tar and petroleum pitches, as described in Properties
the product they are buying fits their requirements and pro-
of Petroleum Pitch.
cess line. Currently, there are two m a i n practices used for
pitch transportation. The most frequent practice involves TABLE 4—Comparison of the five standard test methods used for
transporting pitch as a hquid around 180°C, but some users determining softening point in pitches.
prefer to receive the pitch as a soHd (often referred to as pen- Method Description
cil pitch from its extrusion into small rods). Due to the D 3461 Softening point of asphaltene and pitch (Mettler cup-
various ways of handling, some localized variation in pitch and-ball method)—The pitch is loaded in a small
composition can occur. Hence, an important tool for estab- metal cup with a bottom orifice and a ball is placed
on top of the solid pitch. The assembly is placed in a
lishing sample uniformity is the use of ASTM D 4296, Stan- furnace and a light beam is used to detect the
d a r d Practice for Sampling Pitch. The strength of this temperature when the ball is penetrating the pitch
method lies in its compatibility with both solid and liquid (the softening point).
pitch. A proper sampling lays the foundation for valuable D 36 Softening point of bitumen (ring-and-bsdl apparatus)—
data collection from the following standard test methods. The pitch is loaded in a small metal ring and a ball
placed on top of the pitch. The assembly is placed in
a bath and the temperature when the ball is
Softening Point penetrating the pitch is manually detected (the
softening point).
Petroleum pitches are mixtures of condensed aromatic com- D 2319 Softening point of pitch (cube-in-air method): Molded
pounds. As a result, petroleum pitches are eutectic, i.e., cubes of pitch with center holes are placed on hooks
soften at a lower temperature than the individual melting and suspended in an oven. The temperature of the
points of the different compounds that make u p the pitch. hooks when the pitch is flowing is manually detected
At ambient temperatures, the pitch has an isotropic struc- (the softening point).
D 61 Softening point of pitch (cube-in-water method):
ture and is generally characterized as a glassy solid (hard- Molded cubes of pitch with center holes are placed
pitch). When the pitch is heated in an inert atmosphere, it on hooks and suspended in water. The temperature
has no defined melting point, but will pass through a glass of the hooks when the pitch is flowing is manually
transition region before it becomes an isotropic liquid. detected (the softening point).
While a pure compound, e.g., anthracene, goes from a solid D3104 Softening point of pitches (Mettler softening point
method): The pitch is loaded in a small metal cup
to liquid at 217.5°C, a mixture of similar aromatic com- with a bottom orifice. The assembly is placed in a
pounds and their alkylated derivatives will exhibit a wide furnace and a light beam is used to detect the
temperature interval (4Tg can range from 10' to over 10^°C) temperature when the pitch is flowing through the
from the end of the solid phase to a fully liquid state. The orifice (the softening point).
transition from a glassy solid to a viscous substance gives
rise to a physico-chemical characteristic CcJled the glass
transition temperature, Tg [33]. Although there is no ASTM
method yet developed, both the Tg and the temperature in- Viscosity
terval, ZlTg can be determined by different methods [34] The determination of changes in viscosity and other rheolog-
such as ' H N M R , electron-nuclear double resonance (EN- ical properties during and after the glass transition region is
DOR) or differential scanning calorimetry (DSC). The en- crucial for applications of pitch as a binder for electrodes and
thalpy, /IH, and activation energy, Ea, for pitches can then road aggregate. ASTM D 5018, Standard Test Method for
be derived from the above techniques, ft has been shown Shear Viscosity of Coal-Tar and Petroleum Pitches, is a good
that the Ea can be considered to be proportional to the tool to follow the rheological properties of pitches at temper-
mean molecular size in pitch, and can give an estimate of atures of 40-100°C over its softening point, since it requires a
the degree of condensation [35]. relatively simple setup. The setup consists of a hotplate, a
During the transition from a glass to a liquid, the viscosity temperature controller, a thermometer, and a rotational vis-
of the pitch changes drastically (see Viscosity). However, it is cometer. The pitch is melted into a cup on the hotplate where
relatively tedious and labor intensive to determine the vis- the rotor from the viscometer is inserted, and at different
cosity behavior for every single pitch. Therefore, several stan- temperatures the viscosity is measured. The method is lim-
dard test methods, ASTM D 3461, D 36, D 2319, D 61, and D ited to 230°C and 15 000 cps (15 Pa s).
3104, have been developed to establish when a pitch reaches Viscosity, 17, is defined as the ratio of the shear stress, T, to
a viscosity of about 10^ Pa s, generally referred to as the the rate of change of shear strain, ySR, at constant tempera-
softening point of the pitch [36]. Table 4 lists the differences ture and pressure, TJ = r/ySR [37]. When the viscosity of a
between the five standard test methods given by ASTM. D system is only a function of temperature and pressure, and
3104, Mettler Softening Point Method or D 61, Ring and Ball independent of the shear rate at constant temperature and
Softening Point, are the most commonly used. D 3104, Met- pressure, the fluid can be classified as Newtonian. For non-
tler Softening Point Method, provides fast and accurate de- Newtonian systems, such as polymers and most liquid crys-
termination of the softening point but requires the purchase tals, the viscosity is dependent on the shear rate as well [34].
of an instrument. D 61, Ring and Ball Softening Point, is fast Isotropic pitches before thermal decomposition are mainly
and inexpensive, and, therefore, it is also frequently used. Newtonian [38]. However, non-Newtonian flow, such as
The softening points can be given both in °C or °F, and some- Bingham behavior, has been detected where there is no flow
times they give rise to pitch nomenclature, where Ashland until the shear stress exceeds a critical value called the yield
petroleum pitches A-170 and A-240 have softening points of stress [39]. The variations in viscosity with temperature for
170 a n d 240°F, respectively. Furthermore, it has been re- the petroleum pitch Ashland A-240 is compared to a coal tar
ported that pitches having similar softening point can have pitch and its solvent fractions (see Solvent Fractionation in
different Tg, which can be associated to differences in viscos- Fig. 2 [40]. With increasing temperature, there is a rapid de-
ity as described below. crease in viscosity during softening of the pitch. In the tem-
FIG. 2—Changes in viscosity with temperature for Ashland A-240 petroleum

pitch compared with a coal tar pitch, its toluene soluble (TS) and insoluble (Tl)
fraction together with various TS:TI mixtures [40]. Reprinted with permission
from Elsevier Science.
TABLE 5—Nomenclature and solvents used historically in the petroleum and coal tar pitch industries.
Petroleum Pitch Coal Tar Pitch
Carboids Insoluble in CS2 a-resin Insoluble in quinoline (pyridine)
Carbenes Insoluble in CCI4, but /3-resin Insoluble in toluene (benzene,
soluble in CS2 dimethylformamide), but
soluble in quinoline
Asphaltenes Insoluble in n-pentane, y-resin Soluble in toluene
but soluble in CCI4
or CeHft
Resinoid Insoluble in n-hexane (petroleum
ether), but soluble in toluene
Crystalloid Soluble in n-hexane
perature region prior to the pitch becoming a hquid, there is petroleum industry used CS2, CCI4, CsHe, and n-pentane,
a tail off in the viscosity reading, e.g., from 150-2008C for A- while the coal tar pitch producers used quinoline or pjridine,
240 petroleum pitch. ASTM D 5018 deals with the change in benzene or toluene, and petroleum ether or n-hexane. Table
viscosity in this region. From the rheological measurements, 5 lists the nomenclature associated with each solvent for the
the suitability of a pitch for certain applications can be es- two industries.
tablished, e.g., as a binder or for impregnation purposes. In The standard test methods developed by ASTM Eire largely
Fig. 2, the increase in the viscosity after 4508C is due to based on the nomenclature and solvent fractionation scheme
t h e r m a l induced chemical reaction in the pitch, such as originally developed for cocJ tar pitch that has become the
coking (Coking Value), or the development of mesophase common terminology in pitch fractionation [43]. The a-resin,
(further explained in F o r m a t i o n of Coke Microtexture in or QI (quinoline-insoluble) content, is determined using ei-
Coking Processes). ther ASTM D 4746 or D 2318. Table 6 compares the two
In addition, rheology studies give information about elastic methods for determining the QI content. Generally,
properties important for the thermo-forming process of fibers petroleum pitches contain very little or n o QI unless they
and composite impregnation [41]. An example of the effects have been heat-treated (see below). The 7-resin, or TS
of the elastic properties is the die-swell during the extrusion (toluene-soluble), content can be established using ASTM D
process in fiber spinning, which often is undesirable [42]. 4072, D 4312, or D 2764. Table 7 compares the three methods
for obtaining the TS content. From the two previous mea-
Solvent Fractionation surements the ;8-resin, or TI - QS (toluene-insoluble and
A drawback in pitch characterization is that the nomencla- quinoline-soluble), can be calculated by difference. The dif-
ture used for solvent fractionation of petroleum pitch and ferent resin fractions above consist of c o m p o u n d s with
coal tar pitch has been different in the past [36]. The different molecular masses and heteroatom contents. A sim-
TABLE 6—Comparison of the two ASTM methods for determining TABLE 8—Pitch apphcations depending on QI content [43].
the QI content in pitches.
Application '-Resin (QI) content of pitcli, %
Method Description Binder pitch 9-18
D 4746 Determination of quinoline insolubles (QI) in tar and Impregnating pitch 2-5
pitch by pressure fihration; The pitch is dissolved in Needle coke manufacture <1
quinoHne at 75°C and fihered through a porcelain (highly anisotropic)
filtration crucible with a medium-porosity bottom at
a pressure in the range of 10-30 psig using nitrogen.
The sample is washed in hot quinoline until clear
followed by acetone and dried. The portion of the
pitch remaining in the crucible is defined as the QI purities. The primary fraction consists of material that par-
fraction. tially retards coalescence during carbonization of pitch. The
D 2318 Quinoline-insoluble (QI) content of tar smd pitch; The secondary fraction is in itself able to coalesce and is therefore
pitch is dissolved in quinoline at 75°C and digested referred to as the mesophase QI. The impurities consist of
for 20 min. The solution is filtered through a dirt and metal particles, and in the case of coal tar pitch,
porcelain filtration crucible with a fine-porosity (7 c a n y over coke from the by-product furnace. Both the pri-
yum) bottom using a suction filter apparatus. The
sample is washed in hot quinoline until clear, mary and the secondary QI consist of high molecular mass
followed by toluene, then acetone and dried. The species as reflected in low atomic H/C ratios (tjrpically 0.25
portion of the pitch remaining in the crucible is and 0.35, respectively). The effect of the QI on pitch car-
defined as the QI fraction. bonization is heavily dependent on the size and the distribu-
tion of primary and secondary QI in the a-resin.
Petroleum pitches are generally free of primary QI. On the
TABLE 7—Comparison of the three ASTM methods used for other hand, the j3-resin can be a substantial component of the
determining the TS content in pitches. pitches produced from petroleum (ranging from 0-80%),
Method Description while coal tar pitches for binder purposes contain around
D 4072 Toluene-insoluble (TI) content of tar and pitch: The 10-20% ;S-resin. Even though the H/C ratio of around 0.40 of
pitch is dissolved in toluene at 95°C for 25 min and the 13-resin fraction is close to that of the secondary QI, the
filtered through an extraction thimble using a first will undoubtedly have a lower molecular mass since
gravimetric filtration tube. The extraction thimble is thermal treatment of the /3-resin could transform it partially
transferred to an extraction apparatus where it is
further extracted for 18 h using a toluene reflux rate into secondary QI. This suggests that the structures of sec-
of 1 to 2 drops/s. The extraction thimble is dried at ondary QI and /3-resin are relatively similar and only differ by
105°C for 30 min and the portion of the pitch some degree of condensation [26]. The y-resin, i.e., the
remaining in the thimble is defined as the TI fraction. toluene-soluble fraction, has the highest H/C ratio and, due to
D 4312 Toluene-insoluble (TI) content of tar and pitch (short its high solubility, it can be readily investigated by chro-
method): The pitch is dissolved in toluene at 95°C for matographic a n d other analytical techniques. Such tech-
25 min and filtered through an extraction thimble niques include high-pressure liquid chromatography (HPLC)
using a gravimetric filtration tube. The extraction
thimble is transferred to an extraction apparatus where different aromatic compounds can be identified by
where it is further extracted for 3 h using a toluene their UV spectra following a separation by elution through a
reflux rate of 120-150 drops/min. The extraction packed column with different solvents, gel permeation
thimble is dried at 110°C for 30 min and the portion chromatography (GPC) to identify the molecular mass distri-
of the pitch remaining in the thimble is defined as the butions, and nuclear magnetic resonance (NMR) for the de-
TI fraction.
termination of the average hydrogen and carbon skeletal
D 2764 Dimethylformamide-insoluble (DMF-I) content of tar parameters [26,27].
and pitch: The pitch is dissolved in dimethyl-
formamide at 95-100°C and digested for 30 min. The The influence of primary QI on pitch carbonization has
solution is filtered through a porcelain filtration been the subject of intensive research. Primary QI has some-
crucible with a fine-porosity (7 /xm) bottom using a
suction filter apparatus. The sample is washed in hot times been referred to as "carbon black-like" due to its smeJl
dimethylformamide until clear followed by acetone particle size. However, there are several differences between
and dried at 105-110°C. The portion of the pitch the two forms. First of all, primary QI can reach a particle
remaining in the crucible is defined as the DMF-I size of about 1 /xm and secondary QI much higher, while car-
fraction (mainly used as a rapid TI determination). bon black particles have an average size of 20-30 n m [44].
Scanning electron microscopy (SEM) studies have shown
that primary QI particles are generally spherical, reaching an
plified comparison between the three fractions could be that average particle size of 0.1-1 fim. Figure 3 illustrates the par-
the y-resin (TS) is the lowest molecular weight fraction, the ticle size distribution of (a) typical primary QI of a coal tar
;8-resin is an intermediate, while the a-resin (QI) is very high pitch and compares those to (b) the particle size of secondary
molecular weight material. These differences result in the QI particle from a heat-treated petroleum pitch. The differ-
TS having high H/C atomic ratio and low softening point, ences are clearly observed in Positions A, B, and C in Fig. 3
while the QI has low H/C atomic ratio and generally does (a) and Position N in (b). The coal tar pitch has a range of par-
not soften. ticle sizes between 0.1-1 /xm in diameter, while the
The a-resin (QI) is a primary specification of pitches in the petroleum pitch contains agglomerated secondary QI parti-
carbon industry, and Table 8 summarizes the desired content cles in the range of 2-10 /xm in diameter. Secondly, carbon
for some applications. A further sub-division of the a-resins black particles have the ability to form chains, where hun-
can be made into primary, secondary QI, and extraneous im- dreds of units are aggregated together, with some degree of
an ordered microstructure and smooth particle surfaces. In 1 iMui, and an attempt has been made to quantify the sec-
contrast, for primary QI, high-resolution transmission elec- ondary QI content by the difference in particle size. However,
t r o n microscopy (HRTEM) studies have described the secondary QI particles are frequently coating the infusible
microstructure to be generally disordered, without agglom- particles of primary QI, which makes this technique inaccu-
eration of the particulates [45]. Figure 4 shows HRTEM mi- rate [45].
crographs c o m p a r i n g the m i c r o s t r u c t u r e of (a) a c a r b o n
black, and (b) primary QI particle from a coal tar pitch. The Coking Value
c a r b o n black has highly ordered layer planes that form During thermal treatment of petroleum pitch in an inert or
concentric spheres (Fig. 4a), while the QI shows a generally oxygen deficient atmosphere, volatile matter is released as a
disordered microstructure (Fig. 4b). However, it should be result of distillation of smaller constituents and the thermal
mentioned that the term QI is only useful as a guide to decomposition of the pitch [48]. The weight loss as a function
particulate matter in pitch, since isotropic matter that is in- of temperature is normally measured by thermogravimetric
soluble in quinoline can be soluble in the pitch [46]. This has analysis (TGA). In general, there is no or little loss before
been shown through heating QI where some of the material 200-3 00°C followed by a rapid release, which goes through a
becomes fusible. As mentioned earlier, secondary QI is less m a x i m u m weight loss rate at a fixed temperature, Tmax. This
condensed with higher H/C ratios than the primary fraction Tmax is found by taking the derivative of the TGA slope
[47]. Secondary QI in binder pitch is unwanted due to its (DTG). The rate of weight loss decreases after Tmax, reaching
fusibility, which makes the pitch more viscous than that of a m i n i m u m at 500-600°C. The standard test methods of
pitches solely containing primary QI. For a potential binder ASTM do not consider the weight loss profiles of pitches, but
pitch, it is therefore important to estimate the secondary rather the remaining carbon content, or coke, after heating to
QI content. Secondary QI particles are in general larger than temperatures well over 500°C, which is a general coking
temperature of pitch (Fig. 2). After the pitch has formed coke,
the weight loss is minimal. Hence, the standard test method
ASTM D 4715, or "Alcan" coking value, requires 2 h heat-treat-
ment at 550°C, while the "Modified Conradson" coking value,
ASTM D 2416, is established after only 30 min at 900°C.
The thermal weight loss, as determined by TGA, for a coal
tar pitch is shown in Fig. 5 and the weight loss curve for a
petroleum pitch is similar. The loss is initiated around 200°C,
with the highest loss rate between 300-400°C, then levels out
at 500-550°C, and decreases very slowly at higher tempera-
tures. Hence, the "Alcan" coking value (D 4715) must be es-
tablished using sufficient time for the coke to form—2 h
holding time at 550°C. Increasing the temperature to 900°C,
(a) (b) as for the "Modified Conradson" (D 2416), shortens the cok-
ing time, but there is also some loss of gaseous products that
FIG. 3—SEM micrographs comparing the particle size distri- does not occur during D 4715. Therefore, the "Alcan" coking
bution of (a) typical primary QI of a coal tar pitch and (b) the
value (D 4715) is generally 2 wt% higher than the "Modified
particle size of secondary QI particle from a petroleum pitch.
Position A, B and C: primary QI spheres ~ 0.1 /xm in dia., ag- Conradson" coking value (D 2416). For comparison with the
glomerated, and ~1 fim in dia., respectively. Position N: Ag- whole pitch, the weight-loss profiles for its three solvent frac-
glomerated secondary QI particles. Reprinted with permission tions, TS (y-resin), beta-resin ()3-resin), a n d QI (a-resin),
from Elsevier Science. weighed on their extraction yield are also stack-plotted in
(a) (b)
FIG. 4—HRTEIVI micrographs comparing the microstructure of (a) a carbon black,
and (b) primary QI particle from a coal tar pitch. Reprinted with permission from El-
sevier Science.
100%- F o r Sulfur I n Petroleum P r o d u c t s (High-Temperature

•1VI1..1 > TT'
;^ ^'^^ Method, can be used for petroleum pitches. The petroleum
1^
T3
NX^ n pitch is combusted either in an induction or resistance type
1
H
75%-
^^; X ^ • ^ ^
s Ivl.i-l -1II1
furnace. The sulfur is released as SO2 that is retained in a KIO3
solution and quantified by titration. ASTM D 2492, Standard
Test Method for Forms of Sulfur in Coal, is often specified for
1 50%-
' --', coal tar pitches, where sulfate sulfur is extracted from the
a pitch using dilute HCl and pyritic sulfur is calculated as a sto-
25%- ichiometric c o m b i n a t i o n with iron. However, as for
'^ petroleum pitch, a Leco sulfur analyzer is generally used.
0%- ' 1
.r'J
1
}*j*j
r
\}*J
1
o'ju
1
"Jo I'OO
Ash
Temperature / °C Petroleum pitches have generally low ash contents below
0.1%. The standard test method for ash in pitch is described
FIG. 5—Comparison of TGA traces for a coal tar pitch and its in ASTM D 2415 and applies to both hard and soft petroleum
TS, beta-resin and Ql fractions. pitches. The m a i n elements in ash from petroleum pitch are
iron, nickel, and vanadium [23], and these heavy metals are
Fig. 5. There is a good agreement between the whole pitch known to m a r the carbon products used in the aluminum and
and the added loss profile from its solvent fractions. From the steel industries [49].
individual solvent fractions, it is clear that the QI loses very
little weight, which is also the case for the )3-resin. The main
weight loss occurs in the TS fraction, which indicates that the Conclusions
weight loss is particularly dependent on the y-resin content. The ASTM standard methods for pitch chetracterization Eire
Hence, a particular concern for the utilization of petroleum i m p o r t a n t tools for the establishment of petroleum pitch
pitch as a binder for carbon artifacts is its low content of properties such as softening point a n d viscosity behavior, sol-
insolubles, in particuljir QI and to some extent also )3-resin. ubility, density and coking yield, and ash and sulfur levels, as
described in the above sections. The monitoring of pitch
Density quality through standardized methods is crucial for the fu-
The density of pitch is a property closely watched by con- ture of the carbon industry, due to its dependence on high
sumers, since low pitch density is generally related to low performance pitches for purposes such as binders and for im-
coking value, increased costs, and reduced quality of the pregnation of carbon materials, and precursors for carbon
resultcint carbon products. The ASTM standard methods dif- fibers and composites. Although coal tar pitch is presently
ferentiate between specific gravity (density) and relative dominating the market, a decline in its availability is fore-
density, however, specific gravity is usually reported for casted, especially in the U.S., due to the reduced numbers of
pitches. Due to the different appearance of pitch, three stan- by-product coke ovens. Hence, petroleum pitch cam gain ac-
dard methods for specific gravity have been developed by cess to these markets through innovative manufacturing pro-
ASTM: D 2320 deals with sohd fragmented hard pitch, D 70 cesses for tailored properties. The ASTM standard methods
concerns soft pitch, and D 4892 applies to pulverized pitch. will be important reference points for the development of
All three methods involve the use of pycnometer. Since the high performance petroleum pitches.
pitch density is dependent on temperature, ASTM has devel-
oped a standard test method, D 2962, for calculating a vol-
ume-temperature correction. However, this test method is PETROLEUJVI COKE
only developed for coal tar pitch and there is no equivalent
m e t h o d for p e t r o l e u m pitch. The d e p e n d e n c e of specific Petroleum coke is a generic term used to describe a variety of
gravity upon pressure is normally ignored. The standard test carbonaceous solid products intentionally produced by se-
method for relative density, D 71, utilizes water displace- vere thermal cracking of p e t r o l e u m heavy fractions. The
ment, a n d is therefore a quick method. However, relative composition, microstructure, and properties of petroleum
density of pitch is rarely reported. cokes depends on the nature of the feedstock and the coking
Petroleum pitches have densities spanning from 1.10-1.30 process. Specific chemical a n d physical properties a n d mi-
gcm^^ cind are somewhat lower than that of coal tar pitches, crotextural characteristics of petroleum cokes are critically
which have specific gravity in the range 1.30-1.40 gcm~^. important for their industrial/commercial uses. Petroleum
Hence, increasing the density of petroleum pitches is a key is- coke production processes, the composition and properties
sue in their competition with coal tcir pitches. of coker feedstocks, and the formation of coke microtexture
in coking processes are described a n d discussed in this sec-
Sulfur Content tion along with classification, properties, and uses of
The sulfur content in some oil crudes may be very high (3-5 petroleum cokes.
wt%) and correspondingly can result in high sulfur levels in
the resultant petroleum pitch, where levels u p to 4 wt% have
Petroleum Coke Production Processes
been reported [23]. Since there is no specific ASTM method
for sulfur determination in pitch, it is typical to use a Leco sul- Low-temperature carbonization (coking) at temperatures be-
fur analyzer. However, ASTM D 1552, Standard Test Method low 500°C converts high-boiling petroleum fractions or
residua into mixtures of gases, distillate liquids (naphtha and OPTICAL

APPEARANSi TEXTURE
gas oils), and carbonaceous solids (petroleum cokes). In the
general petroleum refining scheme, coking is a severe thermal
cracking process that is used primarily for producing distil-
late liquids from heavy ends, such as vacuum distillation
residua (VDR). The resulting petroleum coke is considered a
by-product that may have some commercial value depending
on the nature of the coke. More specialized coking processes
also exist to produce a high-value premium petroleum coke as
the primary product from more aromatic feedstcoks, such as < - t
Fluid Catalytic Cracking Unit Decant Oil (FCCU DO). Two

NEEDLE COKE OPTICAL MICROGRAPH
principal coking processes used in petroleum refining are - OF NEEDLE COKE
Delayed Coking and Fluid Coking [50]. Figure 6 shows simple

flow diagrams of Delayed Coking and Fluid Coking Processes.
Delayed Coking is the most commonly used coking process
in petroleum refining. It is a semi-continuous process. The
coker feed is preheated in externally fired tube furnaces and
continuously charged into a large insulated d r u m where coke
formation takes place at approximately 475°C as the drum is
filled [51]. The pressure in the coke d r u m varies in the range
40-50 psig (0.35-0.45 Mpa). Gases and distillate liquid prod-
ucts from severe thermal cracking reactions are collected SPONGE COKE OPTICAL MICROGRAPH
OF SPONGE COKE
from the top of the d r u m . Once the coke d r u m is filled, the
feed is switched to another d r u m for continuous charging.
Upon completion of the coking cycle, the coke product is
mechanically removed from the d r u m using high-pressure
water jets to cut the coke. Thus, the production of coke is
intermittent, although the feed is charged continuously. The
resulting delayed coke is usually regarded as a low-value by-
product, generally used as fuel coke. Higher quality delayed
cokes with lower sulfur and metal contents, called sponge
cokes because of their porous nature (see Fig. 7), are further SHOT COKE OPTICAL MICROGRAPH
OF SHOT COKE
FIG. 7—Appearance and optical textures of

needle, sponge, and shot cokes.
(TvTSs /"^^"N
processed to manufacture carbon anodes used mainly for
aluminum production [52]. An occasioned and usually unde-
NAPHTHA
sired co-product from delayed coking of VDR is called shot
coke because of its morphology that resembles the clusters of
buckshot [53] (see Fig. 7). Shot coke is extremely hard to
grind; it does not have any significant commercial use except
for some small-scale niche applications, such as the produc-
tion of TiOa [52]. An important property of fuel coke is its
grindability, which can be measured by ASTM D 5003, Hard-
groveGrindability Index (HGI) of Petroleum Coke. Fuel grade
cokes should have an HGI of greater than 80.
Slurry oils (or decant oils), highly aromatic bottoms prod-
uct from Fluid Catalytic Cracking Unit (FCCU DO), are also
used as feedstocks for delayed coking. Coking takes place
u n d e r slightly different conditions, e.g., higher pressures
(60-80 psig) and lower temperatures (450°C), to produce a
premium petroleum coke, needle coke. The term needle coke
derives from the splintery appearance of this coke because
of its highly anisotropic microtexture (see Fig. 7). After
SEPARATOR calcination, needle coke is used as a filler for manufacturing
graphite electrodes for electric-arc furnaces to mEmufacture
iron and steel [54]. In addition to FCCU DO, thennal tars
from naphtha and gas oil cracking are also used as feedstocks
for needle coke production. Compared to decant oils, how-
FIG. 6—Schematic flow diagrams for Delayed ever, thermcJ tars usually produce lower quality needle cokes
Coking and Fluid Coking. under comparable coking conditions.
Very different in design and operation from Delayed Cok- anisotropic solid crystals, is similar to that of the nematic
ing, Fluid Coking is another commercial coking process com- (thread-like) liquid crystals [55]. The basic molecular units of
monly used in petroleum refining to convert VDR and other mesophase are, however, disc-shaped alkyl substituted poly-
heavy fractions into distillate liquids, gases, and fluid coke. In aromatic hydrocarbons and range widely in size [56].
contrast to the semi-continuous nature of Delayed Coking, Polarized-light microscopy makes use of an incident plane-
Fluid Coking is a continuous process (see Fig. 6). In Fluid Cok- polarized light that is reflected from polished specimen sur-
ing, the feed is sprayed onto fine size hot coke particles in the faces to reveal the extent of microstructural order present in
coker where coke is deposited on these seed particles by ther- the sample [57]. In plane polarized-light, the waves of light
mal cracking of the feed at temperatures between 480-525°C. are confined to a single plane, in contrast to random orienta-
Some of the coke product is introduced into a combustor tions of waves in ordinary light. Using polarized-light mi-
where partial combustion of the coke particles with air takes croscopy, uninhibited formation a n d development of
place. Partially combusted hot coke particles are returned to m e s o p h a s e can be observed to occur in three sequential
the coker to provide the heat necessary for thermal crack- stages: 1) nucleation of anisotropic spheres (0.5-10 m m in
ing/coking to complete the cycle. The resulting coke product, size) from an isotropic liquid; 2) growth of anisotropic
fluid coke, has a different structure and different properties spheres; and 3) their coalescence to form anisotropic micro-
compared to those of the delayed cokes, as discussed in the textures in cokes upon solidification. The polarized-light mi-
following sections. Fluid coke is used principally as fuel with crographs in Fig. 8 show the three stages of mesophase
some limited use in the manufacture of carbon materials. development as a function of time during carbonization of a
Flexicoking process is a variation of Fluid Coking where the decant oil (CCB) and an ethylene tar residue (ETR) sample in
fluid coke product is partially or completely gasified with air a laboratory batch reactor at 4758C. The extent of micro-
and steam to produce fuel gas in the refinery [50,52]. textural anisotropy in the resulting cokes is described and
Table 9 s u m m a r i z e s the coking processes, coker feed- classified with respect to the size and shape of the anisotropic
stocks, different kinds of petroleum cokes and their principal d o m a i n s produced by mesophase development. Under a
industrial applications. Petroleum cokes produced by de- polarized-light light microscope with a phase-sensitive retar-
layed or fluid coking are generically called green cokes be- dation plate, the anisotropic domains are seen on polished
cause of their relatively high volatile matter content (5-15%). specimen surfaces as the same color areas—isochromatic re-
Fluid cokes have generally lower volatile matter contents gions, depending on the orientation of ordered regions.
than delayed cokes (typically around 5%) because of the rel- The overall appearance of the polished sections of the cokes
atively high temperatures used in fluid coking. under a polarized-light microscope is referred to as the opti-
cal texture. Table 10 describes a commonly used classification
scheme to describe the optical texture of green cokes, or other
Formation of Coke Microtexture in Coking
carbonaceous solids [57]. When a phase retardation plate is
Processes
used in a polarized-light microscope, isotropic regions seen as
Delayed cokes produced from VDR (sponge, fuel, and shot light purple areas represent the lack of any structural order in
coke) show substantial differences in microtexture, including units greater than 0.5 /am (the resolution of light microscope).
variations in the degree of structural anisotropy, the size Anisotropic structures display dark purple, blue, and yellow
of anisotropic domains, and porosity. Sponge cokes are more areas of varying shape and size. In the absence of a phase re-
anisotropic, i.e., with a higher degree of microstructural tcirdation plate, the anisotropic regions appear as different
order, and more porous than shot cokes. Fuel cokes have gray levels. The term mosaics describes small structures of
an intermediate degree of anisotropy and porosity between anisotropic units that are 0.5-10 ;u,m in diameter. Small do-
those of sponge and shot cokes. Differences in the degree of mains and domains refer to isometric areas with diameters of
structural anisotropy of delayed cokes (illustrated in Fig. 7) 10-60 ix.m, and >60 îm, respectively. Elongated domains that
can be traced to the development of an intermediate liquid- are greater than 60 ^(,m in length and greater than 10 /am in
crystalline phase, carbonaceous mesophase, during liquid- width are called flow domains. Flow domains are formed by
phase carbonization in the delayed coker. Carbonaceous the deformation, or shearing of anisotropic domains by the
mesophase is a unique, ordered fluid consisting of essentially evolution of volatiles right before the solidification of
planar molecules. The prevailing molecular order, which ex- mesophase to produce coke. The polarized-light micrographs
hibits an intermediate state between isotropic liquids and in Fig. 9 show flow domains and mosaics textures of cokes
TABLE 9—Coking proceses, feedstocks, and commercial uses of petroleum coke.

Process Feedstock Product Commercial Uses of Coke
Delayed Coking Vacuum Distillation Residue Sponge coke Carbon anodes for aluminum industry pr
Vacuum Distillation Residue Fuel coke Fuel for cement kilns, industrial heat and
steam raising, fuel for utility industry
Vacuum Distillation Residue Shot coke No significant commercial use, some niche
applications, e.g., Ti02 production,
packing material
Clarified Slurry Oil from FCCU Needle coke Graphite electrodes for electric-arc furnaces
for iron and steel industry
Fluid Coking Vacuum Distillation Residue Fluid coke Industrial heat and steam raising
Flexi-coking Vacuum Distillation Residue Fluid coke, or fuel gas Industrial heat and steam raising
CCB CCB CCB
ETR
FIG. 8—Stages of mesophase formation during carbonization of a decant oil (CCB)
and ethylene tar residue (ETR) sample, nucleation, growth, and coalescence of
mesophase spheres to form anisotropic coke texture.
TABLE 10—Classification and description of the optical texture of

green cokes as observed by polarized-light microscopy using a
retardation plate [57].
Classification Description
Isotropic Uniform, light purple color
Anisotropic Dark purple, yellow, and blue areas of
varying shape and size
Fine mosaics Isochromatic areas (lA), 0.5-1.5 fim in
diameter
Medium mosaics lA, 1.5-5.0 fjLTn in diameter
Coarse mosaics lA, 5.0-10.0 ^tm in diameter
Small domains lA, 10-60 fim in diameter
Domains lA, >60 ixin in diameter
Flow domains lA, >60 (u.m in length, >10 fitn in width
FLOW DOMAINS
produced by carbonization of a decant oil and a vacuum dis-

tillation residue in a laboratory batch reactor.
Figure 7 shows the optical textures of the samples of needle,
sponge, and shot coke particles, in addition to their external
morphologies, as described before. Commonly, the optical
texture of delayed cokes is heterogeneous, comprising a mix-
ture of structures with different levels of anisotropy from mo-
saics to flow domains. A preponderance of a given texture, or
a mixture of textures, characterizes the principal optical tex-
ture of delayed cokes. The optical texture of needle cokes, for
example, consists mostly of straight flow domains. Sponge
cokes, on the other hand, display a predominance of acicular,
or twisted flow domains and large domains, while shot coke
texture consists mostly of mosaics and some small domains. MOSAICS
In other words, on the two extremes of optical texture scale,
FIG. 9—Flow domains and mosaics textures
needle cokes result from a high degree of mesophase devel- as viewed by polarized-light microscopy.
opment, whereas shot cokes display an inhibited mesophase
development. Distinct differences in the optical texture of de-
layed cokes explain many differences in physical and chemi- described in Petroleum Coke Production Processes. Character-
cal properties of needle, sponge, and shot cokes, as further dis- istically, fluid cokes have layered structures resembling
cussed in the Classification of Petroleum Cokes section. onions, because coke deposition tcikes place in layers on the
Fluid cokes have very different microtextures from those of seed coke particles. Figure 10 shows the optical texture of a
the delayed cokes because of the substantial differences in fluid coke sample. In contrast to liquid-phase carbonization
the operation and conditions of the two coking processes, as in delayed coking, vapor phase cracking and polymerization
istry and the rate of coke formation [59]. In general, feed-

stocks with high aromaticity produce a high degree of
mesophase development, as explained by the planarity and
lower thermal reactivitity of aromatic c o m p o u n d s . Coker
feedstocks, particularly VDR, with a high asphaltene content
produce inferior cokes with a low degree of anisotropy, and
high heteroatom a n d metals contents. It has been shown,
however, that the molecular nature of the asphaltene fractions
is as important as, if not more important than, the asphaltene
contents of the feedstocks for controlling the mesophase de-
velopment [60]. Hydrogen aromaticity, rather than carbon
aromaticity of the asphaltene fractions, appears to be an im-
portant structural parameter that relates to the carbonization
behavior of the coker feedstocks, such as carbonization reac-
FIG. 10—Optical texture of fluid coke (Petro- tivity, and hydrogen shuttling ability of the molecular con-
graphic Atlas, Prepared by Ralph Gray and Jack stituents during carbonization. High hydrogen aromaticity,
Crelling, http://mccoy.lib.slu.edu/cgi-bin/pro-
which indicates small aromatic ring systems and low degree
jects/crelling/pageBuilder.pl?find=P36).
of alkyl substitution on the aromatic rings, gives rise to a high
degree of mesophase development through controlling the
reactions on coke surfaces is primarily responsible for coke rate of molecular growth and fluidity (or viscosity) during car-
formation in fluid coking. The opticcil texture of fluid cokes bonization. Heavily alkyl substituted, large aromatic ring sys-
is, therefore, very different from those of the delayed cokes. tems, as found in the asphaltene fractions of VDR, lead to
Parallel orientation of concentric layers of coke creates more rapid growth of n o n p l a n a r intermediates, and a rapid in-
isotropic structures in contrast to large anisotropic domains crease in the viscosity of the carbonization medium, thus im-
present in sponge and needle cokes. pairing the mesophase development. In extreme cases, these
conditions lead to severe inhibition of mesophase develop-
Coker Feedstocks ment and to the formation of shot coke in delayed coking [53].
A good understanding of the chemistry of mesophase for-
Commonly used coker feedstocks are vacuum distillation mation from complex petroleum feedstocks still remains a
residua (VDR), FCC U decant oils (DO), and thermal tars (TT). current challenge, especially in terms of predicting the qual-
Table 11 summarizes coker feedstock properties, presented ity of needle cokes produced by delayed coking. Differences
either as average values, or ranges of variation for typical in molecular constitution of DO, in terms of the distribution
properties. The important differences between VDR and DO of two- to four-ring aromatic compounds, have been shown
include typically lower °API gravity and higher aromaticity of to affect the mesophase development in laboratory reactors.
DO. VDR contains a large fraction of sulfur and metals (par- An abundance of pyrene and alkylpyrenes in the DO, for ex-
ticularly Ni and V) found in crude oil because of their close as- ample, leads to a high degree mesophase development. In
sociation with asphaltene structures. VDR can contain u p to contrast, high concentrations of biphenyl, fluorene, and alky-
40% wt asphaltenes (defined here as toluene solubles and pen- lated phenanthrenes produce inferior optical textures in the
tane insolubles), whereas the maximum asphaltene content of resulting cokes [58]. Figure 11 shows a two-dimensional
DO is usually not greater than 10% wt [54]. Further, the aro- high-pressure liquid chromatography trace of a decant oil
matic molecules in the asphaltenes of VDR, consisting of poly- sample obtained with a photodiode array detector from nor-
cyclic aromatic ring systems connected with alkyl bridges, are mal phase separation using n-hexane and methylene chloride
much larger than those in DO. Heteroatoms (S, N, and met- as solvents. The HPLC chromatogram (x-axis:time, y-axis:ul-
als) tend to concentrate in these large molecules of VDR as- raviolet light wavelength, and z-axis: intensity of ultraviolet
phaltenes. The aromatic compounds in DO consist of much light absorption) with some indicates the complexity of the
simpler structures, containing mainly two- to six-ring fused molecular structure of the decant oils with a few peaks la-
polycyclic aromatic hydrocarbons (PAH) [54,58] beled (pyrene, methylpyrenes, and methylbenzopyrenes) for
Table 11 shows that despite their high °API gravity (or low demonstration purposes. However, individual compounds in
specific gravity), VDR has a m u c h higher Conradson Carbon
value than DO, mainly because of the high asphaltene con-
tents of VDR. In general, Conradson Carbon value is directly
proportional to coke yield from the delayed coking, or fluid TABLE 11—Typical coker feedstock properties [4,50].
coking processes [50]. Generally higher sulfur contents of Vacuum
VDR compared to those of DO should also be noted. Thermal Distillation
tars are similar in overall properties to DO; although TT tends Feedstock Property Residue Decant Oil Thermal Tar
to be more aromatic than DO, and contain much less naph- °API Gravity 7-15 1-8 -1-4
thenes. These differences in feedstock properties combined Sulfur, wt% 0.5-3.0 0.5-0.8 0.5
with differences in coking conditions control the structure Conradson Carbon, wt% 10-20 5-10 8-9
Molecular Weight 850 300 380
and important properties of petroleum cokes, such as the op-
C/H Ratio, Atomic 0.65 0.8 0.9
tical texture, heteroatom contents, strength, and reactivity. Aromatics, % wt 35 62 68
Chemical composition of coker feedstocks strongly affects Paraffins, % wt 10 0 7
the mesophase development through the carbonization chem- Naphthenes, %wt 55 38 25
the decant oils can be identified, based on their UV spectra, • Graphitization Heat Treatment is a process of heat treat-
if a good chromatographic separation can be achieved. m e n t of nongraphitic carbon, industrially performed at
t e m p e r a t u r e s in the range between 2500-3300 K, to
Classification of Petroleum Cokes achieve transformation into graphitic carbon.
• Green Coke (raw coke) is the primary solid carbonization
Coke is defined as "a soHd high in content of the element car- product from high boiling hydrocarbon fractions obtained
bon and structurally in the non-graphitic state" [61]. It is a at temperatures below 900 K. It contains a fraction of mat-
carbonaceous product from carbonization of organic mate- ter that can be released as volatiles during subsequent heat
rial, which has passed, at least in part, through a liquid or liq- treatment to approximately 1600 K. This mass fraction, the
uid crystalline state. Petroleum coke is generally defined as a so-called volatile matter constitutes 4 and 15wt% of green
carbonization product of high-boiling fractions obtained in cokes.
petroleum processing. The overall classification of green • Needle Coke is a special t5rpe of coke with extremely high
petroleum cokes (sponge, fuel, shot, needle, and fluid coke) graphitizability resulting from a strong preferred parallel
as shown in Table 9, is based on the morphology, mi- orientation of its layered structure and a particular physi-
crostructure, elemental composition, and selected physical cal shape of the grains.
and chemical properties of the cokes. As discussed in the pre- • Premium Coke is a n extremely well graphitizing carbon
vious sections, these important characteristics of the cokes, with a high degree of optical anisotropy and is character-
which determine their commercial applications, depend on a ized by the combination of the following properties: high
combination of factors including feedstock properties, the real density, low reversible thermal expansion, and low ash
coking process, and coking conditions. Definitions of some content combined, in most cases, with low sulfur content.
technical terms relevant to petroleum coke classification are • Puffing is an irreversible expansion of some carbon arti-
reproduced below from lUPAC's "Recommended Terminol- facts during graphitization heat treatment between 1650 K
ogy for the Description of Carbon as a Solid" [61]. and 2700 K.
• Calcined Coke is a petroleum coke obtained by heat treat-
ment of green coke to about 1600 K. It will normally have
Petroleum Coke Properties
a hydrogen content of less than 0.1 wt%.
• Filler (also called grist) is a petroleum-coke fraction of a Green cokes with relatively low sulfur, metal, emd ash con-
green carbon mix or formulation. tents are calcined-heat treated to 1600 K-to remove volatile
• Graphitic Carbon represents all varieties of substances con- matter. Polarized-light m i c r o g r a p h s in Fig. 12 show the
sisting of the element carbon in the allotropic form of shrinkage cracks and pores developed upon calcination of a
graphite. needle coke and a sponge coke. Calcined coke has a mass
• Graphitizable Carbon is a nongraphitic carbon, which upon fraction of hydrogen less than 0.1%. Calcined cokes are used
graphitization heat treatment, converts into graphitic as fillers for carbon anodes, graphite electrodes, or specialty
carbon. carbons. Table 12 lists the specifications of calcinable green
0.030
0.025
0.020
'immnm^KMSm ^375.00
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00

Hinutes
FIG. 11—A two-dimensional HPLC chromatogram for a decant oli sample.

sis, p r o v i d e s u s e f u l g u i d e l i n e s f o r s a m p l e p r e p a r a t i o n f o r a
v a r i e t y of l a b o r a t o r y a n a l y s e s .
Volatile Matter
V o l a t i l e m a t t e r c o n t e n t of g r e e n c o k e s is d e t e r m i n e d b y m e a -
s u r i n g t h e loss i n w e i g h t r e s u l t i n g f r o m h e a t i n g u n d e r r i g i d l y
controlled c o n d i t i o n s (ASTM D 4 4 2 1 , Volatile M a t t e r in
P e t r o l e u m Coke a n d ASTM D 6374, Volatile Matter in Green
P e t r o l e u m Coke, Q u a r t z Crucible P r o c e d u r e ) . T h e volatile
m a t t e r c o n t e n t is p a r t i c u l a r l y i m p o r t a n t for t h e i g n i t i o n c h a r -
Calcined needle coke a c t e r i s t i c s of t h e fuel c o k e s ; t h e h i g h e r t h e v o l a t i l e m a t t e r
TABLE 13—Calcined coke properties [52].

Properties Typical Value
Water Content 0-0.2%
Oil Content 0.1-0.3%
Granulometry
>8 mm 10-20%
8-4 15-25%
4-2 15-25%
2-1 10-20%
1-0.5 5-15%
0.5-0.25 5-15%
<0.25 0
Calcined sponge coke Vibrated Bulk Density
8-4 m m 0.64-0.70 kg/dm^
FIG. 12—Polarized-light micrographs of 4-2 0.73-0.79
calcined needle coke and sponge coke 2-1 0.80-0.86
samples, indicating anisotropic texture, 1-0.5 0.86-0.92
and porosity developed by devolatiliza- 0.5-0.25 0.88-0.93
tion. Grain Stability
8 ^ mm 75-85%
Reactivity in CO2 at lOOOX 5-10%
TABLE 12—Typical green and calcined coke specifications [50-52]. Ignition Temperature 615-630°C
Calcined Coke Reactivity in Air at 600°C 0.1-0.20%/min
Green Coke
Elements
Ash 0.1-1.0% 0.2-1.5% S 1-3%
Calcium 25-500 p p m 25-500 p p m V 80-300 p p m
Fixed carbon 87-97% 97-99% Ni 80-160
Hydrogen 3.0^.5% <0.1% Si 50-250
Iron 50-2000 p p m 50-2000 p p m Fe 50-250
Manganese 2-100 p p m 2-100 p p m Al 50-250
Magnesium 10-250 10-250 p p m Na 30-120
Moisture 0.5-2.0% Negligible Ca 20-100
Nickel 10-100 p p m 10-100 p p m K 5-15
Nitrogen 0.1-0.5% <0.1% Mg 10-30
Real Density 1.6-1.8 g/cc 2.08-2.13 g/cc CI 0.1-0.2%
Silicon 50-300 p p m 50-300 p p m Crystallite Size, Lc 26-30 A°
Sulfur 0.2-2.5% 0.2-2.5% Density in Xylene 2.05-2.09 kg/dm^
Titanium 2-60 p p m 2-60 p p m Specific Electrical Resistance 480-520 Micro O h m m
Vanadium 5-500 p p m 5-500 p p m
Volatile Matter 5-15% <0.5% Total Porosity 15-20%
TABLE 14—Standard test methods for determining calcined

coke properties.
cokes a n d calcined cokes used in c a r b o n a n o d e a n d graphite
m a n u f a c t u r e . N o t all g r e e n c o k e s p r o d u c e d b y d e l a y e d cok- Measurement Method
i n g of v a c u u m d i s t i l l a t i o n r e s i d u a a r e s u i t a b l e f o r c a l c i n a - Granulometry ISO 2325
t i o n . O n l y o n e - t h i r d of a p p r o x i m a t e l y 2 5 m i l l i o n t o n s of Bulk Density DIN 51 916
Grain Stability ASTM 5003-89
g r e e n c o k e p r o d u c e d i n t h e U . S . a r e Ccdcined for f u r t h e r u s e Oil Content (Dedusting Agent) ISO 8723
[ 5 2 ] . S o m e i m p o r t a n t p r o p e r t i e s of t h e g r e e n c o k e s t h a t d e - Xylene Density ASTM 5004-89, ISO 8004
t e r m i n e t h e i r s u i t a b i l i t y for c a l c i n e d c o k e p r o d u c t i o n a r e d e - Ash Content ASTM D 4422-89, DIN 51 903
fined a n d discussed below w i t h reference to t h e industrial Specific Electrical Resistance DIN 51 911
s i g n i f i c a n c e of t h e k e y p r o p e r t i e s . T a b l e 13 lists a d d i t i o n a l Reactivity in CO2 Thermal Gravimetric Analysis
(TGA)
p r o p e r t i e s of c a l c i n e d c o k e s t h a t a r e r o u t i n e l y m e a s u r e d , a n d
Reactivity in Air TGA
T a b l e 14 l i s t s s o m e s t a n d a r d m e t h o d s u s e d f o r m e a s u r i n g Chemical Elements Elemental Analysis, X-Ray
t h e s e p r o p e r t i e s . A S T M D 3 4 6 , S t a n d a r d P r a c t i c e for Collec- Methods, Atomic Absorption
t i o n a n d P r e p c i r a t i o n of C o k e S a m p l e s for L a b o r a t o r y Analy- Spectroscopy
content, the easier the ignition. Emission of PAH from com- sponge cokes used for anodes are related to the contamina-
bustion of fuel grade cokes is an important environmental tion of aluminum, or other produced metals with the heavy
concern that requires strict monitoring and control of emis- metal impurities. Heavy metal contamination requires fur-
sions from the combustors. Fluid cokes have lower volatile ther treatment for purification, or limits the use of the pro-
matter contents than the cokes produced by delayed coking, duced metal in certain applications.
because of higher coking temperatures used in Fluid Coking. High alkali metal contents, e.g., Ca and Na, are also not
Among the cokes produced by delayed coking, needle cokes desired in sponge cokes, since these metals act as strong oxi-
have lower volatile matter contents (5-8%) than sponge and dation catalysts a n d increase anode c o n s u m p t i o n during
shot cokes (10-15%). Green cokes with high volatile matter electrolysis.
content are not suitable for calcination. High volatile matter
content result from i m p r o p e r coking conditions, such as Density
short residence time and low coking temperatures, or feed- Several ASTM standard methods can be used to measure the
stock properties. Calcination reduces the volatile matter con- apparent and real densities of petroleum cokes, including D
tent of the green cokes to less than 0.5% in the calcined cokes 167, Apparent and True Specific Gravity and Porosity of
used for carbon anode, or graphite electrode manufacture. Lump Coke; D 2638, Standard Test Method for Real Density
of Calcined Petroleum Coke by Helium Pycnometer; D 5004,
Ash Real Density of Calcined Petroleum Coke by Xylene Displace-
ment; and D 4292, Determination of Vibrated Bulk Density of
Ash content of petroleum coke can be determined by redu-
Calcined Petroleum Coke. Both apparent and real densities of
cing the sample to an ash by heating in a muffle furnace ac-
petroleum cokes depend on their thermal history and operat-
cording to the standard method ASTM D4422, Standard Test
ing variables in the production processes. For many applica-
Method for Ash in Analysis of Petroleum Coke. For fuel
tions of petroleum cokes, apparent, or real density of the cokes
cokes, high ash contents create operational a n d disposal
are closely monitored, since many industrial properties of
problems. Green cokes with high ash contents are not suit-
cokes, such as strength, thermal and electrical conductivity,
able for calcination mainly because of the detrimental effects
and reactivity of cokes can be related to coke density. Poros-
of inorganic impurities on calcined coke properties, e.g., re-
ity of the petroleum cokes can be calculated from the appar-
activity, as explained below. Ash contents of less than 0.5
ent and true density measurements by the following formula:
wt% are required for sponge cokes used for carbon anode
manufacture [52]. Porosity = 100 - 100(apparent density/true density)
Sulfur For true density measurements, helium pycnometry is com-

monly used to obtain meiximum penetration of the pores by
Sulfur content of petroleum cokes can be measured using helium gas. For petroleum cokes, helium density is usually
several ASTM standard methods including D 1552, Sulfur in 5% below the theoretical density. This difference is attributed
Petroleum Products (High-Temperature Method), D 3177, to "closed porosity" in cokes that is not accessible to helium.
Total Sulfur in the Analysis Sample of Coal and Coke, and D Porosity of cokes is particularly important for applications
4239, Sulfur in the Analysis Sample of Coal and Coke Using where petroleum coke is used as filler in mixed formulations
High-Temperature Tube Furnace Combustion Methods. Sul- with a binder (e.g., carbon anode, and graphite electrode
fur content of petroleum cokes is important for both fuel manufacture), usually coal tar pitch. Desired pitch/coke
cokes, a n d green cokes calcined for c a r b o n anode and ratios and the resulting properties of the baked, and graphi-
graphite electrode applications. For fuel coke and sponge tized carbons, therefore, depend strongly on the porosity, or
coke applications, concerns related to SO2 emission and apparent density of the cokes. Strong correlations were re-
equipment corrosion are the main considerations for limit- ported between the bulk density of the filler cokes and the
ing the sulfur content. Sulfur content in fuel grade petroleum electrical resistivity, strength, and coefficient of thermal ex-
cokes and sponge cokes vary in the range 3-6 wt%, and < 3 pansion of the resulting graphite electrodes [62].
wt%, respectively. Needle coke has a more strict specification
on the sulfur content (<0.5wt%), because sulfur causes puff- The real density of petroleum cokes increases with the in-
ing during the graphitization heat t r e a t m e n t resulting in creasing heat treatment temperature, and depending on the
lower density and lower strength of graphite electrodes. graphitizability of the cokes, approaches the real density of
graphite u p o n graphitization heat treatment. Apparent den-
sity, on the other hand, can go through a m i n i m u m with the
Nickel, Vanadium, and Other Metals increasing heat treatment temperature during calcination of
Nickel, vanadium, a n d other trace metals contents of green cokes, because of porosity formation by devolatiliza-
petroleum cokes can be measured using different ASTM stan- tion. F u r t h e r increase in h e a t t r e a t m e n t t e m p e r a t u r e in-
dard methods, including D 5056, Trace Metals in Petroleum creases the apparent density because of collapsing porosity
Coke by Atomic Absorption; D 5600, Trace Metals in upon increasing the microstructural order.
Petroleum Coke by Inductively Coupled Plasma Atomic
Emission Spectrometry (ICP-AES); and D 6376, Determina- Optical Texture and Crystalline Structure
tion of Trace Metals in Petroleum Coke by Wavelength Dis- Polarized-light microscopy can be used for characterization
persive X-Ray Fluorescence Spectroscopy. For fuel grade of cokes and assessing their graphitizability. The appearance
cokes, nickel and vanadium contents are specified as 300-600 of a polished coke sample viewed under a polarized-light mi-
ppm. For sponge cokes, in addition to limits on nickel and croscope is described as the optical texture, which refers to
vanadium contents (<500 ppm), iron content needs to be less the anisotropy/isotropy of the solid phase. The isochromatic
t h a n < 2 5 0 p p m . Principal concerns with trace metals in regions seen u n d e r a polarized-light microscope represent
sections of the coke with a particular structural orientation. ity, i.e., the degree of anisotropy, cause substantial differences
Generally, the examination of green coke texture proves to be in thermal expansion behavior (or in coefficient of thermal ex-
useful to predict the calcined or graphitized coke quality. Op- pansion (CTE)) of needle coke samples. For example, differ-
tical texture varies greatly depending on the microstructure ent proportions of flow domains and domains in a needle coke
of a given coke and can be broadly defined as isotropic or sample, that are assigned the same OTI value, 30, would give
anisotropic. When viewed under a polarized-light micro- very different CTE in a given direction. Low CTE of needle
scope, a material is considered to be isotropic if the light re- cokes along their long axis is attributed to the dominant flow
flecting from the surface does not change with the direction domain anisotropy parallel to the long axis. On the other
of observation. Non-graphitizable, or poorly graphitizing hand, large isometric domains in needle cokes would give rise
cokes appear to be isotropic because their range of order is to relatively high CTE. The same optical texture index value
smaller than the resolution of the light microscope (<0.5 assigned for both domains and flow domains would, there-
fjLin). Anisotropic cokes, on the other hand, have a much fore, not capture this critical difference in thermal expansion
longer range order, 0.5-500 /xm, resulting from a high degree anisotropy of needle coke particles. Different optical texture
of mesophase development. These cokes show considerable index assignments were proposed by Eser [58], as shown in
change in reflected light intensity with direction of observa- Table 15, to account for the differences in thermal expansion
tion. In general, the larger the size of anisotropic, or isochro- anisotropy of different texture units. Based on point counting
matic regions, the higher is the graphitizability of the coke. data, the optical texture index for a coke sample can be calcu-
This is particularly important for needle cokes used for man- lated using the following formula:
ufacturing graphite electrodes.
OTI = 100*(FD) + 50*(D) + 5*(SD) +1*(M)
Nomenclatures have been developed for a more precise de-
scription of different optical textures in solid carbons [63,64]. where the letters represent the fractions of the flow domains
According to the proposed nomenclatures, an optical texture (FD), domains (D), small domains (SD), and mosaics (M), in
index can be determined by assigning different weight the order of decreasing degree of anisotropy. The higher the
factors to different anisotropic units. Table 15 lists assigned OTI, the higher the degree of anisotropy (or graphitizability),
texture weight factors, or optical texture index (OTI) values, and the lower the CTE edong the long aixis of the coke particles.
proposed by Oya et al. [57] for different anisotropic struc- Calcined needle cokes tend to have larger anisotropic units
tures. The larger the size of the anisotropic unit, the higher than green cokes. Calcination usually increases the size of op-
the optical texture index. As seen in Table 15, mosaics are as- tical domains, but it does not change their shape. Upon cal-
signed relatively small OTI ranging from 1 to 7, depending on cination, flow domain structures keep their shape to form
the size of the mosaics, while domains and flow domains are needle-like grains along with large isometric domains. For
assigned a large OTI, 30. The optical texture of solid carbons calcined needle cokes used as filler for graphite electrode
is usually very heterogeneous, consisting of a variety of dif- manufacture, the size of optical domains becomes less im-
ferent anisotropic structures, such as flow domains, do- portant compared to their shape and orientation. This is of-
mains, and mosaics. Consequently, a point counting method ten demonstrated when coke is over calcined and display
is widely used for characterizing the texture of solid carbons larger anisotropic domains, but poor thermal expansion be-
[57,65,66]. The fraction of points counted for each compo- havior [67]. Figure 12 illustrates optical textures of calcined
nent is multiplied by the corresponding optical texture index sponge and needle coke samples. Using scanning electron mi-
(OTI) value to calculate a factor for each component. The croscopy (SEM), Pysz et al. [68] proposed a different nomen-
OTI of a sample is, then, calculated by summing the factors clature for classification of calcined needle cokes, shown in
for all the texture categories. Table 16, to include larger texture domains. Analogous to
Using the optical texture classification scheme given by Oya green coke texture characterization, using similar OTI desig-
et al. [57], shown in Table 15, in conjunction with a point nations for the texture components of increasing anisotropy
counting procedure one can differentiate between anisotropic as shown in the last column of Table 16, Qiao [69] showed
textures of solid carbons over a broad range of texture qual- good correlations between OTI of calcined needle coke parti-
ity. This general texture classification, however, fails to dis- cles and their CTE measured on the same particles.
tinguish between similcir textures of coke samples that fall There is no standard method for texture characterization
into a more specific category, e.g., sponge cokes, or needle of petroleum cokes. ASTM D 5061, Microscopical Deter-
cokes. Needle cokes, for example, consist predominantly of mination of Volume Percent of Textural Components in -
domains and flow domains. Small differences in texture qual- Metallurgical Coke describes procedures to identify the tex-
TABLE 15—Optical texture index (OTI) assignments to distinguish between different

anisotropic texture components [57,58].
Classification Description OTI [57] OTI [58]
Isotropic No optical activity 0 0
Anisotropic Isochromatic areas (lA)
Fine mosaics lA, 0.5-1.5;u,ni in diameter 1 1
Medium mosaics lA, 1.5-5.O^m in diameter 3 1
Coarse mosaics lA, 5.0-lO.Ojixm in diameter 7 1
Small domains lA, 10-60/!Am in diameter 20 5
Domains lA, > 6 0 ^ m in diameter 30 50
Flow domains lA, >60/Ltm in length, >10/xm in width 30 100
TABLE 16—Nomenclature for and description of microtexture in in the structure of cokes and graphites can also play a role in
calcined needle cokes by scanning electron microscopy [68]. accommodating thermal expansion, especially in the c-direc-
Classification Description Size OTI [58] tion [75-77]. Many researchers have investigated how temper-
I Isometrics <100 ij.m 1 ature affects thermal expansion of cokes and graphites [78-80].
A Acicular 100-300 ixm 5 It is known that, for anisotropic cokes, as the heat treatment
S Stringy 300-1000 fj.m 50 temperature increases, CTE decreases because of increased
F Fibrous > 1000 length, 100
structural ordering. After heat treatment at 600°C, cokes still
> 6 0 /iim width
have high CTE values in both a- and c-directions. There is a sig-
nificant decrease in CTE upon heat treatment between 600 and
1300°C. Although there is not much decrease in CTE upon heat
t u r a l c o m p o n e n t s of coke according to their degree of treatment at temperatures above 1300°C, it has been suggested
anisotropism, c a r b o n form d o m a i n sizes, b o u n d a r y size, that the CTE values in the c-direction decreases with the in-
color of individual isochromatic domains, their morphology, creasing stack height of crystallites (Lc) [81].
relative reflectance, and other optical properties. Represen-
tative crushed particulate coke samples are prepared using Thermal expansion measurements can be made using a
ASTM D 3997, Preparing Coke Samples for Microscopical dilatometer to measure linear expansion as a function of tem-
Analysis by Reflected Light. Gray and Devanney [70] pro- perature in a given direction. A linear variable differential
vided a detailed description of microscopic classification and transformer (LVDT) mechanism is used to measure a dimen-
industrial applications of coke carbon forms. sional expansion. Thermal expansion plots (expansion vs
temperature) are seldom linear. Therefore, the mean CTE,
Texture characterization by optical microscopy and SEM
defined as the slope of the line joining the two defined points,
provides information on the degree of mesophase develop-
depends on the temperature range used for calculating its
ment that leads to the anisotropic microtexture formation in
value, as follows [82]:
petroleum cokes. This information is particularly useful for
studying and controlling mesophase development in delayed Mean CTE = (4L/L)/ (4T)
coking [54,58,66] and predicting the important industrial
properties of calcined cokes such as strength, reactivity, and where zlL = observed changed in sample length over the tem-
thermal expansion. The microtextural properties of cokes are perature range AT, in
related to the prearrangement of carbon atoms into three-di- AT = temperature range of measurement, °C
mensional crystalline structures, which determine the
L = sample length at room temperature, in
graphitizability of cokes. X-ray diffraction is used to deter-
m i n e the degree of crystalline alignment in cokes. For The CTE values are reported using the unit 10~* in/in °C. The
calcined cokes, a p p a r e n t crystallite size (Lc), a n average CTE measurements are made on calcined, or graphitized test
stacking height of graphene layers (see Fig. 13), is a good in- bars prepared by extrusion of calcined coke particles with a
dication of pregraphitic order, and, therefore, their graphiti- standcird binder pitch. Highly graphitizable calcined n

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Fuels and

George E. Totten, Editor

ASTM Manual Series: MNL37WCD

Fuels and lubricants handbook: technology, properties,

Copyright © 2003 ASTM International, West Conshohocken,

Authorization to photocopy items for internal, personal, or

Printed in Glen Bumie, MD

I. PETROLEUM REFINING PROCESSES FOR FUELS

Chapter 1—Petroleum Oil Refining 3

II. FUELS: PROPERTIES AND PERFORMANCE—

Chapter 2—Liquefied Petroleiun Gas 31

Chapter 3—Motor Gasoline 61

Chapter 4—Aviation Fuels 89

Chapter 5—^Automotive Diesel and Non-Aviation Gas Turbine Fuels 115

Chapter 6—Introduction to Marine Petroleum Fuels 145

III. HYDROCARBONS AND SYNTHETIC LUBRICANTS:

Chapter 7—Hydrocarbon Base Oil Chemistry 169

Chapter 8—Hydrocarbons for Chemical and Specialty Uses 185

Chapter 9—Additives and Additive Chemistry 199

Chapter 10—Synthetic Lubricants: Nonaqueous 249

Chapter 11—Environmentally Friendly Oils 267

Chapter 12—Turbine Lubricating Oils and Hydraulic Fluids 297

Chapter 13—Hydraulic Fliiids 353

Chapter 14—Compressor Lubricants 383

Chapter 15—Refrigeration Lubricants—Properties and Applications 413

Chapter 16—Gear Lubricants 431

Chapter 17—Automotive Lubricants 465

Chapter 18—Metalworking and Machining Fluids 497

Chapter 19—Petroleum Waxes 525

Chapter 20—Lubricating Greases 557

Chapter 21—Mineral Oil Heat Transfer Fluids 573

Chapter 22—Non-Lubricating Process Fluids: Steel

rv. PERFORMANCE/PROPERTY TESTING PROCEDURES—

Chapter 23—Static Petroleum Measurement 635

Chapter 24—Hydrocarbon Analysis 649

Chapter 25—Volatility 675

Chapter 26—Elemental Analysis 707

Chapter 27—Diesel Fuel Combustion Characteristics 717

Chapter 28—Engineering Sciences of Aerospace Fuels 729

Chapter 29—Properties of Fuels, Petroleum Pitch, Petroleum Coke,

Chapter 30—Oxidation of Lubricants and Fuels 787

Chapter 31—Corrosion 825

Chapter 32—Flow Properties and Shear StabiUty 833

Chapter 33—Cold Flow Properties 879

Chapter 34—Environmental Characteristics of Fuels

Chapter 35—Lubrication and Tribology Fundamentals 909

Chapter 36—Bench Test Modeling 963

Chapter 37—Lubricant Friction and Wear Testing 1017

Chapter 38—Statistical Quality Assurance of Measurement Processes

Petroleum Oil Refining

Copyright' 2003 by A S I M International www.astm.org

LSR ISOMERIZATION -GASOLINE

HYDROCRACKING •REFORMER FEED

TABLE 2—^Worldwide refining capacity as percent of crude.

TABLE 5—History of U.S. gasoline specifications. Jet Fuel

TABLE 8—Fuel oil specifications.

TABLE 9—Diesel fuel specifications. a n d v a c u u m towers/columns/crude u n i t s to provide the

Atmospheric —•0—iS^S—I I *•'Wet Gas

Reflux "B-' Water • • Light

Preflash Steam -••Topped Crude

QHot Wbll Accumulator [) » Naphtha

FIG. 2—Atmospheric and vacuum distillation units.

FIG. A—Semiregenerative and continuous catalytic reforming units.