ARTICLE IN PRESS

Tribology International 40 (2007) 10351046

www.elsevier.com/locate/triboint

Vegetable oil-based lubricantsA review of oxidation

N.J. Fox, G.W. Stachowiak
Tribology Laboratory, School of Mechanical Engineering, University of Western Australia, Crawley, WA 6009, Australia
Received 20 July 2006; received in revised form 9 October 2006; accepted 11 October 2006
Available online 28 November 2006

Abstract

Vegetable oils are being investigated as a potential source of environmentally favourable lubricants, due to a combination of
biodegradability, renewability and excellent lubrication performance. Low oxidation and thermal stability, poor low-temperature
properties and narrow range of available viscosities, however, limit their potential application as industrial lubricants. This review
addresses oxidation as a limitation of vegetable oil-based lubricants. The basic mechanism of vegetable oil autoxidation is presented,
along with methods used to monitor and analyse the products of oxidation. The potential impact of such oxidation products on
lubrication performance is discussed. A brief discussion of methods used to assess and improve oxidation stability completes the review.
r 2006 Elsevier Ltd. All rights reserved.

Keywords: Vegetable oil; Lubricant; Oxidation; Oxidation stability; Review

1. Introduction vegetable wax, with both long chain monounsaturated

Stronger environmental concerns and growing regula-
tions over contamination and pollution will increase the
need for renewable and biodegradable lubricants. An
annual growth rate of 710% for environmentally favour-
able lubricants is expected on the US market over the next
few years compared to a rate of only 2% for the overall
lubricant market [1]. Vegetable oils are a viable and
renewable source of environmentally favourable oils.
The majority of vegetable oils consist primarily of
triacylglycerides. Triacylglycerides, also termed triglycer-
ides, are glycerol molecules with three long chain fatty
acids attached at the hydroxy groups via ester linkages. A
three-dimensional representation of a triglyceride molecule
is displayed in Fig. 1. The fatty acids in vegetable oil
triglycerides are all of similar length, between 14 and 22
carbons long, with varying levels of unsaturation. Some
particularly interesting variations to the normal vegetable
oils are castor and jojoba oil. Castor oil is a triglyceride,
but the fatty acids are almost exclusively ricinoleic acid, an
18-carbon monounsaturated fatty acid with a hydroxy
branch at the 12th carbon. Jojoba oil is a monoester
Corresponding author.
E-mail address: gws@mech.uwa.edu.au (G.W. Stachowiak).
alcohol and fatty acid, either 20 or 22 carbons. Both castor
and jojoba oils display properties quite distinct to all other
vegetable oils due to the quirks in structure [2,3].
The triglyceride structure of vegetable oils provides
qualities desirable in a lubricant. Long, polar fatty acid
chains provide high strength lubricant lms that interact
strongly with metallic surfaces, reducing both friction and
wear. The strong intermolecular interactions are also
resilient to changes in temperature providing a more stable
viscosity, or high viscosity coefcient. The entire base oil is
also a potential source of fatty acids.
The triglyceride structure is also the basis for the
inherent disabilities of vegetable oils as lubricants. Un-
saturated double bonds in the fatty acids are active sites for
many reactions, including oxidation, lowering the oxida-
tion stability of vegetable oils. Another concern is the
susceptibility of the triglyceride ester to hydrolysis. The
similarity in all vegetable oil structures mean that only a
narrow range of viscosities are available for their potential
use as lubricants. Finally, the strong intermolecular
interactions whilst providing a durable lubricant lm also
result in poor low-temperature properties.
Vegetable oils have displayed excellent lubrication
properties in laboratory investigations. Composition and
selected properties of vegetable oils commonly investigated

0301-679X/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.triboint.2006.10.001
 ARTICLE IN PRESS
1036 N.J. Fox, G.W. Stachowiak / Tribology International 40 (2007) 10351046

Table 1
Selected properties of a variety of common vegetable oils [2,1416]

Fatty acid % Palm Soybean Sunower High oleic Castora

sunower

C 14:0 1.5
C 16:0 43 11 6 2.5 8
C 16:1 Trace Trace
2
C 18:0 5 4.5 3 2 4
C 18:1 40 23 17 89.5 86
C 18:2 10 55 74 6
C 18:3 Trace 6

C 20:0 0.5 Trace
C 20:1
C 22:0 0.5 Trace
Fig. 1. 3-D representation of a triglyceride molecule. Visc mm2/s, 40 1C 40 31 33 41 252
Visc mm2/s, 100 1C 8.3 7.4 8.3 8.8 20
as potential lubricants are displayed in Table 1. Without Viscosity index 190 218 242 202 90
Pour point, 1C 9 15 12 24
additives vegetable oils outperformed mineral base oils in
antiwear and friction [2,4], scufng load capacity [5] and C XX:Y represents a fatty acid chain of XX carbon atoms and Y double
fatigue resistance [6]. Fully formulated vegetable oil bonds.
a
lubricants, in comparison to mineral oil counterparts, Castor oil contains 8090% ricinoleic acid, C18:1 12 OH.
display a lower coefcient of friction, equivalent scufng
load capacity and better pitting resistance, but also poorer lubricant were monitored during eld trials in a variety of
thermal and oxidative stability [712]. At extreme loads agricultural machinery over a period of 6 yr. By the end of
vegetable oil-based lubricants become signicantly less the test period, the machines had operated for over
effective [13]. 35,000 h and more than 21,000 km. The hydraulic uid
Vegetable oils are particularly effective as boundary caused no damage and there was no more leakage than
lubricants as the high polarity of the entire base oil allows with a mineral oil. On average 60% of the machines oil
strong interactions with the lubricated surfaces. Boundary reserve was replaced during the 6-year eld experiment.
lubrication performance is affected by attraction of the The uid also remained biodegradable with low toxicity
lubricant molecules to the surface and also by possible throughout at all stages of its life.
reaction with the surface. Biresaw et al. examined the level Whilst the potential of vegetable oils as hydraulic uids
of attraction between lubricant and surface, calculating the has been the major topic of investigation other avenues are
Gibbs free energy of adsorption using appropriate models being considered. Belluco and De Chiffre evaluated the
[17,18]. Based on the free energies of adsorption triglycer- performance of a range of mineral and vegetable oil-based
ides should outperform the equivalent monoester and the cutting uids in a range of machining operations [23].
level of unsaturation of the fatty acids should play little Vegetable-based oil formulations displayed equal or better
effect on the lubrication performance. Polyunsaturated performance than the reference commercial mineral oil in
fatty acids, however, have displayed greater lubrication all operations. Jojoba oil has been considered as a two-
properties at higher temperatures and loads than less stroke engine lubricant [24]. Formulations of jojoba oil
unsaturated counterparts. Raising the concentrations of with commercial lubricants, displayed good miscibility
oxygen in the oil increased this improvement to lubrication, with petrol, comparable scufng and deposit forming
displaying the importance of reactions on boundary tendencies and improved wear performance. Permuswan
lubrication performance [19]. examined the performance of high-stability vegetable oils
Lubricant formulations are being developed based on in a modied engine test rig [15]. The oils were effective as
the benets and limitations of vegetable oils. The majority lubricants with no failures, but did increase in viscosity
of published data is on the use of vegetable oils as over time and caused deposits on the bore.
hydraulic uids. Honary provided valuable baseline data In summary, vegetable oils display many desirable
for the eld, investigating the performance of soybean oil characteristics, which make them very attractive lubricants
at various degrees of rening in hydraulic uid bench tests for many practical applications. However, the main
and suggesting soy-based hydraulic uids were viable. weakness is their relatively poor oxidation stability. This
Field trials of fully formulated vegetable oil-based hydrau- review addresses the issue of the oxidation of vegetable oil
lic/transmission uids have also been positive [20,21]. lubricants. The mechanism of vegetable oil autoxidation is
Remmele and Widmann, in particular, presented a presented along with techniques used to analyse oxidised
comprehensive, long-term examination of a commercially vegetable oils and how oxidation compounds may inu-
available rapeseed oil based hydraulic uid [22]. Perfor- ence lubrication performance. Finally methods used to
mance, biodegradability and ecotoxicity of the rapeseed assess and improve the oxidation stability are discussed.
 ARTICLE IN PRESS
N.J. Fox, G.W. Stachowiak / Tribology International 40 (2007) 10351046
2. Mechanism of vegetable oil autoxidation
Oxidation stability of triglyceride-based vegetable oils is
primarily limited by the degree of unsaturated double
bonds. Unsaturated carboncarbon bonds function as
active sites for many reactions, including oxidation [25].
A majority of triglyceride-based vegetable oils contain
unsaturated fatty acids and are susceptible to oxidation.
The greater the level of unsaturation, that is, the more
double bonds, the more susceptible the oil becomes to
oxidation [103]. The mechanism for the autoxidation of
vegetable oils is well studied and a classical representation
of the oil autoxidation mechanism is shown in Fig. 2
[2628].
Vegetable oil oxidation is initiated by formation of free
radicals. Free radicals can easily be formed from the
removal of a hydrogen atom from the methylene group
next to a double bond. Free radicals rapidly react with
oxygen to form a peroxy radical. The peroxy radical can
then attack another lipid molecule to remove a hydrogen
atom to form a hydroperoxide and another free radical,
propagating the oxidation process.
The abstraction of a hydrogen atom by the peroxyl
radical to generate a hydroperoxide is the rate-limiting step
of vegetable oil autoxidation [27]. The rate constant for the
rate-limiting step depends primarily on the strength of the
carbonhydrogen bond being broken. The strength of a
carbonhydrogen bond next to a carboncarbon double
bond is lowered and the hydrogen can be removed easily,
thus those oils containing double bonds are more
susceptible to autoxidation. As the number of double
bonds increases there become more sites susceptible to the
abstraction of a hydrogen atom and the autoxidation
process can occur at a faster rate. Vegetable oils containing
a high percentage of monounsaturated fatty acids will
typically autoxidise only at high temperatures, whereas
those oils containing polyunsaturates, such as linoleic and
linolenic acid, readily autoxidise at room temperatures.
Initiation RH
Propagation R + O2
ROO + RH
Branching ROOH
RO + RH + O2
OH + RH + O2
Termination ROO + ROO
ROO + R
R +R
Peroxide decomposition ROOH
Polymerisation ROOH
Fig. 2. Classical representation of the oil autoxidation mechanism.
1037
Hydroperoxides, once formed, can break down to
produce more free radicals. This branching step leads to
the proliferation of radicals that can go back and aid in the
propagation of more hydroperoxides. Not all free radicals,
however, will propagate the oxidation process; some may
react with and terminate each other. Hydroperoxides
continue to build up in the oil via the propagation and
branching steps. At some point the collection of hydro-
peroxides no longer remain stable and decompose into a
myriad of volatile and non-volatile secondary oxidation
compounds. They can also be involved in polymerisation
reactions, leading to deposits.
The vegetable oil autoxidation mechanism presented
here is a simplication of a complex series of reactions. The
process is further complicated by variations in conditions,
such as ultraviolet rays, temperature, pressure and oxygen
availability, or by the presence of other compounds, such
as antioxidants, chelating agents and metals. Metals, for
example, act as a catalyst for the oxidation of vegetable oils
speeding up degradation and the production of free
radicals [29]. Iron and tin are particularly effective catalysts
of the oxidation process, whereas copper and lead have
very little impact. Ultraviolet rays decompose hydroper-
oxides in the process of photo-oxidation [30].
3. Oxidation compounds
Vegetable oils will decay during the lifetime of
the lubricant either in storage or during application.
The physical and chemical changes that occur within the
oil during oxidation are likely to have an impact on
the lubrication performance. The following section out-
lines the major compounds produced during vegetable
oil oxidation, methods that can be used to monitor
and analyse the compounds and their potential impact
on lubrication. A summary of the section is displayed in
Table 2.
R + H
ROO
ROOH + R
RO + OH
ROH + ROO
H2O + ROO
ROOH + O2
ROOH
R-R
various lower molecular weight compounds
various higher molecular weight compounds
 ARTICLE IN PRESS
1038 N.J. Fox, G.W. Stachowiak / Tribology International 40 (2007) 10351046

Table 2
Summary of vegetable oil oxidation compounds, analytical techniques and lubrication impact

Stage Compound Analytical techniques Lubrication impact

Primary Hydroperoxide  Titration [31]  Prowear effect [3841]

 Chemiluminescence [32,33]
 Electron spin-resonance spectroscopy [32]
 Infra-red Spectroscopy [3437]
 Combined techniques [33]

Secondary Volatile  Gas chromatography [49]  Likely negligible

 Gas chromatography/mass spectrometry
[4648]

Non-Volatile  High-performance liquid  Epoxideshigh viscosity, high-oxidation

chromatography/mass spectrometry [52] stability, similar boundary lubrication
 Atmospheric pressure chemical [54,55]
ionization/mass spectrometry [53]  Majority of compounds uncertain

High molecular weight  Gel permeation high-performance liquid  Increased viscosity

chromatography [56]  Uncertain impact on lubrication
 High-performance size-exclusion
chromatography [57,58]

Free Fatty Acid  Titration [68]

 Capillary gas chromatography [68]  Improve boundary lubrication properties
 High-performance liquid [13,51,72,73]
chromatography [69]  Lower oxidation stability [74,75]
 Supercritical uid chromatography [70]
 Nuclear magnetic resonance spectroscopy
[71]

3.1. Primary oxidation compounds
3.1.1. Hydroperoxides
Triacylglyceride hydroperoxides are the primary oxida-
tion compounds of triacylglyceride-based vegetable oils. As
the primary oxidation compound it is important to be able
to analyse hydroperoxides and understand of the impact of
such compounds on the lubrication process. Fully under-
standing the manner in which hydroperoxides affect
lubrication will allow the development of more effective,
and durable, vegetable based lubricants. Hydroperoxides
are particularly important, as they are the primary
oxidation compounds; all secondary oxidation compounds
derive from hydroperoxide decomposition.
3.1.1.1. Analysis. Peroxide value, or PV, is commonly
used as an indication of the level of peroxides in the system
and is determined using AOCS Ofcial Method Cd 8b-90
[31]. It is chemical method, based on an iodimetric
titration. The oil sample is dissolved by solvents and added
to a solution containing potassium iodide. Hydroperox-
ides/peroxides in the oil oxidise the iodide to iodine and the
level of iodine determined via a titration against thiosul-
fate. By back calculation the concentration of peroxides
is then determined. The method is time consuming and
the titration end point can be questionable, but it is a
standard analytical method that can be performed by any
laboratory.
Instrumental methods of analysis are being developed
for the study of peroxides in vegetable oils. The aim is to
produce rapid and reliable instrumental methodologies
that can be used by different laboratories with low
variation in results. Instrumental methods are generally
advantageous over chemical methods, as they require
smaller sample volumes, involve less sample preparation
and have lower reliance on fresh reactants. The major
disadvantage, of course, is the need for the instrument. Not
only must the instrument be available it must also be
regularly maintained and calibrated.
Chemiluminescence, electron spin-resonance spectro-
scopy, ultraviolet spectroscopy and infra-red (IR) spectro-
scopy have all been utilised in studies of peroxides in
vegetable oils. Chemiluminescence trials involve reaction of
hydroperoxides/peroxides in the oil sample with a photo-
active compound, luminol for example, in the presence of a
catalyst. The light produced from the reaction is detected
via a photomultiplier to give the levels of peroxide [32,33].
Electron spin resonance (ESR) spectroscopy studies the
spin state of radicals. Radicals are reaction intermediates
and examining the type and level of radicals in a sample
can provide information regarding the chemical reactions
occurring. Compounds, called spin traps, are added
to react with radicals present in a system, in order to
stabilise them long enough to be examined by ESR
spectroscopy. Researchers have demonstrated that lipid
hydroperoxides oxidise 2,2,6,6-tetramethyl-4-piperidone to
 ARTICLE IN PRESS
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stable nitroxide radicals. The level of nitroxide radicals and
hence hydroperoxides can then be determined by ESR
spectroscopy [32].
IR spectroscopy has been the tool used in a number of
studies examining hydroperoxides in vegetable oils. IR
spectroscopy examines vibrations of chemical bonds upon
application of IR beams, with emission frequency related
to bond type. Early IR studies utilised spectra in the mid
IR region4000200 cm 1 [34]. More recent studies utilise
the near IR region12 8004000 cm 1 [3537]. The analy-
sis of peroxides via IR spectroscopy is not a simple one-
peak method. It requires mathematical analysis of the
changes occurring in the spectra during oxidation along
with calibration against compounds that can confuse the
peroxide spectra, such as alcohols, free fatty acids,
moisture and glycerides [34,35]. Once a calibration
procedure is established IR spectroscopy methods become
routine and effective.
The instrumental methods described above are primarily
concerned with the level of peroxides in oxidised oil
samples. These detection methods can be used in combina-
tion with a chromatographic technique to provide in-
formation regarding the type of hydroperoxides present
as well as the amount. The chromatographic technique,
such as high-performance liquid chromatography (HPLC),
separates the hydroperoxides in the solution based on
their interaction with stationary and mobile phases.
The detection method then determines the level of
the separated compounds. HPLC coupled with a chemilu-
minescence detection system has been used to characterise
the hydroperoxides formed during autoxidation and
photosensitised oxidation of vegetable oils [33]. Mono
hydroperoxides were predominantly observed in the
early to middle stages of oxidation, with bis OOH
and tris OOH apparent at high levels after prolonged
oxidation.
3.1.1.2. Impact on lubrication. Very little work has been
published examining the impact of hydroperoxides on the
lubrication properties of vegetable oils. Increased levels of
hydroperoxides have been linked to increased wear during
boundary lubrication trials of oxidised sunower oil.
Increased wear was also linked to degradation of the
triglyceride fatty acids. It was uncertain as to which factor
had the most impact-presence of hydroperoxides, degrada-
tion of triglyceride fatty acids or both [38].
The impact of hydroperoxides on the lubrication
performance of mineral oils has been the subject of a few
studies. Newley et al. monitored the lubrication perfor-
mance and peroxide levels of an ester base stock during
boundary lubricated fretting wear tests [39]. A close
relationship was observed between increased wear and
peroxide accumulation. Addition of antioxidants, peroxide
decomposers and radical scavengers, to the lubricant
reduced both peroxide accumulation and wear.
Habeeb and Stover examined the role of hydroperoxides
in engine wear [40]. A commercially available engine oil,
1039
with a ZnDDP antioxidant package, was subjected to both
motored and red 2.3 L engine dynamometer tests and eld
trials. In all cases fresh oils displayed little wear. Addition
of hydroperoxides to the fresh oils caused a dramatic
increase in wear, correlated to the overall concentration.
Initially the authors believed that addition of t-butyl
hydroperoxide caused excessive wear by degrading the oil
and in the process, generating strongly corrosive com-
pounds. However oil samples from the experiments showed
that although signicant wear had occurred, relatively little
oil oxidation had taken place. The results suggested that
the hydroperoxides themselves were responsible for the
observed wear.
Rounds presented a general examination of the impact
of hydroperoxides on wear [41]. Tests were conducted
using a four-ball wear rig, with a napthenic mineral oil the
subject of most the study. Addition of hydroperoxides to
the base oil at low to medium loads increased wear, with
the prowear effect related to the concentration. With
ZnDDP additives present hydroperoxides had to reach a
threshold concentration before the prowear effect was
observed. At high loads addition of hydroperoxides
reduced wear, suggesting some extreme pressure properties.
A synthetic diester base oil was also examined. In the
diester, hydroperoxides acted as antiwear agents at low
concentrations suggesting that the hydroperoxide hydro-
lysed the ester-forming acids that either helped protect the
surface or reacted with the hydroperoxide remaining in the
oil. This is an interesting nding in relation to vegetable
oils, which are primarily triesters. The prowear effect of
hydroperoxides was observed when using low alloy steel
balls. When stainless steel balls were utilised wear was
signicantly reduced.
In these mineral oil studies the impact of hydroperoxides
on lubrication performance was inuenced by a number of
factors including; base oil, lubricated surfaces, lubrication
conditions, additives and type of hydroperoxide. Conduct-
ing similar studies using vegetable oil lubricants dosed with
known levels and types of hydroperoxides would improve
our understanding of the lubrication process, particularly
during the early stages of oxidation. Triacylglyceride
hydroperoxides, the primary oxidation compounds of
vegetable oils, can be synthesised. Hui et al. describe
methods for producing monohydroperoxides of three
different triglycerides [42]. Gargouri and Lagoy describe
the bioconversion of polyunsaturated fatty acid triglycer-
ides to the corresponding hydroperoxides [43]. It is also
possible to synthesise hydroperoxides of individual fatty
acids [44,45].
3.2. Secondary oxidation compounds
3.2.1. Volatiles
Volatile organic compounds are produced during the
secondary stages of vegetable oil oxidation. They are
formed following the decomposition of the triglyceride
hydroperoxides.
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3.2.1.1. Analysis. Volatile compounds are primarily re-
sponsible for the rancid avours and odours of oxidised
vegetable oils. The food industry is particularly interested
in the avour and quality of vegetable oils and as such,
techniques for analysing volatile organic compounds are
well established along with knowledge of the major volatile
components of oxidised vegetable oils. Volatile compo-
nents of oxidised vegetable oils are generally analysed via
gas chromatography (GC) and gas chromatography-mass
spectrometry (GC-MS) [4648]. Common gas chromato-
graphic methods for measuring the volatile organic
compounds in fats and oils are described in AOCS
Recommended Practice Cg 4-94 [49].
During the oxidation of vegetable oils polyunsaturated
fatty acids in the triglyceride breakdown rst and produce
the greatest amount of volatiles. Linolenic acid (C18:3)
decomposes primarily into 2,4-heptadienal and propanal,
with linoleic acid (C18:2) producing mainly pentane,
pentanal, hexanal and 2 heptenal. Monounsaturated fatty
acids in the triglyceride decompose at a much slower rate
and release minimal levels of volatile compounds when
compared to their polyunsaturated counterparts. Oleate
(C18:1) rich oils primarily produce octanal and nonanal,
with some heptanal [47,48].
3.2.1.2. Impact on lubrication. Volatiles formed during
vegetable oil oxidation are primarily short-chained hydro-
carbons and alcohols. Polarity and chain length are critical
factors to consider for wear/friction modiers [50]. The low
polarity and short chain length of these volatile compounds
means they are unlikely to have any impact on lubrication
performance. With a study suggesting long chain alcohols,
1218 carbons, to have virtually no effect on the wear
resistance and load-carrying capacity of vegetable oils [51], it
becomes even less likely that short chain volatile compounds
will signicantly impact lubrication performance.
3.2.2. Non-volatiles
Decomposition of hydroperoxides leads to short chain
volatile compounds along with the corresponding chain-
shortened, non-volatile compounds.
3.2.2.1. Analysis. A method to analyse the non-volatile
organic compounds formed during the oxidation of
vegetable oils has been developed by SteenhorstSlikkerv-
eer et al. [52]. Normal phase HPLC was used to separate
the oxidation products and a mass spectrometer (MS) was
used for identication. Vast ranges of non-volatile organic
compounds were identied in the oxidised oil, but they
could be separated into three major categories.
 Triacyglyceride with intact fatty acid chains, one of
them containing an oxygen, hydroxy, epoxy or peroxy
groups.
 Triacyglyceride with intact fatty acid chains, two of
them containing an oxygen, hydroxy, epoxy or peroxy
groups.
 Triacyglyceride with intact two fatty acid chains and one
shortened chain ending in an oxygen or hydroxy groups.
Different vegetable oils decomposed into distinctly
different variations of the major categories.
Byrdwell and Neff also developed a technique to
characterise the vast range of potential oxidation products
of triglycerides [53]. The technique, termed atmospheric
pressure chemical ionisation mass spectrometry (APCI-
MS), involves liquid chromatographic separation of intact
oxidised TAGs, followed by online mass spectrometric
detection. The most commonly observed non-volatile
products of vegetable oil oxidation were hydroperoxides
and expoxides. The primary hydroperoxides that remained
intact were those formed from oleic acid and to a lesser
extent linoleic acid. Hydroperoxides formed from linolenic
acid and most of those from linoleic acid decomposed
further to yield other secondary compounds. Epoxides
formed stable and long lived species and resulted mainly
from the oxidation of monounsaturated fatty acids.
3.2.2.2. Impact on lubrication. It would be near impos-
sible to determine the impact of all non-volatile oxidation
compounds on lubrication performance, there are simply
too many, often with short lifetimes. Epoxides, as long-
lived products of oxidation, could impact on lubrication
performance. The lubrication performance of vegetable oil
epoxides has been examined [54,55]. Epoxidised vegetable
oils have a higher viscosity, greater oxidation stability,
lower deposit forming tendencies and display similar
boundary lubrication properties when compared to the
corresponding vegetable oil.
3.2.3. High molecular weight compounds
High molecular weight compounds are the product of
cyclisation and polymerisation reactions that occur at high
temperatures and pressures and represent the nal stages of
the oxidation process.
3.2.3.1. Analysis. AOCS Ofcial Method Cd 22-91 out-
lines the analysis of polymerised vegetable oils by gel
permeation, HPLC [56]. The method provides a distri-
bution of compounds based on molecular size, with
results presented as a percentage of high-molecular
weight compounds. No specic information is obtained
regarding the chemistry of the high-molecular weight
compounds.
Greater separation and identication of high-molecular
weight compounds has been obtained through the use of
high-performance size-exclusion chromatography (HPSEC)
[57]. Gomes et al. extended the ability to analyse oxidised
compounds by combining HPSEC with an initial separa-
tion of polar material [58]. Compounds with a polarity
greater than unaltered triglycerides, including triglyceride
oligopolymers, oxidised triglycerides, partial glycerides and
fatty acids, were rst separated from the oxidised vegetable
oil by silica gel column chromatography. The polar
 ARTICLE IN PRESS
N.J. Fox, G.W. Stachowiak / Tribology International 40 (2007) 10351046
compounds were then examined, with a high degree of
separation, by HPSEC.
The resistance to polymerisation of vegetable oil
lubricants has been examined using the Penn State
Microreactor, a technique described in greater detail later
during discussions on the assessment of oxidation stability
[2,4,59]. The level of unsaturation was determined to be the
major factor in the degree of oxypolmerisation experience
by the oil-increased unsaturation led to increased poly-
merisation. The level of polymerisation of vegetable oils
has also been assessed by changes in sample weight over
time [60].
3.2.3.2. Impact on lubrication. Polymerisation is generally
considered an undesirable aspect of lubricants, leading to
the formation of deposits and lacquers on lubricated
surfaces and substantial increases in viscosity. But poly-
merisation does not necessarily lead to failure of the
lubrication mechanism. In a study of oxidised vegetable oil,
extended oxidation led to polymerisation and release of
acids but also to reduced friction and wear under boundary
lubrication conditions [38]. It was uncertain, however, as to
which aspect led to the improved performance, increased
viscosity, free acids or polymerisation.
Polymerisation may even play a part in the lubrication
mechanism of vegetable oils under extreme conditions.
Murakami et al. observed an improvement in the lubrica-
tion performance of vegetable oils containing polyunsatu-
rated fatty acids at high temperatures, suggesting the
formation of friction polymers as a possible reason [19].
Hsu et al. examined the tribochemistry of copper and steel
surfaces lubricated by stearic acid and suggested the
tribochemical reaction products, including metal stearates,
were similar to those observed during thermally induced
reactions [61].
3.2.4. Fatty acids
Free fatty acids appear during the degradation of
vegetable oils. Fatty acids are primarily released from the
triglyceride by b hydrogen elimination and hydrolysis.
Both b hydrogen elimination and hydrolysis are not
oxidation reactions but are likely to occur coincidentally
with oxidation as another degradation process.
In triglycerides, there is a lone hydrogen on the 2nd, or b,
carbon. This b-hydrogen is readily susceptible to elimina-
tion. If the b-hydrogen is removed, the middle carbonoxy-
gen bond grows weak, and a free fatty acid will form [62].
Hydrolysis is the reaction of an ester with water
producing an alcohol plus an acid. In the case of vegetable
oils water reacts with the triglyceride removing a fatty acid
and leaving an alcohol group.
3.2.4.1. Analysis. The level of free fatty acids in vegetable
oils can be determined using the AOCS Ofcial Method Ca
5a-40 [63]. The method is a simple titration against sodium
hydroxide, with results reported as percentage by weight of
oleic acid. IR spectroscopy has been suggested as a
1041
instrumental tool for rapid determination of free fatty acid
levels [6467]. Each IR method was based on comparison
of oil samples with calibration standards containing known
levels of fatty acids using one peak [67] or a wavelength
range [66].
AOCS Ofcial Method Ca 5d-01 describes the analysis
of free fatty acids in vegetable oils by capillary gas
chromatography [68]. The vegetable oil rst undergoes
silylation, which derivatizes free fatty acids but leaves
triglycerides intact. The silyated fatty acids are then
detected and measured by the capillary gas chromato-
graph. This method allows both type and level of fatty acid
to be assessed. HPLC [69], supercritical uid chromato-
graphy [70] and nuclear magnetic resonance spectroscopy
[71] have also been successfully used to provide informa-
tion on both free fatty acid type and levels.
3.2.4.2. Impact on lubrication. The impact of free fatty
acids on the lubrication performance of vegetable oils has
been the subject of a number of studies [13,51,72,73]. Each
study suggests free fatty acids can improve the boundary
lubrication properties of vegetable oils.
Vizintin et al. examined the boundary lubrication
properties of rapeseed oil dosed with oleic acid using a
high-frequency, linearly oscillating friction and wear test
machine [13]. The addition of oleic acid (C18:1) to rapeseed
oil improved the wear performance up until a 3.17 GPa
load. At higher loads the blend and the base oil displayed
equal performance. The concentration of oleic acid
considered for optimal improvement was 5% by weight.
A four-ball machine was used by Cao and Yu to examine
the effect of saturated free fatty acids on the antiwear and
extreme pressure properties of rapeseed oil [51]. Fatty acids
improved wear resistance and the improvement was related
to chain length. The 12, 14 and 16-carbon chain fatty acids
all provided similar improvements. The 18-carbon chain
fatty acid (stearic) provided the greatest improvement out
those tested.
Minami et al. conducted experiments on high oleic
sunower oil using a pin on disc machine at bulk
temperatures of 50 and 75 1C and at a variety of loads
[72]. At 50 1C, the high oleic sunower oil performed
extremely well with additives playing little effect. Only at a
bulk temperature of 75 1C and high loads did the addition
of stearic acid (C18:0) improve the lubrication properties.
Fox et al. examined the effect of stearic (C18:0), oleic
(C18:1) and linoleic (C18:2) acids on the boundary
lubrication performance of sunower oil using a recipro-
cating ball on plate rig [73]. Stearic acid was the most
effective boundary lubrication additive in sunower oil,
reducing wear and providing a steady reduction the
coefcient of friction. Increasing the level of unsaturation
in the fatty acid had a negative inuence on the
performance as a boundary lubrication improver, with
the addition of linoleic acid displaying little to no
improvement. The stearic acid/sunower oil blend was
very effective until temperatures approached 150 1C.
 ARTICLE IN PRESS
1042 N.J. Fox, G.W. Stachowiak / Tribology International 40 (2007) 10351046
Whilst free fatty acids may provide some improvement
to the lubrication performance they may reduce the
oxidation stability [74]. Frega et al. evaluated the impact
of free fatty acids on the oxidation stability of the vegetable
oils using a Rancimat device [75]. Addition of free fatty
acids shortened the induction time of all the vegetable oils
tested.
4. Oxidation stability
Low oxidation stability is one of the major factors
hampering industry acceptance of vegetable oil-based
lubricants. The oxidation stability of vegetable oils can be
improved. Selective breeding programs and genetic mod-
ication can increase stability by reducing the level of
unsaturated fatty acids in the oil [25,76,77]. Similarly,
stability can be increased by chemical modication of the
oil structure by techniques such as blending, interesterica-
tion, hydrogenation and epoxidation [54,78,79]. Wagner et
al. have presented a thorough review of the techniques
available to modify and improve vegetable oil character-
istics from a lubricant industry perspective [80]. After
modication to the base oil, the stability of the formula-
tions can also be improved by addition of antioxidant
packages.
A balance, however, must be met between improving the
oxidation stability and preserving the lubricating properties
of vegetable oils. Too many modications may destroy the
properties that make vegetable oils useful in the rst place.
Reducing the level of unsaturated fatty acids, for example,
whilst increasing the oxidation stability, also reduces the
effectiveness of the lubricant at low temperatures. Major
chemical modications to the base oil would also
signicantly raise the cost of the lubricant.
Vegetable oils containing a large percentage of mono-
unsaturated fatty acids are the most likely candidates for
vegetable-based lubricants. They have a greater oxidation
stability than polyunsaturated oils, and also remain as a
uid over a much larger range of temperatures than fully
saturated oils. In common oilseed crops, the most
abundant monounsaturated fatty acid is oleic acid, an 18-
carbon atom chain.
4.1. Antioxidants
Antioxidants are used to improve the oxidation stability
of vegetable oil formulations and there are vast numbers of
papers assessing their effectiveness [2,4,19,57,60,8187].
Reviews discussing the effectiveness of a variety of
synthetic and natural antioxidants in limiting vegetable
oil autooxidation are available from both a food [28,8890]
and lubricant perspective [91]. Becker and Knorr presented
a particularly comprehensive evaluation of antioxidant
effectiveness in vegetable oils at elevated temperatures [92].
There are two major classes of antioxidant; chain
breaking radical scavengers and peroxide decomposers.
Chain breaking antioxidants react with radicals to form
stable compounds and prevent propagation of the oxida-
tion reaction. The most effective of the type quench the
initial peroxy and hydroperoxy radicals as well as the
alkoxy and hydroxy radicals formed during the branching
stages. Some less effective free radical scavengers only
quench the alkoxy and hydroxy radicals formed during
the branching stages. Commonly utilised chain-breaking
antioxidants include butylated hydroxy anisole (BHA),
butylated hydroxy toluene (BHT), mono-tert-butyl-hydro-
quinone (TBHQ), propyl gallate (PG) and the naturally
occurring tocopherols. Amine-based antioxidants, such as
diphenylamine, are not very effective in vegetable oils.
Bond dissociation energies can be used for the selection
and design of chain-breaking antioxidants. Zhu et al.
discussed a method used to determining the bond
dissociation energy of acidic HA bonds, along with the
potential benets to predicting antioxidant effectiveness
[93]. Bond dissociation energies inuence the effectiveness
of hydrogen atom transfer reactions from the antioxidant
molecules to the reactive radical intermediates such as
hydroxyl, alkoxyl, peroxyl and hydroperoxyl radicals
formed during the degradation reactions. For an antiox-
idant to efciently quench all destructive radical inter-
mediates its bond dissociation energy would have to be
lower than that of the peroxyl and hydroperoxyl radicals.
Peroxide decomposers are the other major class of
antioxidant. The role of peroxide decomposers is to react
with and decompose hydroperoxides. Generally hydroper-
oxide decomposition produces more free radicals that
propagate and branch the oxidation process. Hydroper-
oxide decomposition by peroxide decomposers, however,
results in stable compounds and thus limiting oxidation.
Common examples of peroxide decomposers used in
vegetable oils are catalase and glutathione.
Some antioxidants display multiple functionality. Zinc
dithiophosphates (DTP) and dithiocarbamates (DTC), for
example, act as both radical scavenger and peroxide
decomposer. Ascorbic acid, a natural antioxidant, acts by
scavenging oxygen, getting preferentially oxidised to water
and dehydroascorbic acid. Reaction with reduced glu-
tathione can then regenerate the ascorbic acid. Ascorbic
acid can also acts as a metal chelator.
Metal-chelating agents and UV absorbers are not strictly
antioxidants, but can assist in the prevention of oxidation.
UV absorbers, such as phenylsalicylate and hydroxyben-
zophenone, prevent decomposition of hydroperoxides by
UV exposure. Metal-chelating agents, such as citric acid
and ethylene diamine bind metal ions that can catalyse
hydroperoxide decomposition. These compounds often
complement the action of antioxidants.
Certain combinations of antioxidants can result in
synergism, where the result of the whole is better than
the two parts. Butylated hydroxy anisole with butylated
hydroxy toluene or propyl gallate is a synergistic combina-
tion of antioxidants for storage at ambient conditions, but
combining butylated hydroxy toluene and propyl gallate
results in negative synergism. At higher temperatures
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synergism is displayed with combinations of phenols with
sulphides or aromatic phosphates. Combining phenols and
aromatic amines display slightly negative effects.
Antioxidant effectiveness is affected by several factors
including the base oil composition, environmental condi-
tions and the presence of other additives. The presence of
high levels of polyunsaturated fatty acids in the vegetable
base oil severely reduces the benet of any added
antioxidants. Temperature is a major contributing factor.
Some antioxidants decompose at higher temperatures, e.g.
propyl gallate, others simply become less effective, e.g.
tocopherols. Becker and Knorr established that protection,
or hindering, of the active hydroxyl group was critical for
continued effectiveness of free radical scavengers at high
temperatures [92].
4.2. Assessment of oxidation stability
The methods used to assess the oxidation stability of
vegetable oil formulations must be carefully matched to the
intended application in order to obtain realistic estimates.
Hsu has reviewed laboratory bench tests for automotive
industry, including those used for estimating oxidation and
high-temperature stability [94,95]. Hamblin later discussed
Hsus review of assessing lubricant stability with the view
of selecting tests suitable for vegetable oils [91]. Frankel
reviewed the techniques used by the food industry to assess
oxidation stability [96]. Not all techniques used to estimate
the oxidation stability of mineral oil formulations are
directly applicable to vegetable oils. Of particular concern
is the presence of water in the trials, especially if the end
point is determined by acidity. Vegetable oil triglycerides
are susceptible to hydrolysis, breaking down with water
into glycerol plus free fatty acids. Assessing just acidity as
the end point of an oxidation trial may give a false
estimate. Effective methods of assessing the oxidation
stability of vegetable oil formulations are discussed below
and summarised in Table 3.
The Schaal oven test, used by the food industry, has the
fewest limitations associated with it when considering the
shelf life of vegetable oils. The test conditions are described
in the AOCS Recommended Practice Cg 5-97; Oven
Storage Test for Accelerated Aging of Oils. Samples,
stored in a dark, forced draught oven at a temperature
between 60 and 70 1C are periodically monitored for
changes in primary and/or secondary oxidation com-
pounds. The test is ended when a dramatic change is
observed in the oil. The test is most accurate when both
primary and secondary compounds are monitored. The
major advantage of the test is that the conditions, and thus
results, are truly representative of storage at ambient
conditions. The concerns are that the method is slow and
requires a large number of analyses.
Increasing sample temperatures and automating the
analysis can accelerate oxidation stability trials. A com-
monly used accelerated test for vegetable oil stability is the

Table 3
Summary of methods used to assess the oxidation stability of vegetable oil formulations

Oxidation trial Description Advantages Disadvantages

Schaal oven test [97]  Long-term storage at elevated  Excellent representation of  Long trial periods
temperatures storage  Large number of analytical trials
 Monitor products of oxidation  Simple experimental
conditions

Field trials  Assess lifetime and performance  Excellent representation of  Long-term trials
during application in eld lubricant service lifetime  Complex
 Monitor products of oxidation/  Expensive
variation in performance

Active oxygen  Bubble air through oil held at 98 1C  Reduced trial times  Rapid loss of volatiles or degradation
method/Rancimat  Monitor volatile acids and/or  Rancimat is a commercial, of peroxides can make end point
[98] peroxides automated variation questionable
 Large variations in acidity/peroxides  Accelerated trials may not represent
signies end point reality

Penn State  Small sample oxidised over xed  Small volume  Requires access to /establishment of
microreactor [2,4,59] period of time  Accelerated trials microreactor
 Oxidised sample washed with  Characterises oxidation  Accelerated trials may not represent
THFTHF/oxidation solution analysed compounds reality
by gel permeation chromatography

Differential scanning  Small sample subjected to temperature

calorimetry program  Small volume
[25,82,99,100]  Thermodynamic variations monitored  Accelerated trials  Requires access to calorimeter
 Oxidation observed as rapid release of  Accurate thermodynamic  Accelerated trials may not represent
energy information reality
 ARTICLE IN PRESS
1044 N.J. Fox, G.W. Stachowiak / Tribology International 40 (2007) 10351046
active oxygen method (AOM). The AOM involves
bubbling air through oil held at 98 1C. The Rancimat is
commercial, automated version of the AOM that measures
large variations in volatile acids or peroxides as the
endpoint. Tests can range in length from less than an hour
to above 300 h using the AOM and up to weeks with the
Schaal oven test [98].
The Penn State Microreactor is an effective technique
that provides estimates of vegetable oil volatility, oxidation
stability and deposit-forming tendencies [2,4,59]. Accelera-
tion of the oxidation process is achieved through a
combination of small volumes, large surface areas, elevated
temperatures, catalysis and plentiful availability of oxygen.
A small sample volume, 40 uL, is injected onto a heated
catalyst surface and held at a constant temperature with a
controlled supply of dry air for the test duration. At the
end of the trial the catalyst is washed with THF and the
solution analysed by gel permeation chromatography to
determine the degree of polymerisation. The catalyst
container is weighed before and after sample addition to
determine sample weight. After the test, but before
washing, the container is weighed again to determine any
loss or gain in the sample. The container is weighed for the
last time after washing with THF to check any weight
change from possible attacks on the surface. The Penn
State Microreactor is effective as its rapid and provides a
variety of information regarding the oxidation degradation
process.
Differential scanning calorimetry (DSC) is another
technique that has been used to examine the oxidation
stability of vegetable oil formulations. DSC is an analytical
technique used to measure the thermal transitions oc-
curring within a test sample, whilst subjected to a precisely
programmed temperature change [99]. Tan and Che
Man presented a comprehensive review of the potential
of DSC in studying vegetable oil oxidation [100]. Estimates
of oxidation stability and antioxidant effectiveness by
DSC compare well with other accelerated techniques.
As changes in energy are accurately measured during
DSC trials, the technique is also well suited for examining
kinetic studies. A combination of PDSC/NMR was
recently used to examine the oxidation kinetics of
genetically modied vegetable oils [25]. Quantitative H1
and C13 NMR provided structural information regarding
the vegetable oils, which were statistically compared to
kinetic data from the differential scanning calorimeter to
elucidate behaviour.
The major concern with all temperature accelerated
oxidation tests used to consider storage life is that the test
conditions are no longer representative of storage at
ambient conditions. One difculty is that the mechanism
for vegetable oil autoxidation alters as temperatures rise
above 80 1C. At high temperatures side reactions involving
polymerisation and cyclisation become more important.
Hydroperoxides also decompose more rapidly at elevated
temperatures into secondary compounds, so using mea-
surements of peroxide level in determining the extent of
oxidation become limited. Alterations in effectiveness, or
possible decomposition, of antioxidants also need to be
considered. In order to predict performances at lower
temperatures, accelerated oxidation tests should be con-
ducted at multiple temperatures to assess the impact of
temperature on results.
Correlating results of oxidation stability trials of
lubricants to actual application lifetimes is even more
difcult than predicting storage life. The conditions
the lubricant is subjected to during the application should
be determined and trial conditions established to mimic
the application as close as possible. Conditions would
include, but not be limited to, oxygen availability,
presence of catalysts, pressure, temperature and lubricant
replenishment. How oxidation impacts on lubrication
performance should also be understood in order to
determine what indicators would be best used to assess
lubricant lifetime. Chen and Hsu recently presented an
attempt to combine bench tests and computer models to
predict lubricant performance over time [101,102]. A
chemical kinetics model, using constants derived from
bench tests, was combined with a nite difference
programme, simulating engine-operating conditions, to
predict lubricant performance in diesel engines. The
simulations displayed good agreement with engine dynam-
ometer trials.
5. Summary
Low oxidation stability hampers the acceptance of
vegetable oils as a potential source of environmentally
favourable lubricants. The mechanism of vegetable oil
oxidation is well studied along with methods for improving
the oxidation stability, such as antioxidant addition or
modication of oil composition. Oxidation has an impact
on the lubrication performance of vegetable oils and quite
possibly plays a role in the lubrication process. Correlating
studies of oxidation with lubrication performance will lead
to greater understanding into the role of oxidation in the
lubrication mechanism of vegetable oils.
Acknowledgements
The authors wish to thank the School of Mechanical
Engineering, University of Western Australia for its
support during the preparation of this paper.
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