AWT -F-93 (Nov-93)

Association of Water
Tecllnologies
Association of Water Technologies, Inc.
5
th
Annual Convention & Exposition
Water Technologies '93, 7 to 10 November 1993
Caesars Palace, Las Vegas, Nevada
The Role of Polymers
In Water Treatment Applications
And Criteria for Comparing Alternatives
Robert W. Zuhl, P .E. and Zahid Amjad, Ph.D.
Lubrizol Advanced Materials, Inc. (Cleveland, OH)
Lubrizol
.., --..
Carbosperse K-700
Water Treatment Polymers
@ 2007 The Lubrizol Corporation, all rights reserved.
* Formerly BFGoodrich Performance Materials.
** Formerly Good-Rite K-700 Water Treatment Polymers.
Table of Contents
ABSTRACT ~ ..................................................................................................................................... 1
INTRODUCTlON ........................................................................................................................... .
AN OVERVIEW OF POL YMERS ............................................................................................... ..
SYNTHETIC POL YMERS............................................................................................................. 1
PoIymerizationMethods.......................................................................................................... 1
Polymerization Processes.................................. .......................... ................. ...... ........ ............. 2
Polymer Characteristics................ ...... ......... ....... ..... ............. .............. ........ ........... ............. ..... 3
Parameters Typiiying Polymer Properties and Specifications.... ............ ...... ...... ........ ...... ........ 5
Differatces Between Water Treatment Polymers.................................................................... 7
1HE ROLE OF POLYMERS IN WATER TREATMENT APPliCATIONS.............................. 9
Overview ................................................................................................................................ 9
HistoIy..................................................................................................................................... 10
Deposit Contro\ Mecbanisms........................... ...................... ...................... ...... ..................... II
CRITERIA FOREV ALUATING WATER TREATMENT POLYMERS.................................... 12
EXPERIMENTAL PROCEDURES.................................................................... ............................ 12
RESULTS AND DISCUSSiON...................................................................................................... 12
Products Evaluated. ........................... ..................................................... ............................ ..... 13
Calcium Carlxmate Inhibition.................. ....... ............. .............. ......... ......... ............................ 13
Calcium Ion Tolerance............................................................................................................ 13
Calcium Phosphate InIubition.................................................................................................. 14
Calcium Phosphonate InIubition................... ........................................................ ................... 14
Iron Stabilization................................................................................................. .................... 14
Iron Oxide Dispersion........ .................... ................................................................................. 14
SilIlJlated Boi1er Water Treatment Conditions....................... ................................................ 14
CONCLUSiONS............................................................................................................................. 15
ACKNOWLEDGMENTS............................................................................................................... 16
REFERENCES................................................................................................................................ 16
TABLES AND FIGURES
Table I: Polymer Molecular Weight Measurement Methods..... ......... ................................. 19
Table 2: Parameters Typifying Water Treatment Polymer Properties and Specifications..... 20
Table 3: Appearance of Competitive Water Treatment Polymers Supplied as Uquids......... 20
Table 4: Comparison ofTwo 5,000 Mo1ecu1ar Weight Polyacrylates................................ 21
Table of Contents (continued)
Table 5: Comparison of Two 2,000 Molecular Weight Polyacty\ates.................................... 21
Table 6: Types of Water Treatment Polymers........................................................................ 22
Table 7: Role of Polymers as Deposit Control Agents in Cooling and Boi1er Water
Treatment App1ications............................................................................................. 22
Table 8: BFG's Criteria for Evaluating Water Treatment Polymers........................................ 23
Table 9 Testing Procedures for Evaluating Water Treatment Polymers................................ 24
Table 10: Commercia1Iy Available Products Tested................................................................. 28
Figure 1: Typica1 MoIecu1ar Weight Determinations for GOOD-RITE K-752 and
K-732 PoIyacryIates.................................................................................................. 30
Figure 2: Quantity of Caustic Soda Needed to Neutralize GOOD-RlTE K-7028 and
K-7058 PoIyaayIates to a Desired pH...................................................................... 30
Figure 3: Chemical Structure for Three Homopolymers.......................................................... 31
Figure 4: Chemical Structure for Four Acrylate Copolymers.................................................. 31
Figure 5: Cooling Water Treatment Prognuns......................................................................... 32
Figure 6: Calcium Carbonate Scale Inhibition for Competitive Polyacrylates
(Under Stressed Test Conditions)............................................................................. 33
Figure 7: Calcium Carbonate Scale InIubition for Competitive PolyaayIates
(Under Moderate Test Conditions)........................................................................... 34
Figure 8 Calcium Carlxmate InIubition for Products (Under Moderate Test Conditions)...... 34
Figure 9: Calcium Ion Tolerance ofGOOD-RlTE K-752 and K-732 as a Function
of Temperature........................................................................ ................................. 35
Figure 10: Calcium Ion Tolerance ofGOOD-RlTE K-700 Polyacrylates and
Competitive Deposit Control Agents................................ ........................................ 36
Figure 11: Calcium Ion Tolerance for Various Copolymers...................................................... 36
Figure 12: Calcium Phosphate InIubition................................................................................... 37
Figure 13: Calcium HEDP InIubition.......................................................................................... 37
Figure 14: Iron Stabi1ization....................................................................................................... 38
Figure 15: Iron Oxide Dispersion for Competitive CWT Polymers....................... ..................... 38
Figure 16: Iron Oxide Dispersion for Competitive BWT Polymers Before and After
Thermal Treatment ................................................................. ,. ........... ..... .... .... ........ 39
Figure 17: Hydroxyapatite Dispersion for Competitive BWT Polymers Before
and After Thermal Treatment............. .......... ............... ................... .......................... 39
ABSTRACT
Water treatment technology has made significant advances since the introduction of synthetic water
treatment polymers in the 1950s. A wide range of homopolymers, copolymers, and terpolymers are
available for use by water treatment formulators. This paper provides a guideline for evaluating
alternative polymers.
INTRODUCTION
This paper reviews synthetic polymers and specifically those used for deposit control in the water
treatment industry. The parameters by which polymers may be characterized are discussed. The role
of polymers and criteria for characterizing their properties are presented. The criteria for evaluating
water treatment polymers were used to compare several commercially available polymers. The results
indicate that BFGoodrich's GOOD-RITE K-700 polymers provide excellent performance which
meets or exceeds that of competitive products.
AN OVERVIEW OF POLYMERS
The word "polymer" has Greek origin from the words "poly" (many) and "mer" (part).
A polymer is a substance made of giant molecules formed by the union of many small molecules
(monomers) into long chains. Generally, organic polymers have carbon backbones such that the links
between the monomer consist of carbon-carbon bonds.
Polymers may be either natural such as tannins and lignosulfonates or synthetic such as polyacrylic
acids and acrylate copolymers.
SYNTHETIC POLYMERS
Polymerization Methods
Polymerization refers to the bonding of two or more monomers to produce a polymer. Polymerization
is also any chemical reaction that produces such a bonding. Polymerization methods for synthetic
polymers include precipitation, solution, suspension, emulsion, and bulk as discussed below. All of
these polymerization methods have the advantage of heat and viscosity control during the
polymerization. The desired product properties dictate the choice of the polymerization process.
Precipitation Polymerization
In precipitation polymerization, all reactants are initially soluble in the polymerization solvent.
Polymerization proceeds in solution until the polymer reaches a critical molecular weight when
precipitation of the polymer occurs due to polymer insolubility in the solvent. Polymerization then
proceeds in the heterogeneous medium by absorption of monomer and initiator in to the polymer
particles.
Solution Polymerization
In solution polymerization, all reagents including the polymeric product remain soluble in the
polymerization solvent throughout the reaction.
Suspension Polymerization
In suspension polymerization, droplets (50 to 500 mm) of a water insoluble monomer are suspended in
water by means of a suspending agent (usually less than 0.1 weight % of the aqueous phase). Both the
suspending agent and agitation are necessary in order to keep the monomer droplets from coalescing.
By reusing large amounts of dispersing agent (> 1 weight %), very small monomer droplets can be
produced which give polymer particle size ranging form 0.5 to 10 mm. The process is then called
dispersion polymerization.
Emulsion Polymerization
In emulsion or latex polymerization the polymerization of monomer only occurs with monomer that is
contained within the micelles (colloidal dispersion) that are formed in water by means of a surfactant.
These colloidal dispersions are generally stable, and, once formed, do not need agitation to maintain the
colloidal state. A hydrophilic monomer is emulsified in water and polymerization is initiated with a
water soluble initiator.
Inversion Emulsion Polymerization
In inverse emulsion, a hydrophilic monomer is emulsified in a non polar organic solvent.
Bulk Polymerization
Bulk polymerization is the polymerization of the neat monomer(s).
Polymerization Processes
Reportedly, there are over 50 polyacrylate manufacturers in the United States. Many of these products
are used internally in applications that do not demand the consistent high quality and performance
requirements of the water treatment industry. Less than a dozen manufacturers are actively supplying
the water treatment industry. Not surprisingly, there are wide variations in the manufacturing
processes as well as the product appearance, consistency, and physical properties of the polyacrylates
offered.
Manufacturers of water treatment polymers supplied to water treatment formulators use a variety of
manufacturing techniques. For example, BFGoodrich uses different solution polymerization processes
for the GOOD-RITE K-700 polymers. The choice of a polymerization process depends upon
2
several considerations including technology alternatives, product perfonnance and application
requirements, and economics.
Solution polymerization is the primary method for manufacturing water treatment polymers used as
scale and deposit control agents. Solution polymerization process variables include polymerization
medium (water, solvent), initiator / catalyst, chain transfer agent, monomer(s), temperature, time of
reaction, and agitation. For brevity we will not discuss these variables here. However, it is important
to note that polymer manufacturing complexity increases proportional to the number of monomers in
part because of the different properties and reaction rates of individual monomers.
Polymer Characteristics
Polymers may be characterized by several parameters including molecular weight, tacticity, end groups,
branching, residual monomers, and homogeneity or heterogeneity as discussed below.
Molecular Weight
A polymer sample consists of varying ("short" and "long") chain lengths as opposed to a monomer
sample where all molecules have exactly the same length. Hence, a polymer sample does not have a
unique molecular weight, unlike a monomer which has a precisely defined molecular weight. A
polymer sample is characterized by an average molecular weight and a molecular weight distribution.
The actual number depends upon the measurement method and there may be considerable associated
bias.
Table 1 provides a listing of molecular weight measurement methods among which gel permeation
chromatography (GPC) and viscosity are the two most frequently used by water treatment polymer
manufacturers. The major measurements used to characterize the molecular weight of a polymer are
summarized below:
- Mw
=
-Mn =
=
-M.
=
- Mw'Mn
=
weight average:
number average:
emphasizes the central portion of the molecular weight
distribution
emphasizes the low molecular weight fraction
high molecular weight fraction; the larger this is compared to Mw, the more
high molecular weight fraction is present
viscosity average:
polydispersity:
used to compare data from gel permeation
chromatography (Ope) molecular weight
measurements; close to the weight-average molecular
weight
measures the breadth of the molecular weight
distribution; the smaller this number, the narrower the
distribution
3
Figure 1 illustrates typical molecular weight determinations for two commercial polyacrylates.
Tacticity
Monomers may contain atomic groups that are not involved in the polymerization reaction that form
the polymer backbone. These groups become pendant to the main chain. The pendant groups may be
arranged in a regular manner about the polymer backbone. This gives rise to polymer tacticity.
When all the pendant groups are on one side of the planar zigzag polymer chain, the polymer is
isotectic. When the pendant groups are located alternately on opposite sides of the plane of the
polymer chain, the polymer is syndiotactic. If the distribution of the pendant groups are random, the
polymer is atectic.
End Groups
Initiator molecules are used to commence the polymerization process. A fragment from the initiator
will bond with the monomer to start a chain. The initiator fragment is then attached to one end of the
polymer chain, thus becoming an "end group" when the polymer chain stops growing due to chemical
reactions that prevent monomer addition to the chain end, another "end group" is formed.
Branching
During the polymerization process, chemical reactions take place on the backbone of a polymer chain
causing the formation of a new polymer chain attached to the original one. This phenomenon is known
as branching.
Residual Monomers
Polymerization reactions or the linking of monomers to form large chains are subject to chain
termination reactions. Thus, at the end of a polymerization reaction, unreacted monomers or residual
monomers will be left admixed with the polymeric product.
Homogeneity and Heterogeneity
When only one monomer is involved in the polymerization process, the product is homogeneous. For
example, if two monomers A and B are copolymerized, and both A and B are equally reactive in the
polymerization reactions, then monomer A and B will be randomly distributed in all of the polymer
chains, and the product is homogeneous. However, a heterogeneous polymer is made, if monomer B
is less reactive then monomer A. In this case, the initially formed polymer chains contain larger
amounts of monomer A vs. monomer B. As the concentration of monomer A decreases, the polymer
chains formed later in the reaction will contain more of the copolymerized monomer B. Further, within
each chain, the distribution of monomers A and B would not be random.
4
Parameten Typifying Polymer Properties and Specifications
Most of the water treatment polymers supplied to fonnulators are supplied as liquid solutions. The
polymers may be characterized by a variety of parameters as shown in Table 2 and discussed below:
Water treatment polymers are typically water solutions. However, powdered sodium salts are supplied
and used for special applications.
Appearance
Water treatment polymer appearance is an aesthetics rather than a performance issue. The goal of
manufacturers and fonnulators should be a consistent product ... batch to batch, lot to lot, and shipment
after shipment. The polymer manufacturer should have procedure in place to ensure that the product
meets a visual appearance specification and is free from any contamination.
The appearance of one polymer compared to another may differ greatly. Examples of the product
literature descriptions for the "Appearance" of several competitive water treatment polymers supplied
as liquids are shown in Table 3.
Total Solids
Total solids is a measurement of the non water component ofa polymer. The higher the total solids
the greater the specific gravity and viscosity of a product. The total solids for a particular polymer are
normally limited by product stability during storage conditions and/or handling considerations.
Total solids measurements are used to verify that the proper level of ingredients have been used to
manufacture the polymer. A polymer manufacturer's product approval should be based on a
specification that states an acceptable total solids range which is typically the midpoint plus or minus
one (1) percent (%).
Polymer manufacturers use a variety of test methods for determining product total solids. Ideally, a
total solids test procedure should be based on removing the volatile or liquid component from the
product without burning or degrading the synthetic or polymeric component. Since the late 1970s,
BFGoodrich has been using a highly reproducible microwave drying that provides a rapid method for
total solids and volatiles determinations.}
Active Solids
The active solids of a polymer is the difference between the total solids and counter ions added by post
polymerization neutralization typically with sodium hydroxide. Post polymerization neutralization is
frequently not the only source of sodium ions in a polymer. Thus, active solids can not be measured
directly. Therefore, active solids values are normally reported as a typical value (calculated) rather than
a measurement.
5
It is important to remember that only the synthetic polymeric component of a product not the counter
ions from neutralization provides value added performance. Unfortunately, most polymer
manufacturers do not report active solids.
Molecular Weight
A consistent molecular weight is critical to a polymer's performance. Unfortunately, the test
procedures for molecular weight determinations are very expensive and time consuming and are
therefore not well suited for use as quality control tests. Molecular weight test methods are likely to be
run by the analytical department of polymer manufacturer's R&D organization but are not typical for
manufacturing operations. Polymer manufacturers typically define a product by total solids and
viscosity specifications which are closely related to a polymers molecular weight. It is also possible
although very time consuming to develop correlations of total solids and viscosity to molecular weight.
BFGoodrich uses GPC molecular weight measurements
2
as well as viscosity methods for molecular
weight determinations.
Measurements of pH are used to verifY that a product has been produced to established specifications
and is direct indication of the extent to which a polymer is neutralized.
Viscosity
A polymer's viscosity as discussed previously is directly related to molecular weight. Therefore,
viscosity measurements are a means to verifY that a product is within established specification.
BFGoodrich uses Brookfield Viscosity measurements as a method to verifY that each polymer is within
established molecular weight tolerances. Product approval is based on an established specifications and
a specific test procedure (i.e., 25C, RVF # spindle, and rpm) for each product.
Acid Number
Acid number measurements are a means to verifY that a copolymer is within established compositional
tolerances.
Specific Gravity
Specific gravity provides a measurement of a product's density. Although specific gravity is a relatively
easy test to run, the information it provides pertaining to a product's composition vs. water is
redundant to total solids measurements.
Color measurements such as Gardner (yellow), Lovibond yellow, and Lovibond red may be used as an
indicator of a product's appearance.
6
Other Parameters
The are a variety of other parameters such as turbidity, haze, iron, and residual monomer levels that
may be of interest for specific water treatment polymers and/or for particular applications. A brief
discussion of each of these parameters follows.
Turbidity and haze measurements are not typical quality control parameters. However, turbidity and/or
haze measurements may provide a means to verifY that a polymer meets an established criteria for
appearance.
Water treatment polymers typically contain low levels of iron as a byproduct of the manufacturing
process or which were present in the raw materials. However, iron measurements are not a typical
quality control test. Only in rare cases will polymer iron levels be a concern. A polymer may contain
excessive iron levels if it turns black when fully neutralized with caustic soda.
Unreacted or residual monomer(s) may be a health / safety work exposure, production process
efficiency, or regulatory issue. Residual monomers are not a typical quality control test. However,
periodic testing of a residual monomer levels may be used by a polymer manufacturer to ensure that the
production process is operating properly or to meet a regulatory agency requirement for new chemical
substances.
BFGoodrich makes certain that all the OOOD-RITE K-700 polymers conform to established criteria
by rigorously controlling manufacturing production process parameters. BFGoodrich applies statistical
process control to manufacturing process control parameters as the principal means for ensuring
quality constituent product quality. In addition, a variety of quality control tests to measure parameter
such as those discussed above are used as a means for confirming that each product meets established
requirements.
Differences Between Water Treatment Polymers
The following discussion was originally developed by BFGoodrich during mid 1992 and provided to
RCavano of Scranton Associates, Inc. for use in the AWT's "Raw Material Specification Manual.,,3
Although much of the discussion below appears in the A WT manual there have been several
modifications and additions.
Acrylate based water treatment polymers are normally polymerized as acids but not all polymerization
processes are the same. Polymers are typically neutralized with sodium hydroxide after polymerization
to various degrees in order to:
Provide pH values above the lower DOT limit for corrosive materials, and/or
Ensure product stability in the drum, and/or
Meet specific customer requirements.
7
However, polymer neutralization adds inactive solids and thus higher pH values
Imply greater gaps between total and active solids and
Necessitate lower total solid levels in order to supply products with manageable viscosities
Accordingly, in addition to molecular weight properties, it is important to examine the pH, total solids,
and active solids of competitive polymers in order to ensure "an apples to apples comparison." The
examples shown in Tables 4 and 5 provide comparisons of two ~ 5 , O O O and two ~ 2 , O O O molecular
weight polyacrylates and present a guideline for how water treatment formulators can compare
"functionally equivalent" polymers. It is obvious from the analysis shown in Tables 4 and 5 that a
water treatment formulator is obtaining a higher value in terms of active polymer content with Products
B and D vs. Products A and C, respectively.
Another way to understand the differences between water treatment polymers supplied at different pH
values is to obtain or develop neutralization CUIVes for water treatment polymers such as shown in
Figure 2 for GOOD-RITE K-7028 and K-7058 polyacrylates ( ~ 2 , O O O and ~ 5 , O O O molecular weight
respectively). BFGoodrich provides neutralization curves for GOOD-RITE K-700 polymers supplied
as liquids.
Extending the discussion above, it is logical and in practice has been found that concentrated polymers
(those supplied at higher total solids and lower pH values) more readily facilitate the preparation of
more concentrated water treatment formulations. In addition, polymers supplied at higher total solids
and lower pH values means less packaging materials and freight costs per active pound of polymer
supplied to water treatment formulators.
Most polymer manufacturers use aqueous polymerization processes. However, solvent polymerization
processes that result in the manufacturer of products and polyacrylates in particular with performance
characteristics that are superior to aqueous polymers. 4,5
One such polymerization process is used by BFGoodrich for manufacturing GOOD-RITE K-732 and
K-752 polyacrylates. The distinguishing properties of GOOD-RITE K-732 and K-752 polyacrylates
vs. other polyacrylates of the same molecular such as those made by aqueous polymerization processes
(e.g., GOOD-RITE K-7058 and K-7028 polyacrylates) respectively include:
Exceptional calcium ion tolerance (facilitating the operation of cooling systems at higher cycles of
concentration),
6
Greater thermal stability (comparable to polymaleates and polymethacrylates),
7
and
Better silt dispersion.
8
8
Elaborating on the second point above, Masler
7
concluded the following based on his testing of
polymers under simulated boiler water treatment conditions (PH 10.5, 250C, 18 hr):
Polyacrylates (manufactured by BFGoodrich's solvent polymerization process), polymethacrylates,
and polymaleates all undergo some thennal degradation.
Polyacrylates displayed about the same resistance to thennal degradation as do polymethacrylates.
Polyacrylates are more thermally stable than polymaleates.
Dubin and Fulks
4
concluded that "polymer structure, molecular weight and even the method of
manufacture and choice of solvent will strongly influence the activity of a polymer. The practical
significance of this is that gross descriptions of polymers such as polyacrylate or copolymers do not
accurately describe a polymer accurately or define its performance, especially under different water
conditions. "
BFGoodrich believes that "it is often desirable to use a polymer product in which the molecules are as
similar as possible,,6 or to have a polymer with a narrow molecular weight distribution. However,
others
9
have found that polyacrylates with broad molecular weight ranges are generally more cost
effective than polyacrylates with narrow molecular weight ranges. Regardless of whether broad or
narrow molecular weight distributions are optimal, there is a consensus that molecular weight is a key
factor in determining the optimal polymer(s) for a particular application.
4
,9,lO,1l
IRE ROLE OF POLYMERS IN WATER TREATMENT APPUCA nONS
Oveniew
Deposit control methods for water treatment applications include:
Maintaining water chemistry below saturation levels by controlling the:
Cycles of concentration:
pH
Temperature
Pretreatment of feed waters
Threshold treatments
by controlling blowdown
by sulfuric acid addition
by controlling flow rates, heat loads, etc.
via mechanical (e.g., reverse osmosis) or chemical (e.g.,
clarification) means
using chemicals at sub stoichiometric dosages
9
History
Table 6 provides a summary of the various types of polymers used as deposit control agents by the
water treatment industry. Figures 3 and 4 show the structures for several homopolymers and acrylate
copolymers, respectively. Additional information is provided by Wilkes
l2
in his recent NACE
CORROSION/93 paper entitled "A Historical Perspective of the Scale and Deposit Control -
(1943-1993)."
The use of synthetic water treatment polymers (polyacrylates, polymethacrylates, hydrolyzed
polyacrylamide, acrylic acid/acrylamide copolymer, and styrene maleic anhydride copolymers) dates
back to the 1950s.1
2
The early synthetic polymers used were high molecular weight (100,000+ Mw)
homopolymers of acrylic acid. With the passage of time, lower molecular weight polyacrylates as well
as polymethacrylates and polymaleic acids were found to be more efficacious. Researchers have
shown that polyacrylate molecular weight is an important consideration relative to performance.IO,ll
Eventually, copolymers of acrylic acid, methacrylic acid, and maleic acid were found to provide
improved performance characteristics for specific applications.
In the late 1970s, Betz Laboratories introduced the Dianodic II stabilized phosphate cooling water
treatment program which incorporated the use of an acrylic acid I hydroxypropyl acrylate (AA/HP A)
copolymer. Reportedly, the AA/HP A copolymer technology which Betz patented and used for this
application was not originally intended for use in cooling water treatment but in the pulp and paper
industry. The Dianodic II program dominated the heavy industrial cooling water treatment market
place for a number of years as it provided an environmentally acceptable alternative to chromate
programs.
In the mid 1980s, Calgon Corporation introduced its pHreeGUARD cooling water treatment
program based on an acrylic acid I sulfonic acid (AAlSA) copolymer called TRC-233. This
copolymer technology was touted as having and "improved operating conditions by eliminating or
minimizing acid feed, removed the potential for deposit formation, and increased cycles of
concentration."
l3
Subsequently, a barrage of technical papers touted successful applications of non chromate cooling
water treatment programs or polymers for use in these programs including alkaline all-organic, 14, 15
phosphate-based, 15, 16,17 molybdate-based,18 and alkaline-zinc
I9
. These papers and several others20,2l,22,23
point out that the secret to the successful application of non chromate cooling water treatment
programs was the evolution of copolymer technology that is capable of supporting the alternative
corrosion inhibitor programs.
The success of the Betz Dianodic II program is largely responsible for triggering efforts by other water
service companies and merchant market polymer manufacturers to develop alternative polymer
technology. The rapid research and development period occurred during the 1980s and led to the
introduction of a variety of new merchant market polymers. These new copolymers as a class have
been targeted to provide specific performance properties. However, these products have been
progressively more expensive and several are very special niche products.
10
The role of water treatment polymers as deposit control agents in cooling and boiler water treatment
programs is summarized in Table 7. Wilkes
12
provides a review of the functions and mechanisms of
polymers as deposit control agents. Other paperslS,16,20,21,24 outline the generic components used in non
chromate cooling water treatment programs and how these programs should be selected and applied. 16
Deposit Control Mechanisms
The major non chromate cooling water treatment programs in use today and the roles of synthetic
polymers are summarized below:
CWTProgram
All-organic
Stabilized phosphate
Molybdate-based
Alkaline zinc
Polymer Functions
Ca-phosphonate inhibitor, dispersant
Ca-phosphate inhibitor, dispersant
Ca-phosphonate inhibitor, Ca-phosphate inhibitor, zinc stabilizer,
dispersant
Ca-phosphonate inhibitor, zinc stabilizer, dispersant
Macdonald
16
prepared an excellent guideline article entitled "Choosing the Correct Cooling-Water
Program" which provides a framework for identifYing the best program for a particular site. This
article includes a diagram reproduced in Figure 5 which presents the most appropriate pH range for the
cooling water treatment programs noted above.
Boiler water treatment programs in use today may be categorized and their treatment objective
described as outlined below:
"Precipitation"
"Carbonate cycle" programs depend upon the dispersion of calcium carbonate as boiler
sludges. Normally, natural organic polymers such as starch and lignin derivatives are used in
carbonate cycle programs.
"Phosphate cycle" programs rely upon the precipitation and dispersion of calcium phosphate
sludge (ideally calcium hydroxyapatite) to minimize accumulations on heat transfer surfuces.
Synthetic polymers are used to ensure that the sludge remains fluid until removal via
blowdown.
"Coordinated phosphate" programs are typically used in boilers operating at 800 psig and
above. Alkaline and acid phosphates (e.g., mono-, di-, and trisodium) are used to control free
caustic that accumulates in restricted flow areas. Neutralizing amine and oxygen scavengers
are used (usually fed separately) as appropriate. Synthetic polymers are used to disperse iron-
containing suspended solids and stray calcium compounds.
11
"Chelant" programs typically use chelating agent such as EDT A or NT A to complex feedwater
calcium or magnesium so it can not form boiler scale. Synthetic polymers are required to disperse
suspended iron compounds and any salts that precipitate as a result of fluctuations in feedwater
hardness and/or treatment program upsets.
"All Polymer" programs rely on the stabilizing properties of polymers as alternatives to EDT A and
NT A in chelant programs. Polymers also disperse iron and other suspended solids in these
programs.
Accordingly the role of polymers in boiler water treatment programs is a sludge conditioners,
dispersants, and hardness stabilizers.
In summary, the mechanisms for deposit control using polymers in cooling and boiler water treatment
applications include
Sequestration and Solubilization:
Threshold Inhibition:
Crystal Modification:
Dispersion:
EXPERIMENTAL PROCEDURES
by maintaining and/or extending the solubility of
sparingly soluble materials
by preventing the precipitation of scale forming salts
by distorting the formation of scalant crystals such that
the will not adhere to equipment surfaces and are more
readily dispersed
by preventing deposition of suspended matter and
preventing flocculation
The water treatment industry does not have any well recognized standard test methods for evaluating
polymers for cooling and boiler water treatment applications. The efforts ofNACE's T-3A-8fWork
Group to develop a screening test for evaluating calcium carbonate inhibitors typifies the difficulty in
achieving a consensus for a specific test method.25 However, there are several parameters that are
routinely used to evaluate performance. These parameters are reflected in BFGoodrich's criteria for
evaluating water treatment polymers shown in Table 8. The experimental laboratory procedures used
to evaluate the performance of various deposit control agents are described in Table 9.
RESULTS AND DISCUSSION
The test procedures and criteria noted in Table 9 for scale inhibition, iron stabilization, iron oxide
dispersion, simulated boiler water treatment conditions, and product use considerations were used to
evaluate the efficacy of the commercially available deposit control agents noted in Table 10.
12
BFGoodrich products which were evaluated included GOOD-RITE K-752, K-732, K-7028, and
K-7058 K-775 acrylate and K-781, K-797, and K-798 acrylate terpolymers.
GOOD-RITE K-775 acrylate copolymer is a new product. Thus, many of BFGoodrich standard
screening test data are not yet available and therefore do not appear in this paper for this product.
Calcium Carbonate Inhibition
Figure 6 presents the calcium carbonate inhibition under high hardness and alkalinity conditions (BFG's
stirred threshold inhibition test) for competitive polyacrylates. The results indicate that
molecular weight polyacrylates outperform molecular weight polyacrylates. In addition,
BFGoodrich's GOOD-RITE K-700 polyacrylates outperform competitive products of the same
molecular weight. For both molecular weight groups, BFGoodrich's solvent polymerized polyacrylates
(K-752 and K-732) provided superior performance. The performance of BFGoodrich's water
polymerized polyacrylates (K-7028 and K-7058) was second in their respective molecular weight
group to GOOD-RITE K-752 and K-732 polyacrylates, respectively. Under the stressed conditions of
this test, the exceptional calcium ion tolerance of GOOD-RITE K-752 and K-732 polyacrylates may
explain the performance observed.
Figure 7 present the calcium carbonate inhibition for several scale control agents under moderate test
conditions. The results parallel those from the STIT conditions. However, the relative difference
between products is not as great.
The performance of several products touted for their calcium carbonate inhibition properties are
compared against competitive copolymers in Figure 8. The results generally indicate that commercially
available copolymers and terpolymers do not perform as well as HEDP and homopolymers. It appears
that polymer carboxyl content is critical to calcium carbonate inhibition and the lower the polymer
carboxyl content, the poorer the performance.
Calcium Ion Tolerance
BFGoodrich uses two test procedures for evaluating the calcium ion tolerance of polymers as noted in
Table 8 and described in Table 9. The long-term method
6
is time and labor intensive but provides
graphic results. The short-term method
26
provides a quick and reliable comparative tool.
The long-term calcium ion tolerance of GOOD-RITE and K-732 polyacrylates as a function
of temperature is shown in Figure 9.
6
Although not shown in Figure 9, the performance of other
polyacrylates in the 2,000 to 5,000 molecular weight range is significantly lower than GOOD-RITE
K-752 polyacrylate and typically to left and below the line describing the calcium ion tolerance of
GOOD-RITE K-732 polyacrylate.
Figure 10 presents the results of BFGoodrich's testing of calcium ion tolerance using the short-term
method for competitive polyacrylates and deposit control agents. As with the calcium carbonate
inhibition testing, GOOD-RITE K-700 polyacrylates outperform competitive products of similar
molecular weights.
13
The calcium ion tolerance of competitive copolymers is shown in Figure 11. The data indicate that the
SS/MA copolymer, the AA/SA copolymers, and the acrylate terpolymers exhibit superior calcium ion
tolerance in comparison to the polyacrylates shown in Figure 10.
Calcium Phosphate Inhibition
The results of BFGoodrich's testing of competitive polymers for calcium phosphate inhibition in the
presence and absence of soluble iron are shown in Figure 12. The data indicate that the performance of
all polymers is adversely impacted by the presence of iron. The greater the level of iron, the lower the
performance. In general, copolymers containing two (2) different monomers do not provide the same
level of high performance as do terpolymers containing three monomeric groups. Among the
copolymers, GOOD-RITE K-775 provides the best performance. Similarly with the terpolymers,
GOOD-RITE K-798 followed closely by GOOD-RITE K-781 is best. Under test conditions up to
and including 1 ppm iron, GOOD-RITE K-797 is comparable to the other terpolymers and is
superior to all other products tested.
Calcium Phosphonate Inhibition
Figure 13 presents the results for calcium phosphonate (HEDP) inhibition testing of competitive
products. The conclusions drawn from the data in Figure 13 are similar to those for calcium phosphate
inhibition testing in Figure 12. Specifically, terpolymers outperform copolymers and GOOD-RITE
K-798 provides the best performance.
Iron Stabilization
The results of BFGoodrich's testing of the iron stabilization properties of competitive polymers are
shown in Figure 14. The data once again indicate that terpolymers outperform copolymers and that
GOOD-RlTE K-781 is the best product followed by GOOD-RITE K-798.
Iron Oxide Dispersion
Figure 16 shows the results ofBFGoodrich's iron oxide dispersion testing of competitive cooling water
treatment polymers. The results show that the well known SS/MA copolymer provides excellent
performance comparable to GOOD-RITE K-798 acrylate terpolymer. However, GOOD-RITE
K-781 acrylate terpolymer and AA/SAINI provide better performance than either SS/MA or K-798.
Further, the three AA/SA copolymers do not perform as well as the other products tested.
Simulated Boiler Water Treatment Conditions
BFGoodrich's efforts to evaluate the performance of several commercial polymers promoted for use in
boiler water treatment applications was first reported in 1982? A similar test methodology
incorporating an autoclave (see Thermal Stability in Table 9) was used to evaluate competitive boiler
water polymers. Preliminary results were reported at the 1990 A WT Spring Conference in Las Vegas,
NY. The results of this woJi?1 which is still in progress, are shown in Figures 16 and 17 for iron oxide
and hydroxyapatite dispersion, respectively. The data indicate excellent thermal stability for the sodium
14
polymethacrylate and the two polyacrylates evaluated at both 150 and 250C. The baseline
performance for the two acrylate terpolymers is better than for the homopolymers tested. However,
the thermal stability of the acrylate terpolymers is not as good even though the absolute performance at
150 and 250C is better than for the homopolymers.
A comparison of the two acrylate terpolymers which have the same baseline performance indicates that
thermal stability as determined by retention of performance following thermal treatment is better for
GOOD-RITE K-781 acrylate terpolymer than the competitive AAlSNNS terpolymer. Two of the
three monomers used to manufacture these acrylate terpolymers are the same. Accordingly, we
speculate that the third monomer is a key factor in explaining the better performance for
GOOD-RITE K-781 acrylate terpolymer.
CONCLUSIONS
The information presented herein leads to the following conclusions:
Synthetic polymers playa significant role in CWT and BWT programs
Not all polymers are created equal
Compare polymer peIformance and properties including pH, total solids, and active solids
Solvent polymerized polyacrylates provide superior performance for high hardness and/or
alkalinity conditions
- Copolymer composition and structure significantly impact perrormance in the presence of iron
Polymer selection should be based on several criteria
Copolymers have specific niches where phosphates, phosphonates, molybdates, and/or zinc are
water treatment program components
- BWT polymer selection should be based on performance criteria reflecting use conditions and
regulatory considerations
CWT polymer selection should be based on performance criteria relevant to the specific
program
15
ACKNOWLEDGMENTS
The authors express their thanks to The BFGoodrich Company, Specialty Chemicals for permitting us
to prepare and present this paper.
References
l. The BFGoodrich Company, "Total Solids Via Microwave," Technical Bulletin GR-MWTS
Test Procedure, Cleveland, OR, 1986.
2. The BFGoodrich Company, "Molecular Weight by Gel Permeation Chromatography,"
Technical Bulletin GR-MWGPC, Cleveland, OR, 1986.
3. Association of Water Technologies, "Raw Materials Specifications Manual," AWT, Arlington,
VA, 1993.
4. L.Dubin and K.E.Fulks, "The Role of Water Chemistry on Iron Dispersant Performance,"
CORROSION/84, Paper No. 118, NACE, Houston, TX, 1984.
5. A Yeoman and P.Sullivan, "Polymer I HEDP Blends for Calcium Carbonate Deposit Control,"
Cooling Tower Institute, 1989 Annual Meeting, Paper No. TP 87-06, Houston, Tx, 1989.
6. The BFGoodrich Company, "GOOD-RITE K-700 Polyacrylates for Use in Water Treatment
Applications," Technical Bulletin GC-77, Cleveland, OR, September 1983.
7. W.F.Masler, "Characterization and Thermal Stability of Polymers for Boiler Water Treatment,"
International Water Conference, Paper No. IWC-82-37, Pittsburgh, P A, 1982.
8. The BFGoodrich Company, Confidential Customer Files.
9. B.L.Libutti, IG.Knudsen, and R W.Mueller, "The Effects of Antisca1ants on Fouling by
Cooling Water," CORROSION/84, Paper No. 119, NACE, Houston, TX, 1984.
10. P.A.Thomas and M.A.Mullins, "A Current Review of Polymeric Structures and Their Practical
Significance in Cooling Water Treatment," CORROSION/85, Paper No. 130, NACE,
Houston, Tx, 1985.
11. Z.Amjad and W.F.Masler, "The Inhibition of Calcium Sulfate Dihydrate Crystal Growth by
Polyacrylates and the Influence of Molecular Weight," CORROSION/85, Paper No. 357,
NACE, Houston, Tx, 1985.
16
12. IF.Wilkes, "A Historical Perspective of Scale and Deposit Control," CORROSION/93, Paper
No. 458, NACE, Houston, TX, 1993.
13. B.C.Boffardi and G.W.Schweitzer, "Advances in the Chemistry of Alkaline Cooling Water
Treatment," CORROSION/85, PaperNo. 132, NACE, Houston, TX, 1985.
14. D.A.Little, IE.Waller, and C.Soule', "Alkaline All-Organic Cooling Water Treatment,"
Cooling Tower Institute, 1987 Annual Meeting, Paper No. TP 87-5, Houston, TX 1987.
15. W.F.Masler and Z.Amjad, "Advances in the Control of Calcium Phosphonate with a Novel
Polymeric Inhibitor," CORROSION/88, Paper No. 11, NACE, Houston, TX, 1988.
16. RW.Zuhl, Z.Amjad, and W.F.Masler, "A Novel Polymeric Material for Use in Minimizing
Calcium Phosphate Fouling in Industrial Cooling Water Systems," Cooling Tower Institute,
1987 Annual Meeting, PaperNo. TP 87-7, Houston, TX, 1987.
17. G.A.Crucil, IRMacdonald, and E.B.Smyk, "Role of Polymers in the Mechanisms and
Performance of Phosphate-Based Cooling Water Treatment Programs," International Water
Conference, Paper No. IWC-87 -40, Pittsburgh, P A, 1987.
18. KF.Soeder and IS.Roti, "Molybdate-Based Cooling Water Treatment: New Developments
which Expand Their Application Areas," International Water Conference, Paper No. IWC-
87-12, Pittsburgh, PA, 1987.
19. G.A.Crucil and RH.Schild, "An Alternative Cooling Water Treatment Program for the
Replacement ofChromates," Cooling Tower Institute, 1988 Annual Meeting, Paper No. TP
87-11, Houston, TX, 1988.
20. E.B.Smyk, IE.Hoots, KE.Fulks, and KP.Fivazzani, "The Design and Application of
Polymers in Cooling Water Treatment Programs," CORROSION/88, Paper No. 14, NACE,
Houston, TX, 1988.
21. IP.Teny and Crystal W.Yates, "Current Cooling Water Corrosion Control Technology,"
International Water Conference, Paper No. IWC-90-13, Pittsburgh, PA, 1987.
22. T.IYoung, "The Proper Use of Modern Polymer Technology in Cooling Water Programs,"
A WT, Third Annual Convention, Lake Buena Vista, FL, 1990.
23. TJ.Young, "The Use of Zinc for Corrosion Control in Open Cooling Systems," AWT, Spring
Conference, San Antonio, TX, 1991.
24. IRMacdonald, "Choosing the Correct Cooling Water Treatment Program," Chemical
Engineering, New York, NY, January 19, 1987.
17
25. R.W.Zuhl, "NACE T-3A-8fWork Group's Efforts to Develop a Calcium Carbonate Threshold
Inhibition Screening Test for Cooling Water Treatment Applications," CORROSION/88,
PaperNo. 431, NACE, Houston, TX, 1988.
26. The BFGoodrich Company, GOOD-RITE K-XP82 and K-XP83 Polyacrylate Scale I
Deposit Control Agent," Technical Bulletin GC-XPIWP, Cleveland, OR, August 1987.
27. Z.Amjad, "Thermal Stability of Polymers for Boiler Water Treatment Applications,"
BFGoodrich Internal Technical Report, Avon Lake, OR, August 1990.
18
Table 1
Polymer Molecular Weight Measurement Methods

Freeze Point Depression

Boiling Point Elevation

Osmotic Pressure

Vapor Pressure Lowering

Viscosity

Light Scattering

Ultra centrifugation
I-'
I.D

Sedimentation

Gel Permeation Chromatography
Table 2
Parameters Typifying Polymer Properties and Specifications

Form

Appearance

Total Solids (%)

Active Solids (%)

Molecular Weight (M,.)

pH

Viscosity (cp at 25C)

Acid Number (mg KOH/g dry polymer)

Specific Gravity

Color
Recommended specification parameter for homopolymers
Recommended specification parameter for copolymers
Table 3
Appearance of Competitive Water Treatment Polymers
Supplied as Liquids
Product Type
Solvent polymerized PAAs
water polymerized PAAs
Appearance
Clear to hazy, colorless to amber colored
Light amber with a slight haze
Light straw
Water white to amber, slightly hazy
Light to amber colored
Clear to slightly hazy
Clear straw colored
PAA with phosphinate groups Clear to slighty turbid yellow
Sodium polymethacrylate Clear amber
Clear pale yellow
Polymaleic acid Amber
AA/Acrylamide copolymer Straw colored
MA/EA/VoAc terpolymer Clear to slightly turbid amber
Maleic anhydride copolymer Amber with a slight haze
SS/MA copolymer
AA/MA copolymer
Acrylate ester copolymer
Sulfonate copolymer
AA/SA copolymers
AA/ SA terpolymers
PAA
MA
EA
SS
= Polyacrylic acid
= Maleic acid or maleic
= Ethyl acrylate
= Sulfonated styrene
Clear amber
Pale yellow and clear
Clear to cloudy, amber to slightly pink
Clear, dark brown
Clear yellow
Clear
Clear to slightly hazy
Water white to amber, clear to slightly
hazy
Clear yellow
Water white to amber, clear to slightly
hazy
AA =
anhydride
voAc =
SA =
Acrylic acid
Vinyl acetate
Sulfonic acid
20
tv
I-'
Table 4
Comparison of Two ::= 5,000 Molecular Weight Polyacrylates
Two ... 5,000 molecular weight PAAs have the following typical properties:
Product A Product B
Total solids (TS) 48% 50 %
Active solids (AS) 43.5 %. 49.2 %
pH 3.6 2.5
Estimated Reported
How much of Product B plus NaOH and water is required to be equivalent
to 100 pounds of Product A?
Equivalent active solids:
Product B (0.492) = 100 lb (product A) x (0.435)
= 88.4Ib
50% NaOH required to raise pH of Product B to pH 3.6:
lb NaOH = 88.4 lb Product B x (12 Ib NaOH I 100 lb Product B)
= 10.6 pounds
Water required to dilute Product Band NaOH mixture:
Water = (100 - 88.4 - 10.6) Ib
1.0lb
.... 100 lb Product A... 88.4 lb Product B
+ 10.6 lb NaOH
+ 1.0 lb water
100 lb
Table 5
Comparison of Two ::= 2,000 Molecular Weight Polyacrylates
Two ... 2,000 molecular PAAs have the following typical properties:
Parameter Product C
Total solids (TS) 48% 55 %
Active solids (AS) 45.1 %. 51.7 %
pH 3.6 3.7
Estimated Reported
How much of Product D plus NaOH and water is required to be equivalent
to 100 pounds of Product C?
Equivalent active solids:
Product D (0.517) = 100 lb (product C) x (0.451)
= 87.21b
No pH adjustment as pH Product C ... pH Product D:
Water required to dilute Product D:
Water = (100 - 87.2) lb
= 12.81b
.... 100 Ib Product C... 87.2 lb Product D
...U..8 lb water
100 lb
Table 6
Types of Water Treatment Polymers
Homopolymers
Polyacrylic Acid (PAA)
Polymethacrylic Acid (PMAA)
Polymaleic Acid (PMA)
Copolymers of Acrylic Acid and/or Methacrylic Acid and

Acrylamides

Acrylate esters

Maleic acid or maleic anhydride
tv
tv

Sulfonic acid monomers
Copolymers of Maleic Acid or Maleic Anhydride and
Acrylic or methacrylic acid
Sulfonic acid monomers
A1kenes
Acrylate and alkenyl esters
Table 7
Role of Polymers as Deposit Control Agents
in Cooling and Boiler Water Treatment
em mIT
Scale inhibitors for
- Carbonate and sulfate scales X X
- Calcium phosphate X X
-
Calcium phosphonate X
General purpose dispersants of particulates
-
Silt, mud, etc. X
- Iron oxide X X
Sludge conditioners X
Metal ion (iron, zinc, etc.) stabilizers X
Copolymers are required
Table 8
BFG's Criteria for Evaluating Water Treatment Polymers
Laboratory Screening Tests
Scale inhibition
- Calcium carbonate (static and stirred)
Calcium sulCate
Barium sulCate
Calcium oxalate
Calcium phosphate (ortho, poly)
Calcium phosphonate (HEDP, AMP)
- Silica I silicate
Calcium fluoride
Particulate dispersion
- Kaolin clay
- Calcium carbonate
- Iron oxide
- Hydroxyapatite
Metal ion stabilization and sequestration
- Iron
- Zinc
- Manganese
- Calcium
- Magnesium
- Calcium I magnesium
Product Use Considerations
Corrosivity
NaOH neutralization (quantity required vs. pH)
Hydrolytic stability (pH < 2 and pH > 12)
Thermal stability
- Simulated storage conditions
- Simulated boiler water conditions
Tendency to cause foaming
Calcium ion tolerance (long-term and short-term)
Chlorine compatibility
- Polymer stability in the presence of polymer
- Chlorine stability in the presence of polymer
Aquatic toxicity (rainbow trout, daphnia, algae)
23
Table 9
Testing Procedures for Evaluating Water Treatment Polymers
Testing Procedures
Threshold Inhibition Testing Methods
Static CaC03 Test
1. Prepare supersaturated solutions of CaC0
3
(Ca +2 =
560 ppm as CaC0
3
, (HC03)-1 = 630 ppm as CaC0
3
,
and (C0
3
) -2 = 30 ppm as CaC0
3
) at a pH of 8.3 con-
taining 0 to 5.0 ppm scale inhibitor.
2. Store in capped 500-ml Erlenmeyer flasks and place in
a 66C oven for 24 hours without agitation.
3. Filter through a 0.22-l'm Millipore filter paper, and
analyze for Ca +2 concentration using standard EDTA
titration.
Static CaS04 Test
1. Prepare supersaturated solutions of 6,220 ppm CaS04
at a pH of 7.0 containing 0 to 2.0 ppm scale inhibitor.
2. Store in capped four-ounce jars and place in a 66C
oven for 24 hours without agitation.
3. Filter through a 0.22-l'm Millipore filter paper, and
analyze for Ca +2 concentration using standard EDTA
titration.
Static BaS04 Test
1. Prepare supersaturated solutions of 118 ppm BaS04 at
a pH of 7.5 containing 0 to 3.5 ppm scale inhibitor.
2. Store in capped four-ounce jars and place in 25C water
bath for 24 hours.
3. Filter through a O.22-l'm Millipore filter paper, and deter-
mine concentration of Ba +2 using atomic absorption
spectroscopy.
STIT for CaC03
1. Prepare supersaturated solutions of CaC0
3
(Ca +2 =
1,000 ppm as CaC0
3
and (HC0
3
)-1 = 1,200 ppm as
CaC0
3
) at a pH of 7.5 to 8.0 containing 0, 7.5, 15 and
25 ppm scale inhibitor.
2. Stir continuously for one hour while maintaining
temperature at 80C using an immersion heater and
maintaining constant water volume by continuously
adding distilled water dropwise.
3. After one hour, discontinue heating and stirring, then
allow the sample to cool. When the sample is cool, filter
through 0.22-l'm Millipore filter paper and determine
concentration of Ca+
2
using standard EDT A titration.
Calculation
% Inhibition = [ Is - [ Ib X 100
[ Ie - [ Ib
Where:
]s = Ca +2 or Ba +2 concentration (ppm) in the sample
containing scale inhibitor after testing.
]b = Ca +2 or Ba +2 concentration (ppm) in the blank
sample after testing.
]e = Ca+
2
or Ba+
2
concentration (ppm) initially.
Deposit Control Testing Methods
CaC0
3
Test
1. Prepare CaC0
3
solutions (Ca +2 = 560 ppm as CaC0
3
and (HC0
3
) -1 = 630 ppm as CaC0
3
) at a pH of 8.0
24
containing 0 to 2.0 ppm deposit control agent in double-
walled glass reaction vessels.
2. CaC0
3
deposition is initiated by immersing a heated
metal surface in the solution vessel. A temperature dif-
ferential is provided by circulating hot water maintained
at 68 1C through the tube and by circulating cold
water maintained at 8C through the outside jacket of
the reaction vessel.
3. Take samples at various times, filter through O.22-l'm
Millipore filter paper, and analyze for Ca +2 concentra-
tion using standard EDTA titration.
4. At the conclusion of the test, determine the amount of
CaC0
3
deposited on the tube (heat exchanger surface).
CaS04 Test
1. Prepare supersaturated solution of 5,560 ppm CaS04
containing 0 to 2.0 ppm deposit control agent in a
double-walled glass reaction vessel.
2. Continue as in steps 2, 3 and 4 of the CaC0
3
test.
Dlspersancy Testing Methods
1. Prepare a 100 ml slurry containing 5 g clay or 5 g CaC03
and 0 to 20 ppm dispersant in a 100 ml graduated
cylinder.
2. Mix samples thoroughly for 30 to 60 seconds.
3. Let samples stand and visually observe the rate of set-
tling by noting the interface between the clear and tur-
bid regions in the cylinder.
Calcium Ion Tolerance Test Method
1. Prepare Ca +2 solutions (Ca +2 = 625 ppm as CaC0
3
) at
a pH of 9.0 with various dosages (0 to 70 ppm) of scale
inhibitor.
2. Store in capped 250-ml Erlenmeyer flasks and place in
a constant temperature (30 to 75C) water bath for 24
hours.
3. Stir continuously and measure percent transmittance of
sample using a fiber optic turbidity probe interfaced with
a colorimeter.
4. Plot percent transmittance against scale inhibitor con-
centration to determine the onset of turbidity.
Total Solids Test Method
The BFGoodrich Chemical Group developed an automatic
computerized microwave oven procedure for determining
percent total solids. They found this test procedure increases
both the accuracy and the speed at which results can be ob-
tained. (A copy of the total solids test method is available
upon request.)
Percent total solids may also be measured in a vacuum
oven. This procedure involves drying a sample for one hour
at 100C followed by two hours at 100C under a vacuum
of 25 mm of mercury or less. A second alternative is to dry
the sample to constant weight under a heat lamp.
While the vacuum oven and heat lamp methods of measur-
ing total solids give reasonably accurate and reproducible
total solids results, the values obtained by these methods
may not exactly match those obtained by the more accurate
microwave oven technique.
Table 9 (continued)
Testing Procedures for Evaluating Water Treatment Polymers
Calcium Phosphate Inhibition
1. Prepare supersaturated solution of calcium phosphate [140 ppm Ca+
2
,
9.0 ppm (P0
4
) -3)] containing 0 to 10 ppm of scale inhibitor in
reaction cells maintained at 50C.
2. stir continuously and maintain pH 8.5 by the automatic addition of
0.1 M NaOH.
3. After 22 hours, filter solution through 0.22 micron filter paper and
analyze filtrate spectrophotometrically for phosphate concentration.
4. Calculate inhibition using the following formula:
% Inhibition = [ (P0
4
l sample - (P0
4
l control ] x 100
(P0
4
) initial - (P0
4
) control
Calcium Phosphonate Inhibition
1. Prepare calcium phosphonate supersaturated solution [150 ppm Ca+
2
,
15 ppm phosphonate (HEDP or AMP), 266 ppm Cl-
1
, 60 ppm (HC0
3
) -1, 22 ppm
Na+
1
)] at pH 8.5 containing 0 to 10 ppm of scale inhibitor.
2. store in capped flasks and place in 50C water bath for 20 hours
without agitation.
3. Filter solution through 0.22 micron
filtrate spectrophotometrically for
phosphonate to phosphate.
filter paper and analyze
phosphate after oxidizing
4. Calculate inhibition using the following formula:
% Inhibition =[ (phosphonatel sample - (phosphonatel control ] x 100
(phosphonate) initial - (phosphonate) control
Iron Oxide Dispersion
1. Prepare 600 mL of synthetic water [100 ppm Ca+
2
, 30 ppm Mg+
2
, 314 ppm
Na+
1
, 570 ppm (S04)-2, 60 ppm (HC0
3
)-I, 264 ppm CI-
1
)] in a 800 mL beaker
containing 1 ppm of dispersant.
2. Add 0.12 g of iron oxide and continuously stir slurries at room
temperature using a six paddle stirrer for 3 hours.
3. Measure percent transmittance using a colorimeter.
4. Calculate percent dispersion using the following formula:
% Dispersancy = [100 - (1.11 x % transmittance)]
25
Table 9 (continued)
Testing Procedures for Evaluating Water Treatment Polymers
Iron Stabilization
1. Prepare synthetic water solutions [100 ppm Ca+
2
, 100 ppm Mg+2, 1,120
ppm Na+
1
, 2,170 ppm Cl-
1
, 700 ppm (S04)-2, 153 ppm (HC0
3
)-1)] containing
3 ppm Fe(III) and add 4 ppm active polymer.
2. Adjust pH of solution to 7.0 and store in capped 4 oz jars at room
temperature for 2 hours.
3. Filter solution through 0.22 micron filter paper and analyze
filtrate for iron by atomic absorption spectroscopy.
4. Calculate percent iron stabilization using the following formula:
% Iron Stabilization = [ (iron) sample - (iron) control ] x 100
(iron) initial - (iron) control
Zinc Stabilization
1. Prepare synthetic water [60 ppm Ca+
2
, 20 ppm Mg+2, 202 ppm Na+
1
, 36
ppm (HC0
3
) -1, 172 ppm Cl-
1
, 200 ppm (S04) -2)] containing 6 ppm zinc and
4.5 ppm scale inhibitor.
2. Adjust pH to 8.5 and store in capped 4 oz jars at 30C for 20 hours.
3. Filter solution through 0.22 micron filter paper and analyze
filtrate for zinc by atomic absorption spectroscopy.
4. Calculate percent zinc stabilization using the following formula:
% Zinc Stabilization = [ (Zn) sample - (Zn) control ] x 100
(Zn) initial - (Zn) control
Calcium Ion Tolerance (Short-Term Method)
1. Prepare Ca+
2
solution (10,000 ppm ca+
2
) and 100 mL of polymer
solution (0.1 g active polymer) at pH 8.0.
2. Titrate polymer solution with calcium solution at 72F (22C) to
determine the onset of turbidity using a colorimeter.
3. Calculate calcium ion tolerance as mg Ca+
2
per 100 mg polymer.
26
Table 9 (continued)
Testing Procedures for Evaluating Water Treatment Polymers
Chlorine compatibility
1. Prepare polymer solution (100 ppm as active) containing 240 ppm of
sodium hypochlorite at pH 9.0.
2. store polymer solutions in capped jars at 22C for 6 days.
3. Test polymer performance for calcium phosphate or calcium
phosphonate inhibition.
Hydrolytic stability (pH <2 and >12)
1. Prepare polymer solutions (10% as active) at pH 1.0 (with HCI) or pH
12.5 (with NaOH).
2. store in capped jars at 80C for 6 days. Check pH daily and adjust
if necessary.
3. Test polymer performance for calcium phosphate or calcium
phosphonate inhibition.
Thermal stability
1. Prepare a polymer solution (1% as active) at pH 10.5 containing 0.3
grams of sodium sulfite as an oxygen scavenger.
2. Heat the polymer solution in a stainless steel reactor maintained at
constant temperature (150C or 250C) for 20 hours.
3. Test polymer performance for iron oxide and hydroxyapatite
dispersion.
Hydroxyapatite Dispersion
1. Transfer 100 ml of synthetic water [100 ppm, Ca+
2
, 30 ppm Mg+
2
, 314
ppm Na+, 571 ppm CI-
1
, 200 ppm (80
4
)-2, 60 ppm (HC0
3
)-1] containing 0 to
2.5 ppm polymer solution (with and w/o thermal treatment) to a 100
ml graduated cylinder.
2. Add 2.5 grams of hydroxyapatite and mix gently for 5 minutes.
3. Let slurries stand for 3 hours and measure transmittance.
4. Calculate percent dispersion using the following formula:
% Dispersancy = [100 - (1.11 x % transmittance)]
27
Table 10
Commercially Available Products Evaluated
Acronym
HEOP
PAA-2M
K-7028
PAA-5M
AC 1000
AC 1100
AR-257
AR-900
BS 161
NaPMAA
PMA
MCP
SS/MA
AA/SA-A
AA/SA-B
K-775
AA/SA/NI
AA/C-l
AA/C-7
AA/C-8
NOTES:
Product
DQ 2010
K-752
K-7028
K-732
AC 1000
AC 1100
AR-257
AR-900
BS 161
T 960
Be 200
BC 283
V-TL 4
AC 2000
BC 400
K-775
AC 3100
K-781
K-797
K-798
Description
l-Hydroxyethylene-l, l-diphosphonic acid
.., 2,000 M" polyacrylate (PAA)
.., 2,000 Mw PAA
.., 5,000 M" PAA
It! 2,000 Mw PAA
It! 5,000 M" PAA
It! 2,000 Mw PAA
It! 5,000 M" PAA
Polyacrylic acid containing phosphinate groups
Sodium polymethacrylate
Polymaleic acid
Maleic acid (MA) / ethyl acrylate (EA) / vinyl
acetate terpolymer
Sulfonate styrene / maleic anhydride copolymer
AA / sulfonic acid (SA) copolymer
AA / SA copolymer
AA / SA copolymer
AA / SA / substituted acrylamide terpolymer
AA/SA/sodium styrene sulfonate (SSS) terpolymer
AA / SA / SSS terpolymer
AA / SA / SSS terpolymer
"DO" is an abbreviation for Monsanto Company's "Dequest- Phosphonates"
"K-700" is an abbreviation for The BFGoodrich Company's GOOD-RITE- K-700
polymers
"AC" and "T" are abbreviations for Rohm and Haas Company's "Acumer-" and
"Tamol-" polymers
"AR" is used here as an abbreviation for Alco Chemical Corporation's
"AQUATREAT
DI
AR" series
"BC" and "BS" are abbreviations for FMC Corporation's "Belclene-" and
"Belsperse-" products
''V-TL'' is used here as an abbreviation for National Starch's ''VERSA-TL-''
polymers
28
I\.)
I.D
Figure 1
Typical Molecular Weight Determinations for Two Polyacrylates
Gel permeation chromatoaraphy molecular weight
determination for Good-rlte
l
K-752 polyacrylate.
Q)
(I)
c::
8.
~
...
o
II
CD
c
1
Molecular Weight
Mn = 970
Mw = 2,030
Mz = 3,690
Mw/Mn =2.1
0' ........
1 10 10
2
10
3
10
4
10
5
Molecular weight
Gel permeation chromatography molecular weight
determination for Good-rite K-732 polyacrylate.
Q)
(I)
c::
o
c..
(I)
~
...
o
U
Q)
CD
c
1
Molecular Weight
Mn = 2,200
Mw = 5,070
Mz = 9,970
MwlMn=2.31
0' , ~ ~
1 10 10
2
10
3
10
4
Molecular weight
10
5
LV
o
Figure 2
Quantity of 50% Caustic Soda Needed
to Neutralize GOOD-RITE K-7028 and K-7058
Polyacrylates to a Desired pH
14 ~ I - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ~
12
10
I 8
0..
6
4
K-7028

K-7058
&
2 1 ~ - - - - ~ - - - - - - ~ - - - - - - ~ - - - - ~ - - - - - - ~ ~
o 10 20 30 40 50
Pounds of 50% Caustic Soda per 100 Pounds
of GOOD-RITE K-700 Polyacrylate
W
I-'
Figure 3
Chemical Structures
for Three Homopolymers
Polyacrylic Acid (P AA)
-tCH
2
CH-rn
I
C0
2
H
Polymethacrylic Acid (PMAA)
CH
3
I
-tCH
2
CTn
I
C0
2
H
Polymaleic Acid (PMA)
-tCH CH-ro
I I
C0
2
H C0
2
H
Figure 4
Chemical Structures
for Four Acrylate Copolymers
Acrylic acid/R copolymer (AAlR)
[-tCH,CH)A ( CH,CH+'- IN
I I
CO,H R
Acrylic acid/Hydroxypropyl acrylate copolymer (AA/HP A)
[-tCH,<j )A ( CH,i r.- IN
CO,H C=O
I
-CH,CH - CH
,
I
OH
Acrylic acid/Sulfonic acid copolymer (AA/SA)
[-tCH,CH )1 ( CH,CH-ir- IN
I I
CO,H 0= C CH,
I I
NH - C - CH,SO,H
I
CH,
K-796 Acrylate Copolymer
CH,
I
[-t CH,Cm.-tCH,CH+'-+CH,C+c--tCH,CH-t,;-IN
I I I I
CO,H CONH, CO,H CO,(CH,CH,O),CH,CH,
Acrylic Acrylamide Methacrylic 2-(2-Ethoxyethoxy) Ethyl
Acid Acid Acrylate
W
N
Figure 5
Cooling Water Treatment Programs
Nonmetal I Stabilized phosphate
programs L. ________ _
[- All-organic
Metal
programs
[ Alkaline zinc J
[ Molybdate ]
Chromate/ zinc Alkaline chromate/zinc
I
7 ~ ~ pH
Figure - When selecting a cooling-water treatment,
considering the system's pH helps to narrow the choices
Source: J .R. Macdonald, "Choosing the Correct Cooling water Treatment Program," Chemical
Engineering. January 19, 1987.
Figure 6
Calcium Carbonate Scale Inhibition
for Competitive Polyacrylates
(Under Stressed Test Conditions)
Residual Hardness (ppm)
750
700
650
600
550
500
450
400
350
o
o 5
GOOD-RITE'" K-752
GOOD-RITE")K-7028 } E
Product A
Product B
GOOD-RITE""K-732 }
GOOD-RITE'" K-7058
Product C F
Product D
E ::: 2.000 Molecular Weight
F ::: 5.000 Molecular Weight
1.000 ppm Ca'! as CaCO,
1.200 ppm (HCO,)" as CaCO,
80
n
e, stirred continuously. I hr
Note: Residual hardness without polymer is 162 ppm
10 15 20 25 30
Active Polymer Dosage (ppm)
33
Figure 7
Calcium Carbonate Inhibition
for Competitive Polyacrylates
(Under Moderate Static Test Conditions)
% Inhibition
100,-----------------------------------------------,
80
60
40
20
o
K-752 K-7028 K-732 K-7058AR-257AC1000 88161 AR-900AC1100
3 ppm polymer, pH 8.3, 66 degrees C,
24 hr, 224 ppm Ca, 262 ppm bicarbonate,
12 ppm carbonate
Figure 8
CCTI-A(11183)
Calcium Carbonate Inhibition
for Products
(Under Moderate Static Conditions)
% Inhibition
100
1,--------------------------------------------------,
80
60
40
20
o
HEDP K-762 PMA MCP V-TL4 AC2000 8C400 K-776 AC3100 K-781 K-797 K-798
3 ppm polymer, pH 8.3, 66 degrees C,
24 hr, 224 ppm Ca, 252 ppm bicarbonate,
12 ppm carbonate
CCTI-BIS/U)
34
Figure 9
Calcium Ion Tolerance of GOOD-RITE K-7S2 and K-732
Polyacrylates as a Function of Temperature
- ()
0
-
CD
~
:J
-
as
40
~
CD
a.
E
~
30
20
10
10
t
Good-rite K-752
I
625 ppm Ca +
2
as CaC0
3
,
pH 9.0, stirred continuously,
24 hours
Good-rite K-732
20 30 40 50 60 70
Good-rite K-700 polyacrylate dosage (ppm)
35
Figure 10 Calcium Ion Tolerance
for Competitive Inhibitors Polyacrylates


CJ

CD

c
.220

(l10
100
\,
80
CJ
c
l!
60 CD
-0
t-
c 40
0
-

20
'"
0
o
* rTlJ of ca+
2
per 100 rTlJ active inhibitor, pH 8.0, 22C
Figure 11 Calcium Ion Tolerance for Various Copolymers
AAlSA-A AAlSA-8 K-nS AA/SA/N K-781 K-797 K-798
* of ca+
2
per 100 active polymer, pH 8.0, 22C
36
Figure 12
Calcium Phosphate Inhibition
% Inhibition
1 0 0 ~ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - .
80
60
40
20
o
SS/MA AAlSA-A AAlSA-B K-775 AAiSAINI K-781 K-797 K-798
_ No iron _ 1 ppm iron D 2.5 ppm iron
9.0 ppm P04, 140 ppm Ca, pH 8.5,
10 ppm polymer, 50 degrees C, 22 hr
Figure 13
Calcium HEDP Inhibition
% Inhibition
1 0 0 , - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ~
80
60
40
20
o
SS/MA AA/SA-A AA/SA-B AAISA/NI K-781
15 ppm HEDP, 150 ppm Ca, pH 8.5, 10 ppm
polymer, 50 degrees C, 266 ppm CI,
22 ppm Na, 60 ppm bicarbonate, 20 hr
37
K-797 K-798
CoHEDP(l1/ea)
Figure 14
Iron Stabilization
(3 ppm Fe III, pH 7, 4 ppm polymer)
% Stabilization
1 0 0 r - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ~
80
60
40
20
o
SS/MA AA/SA-A AA/SA-B AA/SAINI K-781 K-797 K-798
2 hr, 300 ppm Ca, 300 ppm Mg,
1120 ppm Na, 2170 ppm CI, 700 ppm (804)
163 ppm bicarbonate, 23 degrees C
11111'88'
Figure 15
Iron Oxide Dispersion
for Competitive Copolymers
% Dispersion
1 0 0 , - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ~
80
60
40
20
o
88MA AA/SA-A AAlSA-B K-776 AAlSAlNI K-781 K-797 K-798
200 ppm Iron oxide, 1 ppm polymer, 3 hr, pH 7.7-8.0,
100 ppm Ca, 30 ppm Mg, 871 ppm sullate,
80 ppm bicarbonate, 23 degrees C
38
IOD-A(81U'
100
80
60
40
20
0
Figure 16
Iron Oxide Dispersion *
for Competitive BWT Polymers
before and after Thermal Treatment **
% Dispersion
NaPMAA K-732 BS 161 AC 3100 K-781
_ Before Treatment ~ Post Treat. ,,150'C 0 Post Treat. " 250"C
Standard Iron Oxide Test Conditions 'OOTT'''''''
1% Polymer Solution, 20 hr, pH 10.5
100
80
60
40
20
0
Figure 17
Hydroxyapatite Dispersion *
for Competitive BWT Polymers
before and after Thermal Treatment **
% Dispersion
NaPMAA K-732 BS 161 AC 3100 K-781
_ Before Thermal Treat. _ After Thermal Treat.
Std. Hydroxyapatite Dispersion Test
1% Polymer Solution, 20 hr, pH 10.5,
150 degrees C
IDDTTltlleat
39
For additional technical information pertaining to Lubrizol's
Carbosperse (formerly Good-Rite) K-700 Polymers,
please contact us as follows:
Phone:
FAX:
Lubrizol Advanced Materials, Inc.
9911 Brecksville Road
Cleveland, OH 44141-3247, U.S.A.
1-800-380-5397 or 216-447-5000
216-447-6315 (USA Customer Service)
216-447-6144 (International Customer Service)
216-44 7-5238 (Marketing & Technical Service)
E-mail: coatings.csr@Lubrizol.com
Web Site: www.carbosperse.com
Lubrizol
"'-----------.
TM Trademark of The Lubrizol Corporation
Nov-1993 (updated Oct-2(07)
The information contained herein is believed to be reliable, but no representations, guarantees or warranties of any kind are made to its
accuracy, suitability for particular applications, or the results to be obtained therefrom. The information is based on laboratory wor1< with
small-scale equipment and does not necessarily indicate end product performance. Because of the variations in methods, conditions
and equipment used commerciaUy in processing these materials, no warranties or guarantees are made as to the suitability of the
products for the application disclosed. FuU-scale testing and field application performances are the responsibility of the user. Lubrizol
Advanced Materials, Inc. shall not be Uable for and the customer assumes all risk and Habillty of any use or handling or any material
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PURPOSE. Nothing contained herein is to be considered as permission, recommendation, nor as an inducement to practice any
patented invention without permission of the patent owner.
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2007 The Lubrizol Corporation, all rights reserved.