The Effects of Process Variables on Scale Inhibition in Dynamic Scale Testing

Emily R. Clark, PhD*, John Zibrida†, Griffin Rial*, Patrick Sullivan†, and Mitchell Jackson*
*The Lubrizol Corporation (Wickliffe, OH)
†
ZIBEX, Inc. (Duluth, GA)

ABSTRACT
Historically, static tests have been a standard screening method used to evaluate additives used as
deposit control agents for industrial water treatment. Static bottle tests are used extensively because they
can be conducted under controlled conditions and multiple tests can be run simultaneously, they are easy
to set up, and they are economical.,
These static tests provide information on an additive’s activity when encountering a range of chemical
and thermal variables. In identifying effective additives, it is important to incorporate realistic conditions
and situations under which these additives must be able to inhibit scale formation.
An alternate test method that has been developed, dynamic tube blocking, differentiates the properties
for testing additives that would prove useful in industrial water treatment. Evaluating the performance of
an additive in a dynamic environment that includes a heated surface should highlight the chemistry of the
scale inhibitors that can minimize the fouling of an industrial water system.
Taken together, these test methods, static and dynamic, distinguish the mechanisms that lead to an
effective approach in facing the challenges service companies encounter today. Various inhibitor
chemistries are evaluated in a dynamic scale test with the emphasis on the effects of temperature, pH,
and supersaturation to identify effective inhibitor concentrations to prevent fouling.

INTRODUCTION
The accumulation of mineral deposits (calcium carbonate [CaCO3], calcium sulfate [CaSO4], calcium
phosphate [Ca3(PO4)2], etc.) on metal surfaces in cooling towers and industrial water treatment systems
is a persistent problem. As water is cycled through and replenished in these systems, the mineral
concentrations can increase to levels exceeding saturation limits, causing precipitation and mineral
deposition on metal surfaces within the system. These deposits lead to decreased efficiency,
overheating, unscheduled shutdowns, and heat exchanger failure that can have significant economic
impacts for the operators.
The primary objective of a water systems operator is to optimize the heat exchange process by preventing
or delaying the accumulation of deposits on the heat exchange surface, minimizing corrosion, and
preserving the life expectancy of capital equipment. This goal can be achieved by a combination of
chemical and mechanical approaches. In this paper, we investigate the influence of acrylate-based
polymers and their ability to minimize fouling by calcium phosphate. Calcium phosphate can crystallize
as tricalcium phosphate (Ca3(PO4)2), hydroxyapatite (Ca5(PO4)3OH)), and other amorphous crystals. For
this paper, we will identify the precipitation of any one, or the combination, of those crystals as simply
calcium phosphate, and use the abbreviation CaP.
As cooling water programs evolved, the use of zinc, chromate, and other metal-based corrosion inhibitors
was curtailed for regulatory reasons.1 An alternative approach based on inorganic phosphate-based
programs gained popularity. During the 1980s, cooling water programs began operating under more
alkaline conditions. The amount of phosphate in the formulated programs declined; however, phosphate
remained in significant concentrations in the cooling water. Municipalities were required to feed inorganic
phosphates to their water distribution lines to achieve compliance with lead and copper limits (40 Code
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of Federal Regulation [CFR] 141 Subpart 1). The proper treatment of phosphate—whether intentionally
incorporated into cooling water programs or incidentally present in the feed water—is a key factor in
proper water treatment.
Alkaline programs contain other components, specifically for CaCO3 inhibition and ferrous metal
corrosion control, that can contribute phosphate. The most popular phosphonates 2-Phosphobutane-
1,2,4-tricarboxylic acid (PBTC) and 1-Hydroxy ethylidene 1.1-diphosphonic acid (HEDP).2,3
In addition to treatments for corrosion and deposit, control of microbiological activity is a critical aspect of
a successful water treatment program.3 The use of oxidizing biocides is prevalent throughout the industry
to minimize microorganisms in the cooling system. These products, whether based on chlorine or
bromine, can react with phosphonates and cause reversion to ortho phosphate, further contributing
inorganic phosphate to the system.
In addition to monitoring CaP formation, soluble iron levels need to be monitored as well. In the soluble
form, ferrous iron is not particularly problematic; however, at typical cooling system pH values, iron oxide
and iron hydroxide can precipitate. These deposits can be especially difficult to remove. Additionally, the
presence of ferric iron in solution negatively affects the performance of some polymeric dispersants.4-5
As iron concentrations increase, it becomes critical to evaluate and utilize the appropriate polymeric
inhibitor to maximize system performance while also minimizing total operational costs for the operator.
To minimize the economic consequences of these deposits, an effective water treatment program tailored
to a system’s specific conditions is critical. It is important to evaluate the performance of DCPs in
conditions similar to those being treated in the field.
The focus of this work was on CaP because of the challenges it presents in all cooling water application
ranging from moderate to severe service.2
EXPERIMENTAL
The polymeric inhibitors used in this study, all commercially available products, are listed in Table 1. It
has been previously established that co- and terpolymers with sulfonic acid functional groups increase
CaP inhibition at lower doses compared to homopolymers or non-sulfonated polymers.6-7 All polymers
were compared under the same precipitation conditions and treatment doses based on active material.
Precipitation conditions investigated included temperature, saturation index, and pH.

Table 1. Polymeric Inhibitors.

Polymer Chemistry
A Poly(acrylic acid/sulfonic acid) copolymer
B Poly(acrylic acid/sulfonic acid/sulfonated styrene) terpolymer
C Poly( acrylic acid/sulfonic acid/non-ionic monomer) terpolymer
D Poly(acrylic acid/sulfonic acid) copolymer

Dynamic Scale Loop

DCP evaluations were done on a PMAC DSL system. The DSL system covers a wide range of
temperatures, from ambient to 250°C, and pressures (up to 3000 pounds per square inch [psi]). The DSL
uses three HPLC pumps capable of handling up to six separate solutions that are pumped through
stainless steel tubing in an attached oven.
When evaluating scaling tendencies and additive performance, separate solutions of anions and cations
are pumped through the DSL and meet at the sample loop. As described above, the reactions between
ions cause the precipitation of inorganic salts that deposit within the sample loop. As scale builds, the
2
pressure within the sample loop increases. This pressure increase is monitored as a difference between
the pressure before and after the sample loop, and referred to as the differential pressure (Pdiff). The DSL
can monitor a pressure change up to 10 psi. For this investigation, the loop was considered to have built
up sufficient scale when Pdiff was ≥ 2 psi.
Calcium Phosphate.
To specifically target CaP formation, solutions of sodium phosphate and calcium chloride were prepared
separately, and the pH adjusted using dilute NaOH. For experiments involving DCPs, the material was
added to the phosphate solution prior to pH adjustment. Polymer efficacy as a CaP inhibitor was based
on the time required for Pdiff to reach ≥ 2 psi.
System pH not only impacts the efficacy of a DCP, but can also affect the rate and type of precipitation.
The calculated effect of pH changes on CaP scale is shown in Table 2. Unless noted otherwise, the
conditions of this study were 240 ppm calcium and 15 ppm phosphate at pH 9.0.
Table 2. Effect of pH on Scaling Indices of Tricalcium Phosphate and Hydroxyapatite in a
Solution of 240 ppm Ca2+ and 15 ppm PO43-
Times Saturation
pH Tricalcium Phosphate Hydroxyapatite
7.2 1,764 37
8.3 86,202 545,109
8.5 152,087 2,020,000
9.0 392,648 2,645,507
Note: Calculated using French Creek Software.8

The pH of the solution post-DSL also was monitored since the formation of hydroxyapatite (Ca5(PO4)3OH)
can lower the pH. After passing through the sample loop when calcium ions (Ca2+) mixed with phosphate
(PO43-), the water’s pH dropped to 8.0 ± 0.4. The drop in pH was consistent throughout the run, even as
scale formation increased within the sample loop.

RESULTS AND DISCUSSION

Polymers can reduce the deposition of scale on a metal surface by a combination of mechanisms:
1) crystal distortion, 2) dispersancy of precipitated or insoluble particulates, and 3) threshold inhibition.
Depending on the alkaline salts present in the water, one mechanism may dominate in its ability to
maintain a clean surface. In general, the two mechanisms that are the most effective in inhibiting the
formation of scale on a metal surface are dispersancy and threshold inhibition.
Previous investigations by Lubrizol address the activity of different polymer types that were evaluated in
a series of bench tests.5 The performance testing focused on the ability of the polymers to prevent the
precipitation of alkaline salts (CaCO3 and Ca3(PO4)2) and their ability to disperse precipitated salts. The
reason for studying both threshold and dispersancy properties is to predict a given compound’s
performance in applied water treatment. A product must maintain its efficacy when subjected to various
perturbation challenges. Regardless of how effective a threshold inhibitor is, the effectiveness of a
polymer depends on its ability to keep a heated surface clean. Therefore, polymer performance is based
on the innate properties of threshold inhibition and dispersancy.

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In those tests, standard polyacrylates, copolymers (based on acrylic acid [AA]/ sulfonic acid [SA]);
terpolymers (AA/SA/Sulfonated Styrene [SS]), and other polymers were evaluated.
In the threshold testing for inhibiting CaP formation, it has been observed that homopolymers of acrylic
acid are marginally effective in inhibiting CaP precipitation. The copolymers and terpolymers exhibit good
activity. Equally important in maintaining a clean heat exchange surface is the ability of the polymers to
disperse precipitated CaP. The Amjad et al. results reiterate the enhanced performance of copolymers
and terpolymers compared to homoacrylic polymers, but further testing was required to differentiate the
activity of the copolymers and terpolymers.5,9
To objectively evaluate why these polymers dominate industrial water treatment applications related to
CaP, the current study considered a number of options and determined that to objectively test the
performance of the polymers in the presence of CaP, the evaluation would require continuous monitoring.
The approach that could be used to evaluate performance of the polymers on a continuous basis would
be utilization of the DSL system.
Based on the results of these static testing and feedback from customers in the field, the focus of the
study was determined to be specific copolymers and terpolymers. Figure 1 shows the DSL results plotted
as a function of the pressure differential (Pdiff) versus time, comparing DCP performance at 5 mg/L active
in saturated CaP.

240 ppm Ca2+, 15 ppm PO43-, 5 ppm DCP, pH 9.0

2
Differential Pressure (psi)

1.5

1
Uninhibited
Polymer A
0.5 Polymer B
Polymer C
Polymer D
0
0 50 100 150 200 250 300
Time (min)
Figure 1. DSL results plotted as a function of Pdiff vs time comparing DCP performance at 5 ppm active
in saturated CaP. The fluid temperature was held at 70°C and the system pressure at 100 psi.
In general, polymers with a higher percentage of sulfonate monomers have shown better performance
as overall scale inhibitors. Polymer B significantly outperforms the other DCPs.
At an increased concentration of 10 and 20 ppm, Polymer A performance increased (Figure 2). At 5 ppm,
scaling occurred at 140 minutes. Increasing the concentration to 10 ppm extended scaling at 168
minutes, and at 20 ppm, Pdiff reached 2 psi at 202 minutes. However, even at a concentration of 20 ppm,
Polymer A did not perform as well as Polymer B. Increasing Polymer B to 20 ppm active prevented
deposition of CaP for over 24 hours (results not shown). Figure 2 shows the results plotted as a function
of Pdiff versus time comparing Polymer A at 5, 10, and 20 ppm.

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 Polymer A
240 ppm Ca2+, 15 ppm PO43-, pH 9.0
1.95 5 ppm

10 ppm
Differential Pressure (psi)

1.45
20 ppm

0.95

0.45

-0.05
0 50 100 150 200 250
Time (min)
Figure 2. DSL results plotted as a function of Pdiff vs time comparing Polymer A at 5 (solid), 10 (short
dashed line), and 20 (dash-dotted line) ppm. The fluid temperature was held at 70°C and the system
pressure at 100 psi.
Interestingly, the rate of scaling does not seem to be greatly affected by the increased polymer dose, but
rather the time elapsed before scale starts to form in the sample loop. At 20 ppm, Polymer A takes longer
to begin scaling, but once it begins, scale formation proceeds at a similar rate regardless of DCP
concentration. The average rate of CaP formation in solution with Polymer A for the three concentrations
shown in Figure 2 was 0.0167 ± 0.003 psi per minute.
Effect of Iron
Previous research showed that the presence of iron adversely effects DCP performance against CaP
deposits.5,10 Sulfonic acid functional groups within a polymer improve their tolerance to the presence of
iron. That relationship was investigated again using the DSL and is shown in Figure 3.
Soluble iron in the same saturated solution of CaP increased the rate of deposit formation. Polymer B
and Polymer C, both terpolymers, once again inhibited scale formation better than the copolymers, with
Polymer B outperforming all other DCPs. The rate of CaP scale formation changed in the presence of
iron. This could be due to iron oxide precipitating out of solution or the polymer interactions with Fe3+,
and requires further investigation.

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 1 ppm Fe
240 ppm Ca2+, 15 ppm PO43-, pH 9.0
2
Differential Pressure (psi)

1.5

Uninhibited
0.5
Polymer A

Polymer B
0
0 50 100 150 200 250
Time (min)
Figure 3. DSL results plotted as a function of Pdiff versus time comparing DCPs in the presence of 1 ppm
iron. DCPs dosed at 5 ppm active material. The fluid temperature was held at 70°C and the system
pressure at 100 psi.

Field Applications/Case Study

After evaluating DCPs in a laboratory setting, Polymer B, which outperformed the other polymers across
all tests, was used in a water sample derived from commercial water source. With the DSL, rapid testing
of DCPs can be done in a controlled environment while allowing adjustments to variables that can affect
scaling, such as temperature, pressure, ion content, and additive dosage. It is especially useful in high-
stress field applications. Figure 4 shows one example of how the DSL was used to screen DCPs under
stressed conditions of high ion content, high temperature, and high pressure. This example highlights the
practical ability to conduct dynamic testing using field samples and conditions to determine optimal DCP
and dose.

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 pH 7.7, 7 ppm Polymer B
10 Uninhibited

Polymer B
8
Differential Pressure (psi)

0
0 10 20 30 40 50 60 70
Time (min)
Figure 4. DSL results plotted as a function of Pdiff versus time comparing uninhibited brine (dotted line)
to brine treated with 7 ppm Polymer B (dashed line). The fluid temperature was held at 85°C and the
system pressure at 100 psi.
The DSL showed a failure Pdiff of ≥ 2 psi in less than 20 minutes and complete occlusion of the sample
loop (Pdiff ≥10 psi) within 65 minutes, making it faster than the usual 20- to 24-hour SBT.
A sample of water taken from the field was analyzed (Table 4) and synthetic solutions of anions and
cations were prepared such that their final concentration, upon mixing in the sample loop of the DSL,
equated to the concentration of the field water sample.

Table 4. Water Analysis of Field Sample with a pH of 7.7

Compound (mg/L) Compound (mg/L)

Manganese 0.97 Calcium 294.7

Zinc 0.55 magnesium 17.9
Sodium 2500 bicarbonate 75.0
Strontium 9.9 Chloride 4630
Barium 8.5 Sulfate 10.6
Iron 18.1 Phosphate 15.5
Potassium 164.0

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 SUMMARY
Polymer B, the sulfonated terpolymer, provided the best inhibition of CaP with or without the presence of
soluble iron. At a higher concentration of 20 ppm, Polymer A did not perform as well as Polymer B at 5
ppm in test conditions of this study. Additionally, Polymer B can be applied to higher stress waters and
excels at inhibiting scale in these stress conditions found in the field.
The use of a DSL offers many benefits in designing an effective industrial water treatment program,
including:
1. Analyses that can be done in a few hours, versus 20 to 24 hours with SBT.
2. The ion content in the water is continuously refreshed in the DSL sample loop during scaling tests. In
SBT, as CaP forms, soluble ions are depleted, slowing down the scaling process which is less
representative of conditions in IWT.
3. There is no need to adjust pH during analysis with DSL. Changes in pH can change
Calcium/Phosphorus molar ratios and chemical composition of precipitates. In order to determine the
appropriate inhibitor for scaling, the pH must be maintained throughout the SBT.
4. More variable adjustment during testing, including pressure and inhibitor dose.
Future work will look more closely at the effect of iron on DCP performance. It is critical for DCP selection
and performance to understand the mechanism of iron precipitation in a dynamic environment.

REFERENCES
1. Kemmer, F.N. and Nalco Chemical Company. The NALCO Water Handbook (2nd ed.) McGraw-Hill
Co, New York, 1988.

2. Dubin, L. Journal of Cooling Tower Institute, Volume 3, No. 1, 1982.

3. Boffardi, B.P. Fundamentals of Cooling Water Treatment, (6) Calgon, 1986.

4. Marshall, A. and B. Greeves, “The Effect of Water Quality on the Perfomance of Extended Phosphate
Technology,” Paper No 399, CORROSION/86 (Houston, TX: NACE International, 1986)

5. Amjad, Z., Pugh, J., Zibrida, J., and R.W. Zuhl, “Polymer Performance in Cooling Water: The
Influence of Process Variables”, Paper No 160, CORROSION/96 (Houston, TX: NACE International,
1996)

6. Zuhl, R.W., Amjad, Z., and W.F. Masler, “A Novel Polymeric Material for Use in Minimizing Calcium
Phosphate Fouling in Industrial Colling Water Systems,” Paper No. TP 87-7, Cooling Tower Institute,
Houston, TX.

7. Marshall, A. and B. Greeves, “The Effect of Water Quality on the Perfomance of Extended Phosphate
Technology,” Paper No 399, CORROSION/86 (Houston, TX: NACE International, 1986)

8. Ferguson, R. J. and A. J. Freedman. “The Practical Application of Ion Association Model Saturation
Level Indices to Commerical Water Treatment Problem Solving,” ACS (1964).

8
9. Zuhl, R.W. and Z. Amjad, “The Role of Polymers in Water Treatment Application and Criteria for
Comparing Alternatives,” Association of Water Technologies Annual Convention (Las Vegas, NV,
1993).