Paper No.

08077

A New Multi-functional Corrosion and Scale Inhibitor

David Wilson
BWA Water Additives,
2 Brightgate Way,
Manchester, M32 0TB
United Kingdom

ABSTRACT

Products used in Water Treatment programs tend to be either corrosion or scale inhibitors. It is
unusual for a single product to exhibit both of these characteristics. This paper describes a
new product that displays both excellent corrosion and scale control across a wide range of
water chemistries. This product can be used as an effective building block for improved
formulations in the water treatment industry for applications where superior scale and corrosion
inhibition are required

Keywords: Corrosion inhibitor, scale inhibitor, calcium carbonate, jar test, pilot cooling tower,
zinc stability, water chemistry, dynamic corrosion test.

INTRODUCTION

Generally it is accurate to state that improvements in treating cooling waters have typically
been slow to materialise. During the 1930’s through to the 1940’s early cooling water
treatments consisted of formulations variously based on chromate, lignins, polyphosphates and
some organic compounds. In order to be effective these treatments had to be run with the pH
of the system between pH 6 to 7 necessitating acid dosing in most cases. Increasing
environmental pressure on chromate from the 1960’s through the early 1980’s lead to its
substitution by formulations containing zinc in conjunction with a simple polymer addition such
as polyacrylate. These treatments allowed the pH of the systems to operate in the less
corrosive environment between pH 7 and 8. The inhibitor film formed by such treatments was
not as efficient as the chromate film at the operating pH of the system. However, these
treatments were used successfully although they did not totally replace chromate.

Copyright
©2008 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Copyright Division, 1440 South creek Drive, Houston, Texas 777084. The material presented and the views expressed in this paper are
solely those of the author(s) and are not necessarily endorsed by the Association. Printed in the U.S.A.

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 The major breakthrough in effective chemical control of scale and corrosion in cooling water
was the advent of organic phosphorus compounds plus improved polymers based on
polymaleic acid and other chemistries that gave formulators the ability to move to alkaline
water. This allowed the pH of the cooling water to rise to pH 7.5 to 9 significantly reducing the
corrosivity of the system water. At the same time these two innovations allowed the possibility
of higher cycles of concentration with subsequent cost savings, by reducing both water
consumption and chemical demand.

The next major development was stabilized phosphate and zinc programs that could be
employed in these higher pH systems. In both cases these were now possible with the new
polymers. The present trend in water treatment formulations is the move to all organic
treatments with the subsequent removal of inorganic inhibitors, such as orthophosphate,
polyphosphate and zinc. The main corrosion inhibitor that allowed this transition to be made
was hydroxyphosphono acetic acid (HPA)1,2.

Other corrosion inhibitors have come to the marketplace but none have found the wide
acceptance of HPA. The reasons that HPA has such widespread acceptance are that it has a
significantly higher calcium ion tolerance than 1-hydroxyethylidene-1,1-diphosphonic acid
(HEDPA)3 and does not display the limited corrosion inhibition in soft water in the way that
phosphono polymaleic acid (PPMA) does. In effect HPA remains sufficiently soluble in hard
water applications, thereby not fouling the system, and in softer waters it can still form effective
films on metal surfaces and is not aggressive to either mild steel or copper alloys.

This paper describes a new multifunctional scale and corrosion inhibitor, an enhanced
phosphonocarboxylate (EPOC) that seeks to overcome the limitations described above and
offers expanded treatment options by combining both effective scale and corrosion inhibition.

EXPERIMENTAL

In order to accurately assess the EPOC material, a number of test regimes were used to
investigate different aspects of the material.

Rotating Coupon Test

In this test, pre cleaned and weighed mild steel coupons are rotated in aerated synthetic water
for a 42 hour period. The coupons are then removed and any significant rusting brushed off
before cleaning in inhibited hydrochloric acid. After drying the coupons are reweighed and from
the weight loss, immersion time and surface area the corrosion rates are calculated. A
schematic of the equipment is given in Figure 1 and two types of synthetic waters used in this
testing are detailed in Table 1.

Calcium Carbonate Jar Testing

This test is designed to assess the ability of additives to inhibit the precipitation of calcium
carbonate. The water chemistry simulates cooling water and the high temperature represents
the conditions that exist close to a heat exchanger. Air bubbling is used to facilitate carbon
dioxide loss, which moves the equilibrium towards carbonate formation, thereby increasing the
test severity.

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 A solution containing calcium chloride and magnesium chloride is mixed with an equal volume
of a solution containing sodium carbonate and sodium bicarbonate which already contains the
additive under test. The air bubbled solution is heated at 70°C for 30 minutes, after which time
the solution is filtered and the calcium remaining in solution determined by EDTA titration. The
water conditions are tabulated in Table 2. The higher the amount of calcium retained in
solution the greater the scale inhibition ability of the product.

Chlorine Stability Test

A solution of 5 mg/L free chlorine is dosed with 20 mg/L additive as solids. The solution is
buffered to pH 8 with sodium bicarbonate and is allowed to stand at ambient temperature for 5
hours in a cupboard away from light. Chlorine levels are checked at 0, 2, 4 and 5 hours, and
the chlorine consumption of an additive is determined from the uptake of halogen and
expressed as a percentage of the blank.

Zinc Stability Test

An aqueous solution containing 4 mg/L zinc has additive added to it and the pH adjusted to pH
8.0. The solution is then placed into a shaking water bath at 40°C for 24 hours. A sample is
then removed, filtered and acidified to stabilize the zinc remaining in solution before
determining the soluble zinc content by Atomic Absorption spectroscopy.

Pilot Cooling Units

The Pilot Cooling Units were developed to simulate, as closely as possible, the conditions
encountered in open recirculating cooling water systems. Water is recirculated continuously
over two preweighed mild steel heat exchangers and a coupon chamber containing
preweighed specimens of differing metallurgy. The system is heated via two heat exchangers,
each having a heat flux of 10000 BTU/ft2/h (31520 W/m2), and cooled by means of a cooling
coil, operated by a solenoid valve activated by a control system.

The units are fed with fresh additive and water solution by means of make-up pumps, and
blowndown to overflow at a specified system run level. The residence time of the system may
be varied but it is typically set to run with a 24 hour half life. The normal control regimen is that
the units are operated at a high dose period for three days before being changed to a lower
dose level (maintenance period) for eleven days.

Samples are taken daily to be analysed for a number of parametres, including pH, alkalinity
and hardness. Additive levels are monitored via standard procedures for phosphorus
containing additives. A schematic diagram of the units is shown in Figure 2 and the water
chemistries used in the tests given in Table 1.

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 RESULTS

Rotating Coupon Test

Corrosion inhibitors can be generally rated in the following manner:

• Very good if the corrosion rate is <0.05 mm/y (<2mpy)

• Good if the corrosion rate is between 0.05 to 0.076 mm/y (2 - 3 mpy)
• Poor if the corrosion rate is between 0.076 and 0.127 mm/y (3 - 5 mpy)
• Unacceptable if the rate is greater than 0.127 mm/y (>5 mpy)

To demonstrate the corrosion inhibition performance of EPOC, it was evaluated in both 150
mg/L Ca and 300 mg/L Ca waters at 10, 20 and 30 mg/L solids. Blank corrosion rates for these
two waters are 1.78 mm/y (70 mpy) and 0.53 mm/y (21 mpy) respectively. The EPOC gave
good corrosion rates at each dose level in 300 mg/L Ca water:

• 10 mg/L 0.0297 mm/y (1.17 mpy)

• 20 mg/L 0.019 mm/y (0.75 mpy)
• 30 mg/L 0.017 mm/y (0.67 mpy)

The results in the 150 mg/L Ca water is particularly significant given the corrosive nature of this
water, good corrosion rates being achieved at 20 mg/L; 0.037 mm/y (1.46 mpy) and at 30 mg/L
0.0292 mm/y (1.15 mpy), only missing the good rating at the 10 mg/L concentration 0.0914
mm/y (3.6 mpy). These data are given graphically in Figure 3. As can be seen from this one
would expect much higher corrosion rates if EPOC was not effective at controlling corrosion.

Figure 4 and 5 compare the performance of EPOC with two established corrosion inhibitors
PPMA and HPA. In 150 mg/L Ca water the PPMA only achieves the good rating at 40mg/L
dose level whereas both EPOC and HPA provide equivalent results at the 20 mg/L level, which
clearly demonstrates improved performance over PPMA. In 300 mg/L Ca water EPOC and
HPA are equivalent and again PPMA gave unacceptable performance even when it was dosed
at a 30 mg/L level.

Calcium Carbonate Jar Testing

In this accelerated test the scale inhibitor Phosphono butane tricarboxylic acid (PBTC) is
include as a benchmark to assess the other additives. The PPMA performs adequately,
however at the 4 mg/L solids dose is clearly falling off in performance compared to either
PBTC or EPOC. It is known that while HPA is an excellent corrosion inhibitor, it is only a
mediocre scale inhibitor which at best barely reaches 90% inhibition at 4 mg/L. By contrast,
EPOC shows improved performance giving 100% inhibition at 4 mg/L clearly demonstrating
multi-functionality as both a scale and corrosion inhibitor. As can be seen from the data at 4
mg/L EPOC effectively matches the performance of PBTC. Figure 6 presents the data in more
detail.

Chlorine Stability Test

Figure 7 gives the results from the Chlorine Stability Test. Clearly the PPMA is the most
resistant to halogen attack, with 94% chlorine remaining after the 5 hr test period. HPA is the

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 least tolerant to chlorine there being 79% of halogen left after 5 hrs. By contrast, with EPOC an
intermediate amount of halogen, 89% is left after the 5 hr period.

Concern over EPOC halogen stability is not an issue for the same reason that allows HPA to
be used in conjunction with oxidizing biocides. Although HPA can be degraded, in the bulk
cooling water, by halogen releasing biocides, the degree of breakdown is mediated by
variables such as the amount of halogen in the water, the residence (contact) time, water
temperature and the amount of transition metals present. However, once HPA reacts with
either calcium or iron at the metal surface and forms a corrosion inhibiting film, it is significantly
more resistant to halogen oxidation.

In other words, once HPA forms a film on the metal surface, it is not particularly susceptible to
breakdown by either chlorine or bromine. This is why when HPA is used, even in systems that
employ oxidizing biocides, improved corrosion rates are noted. Although the work has not
been completed to confirm that the same will take place with EPOC, it is expected that the
same behaviour will take place.

Since HPA can be effectively used in systems that employ oxidizing biocides and has already
found widespread adoption in cooling waters then EPOC is expected to be a much improved
additive.

Zinc Stability Testing

These data presented in Figure 8 are only included for completeness for formulators wishing to
use EPOC in a zinc based treatment. In all but the softest of waters, it would be expected that
the corrosion inhibition provided by EPOC would be sufficient in its own right to eliminate the
need to employ zinc; however there could be circumstances in very soft waters where a zinc
based formulation would be advantageous.

The data demonstrates the ability of EPOC to stabilize zinc at pH 8.0. Even at the low dose of
0.5 mg/L EPOC, greater than 2.5 mg/L zinc was maintained in solution, more than is adequate
to repair any film damage on a metal surface.

Pilot Cooling Units

Just as corrosion in a system can be rated as described earlier, the fouling of systems can be
ranked in a similar manner:

• Very good if the fouling rate is <0.11 mg/cm2/day

• Good if the fouling rate is between 0.11 – 0.19 mg/cm2/day
• Poor if the fouling rate is between 0.19 – 0.26 mg/cm2/day
• Unacceptable if the fouling rate is >0.26 mg/cm2/day

50 mg/L Calcium Water: Soft water corrosion inhibition is sometimes difficult to achieve
without the help of either orthophosphate, polyphosphate or zinc. The water used in this testing
contains 50 mg/L calcium as calcium carbonate and the blank corrosion results on the two heat
exchangers are 2.283 mm/y (89.9 mpy) and 2.186 mm/y (86.1 mpy) respectively, with fouling
rates of 6.83 mg/cm2/day and 6.6 mg/cm2/day.

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 Figure 9 demonstrates the corrosion control possible in this severe soft water with EPOC
alone. In this example the dose level was 100 mg/L solids for the three day high level followed
by 11 days at the lower 25 mg/L solids dose level. The two heat exchanger corrosion rates
were good at 0.0599 mm/y (2.36 mpy) and 0.0484 mm/y (1.91 mpy) respectively. The fouling
rates are excellent at 0.089 mg/cm2/year and 0.069 mg/cm2/year.

150 mg/L Calcium Water: In the 150 mg/L Ca water the high chloride and sulphate ensure
aggressiveness, as evidenced by blank corrosion rates of 0.403 mm/y (15.87 mpy) and 0.492
mm/y (19.35 mpy), and fouling rates of 1.519 mg/cm2/day and 1.744 mg/cm2/day respectively.

Figure 10 compares EPOC with PPMA and HPA. Dose levels used in this water were 80 mg/L
as solids for the high level 3 day period decaying to 20 mg/L solids for the 11 day maintenance
period. Good corrosion rates were obtained on the two heat exchangers for both EPOC (0.071
mm/y (2.78 mpy) and 0.039mm/y (1.52 mpy)) and HPA (0.046 mm/y (1.79 mpy) and 0.057
mm/y (2.24 mpy)) however the PPMA gave unacceptable corrosion rates on both heat
exchangers at this dose level (0.218 mm/y (8.6 mpy) and 0.248 mm/y (9.75 mpy)).

Unsurprisingly the fouling rate for the PPMA was also unacceptable at 0.67 mg/cm2/year and
0.79 mg/cm2/year respectively. In comparison scaling rates for both the EPOC (0.088
mg/cm2/year and 0.04 mg/cm2/year) and HPA (0.069 mg/cm2/year and 0.09 mg/cm2/year)
were very good.

For ease of comparison and normalizing with respect to HPA the corrosion and fouling rates on
the two heat exchangers are:

The lower the number the better the result

Corrosion Fouling
HX1 HX2 HX1 HX2
HPA 1 1 1 1
PPMA 4.7 4.4 9.7 8.8
EPOC 1.5 0.7 1.3 0.4

300 mg/L Calcium Water: As would be anticipated in a higher calcium water of 300 mg/L Ca
corrosion rates decrease over those in both the 50 mg/L and 150 mg/L Ca waters as
demonstrated by the blank corrosion rate result of 0.223 mm/y (8.78 mpy) and 0.252 mm/y
(9.92 mpy), and fouling rates of 1.37 mg/cm2/year and 1.42 mg/cm2/year respectively.

The dosing regime used for the 300 mg/L Ca water is 40 mg/L solids high level for 3 days and
10 mg/l solids for a further 11 days. Figure 11 demonstrates the superiority of EPOC as a
corrosion inhibitor and scale inhibitor over that of PPMA. In this 300 mg/L Ca water the PPMA
is a poor corrosion inhibitor (0.75 mm/y (2.96 mpy) and 0.71 mm/y (2.78 mpy)) and gives
unacceptable fouling rates (0.274 mg/cm2/year and 0.27 mg/cm2/year).

The EPOC is a good corrosion inhibitor (0.034 mm/y (1.35 mpy) and 0.046 mm/y (1.79)) and is
giving good to very good results on fouling of the heat exchangers at 0.113 mg/cm2/year and
0.13 mg/cm2/year respectively.

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 CONCLUSIONS

1. The data presented in this paper demonstrates the efficacy of EPOC as a combined
corrosion and scale inhibitor that will extend the life of industrial systems.

2. EPOC is a high performance corrosion inhibitor that outperforms existing inhibitors.

3. Additionally EPOC should extend the flexibility of formulators by providing both scale
and corrosion inhibition in one additive.

4. Another benefit of EPOC is that since it is a very effective scale inhibitor it would be
expected that it will provide a more effective corrosion inhibitor film than a compound
that is solely a corrosion inhibitor. It is well known that it is not just the mass of barrier
film that forms which impacts corrosion rates but also the uniformity of the film. Work is
underway to assess the ability of EPOC to generate inhibitor films with more uniform
coverage than those produced by either zinc or HPA alone. This work will be reported in
subsequent reports. However, based on the results seen in these laboratory studies, it
is likely that EPOC is controlling the morphology of the film being formed on the metal
surfaces.

ACKNOWLEDGEMENTS

The author wishes acknowledge the contribution from Adrian Roberts and Kelly Harris in
conducting the testing and to thank BWA Water Additives UK Limited for permission to publish
this paper.

REFERENCES

1. A.M. Yeoman and A. Harris, “Development of an All Organic Ferrous Metal Corrosion
Inhibitor”, CORROSION ‘86, Paper 86014, Annual Conference and Exhibition. Houston,
TX.
2. P.J. Sullivan and B.J. Hepburn, “Evolution of Phosphonate Technology for Corrosion
Inhibition”, CORROSION ’95, Paper 95496, Annual Conference and Exhibition, Orlando,
FL.
3. R.R. Cavano, “Phosphonates as Calcium Carbonate Control Agents”, AWT Analyst,
Spring 2002.

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 Table 1: Corrosion test water chemistries

Ion concentration
50 mg/L Ca 150 mg/L Ca 300 mg/L Ca
Water Water Water
Calcium as CaCO3 50 mg/L 150 mg/L 300 mg/l
Magnesium as CaCO3 25 mg/L 75 mg/L 150 mg/l
Total alkalinity as CaCO3 15 mg/L 350 mg/L 300 mg/l
Chloride as ion 29 mg/L 200 mg/L 212 mg/l
Sulphate as ion 18 mg/L 200 mg/L 142 mg/l
Initial pH at 40°C 7.0 8.5 8.3

Table 2: Calcium Carbonate Scale test conditions and water chemistry

Calcium as CaCO3 375 mg/L

Magnesium as CaCO3 112 mg/L
Carbonate alkalinity as CaCO3 85 mg/L
Bicarbonate alkalinity as CaCO3 440 mg/L
Aeration 500 ml/minute
Duration 30 minutes
Temperature 70°C

FIGURE 1 Rotating coupon Test Schematic

Rotation 150 rpm

Aeration 1 litre/min

Mild steel coupons Volume 1 litre

Temperature 40°C

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 FIGURE 2 Pilot Cooling Unit Test Schematic
A non-evaporative Process Simulation Unit

Coupon chamber

Flow
meter

Cooling coil
Heat
Exchanger

Thermometer

Make-up tank Blowdown

Make-up
pump Recirculation pump

FIGURE 3 EPOC Corrosion Inhibitor Performance

EPOC Corrosion Inhibition Performance

Control = 1.78 mm/y Control = 0.53 mm/y
0.1
0.0875
Corrosion rate (mm/y)

0.075
0.0625
0.05
0.0375
0.025
0.0125
0
150 ppm Ca water 300 ppm Ca water
10 mg/L 20 mg/L 30 mg/L

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 FIGURE 4 Corrosion Inhibitor Comparison in 150 Ca Water

Corrosion Inhibitor Comparison in 150 Ca Water

0.125 Control = 1.78 mm/y

0.1125
Corrosion Rate (mm/y)

0.1
0.0875
0.075 0.05 mm/y = good performance

0.0625
0.05
0.0375
0.025
0.0125
0
EPOC PPMA HPA

20 mg/L 30 mg/L 40 mg/L

FIGURE 5 Corrosion Inhibitor Comparison in 300 Ca Water

Corrosion Inhibitor Comparison in 300 Ca Water

0.125 Control = 0.53 mm/y

0.1125
Corrosion Rate (mm/y)

0.1
0.0875
0.075 0.05 mm/y = good performance

0.0625
0.05
0.0375
0.025
0.0125
0
EPOC PPMA HPA

10 mg/L 20 mg/L 30 mg/L

10

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 FIGURE 6 Calcium Carbonate Inhibition Properties

Calcium Carbonate Inhibition Properties

100

80
% Inhibition

60

40

20

0
HPA EPOC PPMA PBTC

1 mg/L 2 mg/L 4 mg/L

FIGURE 7 Chlorine Stability Test

Halogen Demand

100
90
% Halogen Maintained

80
70
60
50
40
30
20
10
0
0 1 2 3 4 5
Hours

EPOC PPMA HPA

11

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 FIGURE 8 Zinc Stability Test

EPOC Zinc Stabilizing Activity at pH 8

4.5
Theoretical zinc level
4
Zinc in solution (mg/L)

3.5
3
2.5
2
Amount of zinc required for good corrosion performance
1.5
1
0.5
0
0 1 2 3 4 5 6 7 8
Dose level mg/L solids

FIGURE 9 Pilot Cooling Unit Corrosion and Fouling rates in 50 Ca Water

Pilot Cooling Unit Corrosion and Fouling Rates
for EPOC in 50 Ca water

0.07 0.1

0.09
0.06
0.08
0.05 Fouling Rate mgs/cm2/day
Corrosion Rate mm/y

0.07

0.06
0.04
0.05
0.03
0.04

0.02 0.03

0.02
0.01
0.01

0 0
100ppm :25ppm EPOC 100ppm :25ppm EPOC

Corrosion Heater 1 Corrosion Heater 2 Fouling Heater 1 Fouling Heater 2

12

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 FIGURE 10 Pilot Pilot Cooling Unit Corrosion and Fouling rates in 150 Ca Water
Pilot Cooling Unit Comparison of Corrosion
and Fouling Rates in 150 Ca water

0.3 0.9
0.05 mm/y = good performance
0.11mg/cm2/day = good performance 0.8
0.25
0.7

Fouling Rate mgs/cm2/day

Corrosion Rate mm/y

0.2 0.6

0.127 mm/y = unacceptable performance 0.5

0.15
0.4

0.1 0.3

0.2
0.05
0.1

0 0
EPOC PPMA HPA EPOC PPMA HPA

Corrosion Heater 1 Corrosion Heater 2 Fouling Heater 1 Fouling Heater 2

Dose Level 80mg/L High Level 20mg/L Maintenance

FIGURE 11 Pilot Pilot Cooling Unit Corrosion and Fouling rates in 300 Ca Water
Pilot Cooling Unit Comparison of Corrosion
and Fouling Rates in 300 Ca water

0.05 mm/y = good performance

0.08 0.11mg/cm2/day = good performance 0.3

0.07
0.25
Fouling Rate mgs/cm2/day

0.06
Corrosion Rate mm/y

0.2
0.05

0.04 0.15

0.03
0.1
0.02
0.05
0.01

0 0
EPOC PPMA EPOC PPMA

Corrosion Heater 1 Corrosion Heater 2 Fouling Heater 1 Fouling Heater 2

Dose Level 40mg/L High Level 10mg/L Maintenance

13

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