Developing Cooling Water Treatments – Part II

Additional Contributions to Chemical Treatment

Robert R. Cavano, Scranton Associates Inc.

Additional Contributions to Smith and Sherwood1 also observed that:

Chemical Treatment “For collective corrosion control, the ratio of calcium

ion concentration needed to the polyphosphate
Having established the theoretical bases in Part I, we will concentration is at least 0.2 and preferably 0.5 …
return to our task and review the importance of phospho- Reversion of the polyphosphate to orthophosphate
… will only enhance overall protection due to
nates to those efforts. We now turn to additional
the inhibitive properties of orthophosphate.”
resources and to the proven benefits of combinations of
raw materials. At times, polyphosphates are used in a formula for
convenience in manufacture or feeding, and their rever-
Other Corrosion Reducing sion is not necessarily objectionable since the change
to the orthophosphate ions seems to improve overall
Materials performance. At high temperatures, polyphosphate
reversion is rapid and almost complete, so feeding
A number of other chemicals can help us to prevent
it alone can rapidly produce dianodic protection.
corrosion.
Conversely, if the reversion rate is low, the addi-
tion of orthophosphate may become necessary.
A. Phosphates
For many years, we depended upon inexpensive (and Before the introduction of organic phosphorus programs,
often inadequate) inorganic phosphates for the protection we reasoned that:
of water circulating systems. Included in this category “Problems encountered with phosphate program
were the orthophosphates as anionic corrosion inhibi- operation occur at both ends of the water chemistry
tors and the complex phosphates as cathodic inhibitors. spectrum: lower system pH and softer water will
Phosphates of both types also appear, free of charge, in result in accelerated corrosion rates on mild steel.
fertilizer run off or as present in municipal distribution Elevated pH or harder water will result in increased
systems. Orthophosphates, when provided as part of a precipitation of calcium phosphate salts …”2
treatment program, are usually supplied in the form of
phosphoric acid or one of its sodium or potassium salts. Kessler3, extending this concept, also separated those
programs into two categories, depending on phosphate
In general, complex phosphates are chosen for their initial content and pH range:
and sustained solubility. The most widely used products “Neutral pH programs operate in the pH range of 6.8
are sodium hexametaphosphate (SHMP) and tetrapotas- to 8.0 while alkaline programs operate at pH 8.0 and
sium pyrophosphate (TKPP). TKPP has especially good above. … The neutral pH programs are also referred
solubility, stability, and iron sequestering properties. to as stabilized phosphate technology because they

31 the Analyst Volume 15 Number 2

Developing Cooling Water Treatments – Part II Continued

rely on relatively high dosage of inorganic phosphate sumed in providing a protective film is small compared
[10-20 ppm (mg/L)] for mild steel corrosion control.” to that needed to protect copper containing metals,
“Alkaline technology relies on lower concentra- but generous reserves (2-5 mg/L) better guarantee
tions of phosphate (2-8 mg/L) relative to stabilized against film breakdown and surges in demand:
phosphate programs, while sometimes also using
“… common practice (is) … to always main-
zinc (1-3mg/L) for enhanced mild steel protection.”
tain a constant residual of triazole … of
around 2.5 mg/L (as) active product.”7
Hartwick and Jovancicevic4 also described the opera-
tions of inorganic phosphate programs. Among the
merits listed is that phosphates can be used for systems C. Zinc and Molybdate
having as low as 50 mg/L CaH and up to some in If calcium levels are below 20 mg/L, we probably have
excess of 1000 mg/L CaH (as CaCO3). A dosage a corrosive system and should introduce zinc. Zinc also
range of 10-16 mg/L as PO4 is recommended for may be used in the calcite saturation index (CSI) 20-49
high level operations and 5-8 mg/L for the low. range but polyphosphates work equally well. Their
combination into zinc phosphate had constituted the
Boffardi5 indicated that suitable treatment levels
traditional “metal” program with the best pH range for
were approximately 15-18 mg/L expressed as total
multi-metal recirculating systems operating between
phosphate. He further stated that relative concentra-
6.5 and 8.0. Zinc allows even better corrosion control
tions of orthophosphate and polyphosphate were not
in these soft waters when used in combination with
critical, with at least 20 % of either species being suf-
other inhibitors such as the phosphonates (includ-
ficient to create synergism in corrosion reduction.
ing HPA) and AMPS®-containing terpolymers.
The addition of HPA to a formula reduces the
Corrosion protection from zinc is of short duration
need for such high phosphate levels, yet, it allows
because of zinc’s limited solubility8. Sherwood and
the use of an alkaline phosphate technology if
it is accompanied by an adequate polymer con- Eastman9 show that it must be present at 1 mg/L or
tent for phosphate and phosphonate control. more to be effective and that zinc hydroxide precipi-
tates at pH values above 7.5 unless sufficient AA/SA
terpolymer is present. When introduced at levels of
B. Triazoles 1.0 to 3.0 mg/L into a system containing phosphate,
Triazoles are needed for the primary protection it can yield excellent and prolonged anodic/cathodic
of copper-based alloys and to help disperse and/ protection. Such combinations generally utilize a rapid
or sequester stray copper ions. By deactivating free establishment of protection from zinc, with phosphates
copper, these products also help to prevent galvanic contributing later to more durable protection.
corrosion and reduce particulate deposition.
The proper terpolymer can stabilize zinc at pH levels
Benzotriazole (BT, BZT) and tolyltriazole (TT, as high as 9.0. For zinc to be fully available, a polymer/
TTA) are the leading inhibitors for these func- zinc ratio of as much as 3/1 is recommended10. Too little
tions. The most convenient forms are the sodium salt polymer allows zinc hydroxide to form and precipitate.
solutions at 50% (active tolyltriazole at 44 %), and At higher polymer levels, some feel that the metal may be
40 % active BZT (actually closer to 36 % active).
over stabilized and consequently deprived of its inhibitive
powers – a phenomenon not adequately documented.
Other than for very special pretreatment requirements,
TT and BZT are roughly equal in performance. TT
Not only is zinc effectively dispersed by sulfonic acid-
is usually the first choice among the azoles because of
containing terpolymers, it also is synergistic with them
price, but BZT has better solubility, especially at moder-
when they are used for calcium phosphate control. This
ate pH values. Combinations of these triazoles may be
aspect of zinc usage was described by Amjad and others11
advantageous, especially at the time of initial passivation.
as follows:
Vanderpool6 and others indicate that the structure of “…the presence of zinc greatly enhances
the films is similar and that their formation is rapid the calcium phosphate inhibition of poly-
for all of the major azoles. The quantity of azole con- mers AA/SA and AA/SA/SS.”

32 the Analyst Volume 15 Number 2

Developing Cooling Water Treatments – Part II Continued

The synergistic effect of zinc is evident in these tests, use in detergents. His comments on calcium sta-
allowing a reduction in AA/SA of 3 mg/L from the bilization probably also apply to zinc. His results
original 5 mg/L dosage, and a reduction of 2 mg/L for predict some degree of sequestration and describe
AA/SA/SS. the difficulties in determining those levels.
“The binding powers [Calcium Ion Binding Power
Molybdate can be helpful in corrosion control but
(CBP)] for polyelectrolytes did not correspond to the
often also requires the presence of zinc, phosphate, or formation of complexes with a simple stoichiometry.
phosphonates for greatest effectiveness. Molybdate In most cases, more than one equilibrium is involved.”
has historically been used in combination with these
other materials to prevent pitting and as an indicator, Alternatively, stabilization ratios for a single metal/
but its current high price disqualifies it from seri- polymer system can be estimated empirically, but
ous consideration as a general corrosion inhibitor. determining the amount of polymer required for
other functions may be a more difficult problem. The
mechanisms involved are complex and each terpolymer
Polymers for Dispersion varies from the others in many important aspects.
Polymers based on acrylates, acrylamides, AMPS®,
etc., when used alone or in combination, have become It seems unlikely that the high tolerance terpolymers
essential dispersants in cooling water systems. would form a very strong bond with calcium, zinc,
or phosphate. Might it be that polymer redundancy
Where the water is soft, the chance of calcium phos- from over-dosage is costly but perhaps less risky than
phate formation is reduced, but the need for general having an excess of phosphates or phosphonates?
dispersion and for control of stray metal continues
and can be best provided by the terpolymers. In any event, we have tentatively chosen to specify
polymer content to match the total amounts of phospho-
Several interesting observations have been made: nate and metal present and the total orthophosphate
which might evolve from degradation.
“The polymer requirement is determined by
the calcium phosphate super-saturation. In
At this point, we may ask what that matching ratio
general, more phosphate and less polymer are
needed at lower pH and more polymer and should be, or more simply, what levels of terpolymer
less phosphate is needed at higher pH.” 12 should be used.

“It is possible to extend operations to more Ion association model saturation levels can be used
alkaline conditions by reducing the phosphate for predicting calcium phosphate scale formation and
concentration and increasing or supplement-
for determining dosage. Investigations of this type
ing polymer usage with terpolymers.”13
are recommended but, in the interests of brevity, we
While these comments may be applicable to some turn to some more rough and ready recommendations
ternary systems (phosphate, polymer, alkalinity, for for phosphate control. Ratios of active terpolymer to
example), we have a limited ability to control pH in PO4 of between 1:1 and 3:1 are usually recommended,
each system and must primarily match the quanti- depending on the levels of particulate contaminants, the
ties of terpolymer to those of phosphate or zinc. amount of phosphorus complexes, and the dispersion and
stabilization requirements for inhibitors such as zinc.
It has been said that:
A general guide is shown in Table 2:
“…with higher polymer concentrations, the polymer
must be properly balanced with the phosphate concen- Table 2: Terpolymer Dosage
tration. Too high a polymer level can result in over-
stabilization of the phosphates and in increased cor- Function Active Terpolymer/(PO4+Zinc)
rosion rates: too low a concentration can result in bulk Low Hardness & Particulate 1.0 mg/L
precipitation of the calcium salts, fouling the system.”14 Higher Hardness, Phosphate, 1.5 mg/L
Iron, Zinc
Chang15 discussed many properties of the poly- More Stress and Contaminants 2.0+ mg/L
acrylate homopolymer in evaluating it for possible

35 the Analyst Volume 15 Number 2

Developing Cooling Water Treatments – Part II Continued

Combinations
The introduction of phosphonates made a highly tion. Since good things often come in threes, it was
significant contribution to the field of water treat- not at all difficult to anticipate the next development!
ment. It soon became evident that their combination
with phosphates produced better scale and corrosion In October of 1995, Gill applied for a U.S. Patent
protection than the individual contributions might (granted on January 20, 1998)20 describing a way to com-
have led us to expect. Combinations of this type also pletely control calcium carbonate and calcium phosphate
allowed reduction in total phosphorus requirements in a high pH, high scaling water. It recommended a
and became a harbinger of other valuable discoveries. mixture of PAPEMP (a scale preventing phosphonate)/
Aquatreat AR-540 (a dispersant ter/quad polymer)/
Dividends from this discovery were, at times, diminished Belcor 575 (a corrosion inhibiting phosphonate), in ratios
by poor calcium phosphate and calcium phosphonate such as 1/2/1. Gill also reported remarkable reduction
solubility, a shortcoming to later be compensated for by in phosphonate demand for systems treated with these
the introduction of highly effective copolymers and combinations. Gill and others21 later supported these
terpolymers. findings with laboratory and field results, particularly
describing their success under stressed conditions.
We had learned from many sources that the presence
of the proper AA/SA copolymers and terpolymers can Most cooling tower applications benefited greatly from
cause substantial improvement in the performance the presence of multiple functionalities such as those
and calcium tolerance of phosphonates (HEDP in described above, including two, three, and four part
one example16). These sulfonic acid-containing and combinations.
AMPS®-based copolymers are effective for dispers-
ing zinc, calcium phosphate and calcium phosphonate, Debate continues as to whether any mixture can be as
thereby allowing the other components of a formula effective as a single multi-functional molecule (such
to fully execute their originally designated functions. as PBTC or some of the new copolymers and terpoly-
mers). In addition, structural limitations may keep us
Therefore, these polymer/phosphonate blends synergisti- from combining multiple groups into one molecule
cally impeded the tendency for calcium carbonate to with as much flexibility as we can obtain from blend-
precipitate and permitted lower dosages of dispersant ing individual polymers and/or phosphonates. Even
polymers. if it were possible to incorporate a number of desired
functionalities at the ratios we designate, it would be
“…because there are two possible and distinct
mechanisms (stabilization and dispersion), it is difficult to decide upon that unique molecule which
reasonable to suggest that the reason combina- would be most suitable for all of the problems.
tion products are so successful is that they can
take advantage of both of these mechanisms.”17 The movement to ever more complex terpolymers has, in
general, been rewarding, but is not without problems.
Subsequent investigations and patents18 continued to There is evidence that most multi-component (if also
demonstrate that blending phosphonates with polymers multi-functional) formulas are versatile and forgiving,
greatly improved treatment results and this approach is with the various ingredients able to cover for one another
now accepted practice19. to some extent. But water pipes must be protected and
the piper must always be paid. As we continue to design
HPA performance as a corrosion inhibitor was greatly more complex remedies, we also increase the number of
improved by being part of an anodic/cathodic combina- formulas in our line and the cost of maintaining and
tion with the phosphates and with the strongly cathodic stocking them.
zinc. Adding HPA to a scale preventative phosphonate
(HEDP) can also prove rewarding. We strongly commend the advantages of adding multiple
function components, whether introduced in a single
Success in combining these many pairs of materials product or as several distinct products!
was a precursor to even better performance and protec-

36 the Analyst Volume 15 Number 2

References 11 Amjad, Zahid, Butala, Digen and Pugh, Jeff, “The Influence of
Recirculating Water Impurities on the Performance of Calcium
Phosphate Inhibiting Polymers,” CORROSION/99, paper no. 18,
1 Smith, Richard W. and Sherwood, Nancy S., “A New Generation of (Houston, TX, 1999)
Cooling Water Treatment Technology,” National Petroleum Refiners
Association, March 1984 12 Rey, Susan, P., “Carbon Steel Corrosion Control in the Past Twenty
Years and in the New Millennium,” The Analyst, VIII, 3, (2001)
2 Sullivan, Patrick J. and Hepburn, Beverly J., “Changes in Cooling Water
13 Sullivan, Patrick J. and Hepburn, Beverly J., “Changes in Cooling Water
Treatment Program,” IWC, November/December 1993 Treatment Program,” IWC, November/December 1993
3 Kessler, Stephen M., “Phosphate Inhibition Efficacy for the Twenty 14 Sullivan, Patrick J. and Hepburn, Beverly J., “Changes in Cooling Water
First Century,” CORROSION/04 paper no. 076 (Houston, TX, 2004) Treatment Program,” IWC, November/December 1993
4 Hardwick, D. and Jovancicevic, V., “Approach for Reducing Phosphorus 15 Change, D. M., “The binding of Free Calcium Ions in Aqueous
in Cooling Water Programs,” CORROSION/96, paper no. 605 Solutions Using Chelating Agents, Phosphates and Poly (acrylic acid),”
(Houston, TX, 1996) JAOCS, 6, 3, (1983)

5 Boffardi, Bennett P., “Corrosion Control of Industrial Cooling Water 16 Amjad, Zahid, Zuhl, Robert, W. and Zibrida, John F., “The Use of
Systems,” CORROSION/83 paper no. 274 (Houston, TX, 1983) Polymers to Improve Control of Calcium Phosphonate and Calcium
Carbonate in High Stress Cooling Water Systems,” AWT 2004 Annual
6 Vanderpool, Dan, Storp, Rother, J. and Kuron, K., “Comparative Convention
Investigation into Corrosion Inhibitors for Copper,” International 17 Thomas, Peter A. and Mullins A., “A Current Review of Polymeric
Water Conference, paper no. 50 (Pittsburgh, PA, 1986) Structures and Their Practical Significance in Cooling Water
Treatment,” CORROSION/85, paper no. 130, (Houston, TX, 1985)
7 Ward, Eric C., Foster Al L. and Gl;aser, Dane, L., “ Finally an
Alternative to Azoles,” The CTI Journal, 27, 1, (2006) 18 Gill, U.S. Patent No. 5,709,814, “Method for inhibiting calcium salt scale”
8 Terry, John, P., and Brown, Crystal W., “Current Cooling Water 19 Hwa, U.S. Patent No. 4,306,991, “Scale Inhibition,” issued December 22, 1981
Corrosion Control Technology,” International Water Conference, paper
20 Gill, U.S. Patent No. 5,709,814, “Method for inhibiting calcium salt scale”
no. 13 (Pittsburgh, PA, 1990)
21 Gill, Jasbir, S., Parsons, Jennifer R. and Wrede, Peter H., “A New
9 Sherwood, Nancy S. and Eastman, Gordon, E., “A Chromate Cooling Water Treatment to Reduce Blowdown,” CORROSION/97,
Replacement Program for Industrial Cooling Waters That Makes paper no. 482, (Houston, TX, 19897)
Sense,” Cooling Tower Institute paper no 89-07 (Houston, TX, 1989)

10 Schumacher, Paul D., Johnson Roy A. and Romberger, John A., “ Robert R. Cavano is the President of Scranton Associates Inc.
Corrosion Inhibition Techniques in Recirculating Cooling Water,” Bob can be reached at (216) 252-2120 or via email at
International Water Conference, paper no. 37 (Pittsburgh, PA, 1986) [email protected].

37 the Analyst Volume 15 Number 2