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Deposit-Related Corrosion in Industrial Cooling Water Systems

Reprint R-482 By H. M. Herro, Nalco Chemical Company

ABSTRACT
Deposits are frequently associated with corrosion in cooling water systems. Many corrosion processes are understood, while others need further characterization. Attack involves concentration cells, erosion-corrosion, stress-corrosion cracking and galvanic effects. Common sources of cooling water deposits are identified. Corrosion modes are reviewed. Industrial failures are used to illustrate each attack mode. Effects of oxygen, aggressive anions and tuberculation are discussed. Unusual cases of biofouling, and related cases of erosion-corrosion, and stress-corrosion cracking phenomena are detailed. Dealloying is discussed.

systems, however. Often closed systems are employed in critical cooling applications where even a small amount of material can produce substantial heat transfer problems and associated corrosion.

SOURCE OF DEPOSITS
Deposits have either an intrinsic or extrinsic nature. Material is either carried into the system or formed in-situ as corrosion product which is subsequently transported. The distinction between a corrosion product formed in place and deposited material is clear enough. However, in industrial systems, this distinction is not always clear. Intermixed deposits and corrosion products are the rule rather than the exception. Tubercles on steel usually contain both corrosion products and deposits. Due to cathodic processes producing hydroxyl ion, pH increases just outside the tubercle. Carbonate and other species whose solubility decrease with increasing pH are precipitated. Stratification and structural irregularities occur in most scales. Many scales change composition and structure with time, e.g., chloride and sulfate concentrate in a tubercle over time. In the case of biological fouling, the distinction is further blurred. While all the biological matter ultimately comes from outside the system, the biomass may be transported among and grow within cooling water structures.

INTRODUCTION
Cooling water deposits may be protective or harmful. Waters undersaturated with calcium carbonate, containing oxygen and having a negative Langelier Index are often considered more aggressive to steel than waters in which carbonate deposition is favored.1 There are exceptions to this rule of thumb, however.2 Deposits, quite apart from inhibiting heat transfer and water flow, frequently cause serious corrosion problems in a wide variety of cooling water systems. The system environment is critical to the amount, kind and harmfulness of the deposition. Cooling systems are predominantly open or closed. Open systems are those in which evaporation and other water losses occur. Open recirculating systems may use large quantities of water, and consequently, are often exposed to a great amount of suspended solids and precipitates. Since the supply of nutrients is replenished, biological growth and fouling are stimulated. Water is highly oxygenated, making oxygen concentration cells and general attack more active. Closed recirculating systems circulates water in a closed loop. Evaporation is slight; small quantities of makeup water may be added. Usually such makeup water is relatively pure. Since the total amount of waterborne material is slight, deposition is also small. Closed systems contain limited amounts of organic material. Consequently, biological growth is retarded. In a truly closed system, oxygen concentration is often small. Hence, oxygen concentration cell activity is slight. Most deposits consist mainly of corrosion products transported within the system. It is a mistake to believe that deposits are inconsequential in closed

DEPOSIT TYPES
Deposits contain metals and their oxides, biological material, precipitates and contaminants. Of these materials, only contaminants are always foreign to the system. Metal oxides, biological material and soluble species may be either formed within or carried into the system.

IRON AND MANGANESE

Frequently, deposits that form on metal surfaces contain oxides and salts incorporating metals. Commonly, hematite [Fe2O3], magnetite [Fe3O4] and geothite [FeOOH] form on iron. Cuprous oxide crystals, cupric oxide and elemental copper form from corroding cupriferrous alloys. Copper may deposit on less noble alloys. White rust forms on aluminum and is almost always aluminum oxide

Presented at the National Association of Corrosion Engineers Corrosion 89 meeting, New Orleans, Louisiana, April 1721, 1989

trihydrate (Bayerite) [Al2O33H2O3].3 Siderite [FeCO3] can be found in conjunction with iron oxides. Manganese dioxide [MnO2] forms readily in a number of cooling waters. Chlorination and certain bacteria assist manganese oxidation and subsequent deposition. Common calcium salts found in cooling water systems include carbonate, phosphate and sulfate. The common form of CaCO3, is calcite, although aragomite can also occur. Stratified calcium carbonate deposits in a cooling water line are shown in Figure 1. Such scales are usually, but not always, protective. Calcium sulfate as gypsum [CaSO42H2O] is the naturally occurring mineral form of this compound. Hemihydrate [CaSO41/2H2O] is gypsum heated to between 250 and 400F, and so is not often found in low temperature cooling water systems. Forms not containing water exist at high temperatures. Since calcium sulfate dissolves rapidly in water, only small amounts are usually found combined with other scale components. Calcium hydroxyapatite [Ca(OH)2[3Ca3(PO4)2]] has inverse temperature solubility. It has been found in boilers as well as in cooling water deposits.

CONTAMINANTS
Silt, sand, dirt and other detritus are commonly carried into many open cooling water systems. The effects of such material on underdeposit attack, microbiological growth and erosion-corrosion are significant. Process leaks and contamination of cooling tower waters allow considerable foreign material to enter systems.

MECHANISMS
Deposits cause metal wastage by changing the local environment so as to accelerate corrosion. Deposits concentrate aggressive anions, provide shielded regions in which oxygen concentration cells develop, allow favorable sites for the growth of aggressive biological species, produce unfavorable galvanic couples and increase turbulence locally. Examples of each of these mechanisms are discussed.

CONCENTRATION CELLS
OXYGEN
The best understood and most widely accepted cause of corrosion beneath deposits is the oxygen concentration cell. It is accepted both theoretically and practically that localized wastage usually initiates as the result of differential aeration cells.10 Oxygen is depleted beneath a deposit as corrosion proceeds. Replenishment of oxygen from the nearby electrolyte is too slow to return the depleted zone to its previous concentration. Hence, a differential aeration cell is established. The oxygen depleted zone becomes anodic. Cathodic processes are shifted away from the shielded region. Continuance of such cells requires electrical conduction between the electrolyte and the anode. Many deposits are porous, and water undoubtedly couples regions of differing oxygen concentration. Such mechanisms have been thoroughly discussed elsewhere.11 Experience shows that beneath many deposit layers, on mild steel, corrosion consists of in-situ conversion of iron to oxide. This is clearly demonstrated in Figure 2. The corrosion product beneath the deposit contains intact pearlite (lamellar carbide) colonies in the oxide. Figure 3 shows a typical mild steel microstructure containing similar pearlite colonies. This indicates the steel was converted to oxide with little disturbance of the carbide structure. The corrosion product formed at about 70F, and pH = 8.0. Deposits contained fuel oil. Corrosion products and deposits contained over 91 percent iron by weight as geothite and magnetite in Figure 2. Carbonate concentration was 2 percent. Small amounts of aluminum were also present. Experience shows that the concentration of aggressive anions makes such in-situ corrosion unlikely. At lower pH, the oxide becomes more soluble, preventing formation of the oxide layer shown in Figure 2. If aggressive anions are present, such as chloride or sulfate, pH beneath deposits decreases. Underdeposit attack causes the production of Fe+2 ion which oxidizes to Fe+3 once the ion comes into contact with oxygenated water. Ultimately, Fe(OH)3 forms. In-situ oxidation suggests transport of Fe+2 ion from beneath deposits is limited. Corrosion 2

SILICEOUS DEPOSITS
Dissolved silica can react with calcium, magnesium, sodium, and aluminum to form many different compounds. Many have been identified in the study of boiler scales.4,5 Silica usually is produced by the dissolution of rocks and the action of diatoms.

BIOLOGICAL MATERIAL
The classification of biological deposits would be an ambitious project by itself. General statements can be made. Material of biological origin is either living or dead. Dead material my be colloidal or suspended. Seed hairs, insect parts, etc. may gain access to utility condensers by way of cooling towers. Living material may consist of microorganisms such as fungi, slimes, algae and bacteria. Larger organisms such as mussels, clams, diatoms, etc. also foul cooling water systems. Bacteria undoubtedly play a role in many cases of corrosion. Mechanisms of microbiologically induced corrosion have received much discussion recently.6-9 Considerable work remains to be done.

Figure 1 Stratified calcium carbonate scale almost filling two cooling lines.

Figure 2 A corrosion product layer beneath an iron oxide deposit containing oil and grease on a mild steel line carrying cooling water from an annealing furnace. Note the white irregular pearlite colonies entrapped in the oxide indicating little solubilization of the oxide. (Magnification: 200X; Unetched)

Figure 3 Alloy microstructure of steel in Figure 2. Note the dark pearlite colonies. Compare with colonies entrapped in oxide in Figure 2. (Magnification: 500X; 2% Nital Etch)

products beneath many tubercles do not show the Figure 2 morphology. The in-situ oxidation may result from unusually high pH resulting from slow rates of aggressive anion migration beneath deposits. Copper alloys show moderately complex patterns of underdeposit attack. A thin silt layer covers the 90-10 cupronickel condenser tube in Figure 4. A bluish-white layer composed of copper carbonate and precipitates formed beneath the silt is shown in Figure 5. Beneath the carbonate, sparkling purple cuprous oxide crystals were found (Figures 6 and 7). If chloride concentrations are high, a white copper chloride layer is sometimes found beneath the cuprous oxide. Waters containing high concentrations of sulfate, and to a lesser extent, chloride, promote intergranular corrosion. Often, high concentrations of sulfate and/or chloride are found beneath deposits in corroding areas if care is not exercised to remove these soluble species during sample preparation. Most stainless steels are immune to oxygen concentration cell corrosion unless depassivating species such as chloride, sulfate, etc. are present. The resulting form of attack is pitting if passivity is broken locally. Very often, chloride is found in such pits.

Figure 4 Silt layer on admiralty brass heat exchanger tube. (Magnification: 6X) As ferrous ion generated within diffuses out of the tubercle, ferric hydroxide is also generated and deposited on top of the shell. Certain iron-oxidizing bacteria also assist in the iron deposition process. Tubercles formed under flowing conditions may be elongated in the direction of flow and show sharply sculptured contours. (See Figure 11.) Under more quiescent conditions, tubercles are rounded mounds. Beneath the shell, ferrous ions are always generated; other compounds such as siderite can form. (See Figure 12.) Chloride and sulfate migrate into the tubercle, lowering pH. The internal environment is usually acidic regardless of the pH of the bulk water.12 If pH falls below about 4, hydrogen evolution begins, providing a secondary cathodic reaction and thus, accelerating attack. Many incipient tubercles are shown in Figure 13. When the brittle oxide caps are removed, small pit-like depressions are revealed. (See Figure 14). In early stages of formation, tubercles can show concentric growth rings, as in Figure 15. Many tubercles contain hollow chambers. (See Figure 16.) The metal surface usually has an undulating-to-smooth contour beneath a tubercle. (See Figure 17.) Evidence of low pH conditions is often present. Striated surfaces result from preferential attack along microstructural irregularities formed during steel manufacture. As the tubercles increase in size, the 3

TUBERCLES
Tuberculation refers to the formation of a corrosion product and deposit mound above a corroded area, usually on a steel or cast iron surface. Figure 8 shows a heavily tuberculated supply line from a steel mill. Beneath each tubercle, a depression is present. (See Figure 9.) These structures form a friable outer crust of brown ferric oxide and other deposited material, as shown in Figure 10. Just beneath, a hard, black, brittle crust of magnetite-rich oxide forms. Some investigators feel that the magnetite shell is a good electrical conductor and, hence, is cathodic in an active turbercle.12 The hydroxyl ion generated at the top of the shell aids in the precipitation of carbonate and other species exhibiting decreasing solubility with increasing pH.

Figure 5 Silt layer removed to reveal friable copper carbonate beneath (in Figure 4). (Magnification: 6X)

Figure 8 Severe tuberculation in a 4-inch diameter mill water supply line.

Figure 6 Carbonate removed (in Figure 5) revealing sparkling cuprous oxide crystals. (Magnification: 6X)

Figure 9 Wall perforation beneath a tubercle on an emergency cooling water supply line in a nuclear power plant.

Figure 7 Scanning electron microscope picture of cuprous oxide crystals (in Figure 6). (Magnification: 1000X)

Figure 10 A tubercle opened to show the hard dark layer which caps most tubercles. This layer contains magnetite and is a good electrical conductor. (Magnification: 6X)

Figure 11 Sharp, angular tubercles in a steel pipe feeding a test water box in utility service.

Figure 13 Incipient tubercles on a mild steel plate immersed in oxygenated cooling water for six weeks. (Magnification: 6X)

Figure 12 Siderite nodules just above the magnetite shell in a tubercle. (Magnification: 6X) rate of ingress of chloride and sulfate can decrease, ultimately reducing corrosion rates. Anions such as oxygen also find the tubercle less permeable, and oxygen concentrations decrease. If oxygen concentration falls to sufficiently low levels, anaerobic microbiological activity may occur. Such activity is quite complicated and mechanisms are incompletely understood.

Figure 14 Metal surface after tubercles were removed in Figure 13. Note the pit-like depressions. (Magnification: 6X) eral, grooved regions sometimes occur around intact managanese deposits, as in Figure 21. Such patterns suggest galvanic effects between the glassy manganese oxide deposits and copper alloys. Other mechanisms involving erosion-corrosion are also possible. Brasses are susceptible to dealloying beneath deposits, especially if those deposits contain sulfate and chloride. Other accelerating factors include heat transfer and stagnant conditions. Dealloying in brass is the selective removal of zinc from the alloy, leaving behind a spongy porous mass of copper. Figures 22 and 23 show two admiralty brass condenser tubes removed from utility service. Both contained deposits, experienced virtually identical service histories and were fed with the same water. The severely attacked tube was not composed of an inhibited alloy. Plug type dezincification occurred in the uninhibited alloy, while only slight general attack was present on the inhibited alloy.

ANION
Scales containing manganese dioxide exhibit unusual corrosion patterns. Two forms of manganese scales are common. A thin purple glassy deposit forms, especially on high heat surfaces, as shown in Figure 18. A porous, friable, dark deposit also can form. (See Figure 19.) Manganese oxidation can be accelerated by chlorination. These scales often contain chloride, especially if the cooling water is brackish. The porous deposit tends to occur above generally wasted surfaces on both steel and copper alloys. Oxygen concentration cells accelerated by chloride operate. Chloride can concentrate beneath the glassy layer, causing localized spalling. Small bare pits develop at exfoliation sites. (See Figure 18.) Other pits may occur beneath nodules, rich in manganese. (See Figure 20.) Where spalling is more gen5

EROSION-CORROSION
Deposits disturb surface flow and increase turbulence. Protective surface layers are locally removed. The simultaneous action of erosion and corrosion produces intense localized wastage. Water is directed over and around deposits. The resulting pits are characteristically horseshoe-shaped in

Figure 15 Scanning electron microscope picture of a tubercle as shown in Figure 13. Note the concentric or clamshell steps. (Magnification: 450X)

Figure 18 Thin glassy purple manganese dioxide layer on a 7030 cupro-nickel condenser tube. Note the small pits where the manganese has spalled.

Figure 16 Tubercles as in Figure 15, broken open to reveal hollow space and porous oxide floor. (Magnification: 200X)

Figure 19 Porous deposit on a brass heat exchanger tube containing 60% manganese dioxide.

Figure 17 Steel plate with tubercles removed to show mutually intersecting shallow depressions and rolling surface contour.

Figure 20 Manganese rich nodules overlying pits on a cupro-nickel utility condenser tube. (Photo courtesy of Andrew Howell, Public Service of Colorado)

copper-containing alloys. (See Figures 24 and 25). If attack is initiated by turbulence surrounding deposits, a central pillar may develop. Deposit nodules form if detritus such as seed hairs find their way to metal surfaces. Erosion-corrosion can be accelerated by the presence of silt and other deposited particulate. Figures 26 and 27 show deposit mounds in a 9010 cupro-nickel utility condenser tube. The deposit mounds contain seed hairs which assisted silting. The mounds are elongated in the water flow direction. Pits free of deposits and corrosion products are found immediately downstream from the deposit mounds (Figure 28).

Figure 21 Grooves surrounding intact manganese deposits on a cupro-nickel condenser tube. (Photo courtesy of Andrew Howell, Public Service of Colorado)

STRESS CORROSION CRACKING

As the name implies, stress corrosion cracking requires the presence of both tensile stress and corrosion. Tensile stresses may be residual from tube manufacture or applied. Only certain corrosive species can cause cracking in a specific alloy. Ammonia can crack certain brasses. Chlorides are known to cause cracking in many austenitic stainless steels. Relatively high concentrations of these aggressive species are required to produce cracking. Deposits can provide both a source and a concentrating mechanism for the aggressive species. An admiralty brass condenser tube was heavily fouled with organic debris. The biological material rotted, liberating ammonia. Cracks originating on internal surfaces caused failure (Figure 29). Chloride stress corrosion cracking in austenitic stainless steels is rare at temperatures below about 150F. Hence, only systems in which temperatures are relatively high are affected. A plate-type heat exchanger was contaminated by high concentrations of chlorides caused by a process leak. (See Figure 30.) High levels of residual stress were present in the stamped plates.

Figure 22 Transverse cross-section through uninhibited admiralty utility condenser tube. Note the plug type dezincification. (Magnification: 22.5X)

GALVANIC EFFECTS
It is surprising that galvanic effects associated with deposits are rare. However, examples do exist. Figure 31 shows a galvanized pipe with deposits containing elemental copper particles. The zinc layer is consumed beneath the copper deposits. Similar attack often occurs when copper deposits on aluminum. Galvanic effects are magnified by the lack of polarization of the copper-aluminum cell. The usual source of elemental copper is wastage of copper components in the system. Common sources of copper alloy corrosion include erosion and/or wastage by ammonia and dissolved carbon dioxide. Figure 23 An inhibited utility condenser tube experiencing an identical environment as tube in Figure 22. Note only slight general attack on internal surface. (Magnification: 22.5X)

SUMMARY AND CONCLUSION

Industrial cooling water systems vary widely in design, operation, metallurgy and environment. Deposits and associated corrosion are similarly diverse. Concentration cells involving oxygen, chloride, sulfate and other aggressive 7

Figure 24 Impingement pits on copper tubing. Note the presence of deposit atop the characteristic center column. (Magnification: 12X)

Figure 27 Scanning electron microscope photo of deposit mounds shown in Figure 26. Note the tangled seed hairs assisting silt accumulation. (Magnification: 100X)

Figure 25 As in Figure 24, but at higher power. Note the deposit atop the pillar. (Magnification: 34X)

Figure 28 Pits downstream from deposit mound. Only the triangular footprint of the deposit mound remains. (Magnification: 6X)

Figure 26 Deposit mounds on a 9010 cupro-nickel utility condenser tube. (Magnification: 6X) 8

Figure 29 Admiralty brass condenser tube failed by stress corrosion cracks associated with rotting biological material.

ACKNOWLEDGMENTS
Thanks are extended to Andrew Howell, Public Service of Colorado, for photos of manganese deposits.

REFERENCES
21. The Nalco Water Handbook, F. N. Kemmer, ed., McGraw-Hill Book Company, New York, New York, 1979, pp. 4-13. 22. Internal Corrosion of Water Distribution Systems, Cooperative Research Report, The American Water Works Association Research Foundation, Denver, Colorado, 1985, p. 22-24. 23. Aluminum Properties and Physical Metallurgy, ed. John E. Hatch, American Society for Metals, Metals Park, Ohio, 1984, p. 253. 24. Manual on Water, 3 ed., ASTM, STP-442, 1969. 25. J. C. Cowan and D. J. Weintritt, Water-Formed Scale Deposits, Gulf Publishing Company, Houston, Texas, 1976. 26. D. Thierry, Field Observations of Microbiologically Induced Corrosion in Cooling Water Systems, Corrosion 87, Paper No. 364, National Association of Corrosion Engineers. San Francisco, California. 27. B. Little, P. Wagner and J. Jacobs, The Impact of Sulfate-Reducing Bacteria on Welded Copper-Nickel Seawater Piping Systems, Corrosion 88, Paper 81, National Association of Corrosion Engineers, St. Louis, Missouri. 28. D. Pope, J. Zintel, A. Kurvilla and O. Siebert, Organic Acid Corrosion of Carbon Steel: A Mechanism of Microbiologically Influenced Corrosion, Corrosion 88, Paper 79, National Association of Corrosion Engineers, St. Louis, Missouri. 29. R. Soracco, D. Pope, J. Eggers and T. Effinger, Microbiologically Influenced Corrosion Investigations in Electric Power Generating Stations, Corrosion 88, Paper 83, National Association of Corrosion Engineers, St. Louis, Missouri. 10. H. Uhlig, Corrosion and Corrosion Control, John Wiley and Sons Inc., New York, New York, 1963, pp. 273. 11. M. G. Fontana, N. D. Greene, Corrosion Engineering, John Wiley and Sons. 12. G. Butler, and H. C. K. Ison, Corrosion and Its Prevention in Waters, Leonhard-Hill, London, 1966, pp. 45.

Figure 30 Stress corrosion cracked austenitic stainless steel component from a plate-type heat exchanger. Chloride from a process leak caused failure.

Figure 31 Large mound of copper-containing deposits on galvanized pipe. Copper is light-colored spots in mound. Note the break in the galvanized layer beneath. (Magnification: 200X) anions occur on virtually all alloys. Tuberculation frequently occurs. Erosion-corrosion, stress corrosion cracking and galvanic attack all are observed. Although some deposit-related corrosion mechanisms are understood, others are less well characterized. In-situ oxidation beneath tubercles and unusual corrosion patterns associated with manganese deposits are worthy candidates for study. Microbiologically induced or influenced corrosion is very poorly characterized.

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