«51 Carbon Steel—Corrosion in

Fresh Waters

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I. MATSUSHIMA
Maebashi Institute of Technology
Maebashi, Japan

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A. INTRODUCTION

Corrosion of steel in fresh water proceeds electrochemically by the action of dissolved oxygen:
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Anodic reaction Fe -> Fe2+ + 2e~ (1)
Cathodic reaction \ O2 + H2O + 2e~ -> 2 OH~ (2)
Overall Fe + \ O2 + H2O -> Fe(OH)2 (3)

Most natural fresh waters are air saturated, and the concentration of dissolved oxygen at ordinary
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temperatures is 8-10ppm. For corrosion of steel to occur, dissolved oxygen must be supplied to the
steel surface by diffusion through water and possibly through surface films on the steel surface that
act as diffusion-barrier layers. Because of its concentration and diffusion coefficient, the supply of
dissolved oxygen is slow unless the velocity of water relative to the steel surface is sufficiently high.
The corrosion reaction proceeds as rapidly as oxygen reaches the steel surface. Thus, the corrosion is
under diffusion control of dissolved oxygen.
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In the absence of diffusion-barrier layers on the surface, the theoretical corrosion current density,
i (A/cm2), of steel in stagnant air-saturated fresh water can be calculated as follows:

I=(DnF/6) C x 10~3 (4)

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where D is the diffusion coefficient for dissolved oxygen in water (cm2/s), n is the number of
electrons involved in the reaction, F is the Faraday constant (C/mol), 6 is the thickness of the
diffusion layer (cm), and C is the concentration of dissolved oxygen (mol/L).
Using D = 2 x 1(T5 cm2/s, n = 4, F = 96,500 C/mol, 8 = 0.05 cm, and C= 8/32 x 10~3 mol/L
at 250C, i = 38.6 x 10~6 A/cm2, which is equivalent to a corrosion rate of 0.45 mm/year (18 mils/
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year (mpy)).
In hard waters that contain high concentrations of calcium and bicarbonate, the natural deposition
of calcium carbonate (CaCO3) on the steel surface provides an effective diffusion barrier to oxygen
diffusion, greately decreasing corrosion. In soft waters, the corrosion rate is higher than in hard
waters, but it is lower than the theoretical maximum value because the corrosion product film formed

Uhlig's Corrosion Handbook, Second Edition, Edited by R. Winston Revie.

ISBN 0-471-15777-5 © 2000 John Wiley & Sons, Inc.

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on the surface acts to some extent as a diffusion barrier. The average corrosion rate of steel in
stagnant air-saturated soft waters at ordinary temperatures is roughly 0.1 mm/year.
Increase in oxygen concentration, velocity, and temperature, within limits, accelerates corrosion
in soft water by increasing the supply of dissolved oxygen to the surface. When oxygen
concentration is very high, for example, ~ 12 mL/L or 17 ppm in distilled water at 250C [1] or 25-
35 ppm [2] in natural waters (e.g., when fresh water is saturated with a gas of high oxygen partial
pressure), or water velocity is above a critical value, the corrosion rate drops to a low value. This

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decrease in corrosion rate is caused by passivation of the steel as a result of oxygen being supplied to

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the surface in excess of the amount that can be used for the cathodic reaction. More quantitative data
regarding the effects of environmental factors is given in Section B.
While the supply of dissolved oxygen controls the overall corrosion rate, the cathodic and anodic
reactions do not necessarily occur uniformly over the surface. There are two types of corrosion cells.
In macrogalvanic cells, the anodic and cathodic areas are macroscopic, and their locations are fixed,

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whereas in microgalvanic cells, the anodic and cathodic sites are microscopic and move randomly
with time. When macrogalvanic cells, such as differential aeration cells, are formed on the steel
surface, and the anodic reaction, dissolution of steel, takes place predominantly at some limited areas
in amount equivalent to the cathodic reaction proceeding around the macroanode, the penetration
rate at the anode can be high if the cathode/anode area ratio is large. The extent of the effective
cathode area depends on the conductivity and geometry of the system. In waters of high
conductance, macrogalvanic cells can operate over long distances.
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High corrosion rates of steel are associated with the formation of macrogalvanic cells of some
kind, which may not have been anticipated nor considered at the design stage for corrosion
protection.

B. ENVIRONMENTAL FACTORS
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1. Natural Fresh Waters

While corrosion of carbon steel proceeds by the action of dissolved oxygen, the rate of the reaction
is affected by other species in water. Among the many species dissolved in natural fresh waters,
calcium (Ca2+), bicarbonate (HCOp, and chloride (Cl~) are very important with respect to
corrosion.
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The source of natural fresh waters is meteoric water that falls on the earth as rain, snow, sleet, or
hail. Rainwater comes in contact with the atmosphere and is saturated with dissolved air. Depending
on the kind of atmosphere to which the rainwater is exposed, it also dissolves impurity gases, such as
SOx, NOx, NH3, and HCl, and other matter from suspended atmospheric impurities such as sea salt
and dust.
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When the precipitation comes into contact with the ground, some of it evaporates, but the
rest flows or collects on the surface of the earth as surface water, or sinks into the ground as
ground water. The water dissolves materials with which it comes in contact, and therefore, contains
a variety of species, including Ca2+, Mg2+, soluble silica [e.g., (H2SiO3)J, HCO^, Na+, K + ,
Cr, and SOj-.
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Carbon dioxide in water reacts with minerals containing CaCO3, such as limestone, marble,
chalk, calcite, and dolomite, as follows:

CaCO3 + CO2 + H2O -> Ca2+ + 2HCO^ (5)

Dissolved CO2 also reacts similarly with minerals containing MgCO3 to form Mg2+ and HCO^. The
contents of Ca2+ and Mg2+ as equivalent parts per million CaCO3 are the calcium hardness and the
magnesium hardness, respectively, and the sum is the total hardness. In natural waters, the
concentration of bicarbonate (HCOp corresponds to the methyl orange alkalinity (M. O. alkalinity;

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the equivalent per liter of titratable base to the methyl orange end point), commonly expressed as
parts per million CaCO3. The values of Ca hardness and the M. O. alkalinity are the primary factors
that determine the ease of protective CaCO3 film formation on a metal surface.
The solubility of CaCO3 depends on the dissolved CO2 concentration. Air-saturated distilled
water contains only 0.5 ppm CO2 at room temperature and can dissolve 53 ppm CaCO3. Rainwater,
however, may contain up to 2 ppm CO2 because of the CO2 derived from organic matter in the
atmosphere. The amount of CO2 contained in some natural waters, particularly ground waters, is

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much higher due to the CO2 derived from the decay process of organic matter in the soil, and the Ca

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hardness and M. O. alkalinity may be over 200 ppm. At a given CO2 concentration, the amount of
CaCO3 dissolution depends on the kind of geological strata to which the water is exposed and the
contact time before the water is utilized.
If the dissolution of CaCO3 and MgCO3 is the major source of the total hardness and the M. O.
alkalinity, these two values should be almost identical. In some natural waters, however, the total

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hardness may be significantly higher or lower than the M. O. alkalinity. This difference can occur
because Ca2+ and Mg2+ can derive from water soluble minerals, instead of carbonates, without
the action of CO2, for example, Ca2+ from gypsum, alabaster or selenite and Mg2+ from epsomite,
kainite, picromerite, or loweite. Additional HCO^ may be formed by the reaction of dissolved
CO2 with some minerals other than CaCO3 and MgCO3, for example, albite (NaAlSi3O8). If
the M. O. alkalinity of the water equals or exceeds the total hardness, all of the hardness is
attributed to carbonate hardness. If, on the other hand, the M. O. alkalinity is less than the total
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hardness, the carbonate hardness equals the M. O. alkalinity and the balance is the non-carbonate
hardness.
The results of analyses of dissolved matter in typical soft and hard river waters are listed in
Table 1 [3]. Waters with a total hardness of < 100 ppm are soft, those with 100-150 ppm are slightly
hard, and those with > 150 ppm are hard. Some waters are very hard, the total hardness being
over 300 ppm.
The sources of Cl" in natural fresh waters are sea salt in the atmosphere, pollution of rivers by
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sewage and industrial effluents, some geological strata to which the water is exposed, and road
deicing salts. The average concentration of Cl~ in rainwater is commonly ~ 1 ppm, but near the
seacoast, it can be an order of magnitude higher due to prevailing winds from the sea. The Cl~
content of river waters, about 8 ppm on average, varies in a wide range from a few parts per million to
several hundred parts per million except in some unusually high cases.
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2. Effect of Water Quality

2.1. General The analytical water quality parameters that may affect corrosivity of natural fresh
waters are pH, dissolved oxygen, Ca hardness, M. O. alkalinity, total dissolved solids (TDS), Cl~,
and SOj". The values of pH, Ca hardness, M. O. alkalinity, and TDS are factors that determine the
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saturation index, which is the criterion of whether or not the CaCO3 diffusion-barrier film is formed
on a metal surface, as wil lbe described in the following section (see Section B. 2.5).
The values of pH and of dissolved oxygen concentration are the fundamental factors that affect
the corrosivity of soft waters. They usually do not change the corrosion rate of steel in natural fresh
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waters, because the pH value remains within a certain range and most waters are air saturated.
The ions Cl" and SO^" are always present in natural fresh waters. They affect the penetration rate
of localized corrosion by increasing conductivity, and they also affect the critical concentration of
oxygen and critical water velocity above which passivation of steel occurs.

2.2. Saturation Index For given values of calcium hardness, M. O. alkalinity and total dissolved
salt concentration, a value of pH (pHs) exists at which the water is in equilibrium with solid CaCO3.
The deposition of CaCO3 is thermodynamically possible when the pH of the water is higher
than pHs.

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TABLE 1. Typical Water Qualities of River Waters*'*
Hardnessc
M. O. (as CaCO3)
Alkalinity Total
River Location pH (as CaCO3) Total Ca Cl ~ SO42" SiO2 Dissolved
(Concentration in ppm) Solids

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Bandas Seria (Brunei) 5.3 1 8 1 1 7 6
Kerteh Kerteh (Malaysia) 6.2 3 15 7 10 1 10 78
Yodo Sakai (Japan) 6.7 24 39 29 15 22 6
Vanda Helsinki (Finland) 7.5 38 50 31 12 22 8 145
Enim Tanjung (Indonesia) 8.3 141 73 12 29
Changjiang Wuhan (China) 7.2 99 75 53 17 18 5
Indus Jamshoro (Pakistan) 8.0 92 125 15

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Chaopraya Bangkok (Thailand) 6.8 107 126 73 109 28 26
Thachin Banglen (Thailand) 7.5 150 150 100 35 50 20
Changjiang Shanghai (China) 8.0 102 163 98 153 40 10
Donau Bratislava (Slovakia) 7.8 178 233 169 23 33 9
Thames London (UK) 8.4 215 262 252 19 27 6 904
Red Deer Red Deer (Canada) 8.0 218 290 180 6 37 7
Saskatchewan Saskatchewan (Canada) 7.3 380 604 352 476 298 14 1650
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a
Data were suppliedfromKurita Water Industries, Ltd.fromtheir database. (Reproduced with permission from [3].)
b
Water quality is subject to seasonal fluctuation.
c
Arranged in increasing total hardness.
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 At equilibrium,

K2 = [H+][CO^V[HCO3-] (6)
2+
K1 = [Ca ][CO^] (7)
2+ +
= [Ca ] [HC03-]*2/[H ] (8)

Since —log [H+] here is pHs and [HCO3-] ~ M. O. alkalinity(alk) in natural fresh waters,

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pHs ~ log (KS/K2) - {log [Ca2+] + log (alk)} (9)

For a more thorough derivation of pHs, see the textbook by Uhlig and Revie [4], and for a new
equation based on a rigorous model of CaCO3 saturation, see the paper by Pisigan and Singley [5].

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The value (pHmeasured — pHs) is called the saturation index, or the Langelier index after Langelier
[6] who established this index. A positive value of the Langelier index indicates a tendency for the
protective CaCO3 film to form and a negative value for it not to form.
In the presence of other dissolved salts, the increase of ionic strength depresses the activities of
other ions and increases the values of IQg(K5JK2) in Eq. (9) if K5 and K2 are based on concentrations
rather than activities. On the other hand, the values of \og(Ks/K2) decrease with temperature, making
the saturation index more positive. In practice, the calculation of pHs is carried out on the
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concentration basis with additions of correction factors for ionic strength and temperature to Eq. (9).
The values of the Langelier index of representative river waters, calculated based on the analyses
provided by Suzuki [3] and others, are shown in Figure 1.

Thames
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Colorado
Seine
Nile Missouri Tiber
Michigan Tigris Saskatchewan
Guadalquivir
Donau
Indus Vaal
L Erie Severn
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Chaopraya
Langelier Index

Tees
Columbia
Han Gang -Orange

Cigede
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Ohio
Tone

Ottawa
Sacramento Shinano
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Musi
Amazon

Ca2+ as ppm CaCOa

FIGURE 1. Values of the Langelier index of representative river waters. Data are primarily from [3].
(Reproduced with permission from [3].)

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TABLE 2. Data for Rapid Calculation of the Langelier Index Arranged by Nordell"
A C D

Total Dissolved Ca Hardness M. O. Alkalinity

Solid (ppm) A (ppm as CaCO3) C (ppm as CaCO3) D

50-300 0.1 10-11 0.6 10-11 1.0

400-1000 0.2 12-13 0.7 12-13 1.1

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14-17 0.8 IA 11 1.2

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B 18-22 0.9 18-22 1.3
23-27 1.0 23-27 1.4
Temperature (0C) B 28-34 1.1 28-35 1.5
35-43 1.2 1f\ AA 1.6
0-1.1 2.6 44-55 1.3 45-55 1.7
2.2-5.6 2.5 56-69 1.4 56-69 1.8

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6.7-8.9 2.4 70-87 1.5 70-88 1.9
10.0-13.3 2.3 88-110 1.6 89-110 2.0
14.4-16.7 2.2 111-138 1.7 111-139 2.1
17.6-21.1 2.1 139-174 1.8 140-176 2.2
21.2-26.7 2.0 175-220 1.9 177-220 2.3
27.8-31.1 1.9 230-270 2.0 230-270 2.4
32.2-36.7 1.8 280-340 2.1 280-350 2.5
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37.8-43.3 1.7 350-430 2.2 360-440 2.6
44.4-50.0 1.6 440-550 2.3 450-550 2.7
51.1-55.6 1.5 560-690 2.4 560-690 2.8
56.7-63.3 1.4 700-870 2.5 700-880 2.9
64.4-71.1 1.3 880-1000 2.6 890-1000 3.0
72.2-81.1 1.2
"See [8].
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(1) Obtain values of A, B, C, and D from above table.

(2) pHs = (9.3 + A + B) - (C + D).
(3) Langelier saturation index = pH — pHs

Charts have been prepared by Powell et al. [7] for calculating the Langelier index of waters
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varying widely in relevant dissolved species at various temperatures. The historical charts prepared
by Powell et al. [7] and the table arranged by Nordell [8] (Table 2) are still in use, but correction
factors for ionic strength and temperature have been updated based on recent advances in the
solubility chemistry of CaCO3 and solution chemistry (e.g., by Schock [9]).
While the concept of the Langelier index is correct and helpful, it should be emphasized that a
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positive value of the index can result from waters of totally different quality. As the pH increases, the
Ca2+ concentration decreases drastically. The corrosion protection characteristics of the resulting
CaCO3 film differ accordingly. In other words, waters of different pH, Ca hardness, and M. O.
alkalinity that give the same value of the index have different corrosivity. The buffer capacity and the
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oxygen concentration of the water, and the thickness, composition, and the crystalline state of
deposits all affect the protectiveness of the deposited CaCO3 film. These facts were pointed out
by Stumm [10] as early as 1956 and have not been explained to date either quantitatively or
systematically.
Instead of using the thermodynamic prediction of the tendency for CaCO3 precipitation in terms
of the Langelier index, an experimental method, the marble test, developed by DeMartini [11] and
Hoover [12] can be used. The water is treated with powdered CaCO3, and, after saturation, changes
in pH, alkalinity and concentration of calcium are measured as an estimate of undersaturation. An
improved procedure has been proposed by Merrill and Sanks [13].

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 Another index used in practice for estimating corrosivity of water is the stability index or the
Ryznar index (RI) developed by Ryznar [14].
RI = 2pH s -pH (10)

This index is intended to predict quantitatively the amount of CaCO3 that would be formed and also
to predict the corrosivity of waters that are undersaturated with respect to CaCO3. At RI 6.0, CaCO3

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is in equilibrium. The deposition of CaCO3 increases proportionately as the index drops < 6, and

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corrosivity increases as the index rises >6. Values of 10 or above indicate extreme corrosivity.
Both the Langelier and the Ryznar indexes were derived from thermodymamic considerations.
The CaCO3 precipitation does not occur unless a certain degree of oversaturation is indicated by
these indexes. A new index, practical saturation index (PSI), has been proposed by Puckorius and
Brooke [15], which uses what they called an equilibrium pH (pHe) in the Ryznar equation [Eq. (10)].

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PSI = 2pHs - pHe (11)
pHe = 1.485 x log (total alkalinity) + 4.54 (12)

The coefficient and the constant in Eq. (12) were obtained empirically from the study of hundreds of
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actual case histories recorded and evaluated by the authors over 12-15 years with concentrated
cooling waters, most of which were water treated to a pH level >7.5, often between 8 and 9.5.
Because the values of pHg tend to be smaller than those of the measured pH, making the PSI values
larger than the Ryznar index values to compensate the oversaturation required for precipitation to
occur [cf. Eqs. (10) and (11)], the CaCO3 precipitation takes place below exactly PSI 6.0 according
to the authors.
For soft waters, a desired level of the Langelier index can usually be attained by the addition of
lime, sodium carbonate, or sodium hydroxide to raise the pH to an appropriate value. For very soft
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waters, however, the required pH may be too high for uses such as tap water unless Ca2+ ions are
added simultaneously. A Langelier index of +0.1 ~ +0.5 is considered to be satisfactory to
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1" carbon steel pipe

1/2" carbon steel pipe
Corrosion rate (mdd)

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Langelier saturation index

FIGURE 2. Relationship between the Langelier index and the corrosion rates of water pipes. (Reproduced with
permission from [18].)

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provide corrosion protection and at the same time to avoid excessive deposition or scaling at elevated
temperatures [16]. Data by Flentje [17] and by Fujii [18] show that water with a less negative
Langelier index is less corrosive. Waters with a slightly negative Langelier index may deposit
CaCO3 because of pH fluctuations. The relationship between the Langelier index and the corrosion
rates of water pipes obtained by Fujii [18] from a field test at a city waterworks are reproduced in
Figure 2.
Even though the saturation index is positive, the corrosion rate may remain high if the water

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contains colloidal silica or organic particles, such as algae, because CaCO3 precipitates on them

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instead of on the steel surface. For waters high in dissolved salt or at high temperature, the CaCO3
film is less protective.
The following sections deal with corrosion in soft waters unless otherwise stated.

2.3. pH The pH of fresh waters is determined by the equilibrium of carbonic species.

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pH - 6.35 + log[HCO3-]/[C02aq] (250C) (13)

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Corrosion rate (mm/y)

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PH

FIGURE 3. Effect of pH on corrosion of steel in aerated waters, (a) Soft tap water, Cambridge, MA, USA. pH
adjusted by additions of HCl and NaOH, 220C [19]. (Reproduced with permission from W. Whitman, R. Russell,
and V. Altieri, Ind. Eng. Chem., Vol. 16, p. 665 (1924). Copyright © 1924, American Chemical Society.) (b)
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Aerated water containing 2.5 mmol/L NaHCO3 and 2.5 mmol/L NaOH. pH controlled by continuous addition of
CO2 (22-310C). Linear polarization method applied after 16-day immersion. (Reproduced with permission from
[2O]. © Copyright NACE International, (c) Aerated water containing 2.5 mmol/L NaHCO3 and 0.5 mmol/L
NaOH. pH controlled by continuous addition of CO2 (19-280C). Linear polarization method applied after 16-
day immersion. (Reproduced with permission from [2O]. © Copyright NACE International, (d) Water containing
NaHCO3 (alkalinity: lOOmg/L as CaCO3). pH adjusted by introduction of CO2 and air. Room temperature, 3
days [21]. (Reproduced with permission from Journal AWWA, Vol. 79, No. 2 (February 1987) © 1987,
American Water Works Association.) (e) Soft tap water, Tokyo, Japan. pH adjusted by additions of CO2 and
NaOH. 0.5 in. (21.7mm OD) pipe, 2L/min once-through flow. Room temperature, 32 days [22]. (Reproduced
with permission from [22].)

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where [CO2 aq] is the sum of dissolved [CO2] and [H2CO3] in equilibrium with the partial pressure of
CO2 gas in the gas phase. The pH of surface waters ranges from 5 to 9, but that of underground
waters exposed to a high CO2 partial pressure is often <6.5 and increases on aeration, which
eliminates excessive CO2.
Based on the classic data by Whitman et al. [19], it has generally been considered that, within the
pH range of ~4-10, the corrosion rate is independent of pH, other factors being equal (Fig. 3,
line a). Regardless of the bulk pH of water within this range, the steel surface is always in contact

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with an alkaline solution of saturated hydrous ferrous oxide (pH ~ 9.5).

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Some researchers claimed, however, that water quality (i.e., alkalinity, buffer capacity, and
concentrations of Cl~ and SO^") is the primary factor in corrosion at low flow velocity, and that
the influence of dissolved oxygen and pH on corrosion rates is secondary. Skold and Larson [20],
by polarization resistance measurements, reported the effect of pH on corrosion as shown by
curves b and c in Figure 3, where the corrosion rate increases from pH 7 to a maximum at pH 8.

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The concentrations of NaHCO3 and NaCl were kept constant at 2.5 and 0.5mmol/L,
respectively, throughout the experiment. Carbon dioxide was used to control pH. A similar curve
(Fig. 3, curve d) was obtained by Pisigan and Singley [21] who conducted immersion tests in a
solution containing 1-mmol/L total carbonate species. These authors pointed out that the increase
of the corrosion rate in this pH range corresponds to the decrease of the buffer capacity
provided by HCO3-. The basis of this conclusion is that HCO^" ions act as an inhibitor (see
Section B.2.5)
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Regarding the effect of pH indicated by curves b-d in Figure 3, it should be pointed out that the
waters used in these experiments contained no calcium, unlike natural waters.
Fujii et al. [22] observed an appreciable increase in the corrosion rate with increase of pH from
6.5 to 8.5 (Fig. 3, curve e) with soft Tokyo tap water (Ca hardness: 51.8ppm, M. O. alkalinity:
39.8 ppm, pH 7.1, Langelier index: — 1.4) using CO2 gas or NaOH to control pH. They attributed the
increased corrosion rate to the observed enhanced formation and activity of tubercles at higher pH,
where corrosion products are more adherent and the buffer capacity is less, resulting in a lower pH at
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the anodic areas.

2.4. Chloride and Sulfate Ions As long as diffusion of dissolved oxygen is controlling corrosion,
Cl" and SO2^- ions in concentrations found in fresh waters have essentially no effect on the overall
corrosion rate of steel because they do not affect the solubility of oxygen. Localized attack,
however, is accelerated as the conductivity of water increases with increase in the concentration of
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these ions, expanding the effective cathodic areas.

Above a critical water velocity, passivation occurs, and the corrosion rate of the passivated steel
increases with Cl" concentration. For more details, see Section B. 3.
Some authors have shown that, at a given HCO3" concentration in the absence of Ca2+,
increased Cl" or SO^" concentration caused the water to become more corrosive to steel [21, 23,
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24]. According to these authors, even in the absence of Ca2+, bicarbonates inhibit the corro-
sion of steel, and Cl~ and SO2T are detrimental to this inhibitive action. For more details, see
Section B. 2.5.

2.5. Bicarbonate Bicarbonate (HCO3") is one of the species essential to form a protective CaCO3
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film in the presence of Ca2+ ions at pH above pHs. Some data indicate the effects of HCO^ ions as
an inhibitor of corrosion in the absence of Ca2+ ions. Although it is not likely that in natural waters
an appreciable concentration of HCO3- ions is present without a comparable concentration of Ca2+
ions, it would be worthwhile to consider this inhibitive action.
With solutions that do not contain Ca2+, Larson and co-workers, [23,24] reported that, at a given
concentration of Cl" or SO2", the corrosion rate decreased with increase of HCO3-, and that, at a
given HCO^ concentration, the corrosion rate increased with increase of Cl~ or SO^" and leveled off
at a certain concentration of these ions. In other words, the corrosion rate was determined by the
Cl-/HCO3- or 80^/HCO3- ratio.

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 Corrosion rate (mm/year)

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Velocity (m/s)

FIGURE 4. Effect of water velocity on corrosion of carbon steel (1). (a) Distilled water +lOppm Cl", 5O0C,
14 days. (Reproduced with permission from [26].) (b) Soft tap water, Tokyo, Japan, room temperature, 67 days.
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(Reproduced with permission from [22].) (c) Soft tap water, Amagasaki, Japan, 2O0C, 15 days (killed steel).
(Reproduced with permission from [25].) (d) Soft tap water, Amagasaki, Japan, 2O0C, 15 days (rimmed steel).
(Reproduced with permission from [25].)

These authors, and also Pisigan and Singley [21], suggested that the corrosion product formed in
the presence of HCO^ and in the absence of Ca2+ was FeCO3, instead of Fe(OH)2, the former being
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more protective than the latter. The latter authors, having obtained the effect of pH as shown by curve
d in Figure 3, proposed that the composite effect of pH and alkalinity can be combined into one
parameter, the buffer capacity, P, which is defined as (3 = d (alkalinity )/d pH. If the pH is varied at
constant alkalinity or total carbonate species, P of the water decreases with pH in the range of typical
drinking water systems from a maximum to a minimum at pH corresponding to pKi and to
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\ (pKi + P^f2), respectively, where KI and K2 are the first and the second dissociation constants of
H2CO3. The maximum occurs at pH 6.3 and the minimum at pH 8.3. Curve d in Figure 3 shows the
highest corrosion rate at pH 8.0, at which P is near its minimum.
The beneficial effect of the alkalinity represented by p was explained by its capacity to neutra-
lize the acid generated at the anode by the oxidation of Fe2+ [2 Fe2++^-O2+ 5H 2 O =
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2Fe(OH) 3 +4H + ] and to cause additional carbonate precipitation (FeCO3, or CaCO3 in the
presence of Ca2+) at the cathode, decreasing the strong driving force for corrosion.

3. Effect of Velocity
The effect of water velocity on corrosion of mild steel, from data by Kowaka et al. [25], Fujii et al.
[22], Matsushima [26], and Kinoshita et al. [27], is shown in Figures 4 and 5. According to these
data, the critical velocity above which the corrosion rate decreases because of passivation is in the
range of ~0.3-0.7m/s.

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Corrosion rate (mm/year)

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1% Cr cast iron

Gray cast iron

Mild steel
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Velocity (m/s)
FIGURE 5. Effect of water velocity on corrosion of steel (2). 25ppm Cl~, 3O0C, 30 days. (Reproduced with
permission from [27].)
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100 pprn Cl
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Corrosion rate (mm/year)

50 ppm Cl
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10ppm Cl

O ppm Cl

Velocity (m/s)
FIGURE 6. Effect of water velocity and chloride concentration on corrosion of carbon steel. Distilled
water+ NaCl, 5O0C, 14 days. (Reproduced with permission from [26].)

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 The critical velocity and the corrosion rate at velocities above critical depend on the
concentration of chloride ions that prevent passivation. An example of data by Matsushima [26] is
shown in Figure 6. As shown by LaQue [28], passivity is not established at any velocity in the
presence of high concentrations of Cl~, as in seawater. On the other hand, passivation of mild steel
occurs at a very low velocity, for example, <0.1m/s in high purity water (e.g., conductivity
<0.5nS/cm)[29].
Water at very high velocities, (e.g., 20 m/s), causes erosion-corrosion by removing corrosion

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product films through application of shear stress, thereby exposing the steel surface directly to the

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corrosive environment. It may also remove the metal mechanically, but removal of only corrosion
product films is sufficient for erosion-corrosion to proceed. The free access of dissolved oxygen in
water increases corrosion several times. The maximum penetration rate approaches the rate that
corresponds to the amount of dissolved oxygen supplied from the water without a surface barrier.
Erosion-corrosion often occurs at bends or misaligned joints of high-velocity water pipe even if the

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water does not carry suspended solids.
If conditions of high velocity water are such that low- and high-pressure areas develop and
bubbles form and collapse at the metal-water interface (cavitation), the steel is damaged
mechanically by the impact pressure exerted by the collapsing bubbles. This type of degradation is
called cavitation erosion or cavitation damage. Cavitation-erosion can occur purely mechanically,
but is accelerated by free access of dissolved oxygen. It occurs typically on rotors of pumps and the
trailing side of water turbine blades made of steel and cast iron.
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C. LOCALIZED CORROSION

1. General
Localized corrosion of steel in fresh waters occurs in most cases by the action of macrogalvanic
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cells. The resulting damage tends to be most critical in water pipes because perforation of the pipe
wall by localized corrosion (e.g., pitting) means instant leakage of the water carried by the pipe.
The major types of localized corrosion of steel in fresh water are pitting under tubercles, groove
corrosion of electric resistance welded (ERW) pipes, and pitting at discontinuities in corrosion
product films. For other types of localized corrosion in water see Chapter 34.
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2. Pitting under Tubercles

Tuberculation or formation of mounds of corrosion products (tubercles) occurs frequently on the
steel surface in contact with water. Differential aeration cells are then formed. The areas under
tubercles, where the supply of dissolved oxygen is limited, undergo localized corrosion by the
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galvanic action of the surrounding cathodic areas that receive free oxygen supply. Galvanized water
pipes corrode similarly after the zinc coating has been lost, as often occurs within several years of
service in soft waters.
The penetration rates in millimeters per year (mm/year) and mils per year (mpy) of galvanized
city water pipes are listed in Table 3 [3O]. The periods of protection by the zinc coating were
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neglected in calculating the rates. The rates are not high, ranging generally from < 0.1 to ~ 0.3 mm/
year. (<4 to ~ 12mpy). The highest rate is 0.32mm/year. Masamura and Matsushima [31]
calculated the theoretical penetration rate by assuming the geometry of the corrosion system and the
anodic polarization behavior, and by solving the Laplace equation for the potential distribution. The
rate depended on the resistivity of the water, increasing as resistivity decreased. The penetration rate
corresponding to the resistivities of city waters, 5000-800017 • cm, is about 0.3 mm/year (12 mpy)
(Fig. 7), in good agreement with the observed highest rate.
The penetration rate increases with increase of temperature and decrease of water resistivity. The
highest rate observed by Matsushima [30] for galvanized hot water pipe was about 1 mm/year

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TABLE 3. Penetration Rates of Galvanized Tap Water Pipes Under Tubercles"
Wall Maximum Service Maximum Penetration Rate
Size Thickness Penetration Period
(in.) (mm) (mm) (year) (mm/year) mils/year (mpy)
1 3.2 3 13 0.23 9
1 3.2 1 5 0.20 8
1 3.2 1.5 10 0.15 6

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I1A 3.5 0.8 10 0.08 3

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i 3.2 Perforated 14 0.23 9
I11A 3.5 0.8 14 0.06 2
IA 3.5 1.2 14 0.09 3
2 3.8 0.8 14 0.06 2
1 3.2 1.4 14 0.10 4
iy2 3.5 1.3 14 0.09 3

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5 4.5 2 16 0.13 5
4 4.5 Perforated 15 0.30 12
1 3.2 Perforated 10 0.32 13
6 5.0 Perforated
a
Reproduced with permission from [3O].
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(40 mpy), except for the cases where the rate was extremely high (e.g., 2.8 mm/year (HOmpy)
indicating that the localized corrosion was accelerated by reversal of polarity between zinc and steel
due to the formation of noble corrosion product films on zinc in waters of particular quality at
high temperatures [32], A penetration rate of 3. 8 mm/year (150 mpy) was experienced in black
pipe (as rolled steel pipe with mill scale) carrying warm mine water of low resistivity (pH 8.4,
Ca hardness 32ppm, total hardness 72ppm, M. O. alkalinity 475 ppm, total dissolved solids
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2635 ppm, Cl~ 735 ppm, resistivity 1385 $1 - cm). The presence of mill scale presumably contributed
to the high rate.
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Corrosion rate (mm/y)

Current density (A/cm2)

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Resistivity (Q • cm)
FIGURE 7. Effect of water resistivity on theoretical penetration rate of carbon steel under tubercles [31].

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TABLE 4. Penetration Rates of Steel Pipes Alternately Exposed to Hot Water or Steam and Cold Water a
Service Penetration Rate
Penetration Period
Item Condition6 (mm) (year) (mm/year) mils/year (mpy)
c
Hot water pipe RT/90~95°C 5.8 6 0.97 38
Hot water pipe RT/max 6O0C 3.8c 4 0.95 37
Steam/water pipe 6 h cycle 4.2c 1.2 3.5 140

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Boiler hot water return 48/9O0C 4.5c 4 1.1 43

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line near inlet of cold
make up water
a
See [39].
b
Room Temperature = RT.
c
Perforated.

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It is generally accepted that aerobic iron bacteria greatly accelerate the formation of tubercles by
accumulating large amounts of ferric hydrate [33], but tuberculation can also occur in their absence.
Sulfate-reducing bacteria flourish in tubercles because of the anaerobic condition and may accelerate
corrosion [33]. The corrosion mechanism, however, can be explained solely from electrochemistry
[34], and the significance of bacterial action is unknown.
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3. Groove Corrosion of Electric Resistance Welded Pipe
The welded seam of the ERW pipe is heated locally and then cooled rapidly by the ambient air, and
its microstructure is much different from that of the parent metal that is not heated during welding. It
tends to have more negative, or less noble, potential than the parent metal and, on exposure to
corrosive media, such as water and soil, corrodes locally in the form of grooves. This type of
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localized corrosion does not always occur, but most ERW pipes are potentialy susceptible to it.
A rate in the range of 1 to 3 mm/year (40 to 120 mpy) is common, and can be as high as 10 mm/
year (400 mpy) [35]. The difference of the open circuit potential is a maximum of ~ 70 mV [35]. The
more negative, or less noble, potential of the weld seam has been attributed to the formation of
unstable MnS inclusions in the weld by the thermal cycle of the welding operation [36, 37]. Butt-
welded pipes that have been heated uniformly in the process of shaping and welding are not
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susceptible to this type of corrosion.

Groove corrosion can be mitigated by minimizing the potential difference between the weld seam
and the parent metal. The ERW pipes that are resistant to groove corrosion were developed in the
1970s. The chemical compositions of steels for these new pipes were modified by decreasing sulfur
(e.g., ^ 0.005%), and adding up to 0.3% Cu and small amounts of other elements (e.g., Ca, Ni, or Ti).
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The reduction of sulfur minimizes the formation of unstable MnS, and other elements, such as Ca,
stabilize the remaining sulfur. The potential difference between the weld and the parent metal is
reduced to almost nil. These ERW pipes are being widely used in diameters ^ 125 mm, and no
occurrence of groove corrosion has been reported to date. For pipes of smaller diameter, butt- welded
pipes are used. For more details, see [38].
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4. Localized Corrosion at Discontinuities in Corrosion Product Films

Fitting-type localized corrosion at penetration rates > 1 mm/year (40 mpy) sometimes occurs
without the formation of tubercles in pipes alternately exposed to hot water (or steam) and cold
water. Examples are shown in Table 4 [39].
The inside surface of the pipe is covered by corrosion product films that are tight, dense,
relatively smooth, and dark in color. X-ray analysis identifies Y-Fe2O3 and Fe3O4, unlike the usual
iron oxides, a- or y-FeOOH, Fe3O4 and large amounts of amorphous substances that form in aqueous

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media. The degree of crystallization is much higher, as indicated by high intensities of the diffracted
beams in X-ray diffraction.
The mechanism of this type of corrosion is similar to that of the localized corrosion of mill-scaled
steel in seawater (see Chapter 34, Section B.4, p. 563). The surface covered by corrosion product
films formed during exposure to hot water or steam tends to act as the cathode to the exposed steel at
the defects or discontinuities in the films during exposure to cold water, causing localized corrosion.
The corrosion potential of the film-covered areas was measured in the range of —590 to -67OmV

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versus SCE in 3% NaCl in the laboratory. The localized attack was reproduced in an experiment

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simulating service conditions [4O].

D. REFERENCES

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1. H. Uhlig, D. Triadis, and M. Stern, J. Electrochem. Soc., 102, 59 (1955).
2. S. K. Coburn, in Metals Handbook, 9th ed., American Society of Metals, Metals Park, OH, 1978, Vol. 1,
p. 733.
3. T. Suzuki, Private Communication (Database, Kurita Water Industries, Ltd., Tokyo).
4. H. H. Uhlig and R. W. Revie, Corrosion and Corrosion Control, 3rd ed., Wiley, New York, 1985,
p. 415.
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5. R. A. Pisigan, Jr., and J. E. Singley, J. Am. Water Works Assoc., 77(10), 83 (1985).
6. W F. Langelier, J. Am. Water Works Assoc., 28, 1500 (1936).
7. S. Powell, H. Bacon, and J. LiIl, J. Am. Water Works Assoc., 38, 808 (1945).
8. E. Nordell, Water Treatment, 2nd ed., Reinhold, New York, 1961, p. 287.
9. M. R. Schock, J. Am. Water Works Assoc., 76(8), 72 (1984).
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11. F. E. DeMartini, J. Am. Water Works Assoc,, 30, 85 (1938).
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12. C. P. Hoover, J. Am. Water Works Assoc., 30, 1802 (1938).

13. D. T. Merrill and R. L. Sanks, J. Am. Water Works Assoc., 70(1), 12 (1978).
14. J. W. Ryznar, J. Am. Water Works Assoc., 36, 472 (1944).
15. P. R. Puckorius and J. M. Brooke, Corrosion, 47, 280 (1991).
16. N. R. Reedy, Mater. Protect. Perform., 12(4), 43 (1973).
17. M. E. Flentje, J. Am. Water Works Assoc., 53, 1461 (1961).
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18. T. Fujii, Bosei Kanri (Rust Prevention and Control), 27, 85 (1983).
19. W. Whitman, R. Russell, and V. Altieri, Ind. Eng. Chem., 16, 665 (1924).
20. R. V. Skold and T. E. Larson, Corrosion, 13, 139t (1957).
21. R. A. Pisigan and J. E. Singley, J. Am. Water Works Assoc., 79(2), 62 (1987).
22. T. Fujii, T, Kodama, and H. Baba, Boshoku Gijutsu (Corrosion Eng.), 31, 637 (1982).
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23. T. E. Larson and R. M. King, Corrosion, 10, 110 (1954).

24. T. E. Larson and R. V. Skold, Corrosion, 14,285t (1958); see also R. V. Skold and T. E. Larson, Corrosion, 13,
139t (1957).
25. M. Kowaka, M. Ayukawa, and H. Nagano, Sumitomo Kinzoku, 21, 185 (1969).
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26. I. Matsushima, in Corrosion Protection Handbook (Boshoku Gijutsu Binran), Japan Society of Corrosion
Engineering, ed., Nikkan Kogyo Shinbunsha, Tokyo, Japan, 1985, pp. 176, 179.
27. K. Kinoshita, K. Ichikawa, and N. Kitajima, Boshoku Gijutsu (Corrosion Eng.), 32, 31 (1983).
28. F. LaQue, in Corrosion Handbook, H. H. Uhlig (Ed.), Wiley, New York, 1948, p. 391.
29. K. Sakai, S. Morishita, T. Honda, A. Minato, M. Izumiya, K. Osumi, and M. Miki, Boshoku Gijutsu
(Corrosion Eng.), 30, 450 (1981).
30. I. Matsushima, Paper presented at the Committee on Corrosion and Protection, The Society of Materials
Science, Japan, 19, 94 (1980); reproduced in Corrosion Protection Handbook (Boshoku Gijutsu Binran),
Japan Society of Corrosion Engineering, ed., Nikkan Kogyo Shinbunsha, Tokyo, Japan, 1985, p. 181.

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31. K. Masamura and I. Matsushima, 23rd Annual Symposium on Corrosion and its Protection, Japan Society of
Corrosion Engineering, Tokyo, Nov., 1978, p. 104.
32. H. H. Uhlig and R. W. Revie, Corrosion and Corrosion Control, 3rd ed., Wiley, New York, 1985, p. 240.
33. F. N. Speller, in Corrosion Handbook, H. H. Uhlig (Ed.), Wiley, New York, 1948, p. 496.
34. U. R. Evans, The Corrosion and Oxidation of Metals, Edward Arnold, London, UK, 1960, p. 296.
35. K. Masamura and I. Matsushima, CORROSION/81, Paper No. 75, NACE, Houston TX, 1981.
36. C. Kato, Y. Otoguro, and K. Kado, Boshoku Gijutsu (Corrosion Eng.), 23, 385 (1974).

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37. C. Kato, Y Otoguro, K. Kado, and Y. Hisamatsu, Com ScL, 18, 61 (1978).

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38. I. Matsushima, Low-Alloy Corrosion Resistant Steels, Chijin Shokan Co. Ltd., Tokyo, Japan, 1995, p. 155.
39. I. Matsushima, Dr-Eng. Thesis, A Study on Localized Corrosion of Steel, 1982, University of Tokyo.
40. I. Matsushima, Annual Meeting of Japan Society of Corrosion Engineering, Tokyo, May, 1979, p. 143;
reproduced in Localized Corrosion, F. Hine, K. Komai, and K. Yamakawa (Eds.), Elsevier Applied Science,
London and New York, 1988, p. 31.

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