Corrosion Science 49 (2007) 240–247

www.elsevier.com/locate/corsci

Effects of temperature and aggressive anions

on corrosion of carbon steel in potable water
Shinichi Takasaki *, Yasuo Yamada
Kurita Water Industries Ltd., 4-7, Nishi-shinjuku 3-chome, Shinjuku-ku, Tokyo 160-8383, Japan

Available online 10 July 2006

Abstract

Experiments on the corrosion of carbon steel in three kinds of artificial potable waters containing
different concentrations of aggressive anions, Cl and SO24 , open to air in the temperature range
from 5 to 60 C were conducted using weight loss and electrochemical methods. The corrosion rate
increased in proportion to the concentration of aggressive anions and with increasing temperature.
At lower concentrations of aggressive anions and temperatures, the corrosion rate was lower and the
corrosion potential was higher, at intermediate concentrations and temperatures, the corrosion rate
increased logarithmically with decreasing potential, and at higher concentrations and temperatures,
the corrosion rate was higher and the potential was lower. The corrosion behavior in potable water
can be determined by the balance between inhibitive action of oxygen (passive film formation) and
aggressive action of Cl and SO24 ions.
 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Mild steel; B. Weight loss; B. Polarization; C. Oxygen reduction

1. Introduction

The corrosion behavior of carbon steels in fresh water or in potable water is undoubt-
edly important in operating water systems for heating and cooling where carbon steels are
applied as piping and tubing materials. There are numerous studies for the effect of water
components, especially Cl ions, on the corrosion, and in most studies test solutions were

*
Corresponding author. Tel.: +81 3 3347 3383; fax: +81 3 3347 3901.
E-mail address: shinichi.takasaki@kurita.co.jp (S. Takasaki).

0010-938X/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2006.05.035
 S. Takasaki, Y. Yamada / Corrosion Science 49 (2007) 240–247 241

prepared using deionized water and particular ions of interest. Larson and Skold [1,2] sug-
gested that the corrosiveness of water depends on the ratio of the concentration of Cl and
SO24 to HCO3 , where Cl and SO24 ions are aggressive ions and HCO3 ions have inhib-
itive properties [3]. Therefore, the corrosion protection would be possible by replacing Cl
and SO24 with HCO3 in water. On the other hand, Mercer and Lumbard [4] showed that
the corrosion behavior in real potable water is very different from that in distilled water
containing the same concentration of Cl . It was pointed out that in the presence of
Ca2+ the formation of CaCO3 film depresses corrosion and in the absence of Ca2+ the for-
mation of passive film occurs as a result of inhibitive action of HCO3 [4,5]. However, only
a limited number of studies have been reported on the effects of aggressive anions and tem-
perature of actual potable water.
We have been developing an anion-exchange method for water treatment for prevent-
ing corrosion in district heating and cooling systems (DHC systems) with large heat stor-
age water tanks. In this water treatment aggressive anions such as Cl and SO24 in water
are replaced with HCO3 ions using ion-exchange resin. The purpose of this work is to
obtain systematic corrosion data to clarify the effects of aggressive anions and temperature
of potable water on corrosion.

2. Experimental

2.1. Test solutions

Three kinds of artificial potable waters containing different concentrations of aggressive

anions, Cl and SO24 , were used as test solutions: Atsugi city water from which ClO and
other oxidants were removed by passing through an active carbon column (ACW), anion
exchanged water prepared from ACW by replacing Cl and SO24 ions with HCO3 ions
using anion-exchange resin (AEW), and simulated Tokyo city water prepared from
ACW by adding 20 mg/L of Cl and 20 mg/L of SO24 using sodium salt reagents
(STCW), respectively. In order to equilibrate with the atmosphere, each solution was kept
open to air for over 24 h before tests. Table 1 shows the composition of test solutions
determined by chemical analyses. The ion products of Ca2+ and CO23 for the test solu-
tions were smaller than the solubility product of CaCO3 except those in AEW at 50
and 60 C.

Table 1
Chemical analysis of test solutionsa
Anion exchanged Atsugi city Simulated Tokyo
water (AEW) water (ACW) city water (STCW)
Conductivity (mS/m) 16.6 18.3 30.8
pH (–) 8.2 7.9 7.9
Alkalinity (g as CaCO3/m3) 74 44 40
Total hardness (g as CaCO3/m3) 60 59 60
Calcium hardness (g as CaCO3/m3) 39 40 40
Cl (g/m3) <1 8 27
SO24 (g/m3) <1 17 39
SiO2 (g/m3) 28 27 28
a
All data show average values for six waters prepared on different days.
242 S. Takasaki, Y. Yamada / Corrosion Science 49 (2007) 240–247

2.2. Immersion tests

A rotating corrosion-test equipment in reference to JIS K0100 [6] was used for the mea-
surement of weight loss. Coupon specimens of carbon steel (JIS SPCC, 50 · 30 ·1 mm)
were abraded up to grade 400 with emery paper, degreased with toluene, dried and
weighed. Each specimen was attached to a rotating shaft with polytetrafluoroethylene
(PTFE) washers and a plastic screw, and immersed in a glass beaker containing 1 L of
the test solution. Test solutions were open to air and brought to the required temperatures
in the range from 5 to 60 C before tests. Specimens were rotated at 160 rpm (linear veloc-
ity of 0.5 m/s) for test periods up to seven days. At the end of test period the rotating shaft
with a specimen was withdrawn, and the corrosion product was removed in 15% HCl con-
taining 0.5% of an acid inhibitor (IBIT2s, Asahi Chemical Co.). Weight loss determined
from the difference between the weights of specimen before and after immersion was used
in the corrosion rate calculation.

2.3. Electrochemical experiments

Measurements of corrosion potential (Ecorr) and polarization resistance (Rp) using Cor-
rosion Monitor 7660 (Toho Technical Research) were conducted in three kinds of test
solutions: AEW, ACW and STCW at 5, 15 and 25 C. The test electrode of carbon steel
rod (JIS SS400, /10 · 30 mm) mounted on a PTFE holder was in contact with lead wire
via the central steel rod inside the holder. A saturated silver–silver chloride electrode (SSE)
as a reference electrode was placed in a glass holder with a capillary having a ceramic plug
at its tip for preventing contamination by KCl. A stainless steel electrode with the same
shape as the test electrode was used as a counter electrode. Test solutions (1 L) were agi-
tated by magnetic stirrer at a constant rotation speed of 300 rpm. The Corrosion Monitor
provides automatically recorded Rp data with corrections of solution resistance by apply-
ing square wave currents of two different frequencies: 2.6 kHz for estimating solution resis-
tance and 0.05 Hz for total resistance (Rp + solution resistance). Ecorr and Rp were
monitored at the same time every one-hour for the test period of seven days.

3. Results and discussion

3.1. Weight loss measurements

The observations of specimens at the end of test periods in AEW, ACW and STCW at
the typical temperatures of 15, 30 and 60 C are shown in Table 2. At 15 C no corrosion
was observed in AEW. Thin dark colored corrosion products were formed covering par-
tially the surface of specimens in ACW and STCW and also pits were detected in STCW.
At 30 C small corrosion products were observed around PTFE washers in AEW. In
ACW and STCW many pits were detected and dark orange corrosion products were
formed uniformly covering the specimen surface. At 60 C a few pits were detected in
AEW. In ACW and STCW severe general corrosion took place forming thick corrosion
products uniformly and no pits were detected.
Changes in weight loss with time in AEW, ACW and STCW at 15, 30 and 60 C are
shown in Fig. 1. Corrosion in AEW was almost negligible in this temperature range.
The weight loss increase with increasing time of the test period appeared in the order of
 S. Takasaki, Y. Yamada / Corrosion Science 49 (2007) 240–247 243

Table 2
Observations of specimens at the end of test in anion exchanged water (AEW), Atsugi city water (ACW) and
simulated Tokyo city water (STCW)
Temperature Test solutions
AEW ACW STCW
15 C No corrosion No pits A few pits
Thin dark brown oxide Thin dark brown oxide
30 C No pits Numerous pits Numerous pits
Slight corrosion General corrosion General corrosion
around PTFE washers
60 C A few pits No pits No pits
Severe general corrosion Severe general corrosion

0.8
(a) 15 °C
Weight Loss (mg/cm2)

0.6 AEW
ACW
0.4 STCW

0.2

0
0 1 2 3 4 5 6 7
Time (day)

30 30
(b) 30 °C (c) 60 °C
Weight Loss (mg/cm2)
Weight Loss (mg/cm2)

AEW AEW
20 ACW 20 ACW
STCW STCW

10 10

0 0
0 1 2 3 4 5 6 7 0 1 2 3
Time (day) Time (day)

Fig. 1. Changes in the weight loss at (a) 15 C, (b) 30 C and (c) 60 C in anion exchanged water (AEW), Atsugi
city water (ACW) and simulated Tokyo city water (STCW).

AEW, ACW and STCW, where the total concentration of aggressive anions, Cl and
SO24 , increased in that order. At 30 C induction periods were observed before a linear
increase of weight loss in ACW and STCW. The corrosion rates were calculated from
the slope of the linear relationship between the weight loss and the time after the weight
loss was observed. Arrhenius plot of corrosion rate is shown in Fig. 2. The influence of
temperature on the corrosion rate in ACW and STCW was similar to each other. These
corrosion rates showed a sharp rise with temperature up to 30 C, followed by a gradual
rise at higher temperatures. The apparent activation energies obtained from the slopes of
Arrhenius plot were 177.3 kJ/mol in the range of 5–30 C, and 11.3 kJ/mol in the range of
40–60 C. It was reported that the typical activation energy of diffusion in water was 10–
45 kJ/mol [7,8]. Therefore, the small value of the energy obtained here at temperatures
above 30 C suggested that the rate-determining step of corrosion was the diffusion of
some species in water, possibly dissolved oxygen. The large value of the activation energy
244 S. Takasaki, Y. Yamada / Corrosion Science 49 (2007) 240–247

60 50 40 30 20 10 °C
1000

11.3 kJ/mol

100

Corrosion Rate (mdd)

AEW
ACW
177.3 kJ/mol
STCW
10

146.4 kJ/mol
1

0.1
0.0030 0.0032 0.0034 0.0036
1/T (1/K)

Fig. 2. Arrhenius plot of corrosion rate in anion exchanged water (AEW), Atsugi city water (ACW) and
simulated Tokyo city water (STCW). Apparent activation energies obtained from the plot are shown.

obtained at temperatures below 30 C implied that the breakdown of protective oxide films
(passive films) occurred with increasing temperature, and then corrosion proceeded. On
the other hand, the corrosion rate in AEW was low and independent of temperature up

0. 2
(a) Ecorr
0
Ecorr (V vs SSE)

AEW
–0. 2
ACW
–0. 4

–0. 6 STCW

–0. 8
0 50 100 150
Time (hr)

100
(b) 1/Rp
10
1/ R p (S/m2)

1 STCW

0.1 ACW

0.01 AEW

0.001
0 50 100 150
Time (hr)

Fig. 3. Changes in (a) Ecorr and (b) 1/Rp with time at 25 C in anion exchanged water (AEW), Atsugi city water
(ACW) and simulated Tokyo city water (STCW).
 S. Takasaki, Y. Yamada / Corrosion Science 49 (2007) 240–247 245

to 30 C, above which it increased slightly. The changes in weight loss during test periods
were smaller than 0.6 mg in the range of 5–30 C, and low weight losses were sometimes
within experimental uncertainties. To clarify the effect of temperature on the corrosion
rate in the passive state further study is necessary.

3.2. Rest potentials and polarization resistances

Changes in Ecorr and 1/Rp with time at 25 C are shown in Fig. 3(a) and (b). Ecorr was
lower in the order of AEW, ACW and STCW, and reached to around 0.05 V/SSE in
AEW, 0.35 V/SSE in ACW, and 0.62 V/SSE in STCW at the end of the test period.
By contrast, the values of 1/Rp, which are proportional to corrosion rates, increased in
the order of AEW, ACW and STCW. Fig. 4 summarizes the relationship between Ecorr
and 1/Rp at 5, 15 and 25 C. From all the data at different temperatures, three corrosion
rate regions can be distinguished: a low constant corrosion rate at noble potentials (region
1); corrosion rates increasing logarithmically with decreasing potential (region 2); and a
high constant corrosion rate at less noble potentials (region 3). At 5 C, the data in
AEW and ACW, and the most of data in STCW were in region 1. At 15 C the data in
AEW and ACW were still in region 1, but data in STCW moved to region 2. At 25 C
the data only in AEW were still in region 1, but the data in ACW moved to region 2
and the data in STCW moved from region 2 to region 3 during the test period. These

0.2
(a) 5 °C
0
AEW
(V/SSE)

ACW
-0.2
STCW
E corr

-0.4 region 1
region 2

-0.6
region 3
-0.8
0.001 0.01 0.1 1 10 100
1/R p (S/m ) 2

0.2 0.2
(b) 15 °C (c) 25 °C
0 0
AEW AEW
ACW ACW
(V/SSE)
(V/SSE)

–0.2 -0.2
STCW STCW
E corr

–0.4 -0.4
E corr

region 1 region 1
region 2 region 2
–0.6 -0.6
region 3 region 3
–0.8 -0.8
0.001 0.01 0.1 1 10 100 0.001 0.01 0.1 1 10 100
1/R p (S/m )2 1/R p 2
(S/m )

Fig. 4. Relationship between Ecorr and 1/Rp at (a) 5 C, (b) 15 C and (c) 25 C in anion exchanged water (AEW),
Atsugi city water (ACW) and simulated Tokyo city water (STCW).
246 S. Takasaki, Y. Yamada / Corrosion Science 49 (2007) 240–247

different regions can be assigned to different states of corrosion: region 1 corresponds

to the passive state, region 2 the breakdown of passivity, and region 3 the oxygen
diffusion-controlled corrosion. At low temperatures or low concentrations of aggressive
anions the passive state can be maintained, but with the increase in temperature or in con-
centration of aggressive anions the breakdown of passivity occurs and then oxygen diffu-
sion-controlled corrosion begins to proceed.
In conclusion, the corrosion behavior in potable water can be explained on the basis of
a balance between inhibitive action of oxygen (passive film formation) and aggressive
action of Cl and SO24 ions. At low temperatures the inhibitive action prevails over the
aggressive action. It can be pointed out that the anion-exchange method is useful in pre-
venting the corrosion of carbon steels in DHC systems, especially in chilled water systems.
However, the additional work is needed to make clear the effects of flow conditions and
surface condition of metals for applying this water treatment to actual DHC systems.

4. Summary

The corrosion behavior of carbon steel in potable water has been experimentally inves-
tigated using weight loss and electrochemical methods so as to establish a new method of
water treatment for district heating and cooling (DHC) systems with large heat storage
water tanks. Three kinds of test solutions containing different concentrations of aggressive
anions, Cl and SO24 , were used in the temperature range from 5 to 60 C in the atmo-
sphere: Atsugi city water (ACW), anion exchanged water (AEW) prepared from ACW
by replacing Cl and SO24 ions with HCO3 ions using anion-exchange resin, and simu-
lated Tokyo city water (STCW) prepared from ACW by adding 20 mg/L of Cl and
20 mg/L of SO24 . The corrosiveness of water increased in proportion to the concentrations
of aggressive anions, that is, in the order of AEW, ACW and STCW. The temperature
dependences of the corrosion rate in ACW and STCW were similar to each other. The cor-
rosion rates showed a sharp rise up to 30 C, followed by a gradual rise in ACW and
STCW. At temperatures in the range of 40–60 C the apparent activation energy obtained
from the Arrhenius plot was 11.3 kJ/mol, suggesting that the rate-determining step of cor-
rosion is the diffusion of oxygen in water. On the other hand, the corrosion rate in AEW
was low and independent of temperature up to 30 C, and then increased slightly. From
the results of measurements of corrosion potential (Ecorr) and polarization resistance
(Rp), three corrosion rate regions can be distinguished: a low constant corrosion rate at
noble potentials (region 1); corrosion rates increasing logarithmically with decreasing
potential (region 2); and a high constant corrosion rate at less noble potentials (region
3). These different regions can be assigned to different states of corrosion: region 1 corre-
sponds to the passive state, region 2 the breakdown of passivity, and region 3 the oxygen
diffusion-controlled corrosion. In conclusion, the corrosion behavior in potable water can
be explained on the basis of a balance between inhibitive action of oxygen (passive film
formation) and aggressive action of Cl and SO24 ions. It can be point out that an
anion-exchange water treatment is useful for preventing corrosion in DHC systems.

Acknowledgements

The authors thank Dr. F. Umemura of Tokyo Electric Power Company for his valuable
comments on the corrosion behavior in this work.
 S. Takasaki, Y. Yamada / Corrosion Science 49 (2007) 240–247 247

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