Journal of Nuclear Science and Technology

ISSN: 0022-3131 (Print) 1881-1248 (Online) Journal homepage: http://www.tandfonline.com/loi/tnst20

Effects of Hydrogen Peroxide on Corrosion of

Stainless Steel, (II)

Junichi SUGAMA , Shunsuke UCHIDA , Naoya YAMASHIRO , Yusuke

MORISHIMA , Tatsuya HIROSE , Takahiro MIYAZAWA , Tomonori SATOH ,
Yoshiyuki SATOH , Koichi IINUMA , Yoichi WADA & Masahiko TACHIBANA

To cite this article: Junichi SUGAMA , Shunsuke UCHIDA , Naoya YAMASHIRO , Yusuke
MORISHIMA , Tatsuya HIROSE , Takahiro MIYAZAWA , Tomonori SATOH , Yoshiyuki SATOH ,
Koichi IINUMA , Yoichi WADA & Masahiko TACHIBANA (2004) Effects of Hydrogen Peroxide on
Corrosion of Stainless Steel, (II), Journal of Nuclear Science and Technology, 41:9, 880-889, DOI:
10.1080/18811248.2004.9715560

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 Journal of NUCLEAR SCIENCE and TECHNOLOGY, Vol. 41, No. 9, p. 880–889 (September 2004)

ORIGINAL PAPER

Effects of Hydrogen Peroxide on Corrosion of Stainless Steel, (II)

Evaluation of Oxide Film Properties by Complex Impedance Measurement

Junichi SUGAMA1 , Shunsuke UCHIDA1;
, Naoya YAMASHIRO1 , Yusuke MORISHIMA1 ,

Tatsuya HIROSE1 , Takahiro MIYAZAWA1 , Tomonori SATOH1 , Yoshiyuki SATOH1 ,
Koichi IINUMA1 , Yoichi WADA2 and Masahiko TACHIBANA2
1
Quantum Science and Energy Engineering Department, Graduate School of Engineering, Tohoku University,
01 Aoba, Aramaki, Aoba-ku, Sendai 980-8579
2
Power and Industrial Systems R&D Laboratory, Hitachi, Ltd., 7-2-1, Ohmika-cho, Hitachi-shi, Ibaraki 319-1221
(Received February 4, 2004 and accepted in revised form July 1, 2004)

A high temperature high pressure water loop, which can control H2 O2 concentration with minimal oxygen (O2 ) co-
existence, has been fabricated. In order to evaluate the effects of hydrogen peroxide (H2 O2 ) on intergranular stress
corrosion cracking. Not only static responses, i.e., electrochemical corrosion potential (ECP), of the stainless steel
specimens exposed to H2 O2 and O2 at elevated temperatures but also their dynamic responses, i.e., frequency depend-
ent complex impedances (FDCI), were measured. The conclusions obtained by the experiments are as follows.
(1) The ECP measured for the SUS 304 specimen exposed to 100 ppb H2 O2 reached the saturated level in 50 h,
showed a larger value than the specimen exposed to 200 ppb O2 and kept the same ECP level when the H2 O2
concentration was decreased to 10 ppb.
(2) The FDCI measured for the specimen exposed to 100 ppb H2 O2 showed saturation in the low frequency semi-
circles; this behavior was determined by the electric resistance of the oxide film and caused by saturation of oxide
film thickness. Behavior for the specimen exposed to 200 ppb O2 was determined by the resistance of oxide dis-
solution, which was much larger than that for the specimen exposed to H2 O2 .
(3) The ECPs of the specimens exposed to 200 ppb O2 after 200-h exposure to 100 ppb H2 O2 were higher than those
exposed to only 200 ppb O2 due to memory effects on oxide films. The specimens with pre-exposure to 200 ppb
O2 did not show these memory effects.
KEYWORDS: hydrogen peroxide, stress corrosion cracking, electrochemical corrosion potential, complex
impedance, Cole–Cole plot, BWR type reactors

with a polytetrafluoroethylene (PTFE) inner liner which

I. Introduction
Oxygen and hydrogen peroxide concentrations change
along the recirculation flow path so that the corrosive condi-
tions differ between locations in BWR primary cooling sys-
tems.1) Several indexes for corrosive conditions have been
proposed to evaluate the effects of hydrogen water chemistry
(HWC) in BWR plants.2–5) One of the most common indexes
of corrosive conditions is electrochemical corrosion poten-
tial (ECP).3–5) Electrochemical corrosion potential is deter-
mined by a combination of factors; these are specimen sur-
face conditions and concentrations of oxidants, e.g., oxygen,
hydrogen peroxide and other corrosive radiolytic species.
Unfortunately, most data concerning the effects of ECP on
intergranular stress corrosion cracking (IGSCC) have been
obtained by changing oxygen concentration. There are only
limited data concerning the relationship between hydrogen
peroxide concentration, ECP, and generation and propaga-
tion of IGSCC.6)
One of the reasons why fewer experimental data dealing
with hydrogen peroxide have been reported is the difficulty
of making experimental measurements because of hydrogen
peroxide decomposition at elevated temperatures.7) The au-
thors fabricated a high temperature, high-pressure water loop


Corresponding author, Tel. +81-22-217-7911, Fax. +81-22-217-
7900, E-mail: shunsuke.uchida@qse.tohoku.ac.jp
minimized hydrogen peroxide decomposition and lowered
possible oxygen concentration7,8) to determine the effects
of hydrogen peroxide on electrochemical corrosion potential
(ECP) of unsensitized type 304 stainless steel.
Previously, the authors introduced the target value of
H2 O2 remaining in research applications of the high temper-
ature, high pressure H2 O2 water loop and they described ma-
jor performance values of the loop.8) More than 90% of the
injected hydrogen peroxide was present at the autoclave out-
let and exposure conditions were established under which
hydrogen peroxide concentration was controlled at the de-
sired concentration without co-existence of oxygen. In this
paper, experimental results on not only static responses,
i.e., in-situ ECP measurements, of the stainless steel speci-
mens exposed to H2 O2 and O2 in the high temperature, high
pressure hydrogen peroxide water loop, but also their dy-
namic responses, i.e., in-situ complex impedance measure-
ments, were introduced to better understand the mechanism
of IGSCC in BWRs.
II. Experimental
1. Experimental Setup
A schematic diagram of the high temperature, high pres-
sure hydrogen peroxide water loop is shown in Fig. 1.8)
The water, which was dearated in the make-up water tank

880
Effects of Hydrogen Peroxide on Corrosion of Stainless Steel, (II) 881

ion exchange regenerating

cooler heat exchanger outlet
resin column
air pH: pH
DO: dissolved oxygen upper SUS H2O2 detection
N2 gas main κ: conductivity electrode
pH heater
(bubbling)
main pump liquid junction
DO
DO sampling line reference electrode
make-up
cooler lower SUS (Ag/AgCl)
water κ (flow rate:10 l/h)
tank autoclave with electrode PTFE inner liner autoclave
PTFE inner liner (inner diameter: 30mm)

H2O2 storage tank PTFE PTFE inner liner

recirculation pump inner liner
injection pump heater H2O2
inlet injection system

Fig. 1 Schematic diagram of high temperature, high pressure hydrogen peroxide water loop

and had its O2 concentration controlled at the target level in Table 1 Major parameters for the experimental loop
the make-up water tank, was fed to the autoclave through the
regenerating heat exchanger and the main heater. The efflu- Item Parameter Parameter range
ent water was cleaned by an ion exchange resin column to Autoclave Temperature 553 K
remove impurities and then fed back to the make-up water Pressure 8.0 MPa
tank, where it was dearated to remove oxygen and prevent Flow rate 2.8 mls1
its accumulation from decomposition of H2 O2 . Flow velocity 5.5 cms1
The autoclave and hydrogen peroxide injection line and Conductivity <0:2 mS/cm
sampling line were lined with PTFE to minimize surface de- [O2 ] 0–8,000 ppb
composition of H2 O2 .9,10) A thick PTFE liner (inner diame- [H2 O2 ] 0–1,000 ppb
ter: 8 mm) was coated onto the autoclave to reduce residence Feed water tank Temperature 280–300 K
time of the main flow in the autoclave and then to improve Pressure 0.1 MPa
H2 O2 remaining rate at the measurement location. The work Conductivity <0:2 mS/cm
electrodes were installed in the autoclave to measure ECP [O2 ] 0–8,000 ppb
while changing hydrogen peroxide concentration ([H2 O2 ]) [H2 O2 ] 0 ppb
at the autoclave inlet.7,8,11–13) In order to quantify the corro-
sive environment, [H2 O2 ] was measured in the sampling line
located at the autoclave outlet, and ECP was also measured The distributions of hydrogen peroxide concentration
at several locations in the autoclave (bottom and top) along the autoclave and sampling line were calculated by us-
(Fig. 1). Figure 2 shows the high temperature, high pressure ing temperature dependent hydrogen peroxide decomposi-
hydrogen peroxide water loop and Table 1 lists its major pa- tion constants.8) As a result of using the PTFE liner to nar-
rameters. row the inner diameter of the autoclave, more than 90% of
the hydrogen peroxide was estimated to still remain at the
autoclave outlet. The concentration of hydrogen peroxide
make-up water tank autoclave with PTFE inner liner in the sampled water was determined with a flow cell type
hydrogen peroxide detector based on chemical photolumi-
nescence spectroscopy using a luminol photoluminescence
reaction.14,15) The lowest detection limit of the detection sys-
main heater tem was less than 0.1 ppb H2 O2 . The measured concentra-
tions of hydrogen peroxide remaining at the sampling line
H2O2 outlet are shown with the estimated values at the autoclave
storage tank and sampling line outlets in Fig. 3. More than 93% of hydro-
gen peroxide remained at the autoclave outlet, while more
than 90% remained in the sampled water.

2. Electrochemical Corrosion Potential and Frequency

main pump sampling line Dependent Complex Impedance
In order to evaluate the static and dynamic responses of
Fig. 2 High temperature, high pressure hydrogen peroxide water stainless steel exposed to H2 O2 , ECP and frequency depend-
loop ent complex impedance (FDCI) of specimens (type 304

VOL. 41, NO. 9, SEPTEMBER 2004

882 J. SUGAMA et al.

: measured at sampling line outlet (2) Frequency Dependent Complex Impedance (FDCI)
: sampling line outlet In order to measure frequency dependent complex impe-
flow rate in : autoclave outlet dance of specimens, an alternating voltage with a sine wave
main loop (l/h) pattern was supplied between the counter and lower elec-
10 trodes by changing frequency from 0.1 mHz to 100 kHz,
the very small current between the specimens was measured
5 with a potentiostat (Toho-Giken, Model-2000) and then fre-
quency dependent current was analyzed with a frequency re-
3 sponse analyzer (NF Electronic Instrument, Model S-5720)
0 20 40 60 80 100 which measured the complex impedance between the elec-
hydrogen peroxide remaining (%) trodes. In order to minimize the potential input for the impe-
dance measurement and perturbation of corrosion reactions
Fig. 3 H2 O2 remaining at autoclave and sampling line outlets on the specimens, potential of the lower SUS electrode
was kept as high as the natural potential in the autoclave
environment, while that of the counter electrode was the
stainless steel, 10 mm10 mm1 mm) were measured. A minimum alternative voltage (10 mV) for measurement.16)
schematic diagram of the impedance measurement system Figure 5 shows the test specimens (electrodes) for impe-
is shown in Fig. 4. Chemical composition (mass %) of the dance analysis inserted in the autoclave. To keep the gap dis-
specimens is listed in Table 2. tance between the specimens, they were installed in grooves
(1) Electrochemical Corrosion Potential (ECP) on the inner face of the PTFE liner. The analyzed complex
Electrochemical corrosion potential was measured against impedance data were transferred from the frequency re-
the Ag/AgCl type external reference electrode at both upper sponse analyzer to the PC of the data acquisition system
and lower locations in the autoclave (Fig. 3). Electrochemi- through GP-IB.
cal corrosion potential measurements were automatically
carried out every minute and the measured data were trans- 3. Experimental Conditions
ferred to the PC of the data acquisition system. The ECP and frequency dependent complex impedance of
specimens were measured by changing H2 O2 and O2 con-
centrations. In this series of experiments, test specimens
Table 2 Chemical composition (mass %) of the specimens
were exposed to only H2 O2 or O2 to determine the individual
C Si Mn P S Ni Cr Fe effect of H2 O2 and O2 on ECP and complex impedance. The
exposure conditions are listed in Table 3.
0.06 0.42 0.83 0.028 0.005 8.41 18.31 Bal.
The concentrations of H2 O2 and O2 at the mounted loca-

VECP
external reference electrode
(Ag/AgCl)
potentiostat
I

upper SUS electrode

frequency
response PTFE lined autoclave
analyzer counter electrode (SUS)*
GPIB lower SUS electrode*

PC
(LabVIEW)

* electrodes (10mm x 10mm x 1mm)

Fig. 4 Schematic diagram of impedance measurement system

Table 3 Exposure conditions

Gap between Oxidant Water conductivity

Temperature
Specimens specimens concentration at autoclave outlet
( C)
(mm) (ppb) (mS/cm)
SUS304a) 3 mm [O2 ]: 200–8,000 270 <0:15
(10101 mm3 ) [H2 O2 ]: 5–100
a)
Not heat treated. Surface was polished mechanically by #2000 emery paper and buffing.

JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY

Effects of Hydrogen Peroxide on Corrosion of Stainless Steel, (II) 883

0.1
PTFE
cylinder 0
test
specimen

ECP (V-SHE)
-0.1

-0.2

autoclave -0.3
flange
-0.4

-0.5
0 50 100 150 200 250 300
time (h)
(a) Exposed to 8ppm O2
Fig. 5 Test specimens
0.1

0
tion of the specimens were varied as parameters of the ex-
-0.1

ECP (V-SHE)
periments. As their standard values, 100 ppb for H2 O2 and
200 ppb for O2 were selected as a result of water radiolysis
evaluation in operating BWR plants.17) -0.2
The continuous loop operation was carried out semi-auto- -0.3
matically but exposure conditions, e.g., oxidant concentra-
tions, were changed manually, as follows. -0.4
(1) The loop was cooled down for about half an hour and
the autoclave was opened to take out some specimens -0.5
0 50 100 150 200 250 300
for surface characterization as necessary.
time (h)
(2) Oxygen concentration in the make-up water tank was
(b) Exposed to 100ppb H2O2
changed to the target value.
(3) The loop was restarted and reached the steady state in
Fig. 6 Electrochemical corrosion potential
about half an hour.

III. Experimental Results

1. Electrochemical Corrosion Potential (ECP)
Time dependent ECP of the specimen exposed to 8 ppm
oxygen is shown in Fig. 6(a). Electrochemical corrosion po-
tential increased gradually for 270 h. Data from the specimen
exposed to 100 ppb hydrogen peroxide are shown in
Fig. 6(b). The saturation level was reached at about 50 h.
Difference in the oxidant concentration was large in both
cases, but the difference in the measured ECP was not. It
was understood that the continuous increase of ECP for
the specimen exposed to 8 ppm O2 was caused by continuous
growth of oxide film, while ECP of the specimen exposed to
100 ppb H2 O2 increased as the oxide film grew and then
reached the saturated level when a balance between film
growth and dissolution was reached. The mechanically pol-
ished specimen of Fig. 6(b) showed lower ECP early in the
exposure. Increasing ECP was considered due to oxide film
growth until the saturated level was reached.
Measured ECP of the specimens exposed to different con-
centrations of hydrogen peroxide are shown in Fig. 7. After
300-h exposure to 100 ppb H2 O2 , the concentration was
dropped to 10 ppb, 5 ppb and then, 1 ppb. For each hydrogen
peroxide concentration, ECP was measured. The transient
ECP is shown in Fig. 7(a). Only a slight change in ECP
was observed for the specimen exposed to more than 5 ppb
H2 O2 . When H2 O2 decreased to 1 ppb, ECP decreased.
The measured ECPs for the specimens exposed to 100 ppb,
10 ppb and 5 ppb H2 O2 are shown in Fig. 7(b). The saturated
ECPs for the specimens exposed to 100 ppb and 10 ppb
H2 O2 were almost the same. That for 5 ppb exposure was
lower than for 100 ppb, but it still increased from the initial
value. The time to reach the saturated value increased as the
concentration decreased. It was suggested that the develop-
ment of oxide film affected the ECP response a lot. A de-
tailed evaluation should be made using oxide film character-
ization data.
2. Frequency Dependent Complex Impedance (FDCI)
(1) Comparison of Cole–Cole Plots for Specimens Exposed
to H2 O2 and O2
Example Cole–Cole plots of measured complex impe-
dance between a pair of unsensitized type 304 stainless steel
specimens exposed to O2 and H2 O2 are shown in
Fig. 8(a).18) The plots are the relationship between the real
part of the complex impedance (Re½Zð!Þ)) and the negative
of its imaginary part ( Im½Zð!Þ)). One half circle for low
frequency from 1 mHz to 10 Hz, designated as the ‘‘low fre-
quency semicircle,’’ was observed on the right side of the
graph (the larger real part of impedance (Re½Zð!Þ)), while
the second for high frequency, but less than 10 kHz, desig-
nated as the ‘‘high frequency semicircle,’’ was observed in
the smaller real part of the impedance. When the exposure

VOL. 41, NO. 9, SEPTEMBER 2004

884 J. SUGAMA et al.

0.1 2.0
5h 27h 10ppb 5ppb
0 x105
1.5

-Im [Z] (ohm cm2)

200 h (high frequency
ECP (V-SHE)

-0.1 1ppb semi circle)

275 h
-0.2 1.0
[H2O2] 200 h

-0.3 100ppb 10ppb 5ppb 1ppb 100 h

0.5
50 h
-0.4 (low frequency)
semicircles
0
-0.5 0 1 2 3 4 5
0 20 40 60 80 100 Re [Z] (ohm cm2) x105
exposure time (h)
(a) Effects of change in H2O2 concentration (a) Exposed to 8 ppm O2
after 300 hour exposure to 100ppb H2O2

2.0
0.1
[H2O2]: 100ppb
x105
0 1.5

-Im [Z] (ohm cm2)

200 h (high frequency
10ppb
ECP (V-SHE)

semi circle)
-0.1
5ppb 1.0
-0.2

-0.3 0.5 5-200 h

(low frequency
-0.4 semicircles)
0
-0.5 0 1 2 3 4 5
0 50 100 150 200 250 300 Re [Z] (ohm cm2) x10 5
exposure time (h)
(b) Effects of H2O2 concentration (b) Exposed to 100 ppb H2O2
for long period exposure
Fig. 8 Measured complex impedance for the specimens exposed
Fig. 7 Measured electrochemical corrosion potential of speci- to O2 and H2 O2
mens exposed to H2 O2

might be due to oxide film growth, which reached the satu-

time was increased, there was a small change in the high fre-
quency semicircle, but a big change was observed in the low
frequency semicircle. Frequency dependent complex impe-
dances of unsensitized type 304 stainless steel specimens ex-
posed to 8 ppm oxygen are shown in Fig. 8(a). Unfortunately
the low frequency semicircle did not complete the half cir-
cle. So the data were extrapolated to obtain the cross point
with the x-axis (R). When the exposure time was increased
from 150 to 200 or 225 h, there was a small change in the
high frequency semicircle but the low frequency semicircle
became larger. Increased thickness of the oxide film on the
specimens might affect the measured impedance. The low
frequency semicircles for the specimens exposed to O2 were
larger than those exposed to H2 O2 (Fig. 8(b)), which was
caused mainly by the larger resistance of the dissolution of
oxide on the specimens exposed to O2 .
(2) Dependence of Exposure Time on Cole–Cole Plots
Time dependent ECP and complex impedance for the
specimens exposed to 100 ppb H2 O2 could be compared by
looking at Fig. 9. As mentioned for Fig. 6(b), ECP of the
mechanically polished specimens was low just after expo-
sure started, it increased with exposure time and then
reached the saturation level at about 50 h. Increasing ECP
rated level when the film thickness was constant. The time
dependent Cole–Cole plot shown in Fig. 9(b) had changing
radii for the low frequency semicircles with increasing expo-
sure time and then the radii become constant at 50 h of expo-
sure. The Cole–Cole plot for the specimens exposed to
100 ppb H2 O2 had much smaller radii for the low frequency
semicircles than the specimens exposed in 8 ppm O2 shown
in Fig. 6; this was mainly caused by lower resistance of the
dissolution of oxide on the specimens exposed to H2 O2 .
Though the details of the equivalent circuit of the complex
impedance are mentioned later, the radii of the low frequen-
cy semicircle were determined by the sum of resistance of
dissolution of oxide and resistance of oxide film. For the
specimens exposed to a higher concentration of hydrogen
peroxide, the radii were determined by resistance of oxide
film. The saturation of the radii of the low frequency semi-
circles meant saturation of the total resistance of the film
and a constant film thickness.
Time dependent ECP and complex impedance for the
specimens exposed to reducing H2 O2 after 300-h exposure
to 100 ppb H2 O2 could be compared by looking at Fig. 10.
Only a slight change in ECP was observed for the specimens
exposed to more than 5 ppb H2 O2 , while the radii of the

JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY

Effects of Hydrogen Peroxide on Corrosion of Stainless Steel, (II) 885

0.1 0.1
5h 27h 10ppb 5ppb
0 0

ECP (V-SHE)
-0.1
ECP (V-SHE)

-0.1 1ppb

-0.2 -0.2 [H2O2]

-0.3 -0.3 100ppb 10ppb 5ppb 1ppb

-0.4 -0.4

-0.5 -0.5
0 50 100 150 200 250 300 0 20 40 60 80 100
time (h) exposure time (h)
(a) Electrochemical corrosion potential
(a) Electrochemical corrosion potential

1.0 2.0
4
x10
x105
0.8
-Im [Z] (ohm cm2)

1.5 1ppb

-Im [Z] (ohm cm2)

0.6
100 h 1.0 5ppb
50 h
0.4
10 h
5h 0.5
10ppb
0.2
100ppb (5h, 27h)
0 0
9.0 9.5 10.0 10.5 11.0 0 1 2 3 4 5
Re [Z] (ohm cm2) x104 Re [Z] (ohm cm2) x10 5
(b) Complex impedance
(b) Complex impedance
Fig. 10 Electrochemical corrosion potential and complex impe-
Fig. 9 Electrochemical corrosion potential and complex impe- dance (changing [H2 O2 ] after 300-h exposure to 100 ppb H2 O2 )
dance ([H2 O2 ]: 100 ppb)

slow oxidation of the specimen exposed to lower hydrogen

Cole–Cole plots increased as [H2 O2 ] decreased, which
meant that the resistance of dissolution of oxide increased
with unchanged resistance of oxide film. When [H2 O2 ] de-
creased to 1 ppb, ECP decreased due to a drop in cathodic
current at the specimen surface.
(3) Dependence of H2 O2 Concentration on Cole–Cole Plots
The measured ECP for the specimens exposed to 10 ppb
H2 O2 and the time dependent Cole–Cole plots are shown
in Fig. 11. The saturated ECP was almost the same as that
for the specimen exposed to 100 ppb H2 O2 , but the elapsed
time to reach the saturated level was 150 h, which was 3
times longer than that for 100 ppb H2 O2 . The radii of the
low frequency semicircles also reached the saturated value
at 150 h (data not shown). The saturated radii of Fig. 11(b)
were the same for 10 ppb H2 O2 exposure specimens of
Fig. 10(b).
The measured ECP for the specimens exposed to 5 ppb
H2 O2 and the time dependent Cole–Cole plots are shown
in Fig. 12. The saturated ECP for 5 ppb exposure was less
than those for 100 ppb and 10 ppb H2 O2 . However, it was
still increasing and might reach the same level after a long
exposure time. The radius of the Cole–Cole plot was less
than that for 5 ppb exposure after 300-h exposure to
100 ppb H2 O2 (shown in Fig. 10(b)), which suggested that
peroxide concentration might have produced an unstable ox-
ide film with higher dissolution rate than the film for the
specimen exposed to 100 ppb H2 O2 , and the thickness of
the former film was thinner than for that exposed to
100 ppb H2 O2 . The measured ECP showed a hysteresis pat-
tern vs. H2 O2 ,7) which was caused by memory effects of ox-
ide film previously formed under higher H2 O2 condition.
The saturated Cole–Cole plot differed from that for the
specimen previously exposed to higher H2 O2 concentration
which also suggested a hysteresis effect of oxide film char-
acters for dissolution into hydrogen peroxide water.
3. Effects of Combined Exposure to Oxygen and Hydro-
gen Peroxide
In order to confirm the effects of oxide film properties de-
termined by previous exposure to higher oxidant concentra-
tion, ECP was measured for the specimen exposed to
200 ppb O2 for 200 h and then the corrosive condition was
changed to hydrogen peroxide exposure to measure ECP
for the specimen exposed to 100 ppb H2 O2 for 200 h. The
measured ECP is shown in Fig. 13. The ECP for the speci-
men exposed to 200 ppb O2 reached the quasi-saturated level
in less than 30 h and then increased slowly with exposure
time (Fig. 13(a)). The ECP was 100 mV lower than that

VOL. 41, NO. 9, SEPTEMBER 2004

886 J. SUGAMA et al.

0.1 0.1

0 0

-0.1 -0.1
ECP (V-SHE)

ECP (V-SHE)
-0.2 -0.2

-0.3 -0.3

-0.4 -0.4

-0.5 -0.5
0 50 100 150 200 250 300 0 50 100 150 200 250 300
exposure time (h) exposure time (h)
(a) Electrochemical corrosion potential
(a) Electrochemical corrosion potential
1.0 5h
x105 1.0 5h
10 h x105
0.8 50 h
50 h
0.8 100 h
-Im [Z] (ohm cm2)

100 h

-Im [Z] (ohm cm2)

200 h
0.6 200 h
0.6 300 h
300 h
0.4
0.4
0.2
0.2
0
0.5 1.0 1.5 2.0 2.5 0
0.5 1.0 1.5 2.0 2.5
Re [Z] (ohm cm2) x105 x105
Re [Z] (ohm cm2)
(b) Complex impedance (b) Complex impedance
Fig. 11 Electrochemical corrosion potential and complex impe-
Fig. 12 Electrochemical corrosion potential and complex impe-
dance ([H2 O2 ]: 10 ppb)
dance ([H2 O2 ]: 5 ppb)

for the specimen exposed to 8 ppm O2 . When the corrosive
condition was changed to 100 ppb H2 O2 after 200-h expo-
sure to 200 ppb O2 , ECP increased to the saturated level
(0 V) in 30 h (Fig. 13(b)). The saturated level was the same
as that for the specimen exposed to only 100 ppb H2 O2
shown in Fig. 6(a), while the elapsed time from the first
exposure to 100 ppb H2 O2 was shortened by 20 h.
Measured complex impedance for combined O2 and H2 O2
exposures is shown in Fig. 14. Both Cole–Cole plots have
the same scale. When comparing them, the high frequency
semicircles were almost the same, while the low frequency
semicircle for the specimen exposed to 100 ppb H2 O2
(Fig. 14(b)) was much smaller than that of the specimen
exposed to 200 ppb O2 (Fig. 14(a)).
The effects of pre-exposure to O2 are shown in Fig. 15.
The Cole–Cole plots for the specimens exposed to only
100 ppb H2 O2 are shown in Fig. 15(a); the saturated value
was reached in 50 h. The Cole–Cole plots for the specimens
exposed to 100 ppb H2 O2 after 200-h exposure to 200 ppb O2
had the same saturated value (Fig. 15(b)). The radius of the
semicircle for the specimen with pre-exposure to O2 for 5-h
exposure to H2 O2 was much larger than that without
pre-exposure for the same H2 O2 exposure time. As a result
of changing the corrosion condition from 200 ppb O2 to
100 ppb H2 O2 , the thickness of the oxide film developed un-
der the O2 condition was not expected to increase rapidly,
but the properties of the film might change quickly to those
of the steady state under the H2 O2 condition. A detailed
discussion should be carried out using characterization data
for the oxide films.
IV. Discussion
1. Equivalent Circuit Analysis
An equivalent circuit for the measurement system in ele-
vated temperature water containing sufficient oxidants is
shown in Fig. 16.16) Each element of complex impedance
of the equivalent circuit is also shown there.
Resistance of redox reaction, Rred , is known to be deter-
mined by the following reactions. The radius of the high fre-
quency semicircle is determined by this resistance:
O2 þ 4Hþ þ 4e ! 2H2 O ð1Þ

þ
H2 O2 þ 2H þ 2e ! 2H2 O: ð2Þ
2. Electric Resistance of Oxide Film
The radius of the high frequency semicircle is known to be
determined by the resistance of the redox reaction. The same

JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY

Effects of Hydrogen Peroxide on Corrosion of Stainless Steel, (II) 887

0.1 2.0 5h
x105 50 h
0
100 h
1.5
150 h

Im [Z] (ohm cm2)

-0.1
ECP (V-SHE)

200 h
-0.2 1.0
-0.3
0.5
-0.4

-0.5
0 50 100 150 200 0
0 1 2 3 4
exposure time (h) x105
Re [Z] (ohm cm2)
(a) Exposure to 200 ppb O2 for 200 hours
(a) Exposure to 200 ppb O2 for 200 hours
0.1
2.0 5h
0
x105 10 h
-0.1 50 h
ECP (V-SHE)

1.5

Im [Z] (ohm cm2)

100 h
-0.2 200 h
1.0
-0.3

-0.4
0.5
-0.5
0 50 100 150 200
exposure time (h) 0
0 1 2 3 4
x105
Re [Z] (ohm cm2)
(b) Exposure to 100 ppb H2O2 for 200 hours
after 200 hour exposure to 200ppb O 2
(b) Exposure to 100 ppb H2O2 for 200 hours
after 200-hour exposure to 200 ppb O2
Fig. 13 Measured electrochemical corrosion potential for com-
bined O2 and H2 O2 exposures Fig. 14 Measured complex impedance for combined O2 and
H2 O2 exposures

values for the high frequency semicircle radii were measured

for the specimens exposed to 8 ppm O2 , 200 ppb O2 and
100 ppb H2 O2 , which meant that the resistances of the redox
reaction for both conditions were the same, even though the
oxidant concentrations were very different. Then, the redox
reaction is determined by the concentration at the surface
but not by that in the bulk water. Oxidant concentration at
the surface was determined by either a diffusion process
through the thin boundary layer at the surface or the redox
reaction process at the surface. Smaller changes in the radii
of the high frequency semicircles were observed for both
conditions and for a variety of hydrogen peroxide concentra-
tions, which suggested that the oxidant concentrations at the
specimen surface were determined by the redox reaction
process and it was not much affected by the oxidant species
or by the bulk concentration. Cole–Cole plots were calculat-
ed for the equivalent circuit shown in Fig. 14 for O2 and
H2 O2 and are shown in Fig. 17. Each impedance component
was determined from the measured Cole–Cole plots shown
in Figs. 8(a) and 9(b).
The oxide film on the specimens exposed to O2 consisted
mainly of magnetite,19) the specific resistance of which was
low enough to affect the Cole–Cole plot. The radii of the low
frequency semicircles of the specimens exposed to 8 ppm O2
were determined by the resistance of oxide dissolution
(Fig. 17(a)). The resistance to oxide dissolution on the speci-
men exposed to 100 ppb H2 O2 was low enough to affect the
Cole–Cole plot and then the radii of the low frequency semi-
circles of the specimens exposed to 100 ppb H2 O2 were de-
termined by the electric resistance of oxide film (Fig. 17(c)).
The electric resistance of oxide film on the specimen with
200-h exposure to 100 ppb H2 O2 was 4,000
cm2 , while
the oxide film thickness was measured as 0.3 mm for
100 ppb H2 O2 . The measured specific resistance of the oxide
film developed on the specimens exposed to H2 O2
(1:3108
cm) was a little less than the estimated value
for hematite at elevated temperatures19) but it was more than
ten times that for O2 exposure.
The difference in resistance of oxide film is known to
cause the difference in anodic polarization properties and
then the difference in ECP.19) Increasing the number of data
should allow more detailed evaluation of the impedance
components.

VOL. 41, NO. 9, SEPTEMBER 2004

888 J. SUGAMA et al.

1.0 5h C2 C2
x104 C1 C1
10 h Rsol Zw
0.8 Zw
50 h
-Im [Z] (ohm cm2)

100 h
0.6 Ra Rred Rred Ra
Rf Rf
0.4
Rf: resistance of oxide film
Ra: resistance of oxide dissolution
0.2 Rred: resistance of redox reaction,
H2O/O2 or H2O/H2O2
0 Rsol: resistance of pure water between the specimen
9.0 9.5 10.0 10.5 11.0
Zw: Warburg impedance
Re [Z] (ohm cm2) x104
Zw = Zσ(1-j)/(ω)1/2
(a) Exposed to 100 ppb H2O2 Zσ: Warburg impedance coefficient
C1, C2: capacitances of oxide film/solution interface
1.0 5h
x104 10 h
Fig. 16 Equivalent circuit model based on the corrosion model
0.8 for film growth
50 h
-Im [Z] (ohm cm2)

100 h
0.6
er value than the specimen exposed to 200 ppb O2 and
200 h
kept the same ECP level when the H2 O2 concentration
was decreased to 10 ppb.
0.4
(2) The frequency dependent complex impedance measured
for the SUS 304 specimen exposed to 100 ppb H2 O2
0.2
showed saturation in the low frequency semicircles,
which was determined by the electric resistance of the
0
8.0 8.5 9.0 9.5 10.0 oxide film and caused by saturation of oxide film thick-
Re [Z] (ohm cm2) x104 ness. The behavior for the specimens with 200 ppb O2
exposure was determined by the resistance to oxide dis-
(b) Exposed to 100 ppb H2O2 after
solution, which was much larger than that for the speci-
200-hour exposure to 200 ppb O2
men exposed to H2 O2 .
Fig. 15 Effects of pre-exposure to O2
(3) The ECP of the specimens exposed to 200 ppb O2 after
200-h exposure to 100 ppb H2 O2 were higher than those
exposed to only 200 ppb O2 due to memory effects on
V. Conclusions oxide films. The specimens with pre-exposure to
200 ppb H2 O2 after 200-h exposure to 200 ppb O2 were
The conclusions are summarized as follows. not affected by pre-exposure to O2 .
(1) The Electrochemical corrosion potential (ECP) meas- (4) The measured ECP and frequency dependent complex
ured for the SUS 304 specimen exposed to 100 ppb impedance were well related to understanding the ef-
H2 O2 reached the saturated level in 50 h, showed a larg- fects of oxide film on the specimens and corrosion be-

2.0 exposure measured calculated 7 exposure measured calculated 2.0 exposure measured calculated
x 105 50 h x 104 5h x 104 5h
100 h 6 10 h 10 h
-Im [Z] (ohm cm2)

1.5 200 h 30 h 1.5 30 h

-Im [Z] (ohm cm2)

5
-Im [Z] (ohm cm2)

50 h 50 h
4 200 h 200 h
Ra: 100kΩcm2
1.0 1.0
3
Rf: 7kΩcm2
0.5 70 2 0.5
4
30 1 6
3
0 0 0
0 1 2 5
3 5 6 7 8 9 10 11 12 0.95 1.00 1.05 1.10 1.15
x 10
Re [Z] (ohm cm2) Re [Z] (ohm cm2) x 104 Re [Z] (ohm cm2) x 105
(a) Exposed to 8ppm O2 (b) Exposed to 100ppb H2O2 (c) Exposed to 100ppb H2O2
(low frequency semi circle)

Fig. 17 Evaluation of Cole–Cole plots

JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY

Effects of Hydrogen Peroxide on Corrosion of Stainless Steel, (II)
haviors of stainless steel in BWR primary coolant con-
ditions.
Nomenclature
[H2 O2 ]: Hydrogen peroxide concentration (ppb, mol/l)
[O2 ]: Oxygen concentration (ppb, mol/l)
Rf : Resistance of oxide film
Ra : Resistance of iron dissolution
Rred : Resistance of redox reaction, H2 O/O2 or H2 O/H2 O2
Rsol : Resistance of pure water between the specimens
Z! : Warburg impedance Z! ¼Zs ð1jÞ=ð!Þ1=2
Zs : Warburg impedance coefficient
C1 , C2 : Capacitances of oxide film/solution interface
Abbreviations
BWR: Boiling water reactor
ECP: Electrochemical corrosion potential
GP-IB: General purpose interface bath
FDCI: Frequency dependent complex impedance
HWC: Hydrogen water chemistry
IGSCC: Intergranular stress corrosion cracking
PTFE: Polytetrafluoroethylene
Acknowledgments
The authors wish to express their sincere thanks to Dr. K.
Mabuchi of Hitachi Research Laboratory, Hitachi, Ltd., for
his kind advice on electrochemical impedance measure-
ments. They also wish to express their thanks to Mr. Y.
Miyamoto of Quantum Science and Energy Engineering
Department, Graduate School of Engineering, Tohoku Uni-
versity, for his assistance in preparing the data acquisition
system used for the impedance measurement.
References
1) Y. Wada, S. Uchida, M. Nakamura, et al., ‘‘Empirical
understanding of the dependency of hydrogen water chemistry
effectiveness on BWR designs,’’ J. Nucl. Sci. Technol., 36,
169 (1999).
2) S. Uchida, E. Ibe, K. Nakata, et al., ‘‘Application of hydrogen
water chemistry to moderate corrosive circumstances around
the reactor pressure vessel bottom of boiling water reactors,’’
Nucl. Technol., 110, 250 (1995).
3) R. J. Row, M. E. Indig, C. C. Lin, et al., ‘‘Suppression of ra-
diolytic oxygen produced in a BWR by feedwater hydrogen
addition,’’ Proc. Int. Conf. Water Chemistry of Nuclear
Reactor Systems, Water Chemistry 3, British Nuclear Energy
Society, 23 (1984).
4) R. L. Cowan, M. E. Indig, J. N. Kass, et al., ‘‘Experience with
hydrogen water chemistry in boiling water reactors,’’ Proc.
Int. Conf. Water Chemistry of Nuclear Reactor Systems, Water
Chemistry 4, British Nuclear Energy Society, 29 (1986).
5) F. P. Ford, D. F. Taylor, P. L. Andresen, et al., ‘‘Corrosion
assisted cracking of stainless and low alloy steels in LWR
environments,’’ EPRI NP-5064M Project 2006-6 Final
Report, February 1987, (1987).
6) Y. J. Kim, L. W. Niedrach, C. C. Lin, et al., ‘‘Development
of ECP models for BWR application,’’ Proc. 7th Int. Symp.
VOL. 41, NO. 9, SEPTEMBER 2004
889
Environmental Degradation of Materials in Nuclear Power
Systems—Water Reactors, Breckenridge, CO., National Asso-
ciation of Corrosion Engineers, 699 (1995).
7) S. Uchida, N. Shigenaka, M. Tachibana, et al., ‘‘Effects of
hydrogen peroxide on intergranular stress corrosion cracking
of stainless steel in high temperature water, (I); Effects of
hydrogen peroxide on electrochemical corrosion potential of
stainless steel,’’ J. Nucl. Sci. Technol., 35, 301 (1998).
8) T. Satoh, S. Uchida, J. Sugama, et al., ‘‘Effects of hydrogen
peroxide on corrosion of stainless steel (I); Improvement of
hydrogen peroxide remaining in a high temperature high
pressure hydrogen peroxide loop,’’ J. Nucl. Sci. Technol., 41,
610 (2004).
9) C. C. Lin, F. R. Smith, N. Ichikawa, et al., ‘‘Decomposition of
hydrogen peroxide in aqueous solutions at elevated tempera-
tures,’’ Int. J. Chem. Kinetics, 23, 971 (1991).
10) D. Hiroishi, ‘‘Homogeneous and heterogeneous decomposition
of hydrogen peroxide in high temperature water,’’ Proc. Int.
Conf. Water Chemistry of Nuclear Reactor Systems, Water
Chemistry 5, British Nuclear Energy Society, 311 (1989).
11) S. Uchida, M. Tachibana, A. Watanabe, et al., ‘‘Effects of
hydrogen peroxide on intergranular stress corrosion cracking
of stainless steel in high temperature water, (II); Optimization
of crack propagation rate measurement system,’’ J. Nucl. Sci.
Technol., 37, 257 (2000).
12) Y. Wada, A. Watanabe, M. Tachibana, et al., ‘‘Effects of hy-
drogen peroxide on intergranular stress corrosion cracking of
stainless steel in high temperature water, (III); Crack growth
rate in corrosive envirnment determined by hydrogen perox-
ide,’’ J. Nucl. Sci. Technol., 38, 183 (2001).
13) Y. Wada, A. Watanabe, M. Tachibana, et al., ‘‘Effects of
hydrogen peroxide on intergranular stress corrosion cracking
of stainless steel in high temperature water, (IV); Effects of
oxide film on electrochemical corrosion potential,’’ J. Nucl.
Sci. Technol., 37, 901 (2000).
14) N. Yamashiro, S. Uchida, Y. Satoh, et al., ‘‘Determination of
hydrogen peroxide in pure water by chemiluminescence detec-
tion, (I); Flow cell type hydrogen peroxide detector,’’ J. Nucl.
Sci. Technol., 41, 890 (2004).
15) S. Uchida, Y. Satoh, N. Yamashiro, et al., ‘‘Determination of
hydrogen peroxide in pure water by chemiluminescence detec-
tion, (II); Theoretical analysis of luminol chemiluminescence
processes,’’ J. Nucl. Sci. Technol., 41, 898 (2004).
16) K. Mabuchi, M. Sakai, N. Ohnaka, ‘‘A study on corrosion be-
havior of Type 304 stainless steel with electrochemical impe-
dance spectroscopy in high temperature pure water,’’ Zairyo-
to-Kankyo, 43, 2–10 (1994), [in Japanese].
17) E. Ibe, S. Uchida, ‘‘A water radiolysis model in a circulating
flow system with a boiling region and its application to hydro-
gen alternative water chemistry of boiling water reactors,’’
Nucl. Sci. Eng., 90, 140 (1985).
18) S. Uchida, T. Satoh, K. Furukawa, et al., ‘‘Characterization of
oxide films on stainless steel exposed to hydrogen peroxide
and oxygen in high temperature water,’’ Proc. 11th Int. Symp.
Environmental Degradation of Materials in Nuclear Power
Systems—Water Reactors, Stevenson, Washington, Aug.
10–14, 2003, (2003), (in CD-ROM).
19) Y. Murayama, T. Satoh, S. Uchida, et al., ‘‘Effects of hydro-
gen peroxide on intergranular stress corrosion cracking of
stainless steel in high temperature water, (V); Characterization
of oxide film on stainless steel by multilateral surface analy-
sis,’’ J. Nucl. Sci. Technol., 39, 1199 (2002).