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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
ORIGINAL PAPER
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
880
Effects of Hydrogen Peroxide on Corrosion of Stainless Steel, (II) 881
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.
: 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
PC
(LabVIEW)
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.
0.1 2.0
5h 27h 10ppb 5ppb
0 x105
1.5
2.0
0.1
[H2O2]: 100ppb
x105
0 1.5
semi circle)
-0.1
5ppb 1.0
-0.2
0.1 0.1
5h 27h 10ppb 5ppb
0 0
ECP (V-SHE)
-0.1
ECP (V-SHE)
-0.1 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
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
for the specimen exposed to 8 ppm O2 . When the corrosive 100 ppb H2 O2 , the thickness of the oxide film developed un-
condition was changed to 100 ppb H2 O2 after 200-h expo- der the O2 condition was not expected to increase rapidly,
sure to 200 ppb O2 , ECP increased to the saturated level but the properties of the film might change quickly to those
(0 V) in 30 h (Fig. 13(b)). The saturated level was the same of the steady state under the H2 O2 condition. A detailed
as that for the specimen exposed to only 100 ppb H2 O2 discussion should be carried out using characterization data
shown in Fig. 6(a), while the elapsed time from the first for the oxide films.
exposure to 100 ppb H2 O2 was shortened by 20 h.
Measured complex impedance for combined O2 and H2 O2
IV. Discussion
exposures is shown in Fig. 14. Both Cole–Cole plots have
the same scale. When comparing them, the high frequency 1. Equivalent Circuit Analysis
semicircles were almost the same, while the low frequency An equivalent circuit for the measurement system in ele-
semicircle for the specimen exposed to 100 ppb H2 O2 vated temperature water containing sufficient oxidants is
(Fig. 14(b)) was much smaller than that of the specimen shown in Fig. 16.16) Each element of complex impedance
exposed to 200 ppb O2 (Fig. 14(a)). of the equivalent circuit is also shown there.
The effects of pre-exposure to O2 are shown in Fig. 15. Resistance of redox reaction, Rred , is known to be deter-
The Cole–Cole plots for the specimens exposed to only mined by the following reactions. The radius of the high fre-
100 ppb H2 O2 are shown in Fig. 15(a); the saturated value quency semicircle is determined by this resistance:
was reached in 50 h. The Cole–Cole plots for the specimens
O2 þ 4Hþ þ 4e ! 2H2 O ð1Þ
exposed to 100 ppb H2 O2 after 200-h exposure to 200 ppb O2
þ
had the same saturated value (Fig. 15(b)). The radius of the H2 O2 þ 2H þ 2e ! 2H2 O: ð2Þ
semicircle for the specimen with pre-exposure to O2 for 5-h
exposure to H2 O2 was much larger than that without 2. Electric Resistance of Oxide Film
pre-exposure for the same H2 O2 exposure time. As a result The radius of the high frequency semicircle is known to be
of changing the corrosion condition from 200 ppb O2 to determined by the resistance of the redox reaction. The same
0.1 2.0 5h
x105 50 h
0
100 h
1.5
150 h
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
-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
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)
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)
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The authors wish to express their sincere thanks to Dr. K. stainless steel in high temperature water, (III); Crack growth
rate in corrosive envirnment determined by hydrogen perox-
Mabuchi of Hitachi Research Laboratory, Hitachi, Ltd., for
ide,’’ J. Nucl. Sci. Technol., 38, 183 (2001).
his kind advice on electrochemical impedance measure- 13) Y. Wada, A. Watanabe, M. Tachibana, et al., ‘‘Effects of
ments. They also wish to express their thanks to Mr. Y. hydrogen peroxide on intergranular stress corrosion cracking
Miyamoto of Quantum Science and Energy Engineering of stainless steel in high temperature water, (IV); Effects of
Department, Graduate School of Engineering, Tohoku Uni- oxide film on electrochemical corrosion potential,’’ J. Nucl.
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