Accepted Manuscript

Title: Influence of Conductivity on Corrosion Behavior of 304 Stainless Steel

in High Temperature Aqueous Environment
Author: Jiazhen Wang, Jianqiu Wang, En-Hou Han
PII:
DOI:
Reference:

S1005-0302(15)00223-6
http://dx.doi.org/doi: 10.1016/j.jmst.2015.12.008
JMST 617

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Journal of Materials Science & Technology

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Revised date:
Accepted date:

19-1-2015
16-2-2015
4-3-2015

Please cite this article as: Jiazhen Wang, Jianqiu Wang, En-Hou Han, Influence of Conductivity
on Corrosion Behavior of 304 Stainless Steel in High Temperature Aqueous Environment,
Journal of Materials Science & Technology (2015), http://dx.doi.org/doi:
10.1016/j.jmst.2015.12.008.
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Influence of Conductivity on Corrosion Behavior of 304 Stainless Steel

in High Temperature Aqueous Environment
Jiazhen Wang, Jianqiu Wang*, En-Hou Han
Key Laboratory of Nuclear Materials and Safety Assessment, Institute of Metal Research, Chinese
Academy of Sciences, Shenyang 110016, China
[Received in 19 January 2015; Received in revised form 16 February 2015; Accepted 4 March 2015]
*Corresponding author. Ph.D., Prof.; Tel.: +86 24 23893723; Fax: +86 24 23894149.
E-mail address: wangjianqiu@imr.ac.cn (Jianqiu Wang).

The influence of conductivity on corrosion behavior of 304 stainless steel (SS) in high temperature
water was investigated by using in-situ potentiodynamic polarization curves, electrochemical
impedance spectra (EIS) at 300 C and ex-situ scanning electron microscopy (SEM), X-ray
diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The structures of oxide films
formed on 304 SS change with different conductivities at 300 C. With the increase in conductivity,
the passive current density increases while the resistances of oxide films decrease. But, the
resistances do not decrease lineally with the increase in conductivity. A modified double-layer model
for oxide structure was proposed to explain the influence mechanism of conductivity on the oxide
films on 304 SS in high temperature water. Improving the

10

B enrichment level can reduce the

conductivity of primary water and increase the corrosion resistance of 304 SS.
Key words: Stainless steel; Polarization; Electrochemical impedance spectra;

High temperature

corrosion

1. Introduction

In all pressurized water reactors (PWRs), boric acid is used as a chemical shim to control excess
reactivity in the fuel assemblies during a fuel cycle[1,2]. Although natural boric acid is normally used,
only the 10B isotope has a high capacity for thermal neutron capture by the following reaction[3,4]:
10
5

1
0

7
3

Li

4
2

He

(1)

The injection of B in the typical ingredients of primary PWR coolant is 9001800 ppm (by weight)
1

Page 1 of 20

as burnable neutron absorbers to control nuclear reactions. Besides, 25 ppm lithium hydroxide
(LiOH) is also injected to achieve a desired pH range between 6.9 and 7.4, which minimizes the
corrosion of structural materials, as well as the solubility and transport of activated corrosion
products[1,5].
In support of advanced fuel management trends, a higher 10B content is required at the beginning
of the fuel cycle. About 80% of total B in nature exists in the form of

11

B isotope, which is

essentially useless as a neutron absorber[1,3,6]. Moreover, 11B isotope increases the total concentration
of required boron acid (H3BO3) to obtain a target 10B isotope content[7,8]. However, increasing boron
concentration brings many difficulties associated with the need to increase the concentration of
LiOH in primary PWR to maintain the relative stability of pH values. The increased levels of H3BO3
and LiOH concentration, along with the rise of subsequent conductivity aggravate the boron
deposition on fuel and accelerate the corrosion rates of fuel cladding and Alloy 600[1,2,4,6].
Because the corrosion of alloys in high temperature water is an electrochemical process in nature,
a large number of studies have investigated the influences of temperature[912], pH value[11,13,14],
dissolved oxygen (DO)[15] and dissolved hydrogen (DH)[16] on electrochemical characters of the
alloys by in-situ electrochemical measurement techniques in high temperature water. However, few
studies focus on how conductivity influences the corrosion behavior of stainless steels (SS) and
nickel-based alloys in high temperature water. Liu et al.[14] investigated the influence of pH on the
corrosion behavior of 316L SS at 300 C, and found that the corrosion rate of 316L SS reduced with
the increase of pH value. However, the pH and conductivity of the experimental solutions changed at
the same time and the influence of conductivity on corrosion behavior of 316L SS was not discussed.
Thus, the main purpose of the present work is to study the effect of conductivity on corrosion
behavior of 304 SS in high temperature aqueous environments by means of in-situ potentiodynamic
polarization, electrochemical impedance spectra (EIS), ex-situ scanning electron microscopy (SEM),
X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analysis. One duplex-layer
model is proposed to understand the evolution process of oxides on 304 SS in high temperature
aqueous solutions with different conductivities.

2. Experimental Procedures
2

Page 2 of 20

2.1. Samples and solutions

The composition (wt%) of 304 SS used for this work is 18.65 Cr, 9.27 Ni, 1.88 Mn, 0.035 C,
0.66 Si and Fe balance. The material was solution annealed at 11003 C for 1 h and then water
quenched. The samples with a size of 10 mm 10 mm 1 mm were used for electrochemical
experiments and were carefully ground with SiC papers up to 2000 grit. After that, all the samples
were polished with 3.5 m diamond paste. The samples were subsequently welded to 316 SS wires
shielded with heat-shrinkable polytetrafluoroethylene tubes. There are three parallel electrochemical
samples in each electrochemical experiment and another two parallel samples for SEM, XRD and
XPS analysis. The autoclave was connected with a re-circulation loop, and the water chemistry
parameters were monitored on-line, including DO, DH, pH value and electrical conductivity. The DO
and DH values were automatically controlled and adjusted using software LabView 8.5. The control
error was lower than 1%. The autoclave and re-circulation loop were pre-oxidized in the relevant
testing solution before the formal experiment. The testing electrolytes were four kinds of lithiated
and borated solutions in the high-purity deionized water (conductivity: 18.25 M cm). The
concentrations of B and Li, the pH values and conductivities of the solutions at 300 C are listed in
Table 1. All the data in the table have been calculated using commercial software pHSC4 from Duke
Power Company. The testing solution was firstly deaerated by continuously bubbling with N 2 gas
(99.99%) until the DO was less than 0.01 ppm, and then inflated with H2 gas (99.999%) until the DH
reached 2.3 ppm. The samples were immersed in 3001 C and 10 MPa high temperature water in a
2 L Ni-lined stainless steel autoclave for 72 h.

2.2. Electrochemical measurements

A Gamry Reference 600 Potentiostat and corresponding softwares were used for all
electrochemical measurements. The three-electrode system including working, counter and external
Ag/AgCl reference electrodes were used. The counter electrode was a platinum foil with a size of 20
mm 20 mm, and the concentration of KCl in the Ag/AgCl reference electrode was 0.1 mol/L. Prior
to the heating process of autoclave, the samples were reduced potentiostatically at 1.0 V (vs SHE
standard hydrogen electrode) for 10 min to remove the surface oxides on SS and then kept in the
3

Page 3 of 20

solution at 3001 C for 72 h. According to American Society for Testing and Materials F2129
Standard and Ref.[17,18], 72 h of pre-oxidation could allow the extent of oxide films achieved, and the
open circuit potential (OCP) could reach the quasi-steady condition at the same time.
The OCPs of 304 SS in testing solutions at 300 C were measured at intervals. The EIS
measurements were performed at OCP. The alternating current signal amplitude was 10 mV rms
and the frequency ranged from 100 kHz to 10 mHz. The potentiodynamic polarization experiments
were performed at a scanning rate of 0.5 mV/s starting from 0.1 V vs OCP. A Gamry Echem
Analyst Software was used for calculating the fitting results of EIS.
All the potentials have been converted into SHE by the following equation[19]:
E SHE E obs 0 . 2866 0 . 001 (T T r ) 1 . 745 10

(T T r ) 3 . 03 10
2

(T T r )

(2)

where ESHE is the electrode potential vs SHE, Eobs is the measured electrode potential, Tr is room
temperature (25 C) , and T is the measured experimental temperature (300 C).

2.3. Analysis of surface film

To observe the microstructure of corrosion product on the surface of 304 SS, an FEI XL30 field
emission environmental scanning electron microscope (ESEM) was used. The phases of oxide films
on 304 SS after immersion were identified using a PANalytical XPert Powder X-ray diffraction
(XRD), with AlK radiation. The generator voltage and tube current were 40 kV and 40 mA,
respectively. The scanning range of the detector was from 10 to 90, the step size was 0.05, and the
time per step was 0.8 s. XPS analysis was performed using a VG ESCALAB 250 X-ray
photoelectron spectrometer. Composition-depth profiles were obtained with 2.0 keV Ar ions at a
target current of 2.0 A/cm2. The sputtering rate was estimated to be about 0.1 nm/s (vs Ta2O5). To
characterize the thickness of oxide film qualitatively, the equivalent oxide thickness is defined from
the XPS depth profiles where the atomic percent of O reaches 10%.

3. Results
3.1. Change of OCP and Potentiodynamic polarization curves
4

Page 4 of 20

Fig. 1 shows the evolution of OCPs for 304 SS in different solutions at 300 C. The OCPs of
304 SS reduce with the increase of B and Li injection. The OCP values of 304 SS in 1#, 2#, 3# and
4# solutions are 0.594, 0.625, 0.673 and 0.685 V, respectively.
Fig. 2 shows the potentiodynamic polarization curves for 304 SS after 72 h in different
concentrations of B and Li solutions at 300 C. All the passive potentials of 304 SS are nearly
located around 0.4 V, which can be due to the transformation of FeCr oxides into NiFe oxides
based on the EpH diagram[2023]. The anodic current density, the cathodic current density and the
passive current density all increase with the rise of conductivity. The passive current density of 304
SS in 1#, 2#, 3# and 4# solutions are 26, 62, 96 and 200 A/cm2, respectively.

3.2.Electrochemical impedance spectroscopy

Fig. 3 shows the EIS results for the oxide films on 304 SS after 72 h exposure in different
concentrations of B and Li solutions at 300 C. The impedance magnitude |Z| reduces with the
increase of conductivity and two time constants could be observed according to the bode diagram in
Fig. 3(a). The approximate frequency ranges, where two time constants arise, are shown in Fig. 3(a)
with red arrows. The Nyquist diagram in Fig. 3(b) shows a large semi-circle at high frequency region
and a small semi-circle at low frequency region. With the increase of conductivity, the radiuses of
both the large semi-circle and the small semi-circle decrease.

3.3. Surface film observation and analysis

3.3.1.

SEM results
Fig. 4 shows morphologies of oxide films on 304 SS in different concentrations of B and Li

injection at 300 C. With the rise of conductivity, the sizes of spinel oxide particles on the outer layer
gradually become larger and the number of the particles gradually increases, as shown in Fig. 4(a, b).
Besides, oxide particles with a size of smaller than 200 nm start to appear on the outer layer. But
most interestingly, with the continuing increase of conductivity, while the maximum size of the
outer-layer oxide particles increases and the number of these particles decreases, the number of oxide
particles with relatively smaller size grows obviously (Fig. 4(c)). This suggests that the increase of B
5

Page 5 of 20

and Li injection can apparently alter the morphologies of the oxide films on 304 SS.

3.3.2. XRD results

Fig. 5 shows XRD patterns of the oxide films on 304 SS in different concentrations of B and Li
solutions at 300 C. The diffraction peaks mainly correspond to Fe3O4 (JCPDS 19-0629), FeCr2O4
(JCPDS 34-0140), with the exception of substrate. All the positions of diffraction peaks match well
with those from Fe3O4 and FeCr2O4 according to the published data[21,24,25]. For SSs, Fe3O4 and
FeCr2O4 were considered as the main corrosion products immersed in high temperature water[2628].

3.3.3. XPS results

Fig. 6 shows the normalized composition depth profiles of Cr, Ni, Fe in the oxide films on 304
SS with different injection of B and Li at 300 C. Considering the fact that the sputtering depth is not
linear with the sputtering time for the XPS analysis[21,29], the original sputtering time is used to show
the concentration distributions of elements in the oxide films on 304 SS. For the oxide films in 1#
solution, Fe, Ni and Cr are homogeneously distributed within the whole sputtering range of the oxide
films depth. And the inner layer of the oxide films is slightly Cr-rich. For the oxide films in 3#
solution, the outer layer of the oxide films is obviously Fe-rich while the inner layer is Cr-rich. By
comparing Fig. 6(a) with 6(b), it can be seen that the increase of conductivity can enlarge the Fe-rich
extent in the outer layer and Cr-rich extent in the inner layer of the oxide films. Besides, the
thickness of oxide films increases with the rise of conductivity by comparing Fig. 6(a) with 6(b).

4. Discussion
4.1. Effect of conductivity on the electrochemical behavior of 304 SS
To qualitatively analyze how the B and Li injection affects the electrochemical characteristics in
this study, the Evans diagram is used as shown in Fig. 7. According to Fig. 2, the cathodic current
density, the anodic current density, and the passivity current density for 304 SS increase as the B and
Li injection goes up. It indicates that the increase of conductivity can promote both the cathodic
reaction and the anodic reaction at the same time. The reason could be that the increase of
6

Page 6 of 20

conductivity weakens the compactness of the oxide films and speeds up the diffusion process of
metal atoms, which will be further discussed in 4.2. The increase in the current paths of the cathodic
and anodic reactions can lead to the consumption of the electrical charges generated by anodic
dissolution on the metal surface through oxidation-reduction reaction away from the metal surface,
which increases the area of the cathodic reaction, and thus accelerate the corrosion rate[30,31]. Besides,
the corrosion potentials of 304 SS decrease, indicating that the increase of conductivity has a more
obvious effect on the anodic corrosion promotion of 304 SS as shown in Fig. 7. Thus, the increase of
conductivity can remarkably reduce the corrosion resistance of 304 SS at 300 C.
According to Ref.[32], the relationship between Xi and Ip has been developed to explain the
surface reactions between ith ions Xi (e.g. Li+, Zn2+) and the passive film. And the passive current
density Ip could be expressed as Eq. (3)[33].
1
Ip ( k

s
H

kH OaH O )

I i a Xi / a

ei

OH

ei

K i a Xi / a
i

OH

(3)

where Ii is a composite parameter, which contains the quasi equilibrium constant Ki and the forward
dissolution rate constant kj; the subscript i denotes the ith active ion; s, u, ci and ei are the reaction
orders as to the activity of j, respectively; aj represents the activity of some species j (e.g. H+, Xi and
OH). The other parameters can be deduced based on the dependence of Ip on the concentrations of
ions (e.g. B+, Li+) in Eq. (3). According to Table 1, the four testing solutions in our experiment have
the same pH value at 300 C, so aH+ in the solutions has the same value. Because of the absence of
active ions (e.g. Cl) in solutions, the change of parameters in the bracket of Eq. (3) can be
ignored[21,23,34]. Due to the less protective oxide films on 304 SS by increasing B and Li
concentration, the value of Ki becomes smaller while Ii becomes larger[20,21,23,35]. Thus, the increase
in B and Li concentrations increases Ip and accelerates the dissolution of oxides.
For the materials in high temperature water, the slower oxygen (O) diffusion process across the
oxide films leads to the lower corrosion resistance[36,37]. The impedance modulus |Z| at low frequency
is supposed to reflect how difficult O diffuses through the oxide layer into the substrate[23]. Based on
Fig. 3(a), with the increase of conductivity, the impedance modulus |Z| at low frequency tends to
decrease due to the less protective oxide films. Besides, it can be inferred that the increase of
conductivity promotes the O diffusion process across the barrier layer into the substrate, and thus
7

Page 7 of 20

increases the speed of the cathodic reaction speed. This is consistent with the potentiodynamic
polarization shown in Fig. 2. There are two capacitive arcs obtained from the oxide films on 304 SS
in Fig. 3(b). The larger arc is associated with the relatively difficult electronic transmission of barrier
layer while the smaller one is assigned to the relatively easy transportation of substances at the
barrier layer/solution boundary.
Interestingly, both the bode diagram and Nyquist diagram in Fig. 3 are different from those in
the previous work[14,22,23]. The impedance magnitudes shown in Fig. 3(a) are obviously smaller than
those in the previous work for nickel-based alloys and stainless steels[12,14,15,22,23]. The reason is that
the dissolved hydrogen in high temperature water promotes the cathodic process and reduces the
corrosion resistance of materials[16].
An equivalent circuit R(QR)(QR) is adopted as shown in Fig. 8[9,23,35], where Rs is the solution
resistance, R1 is the charge transfer resistance of the Faraday process, CPE1 is the constant phase
element for the duplex layer, R2 is the oxide resistance, and CPE2 is the constant phase element for
oxide. For the applied equivalent circuit in Fig. 8, the transfer function is given as follows:
Z R s R1[ 1 ( j R1Q1 ) 1 ]
n

R 2[ 1 ( j R 2Q 2 ) 2 ]
n

(4)

where j is the imaginary unit, is the angular frequency, Q denotes the CPE coefficient, n is the CPE
exponent indicating the deviation of pure capacitor, and n1, n2 represent the fitting parameters at the
high frequency and low frequency, respectively. The fitted values of parameters of the above
equivalent circuit are listed in Table 2. Although the change of Rs is irregular with the increase of
conductivity, R1 and R2 reduce with the increase of conductivity. It is interesting that R1 and R2 do not
decrease linearly with the increase in conductivity as shown in Fig. 9. When the conductivity
changed from 113.9 to 164.3 S/cm, a quick reduction of R1 and R2 occurred. However, the
decreasing rates of R1 and R2 become lower at larger conductivity value (>164.3 S/cm). When R1 is
ignored, the value of R2 can denote the protectiveness of the oxide films in high temperature water.
Based on Fig. 9, it can be inferred that a porous oxide film is formed on surface of 304 SS in the
present water chemistry environment with high conductivity.

4.2. Effect of conductivity on the composition of oxide film on 304 SS

Page 8 of 20

Fig. 10 shows the potentialpH diagrams for Ni, Cr, and Fe at 300 C, which were summarized
by Staehle and Gorman[38]. According to Table 1 and Fig. 1, the calculated pH for the test solutions at
300 C during the electrochemical measurements is 7.29, and the measured OCP range in different
solutions is between 0.596 V and 0.684 V. In Fig. 10, pH of 7.29 is shown using red vertical lines,
while the measured potentials at four different solutions are located within the range of the horizontal
bars. Therefore, based on the measured corrosion potentials in the primary water, the stable states of
Cr, Fe, and Ni are Cr2O3, Fe3O4, Ni, respectively. Fe3O4 can be understood as the mixture of Fe2+ and
Fe3+ according to the following reaction[15]:
F eO F e 2O 3 F e 3O 4

(5)

In high-temperature pressurized water, interactions among oxides (e.g. Cr2O3, FeO, Fe2O3, NiO)
are inevitable[15], which are mainly:
FeO C r2O 3 FeC r2O 4

(6)

N iO C r2O 3 N iC r2O 4

(7)

N iO Fe 2O 3 N iFe 2O 4

(8)

2N iO C r2O 3 Fe 2O 3 2N iC rFeO 4

(9)

The concentration of Ni (< 10 wt%) in 304 SS is limited and the stable form of Ni under the
experimental conditions is elemental Ni, so NiCr2O4, NiFe2O4 and NiCrFeO4 in Reactions (7), (8)
and (9) could not be formed. This is consistent with the XRD result shown in Fig. 5. Therefore, the
change of conductivity does not alter the phases of oxide films on the surface of 304 SS.
Fig. 11 shows the atomic percent of Fe oxide to total metal oxides (Fe/(Cr + Fe), = 0.29)
after 72 h immersion in 1# and 3# solutions at 300 C. The ratio of 0.29Fe/(Cr + 0.29Fe) remains
about 50% (blue line) for the oxide films of 304 SS in 1# solution. This indicates that the proportions
of FeCr2O4 and Fe3O4 oxides on 304 SS are about 33 to 67 in 1# solution. However, for the oxide
films on 304 SS immersed in 3# solution, the 0.29Fe/(Cr + 0.29Fe) value of the outer film is much
bigger than 50%, indicating that the main phase of the outer oxide films formed in 3# solution is
Fe3O4. At the meantime, the 0.29Fe/(Cr + 0.29Fe) value of the inner oxide films formed in 3#
solution is about 40%, which proves that the phases of the inner oxide films are FeCr2O4 and Fe3O4
(the proportions are 50 to 50). Based on Figs. 6 and 11, it can be inferred that the diffusion process of
9

Page 9 of 20

Fe toward outer oxide layer is promoted by the increasing conductivity. Besides, for the oxides of Fe,
Cr, and Ni, the diffusion rates of metals in their relevant oxides are shown as follows[37]:
Fe2+ > Ni2+ >> Cr3+

(10)

According to Robertson[37], the metal ions are the faster moving species and determine the
oxidation rates. So, the promoted diffusion rate of Fe ions due to the increase of conductivity
accelerates the corrosion rate of 304 SS. This is consistent with the potentiodynamic results and EIS
results. The metal ions in oxides diffuse toward oxide/solution interface, and the vacancies will be
formed in the inner layer. The rapid diffusion of Fe ions in the oxide films will form a large number
of vacancies in the inner layer, and then these vacancies will gather together and form pores if the
vacancies cannot be supplemented by the diffusion of metal ions from the substrate. These pores
reduce the compactness and protectiveness of the inner oxide layer. This also explains why resistance
R2 of oxide layer in high conductivity solution is smaller than that in low conductivity solution,
although an obvious Cr-rich layer is formed in the inner layer of oxide films in high conductivity
solution (Figs. 6 and 11).
After the protective oxide films are formed on SSs, the oxidation process is virtually a slow
oxidation process along with the simultaneous pseudo steady-state actions of the direct oxidation,
precipitation and dissolution of oxides. Compared with the outer layer of the films in high
temperature water, the inner layer is relatively compact, which is probably formed by solid-state
reaction processes[39,40]. The oxides dissolute and grow at the same time on the surface of each oxide
particle in high temperature water. The dissolved ions are precipitated as the outer particles due to
their oxidation[21]. Based on Fig. 4, a schematic drawing of the double-layer oxide films on 304 SS in
different conductivity solutions at 300 C is shown in Fig. 12. When the conductivity is relatively low,
the high resistance of oxide inhibits the diffusion process of metal ions toward oxide/solution
interface. Thus only oxide particles with a small size are formed through the precipitation of
dissolved ions at the outer layer (Fig. 4(a)). As the conductivity increases, the protectiveness of inner
oxides becomes poor and the diffusion process is promoted, and the size of precipitated oxide
particles at the outer layer of oxide films becomes bigger (Fig. 4(b)). According to Fig. 11, which
shows that Fe3O4 is the main phase of the outer oxide films formed in 3# solution, Fe3O4 is possibly
formed by the following equilibrium equation[14]:
10

Page 10 of 20

3Fe

4H 2O Fe 3O 4 6H H 2

(11)

As the conductivity continues to increase, the increased diffusion channels due to pores in the oxide
layer further promote the diffusion of metal ions (e.g. Fe2+)[41]. Therefore, it can be inferred that the
tendency of Fe3O4 formation increases, leading to more nucleation sites on the surface of oxides.
And more nucleation sites can make the size of oxide particles become smaller, which is also
consistent with the SEM image in Fig. 4(c).
The increase of conductivity has a bad effect on corrosion resistance of 304 SS and other
structural materials. In order to obtain a target 10B isotope content, a proper method is to improve the
10

B enrichment level and decrease the total concentrations of H3BO3 and LiOH in primary water at

the same time. This method will contribute to reducing the conductivity of the primary water and
increasing the corrosion resistance of 304 SS and other structural materials based on the above
results.

5. Conclusions

(1) The structures of oxide films formed on 304 SS change with different conductivities at 300 C.
The oxide films are composed of a mixture Fe3O4 and FeCr2O4 spinel oxides. As the conductivity
increases, the passive current density increases and the resistances of oxide films decrease.
(2) The resistances of oxide films do not decrease lineally with the increase of conductivity in high
temperature water; when the conductivity is lower than 164.3 S/cm, a slight increase in
conductivity causes an obvious change of the resistances of oxide films while further increase in
conductivity shows little effect on reducing the resistances of films.
(3) A modified model with double-layer oxide structure is proposed to interpret the influence
mechanism of conductivity in high temperature water. The increase of conductivity directly
influences the diffusion process and the oxide structure. And the protectiveness of oxide films
decreases with the increase of conductivity in high temperature water.
(4) Improving the

10

B enrichment level can reduce the conductivity of primary water in PWR and

enhance the corrosion resistance of 304 SS.

11

Page 11 of 20

Acknowledgements
This work was jointly supported by the National Key Science and Technology Project of China
(No. 2011ZX06004-017) and the National Natural Science Foundation of China (No. 51025104).

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13

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[41] F. Huang, Corrosion behavior of Alloys 690 and 800 in Simulated Environments of Pressurized
Water Reactor, Ph.D. Thesis, Chinese Academy of Sciences, Shenyang, 2013 (in Chinese).

Table Captions
Table 1 Compositions of testing solutions and the corresponding pH values and conductivities at
300 C
Table 2 Fitting results for 304 SS in different solutions at 300 C

Figure captions
Fig. 1. Evolution of OCP for 304 SS in different solutions at 300 C.
Fig. 2. Potentiodynamic polarization curves for 304 SS in different solutions at 300 C.
Fig. 3. EIS data for 304 SS in different solutions at 300 C: (a) Bode diagram, (b) Nyquist diagram.
Fig. 4. SEM photographs of oxide films on 304 SS in different solutions at 300 C: (a) 1#, (b) 2#, (c)
3#.
Fig. 5. XRD patterns of oxide films on 304 SS in different solutions at 300 C.
Fig. 6. XPS depth profiles of the oxide films on 304 SS in different solutions at 300 C: (a) 1#, (b)
3#.
Fig. 7. Evans diagram used to interpret the influence of conductivity on change of OCP.
Fig. 8. Equivalent circuit used in the present study.
Fig. 9. Change in R1 and R2 as a function of conductivity for the oxide films on 304 SS at 300 C.
Fig. 10. Potential-pH diagrams for Ni, Cr, and Fe at 300 C[38].
Fig. 11. Atomic percent of Fe oxide to total metal oxides (Fe/(Fe + Cr), = 0.29) in the oxide
films on 304 SS in different solutions at 300 C.
Fig. 12. Schematic drawing of the double-layer oxide model on 304 SS in different solutions at
300 C.

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Table 1 Contents of different solutions and the corresponding pH values and conductivities at 300 C
Solution

Li (ppm)

pH300

(S/cm)

1#

0.56

7.29

113.88

2#

50

0.72

7.29

125.31

3#

200

1.24

7.29

164.34

4#
Notes: a,b

B (ppm)

Conductivity300b

480

2.3

7.29

242.64

pH300 and Conductivity300 of testing solutions are calculated by a commercial

software pHSC4.

Table 2 Fitting results for 304 SS in different solutions at 300 C

Rs ( cm2) R1 ( cm2)
1#

1436.7

2#

1882.2

1154.4

CPE1 (mS
s-n)

n1

R2 (

CPE2 (nS

cm2)

s-n)

n2

5.35

0.60

4768.6

30.6

0.89

7.09

0.61

2336.7

21.4

0.88

9.61

0.65

1478.4

34.9

0.91

6.83

0.53

972.2

16.2

0.95

497.4
3#

848.7
328.9

4#

597.9

307.1

15

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Figure List

Fig. 1

Fig. 2

16

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Fig. 3

Fig. 4

Fig. 5

17

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Fig. 6

Fig. 7

Fig. 8

18

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Fig. 9

Fig. 10

Fig. 11

19

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Fig. 12

20

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