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Contents lists available at ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Properties of oxide films formed on 316L SS and model alloys with

modified Ni, Cr and Si contents in high temperature water
Guangdong Han a , Zhanpeng Lu a,b,∗ , Xiangkun Ru a , Junjie Chen a , Jinlong Zhang a ,
Tetsuo Shoji c
a
Institute of Materials, School of Materials Science and Engineering, Shanghai University, 149 Yanchang Road, P.O. Box 269, Shanghai 200072, China
b
State Key Laboratory of Advanced Special Steels, Shanghai University, 149 Yanchang Road, P.O. Box 269, Shanghai 200072, China
c
New Industry Creation Hatchery Center, Tohoku University, 6-6-10 Aramaki Aoba, Aoba-ku Sendai 980-8579, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Oxide films formed on 316L stainless steel, 9Cr–26Ni–1.5Mo, and 9Cr–26Ni–1.5Mo–5Si in de-aerated high
Received 16 August 2015 temperature water have been characterized. High reactivity of Si and high solubility of silicon oxides in
Received in revised form 31 January 2016 high temperature water contribute to Si depletion in the outer oxide layer, Si enrichment in the inner
Accepted 1 February 2016
oxide layer near the metal/oxide interface, and the outer layer of large and continuously packed oxides
Available online xxx
with cavities. A higher Cr content in the alloys favors the formation of a thinner inner oxide layer. Si in
the model alloy affects the distribution of nickel oxide near the metal/oxide interface.
Keywords:
© 2016 Elsevier Ltd. All rights reserved.
A. Stainless steel
B. TEM
B. XPS
C. Oxidation
C. Reactor conditions

1. Introduction Neutron irradiation can cause depletion of Cr and Fe at the grain

Austenitic stainless steels, commonly used as in-core materials
of nuclear power reactors, are susceptible to irradiation-assisted
stress corrosion cracking (IASCC), which is a critical issue for
the safe and economical operation of light water reactors. The
elevated cracking susceptibility is attributed to both irradiation
damage in austenitic stainless steel and the aggressive environ-
ment of the reactor coolants under irradiation. Irradiation can
cause microstructural changes (dislocation loops, precipitate, and
void formation) and microchemical changes (radiation-induced
segregation of solute elements), and these micro-scale changes
enhance the susceptibility to intergranular stress corrosion crack-
ing (IGSCC) [1,2]. Radiation-induced segregation (RIS) at the grain
boundaries in austenitic stainless steels is an important factor
that contributes to IASCC [1,3–5]. RIS results in local composition
changes at grain boundaries and thereby affects the corrosion resis-
tance of austenitic stainless steels [6–8].
∗ Corresponding author at: Institute of Materials, School of Materials Science
and Engineering, Shanghai University, 149 Yanchang Road, P.O. Box 269, Shanghai
200072, China. Fax: +86 2156332475.
E-mail addresses: zplu@t.shu.edu.cn, zplu@t.shu.edu.cn (Z. Lu).
boundaries, along with enrichment of Ni and Si [3–5,9,10]. Bruem-
mer [10] has suggested that the Cr content at the grain boundaries
decreased to 8–10 wt.% and the Si and Ni contents increased to
6 wt.% and 30 wt.%, respectively, in several 300-series irradiated
in LWRs at 300–320 ◦ C up to 65 dpa. The low grain boundary Cr
content may affect the formation of passive film, increasing the
susceptibility to corrosion [5]. The increased susceptibility to IASCC
in highly irradiated stainless steels is closely related to the segre-
gation of Si at the grain boundaries. Was et al. [11] have reported
the high susceptibility to IASCC propagation in high Si alloys. Stain-
less steels with 3–5 wt.% Si exhibit high crack growth rates in high
temperature water environments [12]. Li et al. [13] reported that Si
increases stress corrosion cracking (SCC) susceptibility, and they
proposed three possible mechanisms to explain the Si effect on
environmentally-assisted crack (EAC) behavior. Three mechanisms
proposed by Li et al. are: (1) Si may lower the stacking fault energy,
and therefore facilitating the coplanar dislocation slip and ruptur-
ing the oxide film, (2) Si may decrease the strength of the oxide film,
(3) Si may increase the oxidation tendency of grain boundaries since
Si readily oxidizes. However, Jacobs [14] reported that grain bound-
ary Si enrichment has little impact on IASCC. Fukuya et al. [15]
and Chung et al. [16] found that commercial alloys with higher Si
contents are less susceptible to IG cracking than high-purity alloys
irradiated under the similar conditions.

http://dx.doi.org/10.1016/j.corsci.2016.02.001
0010-938X/© 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: G. Han, et al., Properties of oxide films formed on 316L SS and model alloys with modified Ni, Cr and
Si contents in high temperature water, Corros. Sci. (2016), http://dx.doi.org/10.1016/j.corsci.2016.02.001
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Table 1
Chemical compositions of the test alloys (wt.%).
Material C Si Mn
316L SS 0.020 0.54 1.28
9Cr–26Ni–1.5Mo 0.026 0.35 0.65
9Cr–26Ni–1.5Mo–5Si 0.023 4.54 0.60
The changes of chemical composition at the grain boundary can
affect the oxidation behavior of austenitic stainless steel in high-
temperature water. The properties of the oxide film formed during
service, including the chemical composition, microstructure and
thickness, play important roles in the cracking process, especially
at the initial stages [17,18]. The oxides at the crack tips are rele-
vant to those formed on the alloy surfaces in simulated pressurized
water reactor (PWR) primary water environments, suggesting that
investigation of surface oxides could benefit further elucidating SCC
mechanisms [19]. The objective of this work is to identify the effect
of the chemical composition changes, such as the depletion of Cr
and enrichment of Ni and Si as the simulation of RIS, on the oxi-
dation behavior of alloys in high-temperature water. The present
work investigates the morphologies, cross-section characteristics
and chemical composition of the oxide films grown on 316L SS
and model alloys exposed to high-temperature water for 114 h and
1194 h. Raman spectroscopy, X-ray photoelectron spectroscopy
(XPS), scanning electron microscopy (SEM), and transmission elec-
tron microscopy (TEM) are used as the characterization methods.
2. Experimental
2.1. Material and specimen preparation
The measured chemical compositions of 316L SS and model
alloys are shown in Table 1. The model alloys were made by addi-
tions of pure Ni, Fe and Si in 316L SS, which had a lower Mo
content than that of 316L SS. The model alloy 9Cr–26Ni–1.5Mo
was used to simulate the depletion of Cr and enrichment of
Ni, and model alloy 9Cr–26Ni–1.5Mo–5Si was used to simulate
the depletion of Cr and enrichment of Ni and Si at the grain
boundaries of irradiated austenitic stainless steel. The Mo con-
tents in the model alloys were lower than in 316L SS, which was
not considered critical in evaluating the difference in oxidation
behavior in the present work. Model alloys 9Cr–26Ni–1.5Mo and
9Cr–26Ni–1.5Mo–5Si were hot-forged and hot-rolled into sheets at
1100 ◦ C in the same way. The alloy sheets were solution-annealed at
1100 ◦ C for 20 min and were then quenched in water. Rectangular
specimens (length × width × thickness = 10 mm × 5 mm × 2.5 mm)
were cut from the 316L SS and model alloy sheets. The specimens
were mechanically ground with waterproof abrasive paper up to
2000 grit successively.
Field-emission SEM (FESEM; Apollo 300) along with electron
backscattering diffraction (EBSD) was used to characterize the grain
boundary characteristics of the model alloys. To reduce the residual
stress and strain on the surface, electropolishing was performed
in 20% HClO4 + 80% CH3 COOH electrolyte (vol.%) following pol-
ishing with 1 ␮m diamond paste. The acceleration voltage of the
FESEM beam for the EBSD measurement was 20 kV. The inverse
pole figures (IPF) are shown in Fig. 1. The measured grain size
took into account the twins. The average grain size of the 316L
SS, 9Cr–26Ni–1.5Mo and 9Cr–26Ni–1.5Mo–5Si was approximately
19.1, 9.7, and 19.1 ␮m with the present measurement parame-
ters, respectively. Grain boundaries with rotation angles between
15–180◦ were defined as random grain boundaries (RGB). The
grain boundaries shown
 in Fig. 2 indicated  that the grain bound-
aries were mainly 3 and RGB, and the 3 fractions of 316L
Please cite this article in press as: G. Han, et al., Properties of oxide films formed on 316L SS and model alloys with modified Ni, Cr and
Si contents in high temperature water, Corros. Sci. (2016), http://dx.doi.org/10.1016/j.corsci.2016.02.001
P S Cr Ni Mo Fe
0.014 0.004 17.21 12.46 2.45 Bal.
0.020 0.013 9.29 26.12 1.54 Bal.
0.021 0.018 9.15 26.41 1.47 Bal.
Table 2
Test conditions employed for the oxidation of 316L SS and model alloy specimens
in simulated PWR primary water.
Parameters Range
Water chemistry 1200 ppm (by weight) B in boric acid + 2 ppm
(by weight) Li in lithium hydroxide
Temperature 310 ± 0.5 ◦ C
Pressure 12 MPa
Dissolved oxygen (DO) <5 ppb (by weight)
Dissolved hydrogen (DH) <0.5 ppb (by weight)
Flow rate 5L/h
SS, 9Cr–26Ni–1.5Mo and 9Cr–26Ni–1.5Mo–5Si were about 54.5%,
58.4%, and 46.3%, respectively.
2.2. Immersion tests in high-temperature water
The specimens were exposed to simulated PWR primary water
with boric acid and lithium hydroxide for 114 h and 1194 h in a 5-L
(net volume) stainless steel autoclave equipped with a recircula-
tion loop fabricated by Toshin Kogyo, Co., Ltd. All the test specimens
were mounted vertically at the locations close to the center of the
autoclave. The test conditions are summarized in Table 2. The test
solution in Table 2 is called de-aerated PWR primary water, which
is used for the immersion tests to simulate environments with rela-
tively high oxidizing potentials under the irradiation and the crack
tip environments. To reduce the metallic cations released from the
autoclave body during the immersion tests, the autoclave was at
first tested under similar conditions with the same water chem-
istry. After each test, the used PWR water was removed and new
PWR water was prepared for the new test.
2.3. Surface characterization of the tested specimens
After the immersion tests in high-temperature water environ-
ments, the surface morphologies of oxide films formed on the
immersed specimens were examined using FESEM operated at
15 kV. The oxide films were analyzed using an INVIA laser Raman
spectrometer with laser wavelength of 514.5 nm. XPS measure-
ments were performed on an ESCALAB 250Xi X-ray photoelectron
spectrometer using a monochromatic Al K␣ source. Depth profil-
ing was performed over an area of 2.5 mm × 2.5 mm, and spectra
were collected within a 500-␮m spot. The sputtering rate was set
at 0.25 nm/s with reference to the Ta2 O5 layer.
Detailed cross-section characteristics were studied using a
transmission electron microscope (TEM). Thin-foil specimens for
TEM observations were prepared using a 600i dual-beam focused
ion beam (DB-FIB) with Ga ion sputtering after a protective Pt
layer was deposited on the oxide scale. Large oxide particles were
avoided during the TEM specimen preparation by FIB. Hence, large
oxide particles were not examined and were absent from the TEM
images. High-resolution TEM observations and selected area elec-
tron diffraction (SAED) were performed with a JEM 2010F TEM
instrument operated at 200 kV and equipped with an energy-
dispersive spectroscopy (EDS) system. The K-series was used for
the TEM–EDS analysis.
High angle annular dark field (HAADF) contrast is proportional
to the average atomic number, assuming constant thickness and
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Fig. 1. IPFs of the 316L SS and model alloy specimens. (a) 316L SS, step size = 4 ␮m, (b) 9Cr–26Ni–1.5Mo, step size = 2 ␮m, and (c) 9Cr–26Ni–1.5Mo–5Si, step size = 4 ␮m.

Fig. 2. Grain boundary characteristics of the 316L SS and model alloys. (a) 316L SS, (b) 9Cr–26Ni–1.5Mo and (c) 9Cr–26Ni–1.5Mo–5Si.

Please cite this article in press as: G. Han, et al., Properties of oxide films formed on 316L SS and model alloys with modified Ni, Cr and
Si contents in high temperature water, Corros. Sci. (2016), http://dx.doi.org/10.1016/j.corsci.2016.02.001
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Fig. 3. SEM morphologies of the oxide films formed on 316L SS and model alloys exposed to the simulated PWR primary water at 310 ◦ C for 114 h. (a) 316L SS, (b)
9Cr–26Ni–1.5Mo, and (c) 9Cr–26Ni–1.5Mo–5Si.
Fig. 4. Raman spectra of the oxide films formed on 316L SS and model alloys exposed
to the simulated PWR primary water at 310 ◦ C for 114 h.
density, the intensity in the HAADF images is proportional to the
average Z [20]. In the present work, oxides are darker than the
matrix in the STEM-HAADF images of the oxide film.
3. Results
3.1. Immersion for 114 h
Fig. 3 shows the SEM morphologies of the 316L SS,
9Cr–26Ni–1.5Mo and 9Cr–26Ni–1.5Mo–5Si surfaces after immer-
sion in the PWR primary water at 310 ◦ C for 114 h. Sparsely
distributed polyhedral oxide particles were formed on both 316L
SS and 9Cr–26Ni–1.5Mo surfaces, the size of the outer-layer oxide
Please cite this article in press as: G. Han, et al., Properties of oxide films formed on 316L SS and model alloys with modified Ni, Cr and
Si contents in high temperature water, Corros. Sci. (2016), http://dx.doi.org/10.1016/j.corsci.2016.02.001
particles was inhomogeneous with the large ones dispersed on the
surface and the small ones developing from the subsurface layer. In
contrast, the 9Cr–26Ni–1.5Mo–5Si specimen surface was fully cov-
ered by large and continuously packed oxide particles with some
cavities.
Fig. 4 shows the Raman spectra of the oxide films formed on 316L
SS and model alloys exposed to the simulated PWR primary water
at 310 ◦ C for 114 h. Table 3 shows the Raman shifts of Raman spectra
peaks. The Raman peaks at 298, 320, 420, 472, 550, and 676 cm−1
are characteristics of Fe3 O4 , whereas the Raman peaks at 215, 490,
579, and 700 cm−1 are characteristics of NiFe2 O4 [21]. FeCr2 O4 is
responsible for the Raman peaks at 500 and 685 cm−1 , and NiCr2 O4
is responsible for the Raman peaks at 512 and 686 cm−1 [21]. The
Raman spectra of the oxide film formed on the 316L SS specimen
exhibited strong signals of Fe3 O4 , whereas the oxide film formed
on the 9Cr–26Ni–1.5Mo specimen exhibited the strong signals of
NiFe2 O4 . Both Fe3 O4 and NiFe2 O4 were detected in the oxide films
formed on the 9Cr–26Ni–1.5Mo–5Si specimen.
Fig. 5 shows the XPS depth profiles of the oxide films formed
on 316L SS, 9Cr–26Ni–1.5Mo, and 9Cr–26Ni–1.5Mo–5Si exposed
to the de-aerated, simulated PWR primary water at 310 ◦ C for
114 h. The oxide film formed on 9Cr–26Ni–1.5Mo was consider-
ably thicker than that formed on 316L SS, as shown in Fig. 5a and
b. For 316L SS and 9Cr–26Ni–1.5Mo, the signals generated at the
initial stage of sputtering could come from both the outer and the
inner oxide films, as shown in Fig. 3. 9Cr–26Ni–1.5Mo–5Si speci-
men surface was fully covered by large and densely packed outer
layer oxide particles, and the signals generated at the initial stage
of sputtering were thought to be mainly come from the outer oxide
film rich in Fe. With increasing the sputtering time, the Fe content
at first decreased and then gradually increased to values similar to
that in the matrix. The oxygen content profiles were related to the
difference of outer and inner layer oxides.
Fig. 6 shows the XPS spectra of O1s, Cr2p3/2, Fe2p3/2, Ni2p3/2
and Si2p for the oxide film formed on the 9Cr–26Ni–1.5Mo–5Si
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Table 3
The Raman shifts of Raman spectra peaks of the oxide films formed on 316L SS and model alloys exposed to the simulated PWR primary water at 310 ◦ C for 114 h.

Alloys Raman shift (cm−1 )

316L SS 319 466 547 680

9Cr–26Ni–1.5Mo 332 487 580 696
9Cr–26Ni–1.5Mo-5Si 324 478 566 685

100 sputtering [26,27]. The signals of Cr0 and Fe0 were not detected

80
a O1s
Fe2p
after 3000 s of sputtering, and only weak signals were detected
after 3600 s of sputtering. The signals generated before 3600 s of
Atomic percent (at%)

Cr2p sputtering mainly came from the oxide film. The Si2p characteristic
60 Ni2p peak signals were not detected before 3600 s of sputtering, indicat-
ing that the Si in the oxides formed on the 9Cr–26Ni–1.5Mo–5Si
40 specimen was too low to be detected. No characteristic peak sig-
nals corresponding to SiO2 (103.6 eV) were identified during XPS
20 profiling [28,29].
Peak shape and peak binding energy is useful for the identifi-
0 cation of relatively pure iron oxides. Biesinger et al. [30] reported
0 200 400 600 800 1000 1200 1400 1600
Sputtering time (s) the fitting parameters for Fe 2p3/2 spectral binding energy: Fe3 O4
100 (Fe2+ ), 708.4 and 709.2 9 eV; Fe3 O4 (Fe3+ ), 710.2, 711.2, 712.3, 713.4

80
b O1s
Fe2p
and 714.5 eV; FeCr2 O4 : 709.0, 710.3, 711.2, 713.0 and 713.8 eV;
NiCr2 O4 , 709.5, 710.7, 712.2 and 713.7 eV. McIntyre and Zetaruk
Atomic percent (at%)

Cr2p [31] reported that the binding energies of major core lines in Fe3 O4
60 Ni2p (Fe2+ ) and NiFe2 O4 were 708.3 ± 0.15 and 710.6 ± 0.2 eV. The oxide
film was inhomogeneous thus the signals generated during sput-
40 tering could come from both the outer and the inner oxide films. In
the present work, the oxides formed on 316L SS and model alloys
20 were complex and mixed metal oxides, which were mainly spinel-
type oxides Fex Cry Niz O4 . The exactly chemical states of Fe2p3/2
0 were complicated. The changes of Fe2p spectra were emphasized,
0 600 1200 1800 2400 3000 3600 4200 and 711 eV related to Fe+3 as well as 709 eV related to Fe2+ was
Sputtering time (s)
marked as reference.
100

80
c O1s
3.2. Immersion for 1194 h
Atomic percent (at%)

Fe2p
Cr2p
60 Ni2p
40
20
0 9Cr–26Ni–1.5Mo–5Si specimen surface was fully-covered by large
0 900 1800 2700 3600 4500 5400 6300
Sputtering time (s)
Fig. 5. Composition profiles in the depth of the oxide films formed on 316L SS and
model alloys exposed to the simulated PWR primary water at 310 ◦ C for 114 h. (a)
316L SS, (b) 9Cr–26Ni–1.5Mo, (c) 9Cr–26Ni–1.5Mo–5Si.
specimen after 114 h immersion. In the Cr2p3/2 spectra (Fig. 6b),
the peak at approximately 576.7 eV was assigned to Cr3+ [22,23].
In the Fe2p3/2 spectra (Fig. 6c), the main peak at approximately
711 eV was assigned to Fe3+ , and the peak at approximately 709 eV
was from Fe2+ [24]. Two different chemical states were detected in
the Ni2p3/2 spectra: the peak at 853 eV was assigned to metallic Ni0
and the peak at 855.3 eV was assigned to Ni2+ [22,23]. After approx-
imately 600 s sputtering, no signals corresponding to Cr2p were
generated due to the lower Cr content in the outer layer. However,
strong signals corresponding to Ni0 were detected after 600 s sput-
tering, and the peak decomposition of Ni2p3/2 was similar to that
after 3600 s. Ni-containing oxides are stable in the de-aerated, sim-
ulated PWR primary water according to the potential-pH diagram
of Ni–H2 O at 300 ◦ C [25]. However, Ni-containing oxides is very sus-
ceptible to reduction by ion bombardment during XPS profiling, so
the detected Ni0 might be reduced from Ni2+ during the argon ionic
Fig. 7 shows the morphologies of the oxide films formed
on 316L SS, 9Cr–26Ni–1.5Mo and 9Cr–26Ni–1.5Mo–5Si after
immersion in the simulated PWR primary water for 1194 h. The
oxide films formed on 316L SS and 9Cr–26Ni–1.5Mo specimens
were composed of polyhedral oxides, and the specimen surfaces
were not fully covered by the outer layer oxide particles. The
and continuously packed oxide particles with some cavities. The
average size of the outer oxide particles formed on 316L SS was
smaller than that of 9Cr–26Ni–1.5Mo, as shown in Figs. 3 and 7,
which was consistent with the observation on the surfaces of 316
SS and tailored alloys with various Cr contents from 5 to 20% after
immersion in high-temperature hydrogenated water [19].
Fig. 8 shows the Raman spectra of the surface films formed on
316L SS, 9Cr–26Ni–1.5Mo and 9Cr–26Ni–1.5Mo–5Si after immer-
sion for 1194 h. Table 4 shows the Raman shifts of Raman
spectra peaks. Similar to the results of immersion for 114 h, the
Raman spectra of the oxide film formed on the 316L SS and
9Cr–26Ni–1.5Mo–5Si specimens exhibited the strong signals of
Fe3 O4 and the oxide film formed on the 9Cr–26Ni–1.5Mo specimen
exhibited the strong signals of NiFe2 O4 .
Figs. 9–12 show the TEM results of the oxide films formed on
316L SS exposed to the simulated PWR primary water for 1194 h.
As mentioned previously, the high angle annular dark field (HAADF)
contrast is proportional to the average atomic number, and the
oxides are darker than the matrix in the STEM-HAADF images. Fig. 9
shows the duplex structure of the oxide film formed on 316L SS.
The outer layer was composed of discontinuous and large oxide
grains, whereas the inner layer was composed of dense and fine
oxide grains. The thickness of the inner layer determined by TEM

Please cite this article in press as: G. Han, et al., Properties of oxide films formed on 316L SS and model alloys with modified Ni, Cr and
Si contents in high temperature water, Corros. Sci. (2016), http://dx.doi.org/10.1016/j.corsci.2016.02.001
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3+
a O
2-
c Fe Fe2+

Intensity (arbitrary units)

Intensity (arbitrary units)

0
Fe

600 s
600 s
3600 s
3600 s
6000 s
6000 s

536 534 532 530 528 526 730 725 720 715 710 705 700
Binding energy (eV) Binding energy (eV)
0
b Cr
3+ d Ni

Intensity (arbitrary units)

Intensity (arbitrary units)

2+
0
Ni
Cr 600 s

600 s
3600 s
3600 s
6000 s
6000 s

595 590 585 580 575 570 875 870 865 860 855 850 845
Binding energy (eV) Binding energy (eV)
0
e Si
Intensity (arbitrary units)

6000 s
5400 s

4800 s
4200 s
3600 s
2400 s
600 s

104 102 100 98 96

Binding energy (eV)
Fig. 6. (a) O1s core level spectra, (b) Cr2p3/2 core level spectra, (c) Fe2p3/2 core level spectra, (d) Ni2p3/2 and (e) Si2p core level spectra after different sputtering periods
of oxide film formed on 9Cr–26Ni–1.5Mo–5Si exposed to the simulated PWR primary water at 310 ◦ C for 114 h.

Table 4
The Raman shifts of Raman spectra peaks of the oxide films formed on 316L SS and model alloys exposed to the simulated PWR primary water at 310 ◦ C for 1194 h.

Alloys Raman shift (cm−1 )

316L SS 310 468 551 681

9Cr–26Ni–1.5Mo 329 473 570 689
9Cr–26Ni–1.5Mo–5Si 322 470 563 681

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Fig. 7. SEM morphologies of the oxide films formed on 316L SS and model alloys exposed to the simulated PWR primary water at 310 ◦ C for 1194 h. (a) 316L SS, (b)
9Cr–26Ni–1.5Mo, (c) 9Cr–26Ni–1.5Mo–5Si.

Table 5
Chemical compositions of the outer layer oxide particles shown in Figs. 9, 13 and 20 by TEM–EDS. The scatter band is the standard deviation of measurement over five
different positions of outer oxides.

Fe (at%) Cr (at%) Ni (at%) O (at%) Si (at%)

316L SS 71.55 ± 4.0 1.63 ± 0.64 3.33 ± 0.93 22.38 ± 5.19 1.12 ± 0.36
9Cr–26Ni–1.5Mo 54.52 ± 2.66 0.60 ± 0.28 15.29 ± 1.48 28.75 ± 2.61 0.85 ± 0.21
9Cr–26Ni–1.5Mo–5Si 45.85 ± 3.81 0.66 ± 0.21 18.43 ± 0.15 30.32 ± 3.52 2.04 ± 0.24

Fig. 9. STEM-HAADF image of the oxide film formed on 316L SS exposed to the
simulated PWR primary water at 310 ◦ C for 1194 h.

Fig. 8. Raman spectra of the oxide films formed on 316L SS and model alloys exposed
to the simulated PWR primary water for 1194 h at 310 ◦ C.
was approximately 100 nm. The EDS area mapping of the oxide
film shown in Fig. 10 indicated that the outer layer was Fe-rich and
the inner layer was Cr-rich, which was consistent with the results
of the EDS line scan profiles of the oxide film shown in Fig. 11b.
The TEM–EDS results of the outer oxide particles are shown in
Table 5. The diffraction pattern of the outer layer oxides shown
in Fig. 12b indicated that these oxide particles had the spinel-
type crystal structure, and were likely (Ni, Fe) Fe2 O4 , which was

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Fig. 10. STEM-HAADF image and corresponding EDS mappings (acquisition time = 125.9 s) of the rectangular region for the Cr, Ni, Fe, O, and Si of the oxide film formed on
316L SS after exposure to the simulated PWR primary water at 310 ◦ C for 1194 h.

Fig. 11. (a) STEM-HAADF image of the oxide film formed on 316L SS after 1194 h immersion in the simulated PWR primary water, (b) EDS line scan profiles (acquisition
time = 30 s) shown in (a) along the white line.

Fig. 12. (a) TEM cross-sectional micrograph of the oxide film formed on 316L SS exposed to the simulated PWR primary water at 310 ◦ C for 1194 h, (b) the electron diffraction
patterns of region I shown in (a).

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Fig. 13. STEM-HAADF image of the oxide film formed on 9Cr–26Ni–1.5Mo after
exposure to the simulated PWR primary water at 310 ◦ C for 1194 h.
consistent with the Raman result shown in Fig. 8. The EDS line scan
profiles of the oxide film indicated that the content of Cr was much
higher than Fe and Ni, as shown in Fig. 11b. Ni was enriched near
the oxide/metal interface, which was confirmed in the EDS line scan
profiles of the oxide film.
Figs. 13–19 show the TEM results of the oxide film formed on
9Cr–26Ni–1.5Mo exposed to the simulated PWR primary water for
1194 h. A duplex oxide film was formed on the 9Cr–26Ni–1.5Mo
specimen surface after immersion for 1194 h, as shown in Fig. 13.
Table 5 shows that the outer oxide formed on the 9Cr–26Ni–1.5Mo
specimen surface had a higher content of Ni and a lower content of
Cr than that on the 316L SS specimen. The inner oxide film was inho-
mogeneous, and its thickness, as determined by TEM, ranged from
160 to 700 nm. There were some darker areas (such as area I shown
in Fig. 13) in the inner oxide film. Fig. 16a shows that the darker
areas in the oxide film shown in the STEM-HAADF images were
composed of porous granular oxide. High resolution TEM images
of the dark (granular) zones exhibited lattice fringes, as shown in
Fig. 16c. Images of selected area electron diffraction exhibited poly-
crystalline characteristics, as shown in Fig. 16b, and the dark field
images also indicated the presence of crystals.
There were several factors that could cause the occurrence of
the dark zones in the STEM-HAADF images, such as the chemical
compositions and the quantity of the existing oxides. TEM obser-
vations show that the dark zones were typical granular regions, as
shown in Figs. 16 a and 19 a. Results of TEM–EDS line scan profiles
show that the Fe contents in the dark zones were lower than those
in the relatively bright zones, as shown in Fig. 15a. The contrast of
the TEM–EDS Cr mapping did not show any significant decrease in
the dark zones, as shown in Fig. 14. These results indicated that the
local chemical composition would contribute to the observed dark
zones.
The EDS area mappings shown in Fig. 14 indicated that there was
a Ni-enriched thin layer, which also was confirmed by the EDS line
scan profiles of the oxide film cross-section shown in Fig. 15a. How-
ever, the Ni enrichment layer was not continuous. Fig. 13 shows that
the inner oxide film just beneath the Ni enrichment regions was
thinner than that beneath the regions without Ni enrichment. The
EDS area mappings shown in Fig. 17 showed that Ni enriched adja-
cent to some oxide/metal interfaces, which was consistent with the
results of the EDS line scan profiles of the oxide film cross-section
shown in Fig. 18b.
Fig. 19 shows the micrograph and electron diffraction patterns
of region II shown in Fig. 13. For the inner layer of the oxide film,
the atomic percents of Fe, Ni and Cr were not stoichiometric and
it was difficult to deduce the exact chemical formula of the oxide.
The Cr content in the inner layer formed on 9Cr–26Ni–1.5Mo was
much lower than that of 316L SS. Fig. 19b and c shows the electron
diffraction patterns of the designated area in TEM image (Fig. 19a),
indicating that both inner and outer oxides had the spinel-type
crystal structure Fex Niy Crz O4 .
Figs. 20–24 show the TEM results of the oxide film formed
on 9Cr–26Ni–1.5Mo–5Si exposed to the simulated PWR pri-
mary water at 310 ◦ C for 1194 h. The cross-sectional morphology
shown in Fig. 20 indicated that the oxide film formed on
9Cr–26Ni–1.5Mo–5Si had a duplex layer structure: outer-layer,
large oxide particles covered the specimen surface and the inner
layer was composed of fine oxides. The outer-layer oxides were
inhomogeneous, and the thickness of the inner layer was thinner
beneath the larger oxide particles. The thickness of the inner layer
determined by TEM ranged from 100 to 420 nm. The inner oxide
film close to oxide/metal interface was darker than the common
inner oxide film in the STEM-HAADF image, as shown in Figs. 20–22.
The EDS mappings shown in Figs. 21 and 22 indicated that Fe and Ni
were depleted in the inner oxide film close to oxide/metal interface,
which was confirmed by the EDS line scan profiles of the oxide film
shown in Fig. 23b. The TEM–EDS microanalysis, as shown in Table 6,
indicated that the inner oxide film close to oxide/metal interface
(region I) had higher contents of Si and O and lower contents of
Ni and Fe than the common oxide film, like region II. The electron
diffraction patterns shown in Fig. 24b and c indicated that both the
outer layer oxides and the inner layer oxides had the spinel-type
Fex Niy Crz O4 crystal structure.
4. Discussion
The oxide films formed on 316L SS, 9Cr–26Ni–1.5Mo and
9Cr–26Ni–1.5Mo–5Si after exposure to the simulated PWR primary
water at 310 ◦ C for 1194 h have a duplex structure, as shown in
Figs. 9, 13 and 20. TEM analysis shows that the outer layer oxides
formed on 316L S, 9Cr–26Ni–1.5Mo and 9Cr–26Ni–1.5Mo–5Si are
(Ni, Fe) Fe2 O4 .
Si in the model alloy affects both the chemical composition
profile and the surface morphology of the oxide film. After expo-
sure to the simulated PWR primary water at 310 ◦ C for 114 h
and 1194 h, the 316L SS and 9Cr–26Ni–1.5Mo specimen surfaces
are covered by dispersed faceted oxide particles, whereas the
9Cr–26Ni–1.5Mo–5Si surface is covered by large, continuously
packed oxide particles with cavities. The large oxide particles
on 9Cr–26Ni–1.5Mo–5Si specimen may not mainly deposit from
the metallic cations released from autoclave body corrosion
because they are not observed on the surfaces of 316L SS and
9Cr–26Ni–1.5Mo in the same immersion experiments. According
to the thermodynamic data from HSC software [32], the change
of standard Gibbs free energy for the reaction of Si with water at
310 ◦ C is calculated to be −415.69 kJ/mol (equivalent to standard
electrode potential of −1.08 V(SHE)), taking G0 H2O (310 ◦ C) as
−193.99 kJ/mol and G0 SiO2 (310 ◦ C) as −803.67 kJ/mol, according
to Eq. (1). Si in the model alloy tends to react with high tempera-
ture water to form oxides and at the same time affects the oxidation
behavior of other metals. The solubility of silicon oxides in water
increases with increasing temperature from 0 ◦ C to about 310 ◦ C,
which is strongly affected by the forms of silicon oxides such as
amorphous silica quartz [33,34]. The solubility for amorphous sil-
ica in 310 ◦ C water varied in the range of about 1400 to 1800 mg/kg
[33,34], which is about a half or lower for quartz. Even though the
solubility of silicon oxide in PWR primary water could be different
from that in pure water, it is expected to be still high by referring the
effect of composition of high temperature solutions on solubility of
silicon oxide [33].
Si + 2H2 O = SiO2 + 2H2 (1)
Due to the high solubility of silicon oxides in high temperature
water, the oxidized silicon on the alloy surface can be dissolved

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Table 6
Chemical compositions of regions I and II shown in Fig. 21 by TEM–EDS. The scatter band is the standard deviation of measurement over five different positions of regions I
and II.

Fe (at%) Cr (at%) Ni (at%) O (at%) Si (at%)

Region I 17.35 ± 2.06 18.17 ± 0.99 8.74 ± 1.96 41.51 ± 2.62 14.22 ± 1.17
Region II 23.18 ± 3.27 17.18 ± 0.93 25.62 ± 1.63 31.77 ± 1.93 2.33 ± 0.41

in the solution during the immersion in PWR primary water. This
explains why silicon is depleted in the outer layer of the oxide film,
which has been shown by XPS results in Fig. 6 and TEM results in
Tables 5 and 6.
The HAADF images (Fig. 20) show that the inner oxide film close
to the interface between the oxide/matrix on 9Cr–26Ni–1.5Mo–5Si
is characterized by a lower average atomic number compared with
the common inner oxide film. The inner oxide beneath the interface
of the oxide/metal exhibits higher contents of O and Si and lower

Fig. 14. STEM-HAADF image and EDS mappings (acquisition time = 449 s) for Cr, Ni, Fe, O, and Si in the oxide film formed on 9Cr–26Ni–1.5Mo after 1194 h immersion in
simulated PWR primary water at 310 ◦ C.

a matrix b matrix
inner oxide inner oxide
outer O
oxide Fe O
Counts

Counts

Cr Fe
Ni Cr
Si Ni
Si

0 100 200 300 400 500 600 0 100 200 300 400 500 600 700 800 900
Position / nm Position / nm

Fig. 15. (a) EDS line scan profiles (acquisition time = 56 s) of the oxide film shown in Fig. 14 along the white line a, (b) EDS line scan profiles (acquisition time = 97 s) of the
oxide film shown in Fig. 14 along the white line b.

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Fig. 16. (a) TEM image and (b) electron diffraction pattern of region I shown in Fig. 13, (c) TEM image of circular region in (a).

Fig. 17. STEM-HAADF image and EDS mappings (acquisition time = 210 s) for Cr, Ni, Fe, O, and Si of the oxide film formed on 9Cr–26Ni–1.5Mo after 1194 h immersion in the
simulated PWR primary water at 310 ◦ C.

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Fig. 18. (a) STEM-HAADF image of the oxide film formed on 9Cr–26Ni–1.5Mo after 1194 h immersion in the simulated PWR primary water at 310 ◦ C and (b) EDS line scan
profiles (acquisition time = 81 s) of oxide film shown in (a) along the white line.

Fig. 19. TEM micrograph with electron diffraction patterns of the oxides formed on 9Cr–26Ni–1.5Mo exposed to the simulated PWR primary water at 310 ◦ C for 1194 h. (a)
TEM image, (b) the diffraction pattern of the oxides of region I shown in (a), and (c) the diffraction pattern of the oxides of region II shown in (a). The white dotted line in (a)
indicates the interface between the inner oxide film and the matrix.

Table 7
Experimental results of oxide film formed on 316L SS and model alloys exposed to the simulated PWR primary water at 310 ◦ C.

Alloys Outer oxide film Inner oxide film Near the interface of the oxide/metal

316L SS
Oxide shape: with straight edges and planar Thickness: about 100 nm Local Ni enrichment
faces Fe:Cr:Ni = 71.55:1.63:3.33 (at%)
9Cr–26Ni–1.5Mo Oxide shape: with straight edges and planar Thickness: 160–700 nm Local Ni enrichment
faces Fe:Cr:Ni = 54.52:0.60:15.29 (at%) Exist porous granular areas
9Cr–26Ni–1.5Mo–5Si Oxide shape: with curving edges, blunt angles Thickness: 100 −420 nm Si enrichment beneath the interface of
and some cavities Fe:Cr:Ni = 45.85:0.66:18.43 the oxide/metal
(at%)

contents of Fe and Ni than its surrounding areas, which is different

Fig. 20. STEM-HAADF image of the oxide film formed on 9Cr–26Ni–1.5Mo–5Si
exposed to the simulated PWR primary water at 310 ◦ C for 1194 h. The black dotted
line indicates the interface of the outer- and inner-layer oxide film.
from those on 316L SS and 9Cr–26Ni–1.5Mo. Silicon oxides near
the metal/oxide interface can sustain due to the protectiveness of
the oxide film on it, as shown in Table 6.
The Cr content in the inner oxide is similar to the level of alloy
matrix, and the Cr content in the inner oxide formed on 316L SS
was higher than that on 9Cr–26Ni–1.5Mo and 9Cr–26Ni–1.5Mo–5Si
specimens, as shown in Figs. 11, 15 and 23. The inner layer formed
on stainless steels in high temperature aqueous solutions are
related to the varying diffusion rates of the metal ions in the
oxide, and the diffusion rates follow the order: Fe2+ > Ni2+  Cr3+
[35–38]. The inner oxide film is crucial for the dissolution of metal
atoms from the metal to the oxide film or oxygen diffusion from
the oxide film to the metal matrix [18,35,39–41]. The cation dif-
fusion rate in the Cr-rich oxide layer is slower than that in Fe
or Ni oxides [18,19,41]. The Cr-rich inner layer formed on stain-
less steels favors the decreasing of the growth rate of the oxide
scale, acting as a barrier against the diffusion of metal and oxygen
ions [19,41,42]. Therefore, the oxide film formed on 316L SS speci-

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Fig. 21. STEM-HAADF image of region I shown in Fig. 20 and the corresponding EDS mappings (acquisition time = 1011 s) for Cr, Ni, Fe, O, and Si. The black dotted line
indicates the interface of the outer- and inner-layer oxide film.

Fig. 22. STEM-HAADF image of the oxide film formed on 9Cr–26Ni–1.5Mo–5Si after immersion for 1194 h and corresponding EDS mappings (acquisition time = 1361 s) for
Cr, Ni, Fe, O, and Si.

men has a thinner inner layer than those on 9Cr–26Ni–1.5Mo and
9Cr–26Ni–1.5Mo–5Si specimens, as shown in Figs. 9, 13 and 20. The
effect of Si on the distribution of chromium in the inner layer is not
significant due to the strong tendency of Cr to form oxides.
Results in Figs. 3 and 7 show that the presence of Si in the model
alloy would facilitate the formation of other metallic oxides thus
favors the formation of a continuous iron-rich spinel outer layer
even after a short term immersion in high temperature water. The
cavities in the outer-layer oxide particles on 9Cr–26Ni–1.5Mo–5Si
specimen can be related to the oxidation of Si and the subsequent
dissolution of the Si-bearing oxides in the solution.
It has been reported that adding a certain amount of Si in
austenitic alloys could improve the oxidation resistance in air by
forming protective oxide scales [43]. It has been found that addi-
tion of silicon had the potential of improving the formation of scales
of Ni–Al and Ni–Cr–Al alloys in high temperature atmosphere envi-
ronments [44–47]. The protectiveness of oxides in air and in high
temperature water could be significantly different due to different
oxidation mechanisms. Silicon oxides can act as a protective bar-
rier mitigating further oxidation in high temperature atmospheric
environments while silicon oxides would not provide adequate

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Fig. 23. (a) STEM-HAADF image of the oxide film formed on 9Cr–26Ni–1.5Mo–5Si after immersion in simulated PWR primary water at 310 ◦ C for 1194 h. The black dotted
line indicates the interface of the outer- and inner-layer oxide film (b) EDS line scan profiles (acquisition time = 106 s) of the oxide film shown in (a) by the white line.

Fig. 24. (a) TEM micrograph with SAED patterns of 9Cr–26Ni–1.5Mo–5Si after exposure to the simulated PWR primary water at 310 ◦ C for 1194 h. The white dotted line
indicates the interface of the oxide/metal. (b) and (c) the SAED pattern corresponding to the designated areas I and II in (a), respectively.

protectiveness due to the high solubility in high temperature water
environments [12,33,34].
Local Ni-enrichment near the oxide/metal interface is observed
for 316L SS and 9Cr–26Ni–1.5Mo specimens, as shown in
Figs. 10, 14 and 17. Ni enrichment near the oxide/metal interface or
ahead of the crack tip has been previously observed for austenitic
stainless steels in simulated PWR primary water [48–50]. Ni enrich-
ment near the oxide/metal interface could be related to its lower
oxidation rates compared with Fe and Cr during the formation of
the oxide film. Local depletion of iron in region I and almost uniform
distribution of oxygen in Fig. 17 indicates that the inward diffusion
of oxygen would be more difficult than the outward diffusion of
ferrous/ferric ions in the inner oxide film. Ni is the least likely to
be oxidized due to the lower affinity for oxygen than for Cr and
Fe; therefore the rate of incorporation of Ni in the oxide scale is
lower than that of Cr and Fe, resulting in a high Ni concentration
between oxide and metal [41,51]. Das et al. [18] suggested that Fe
and Cr atoms segregated faster than Ni atoms at the surface, and Ni
enrichment occurred at the inner oxide layer on Fe–Cr–Ni ternary
alloys. Ni enrichment is not continuous, and no Ni enrichment is
observed beneath the porous oxides, as shown in Fig. 14, indicating
that the porous oxides have a negative influence on the Ni enrich-
ment near the interface. The micro pores in the porous oxides are
expected to provide more shortcuts for the inward diffusing oxygen
and outward diffusing metal ions. The enhanced inward diffus-
ing oxygen favors the formation of the Ni-oxides. Moreover, these
shortcuts would contribute to the outward diffusion of nickel ions.
Ni-enrichment near the oxide/metal interface was not observed on
9Cr–26Ni–1.5Mo–5Si specimen, which is likely due to the effect of
Si on the oxidation behavior of Ni. The effect of Si on the oxidation
of other alloying elements in the model alloy has been proved by
the results of the outer surface films, as shown in Figs. 3 and 7.
Table 7 summarizes the experimental results of oxide films
formed on 316L SS and model alloys exposed to the simulated
PWR primary water at 310 ◦ C for 1194 h. In the present work,
the thickness of the inner layer determined by TEM of 316L
SS, 9Cr–26Ni–1.5Mo and 9Cr–26Ni–1.5Mo–5Si is about 100 nm,
160–700 nm and 100–420 nm after 1194 h immersion, respec-
tively. The oxidation rate constants are not calculated because
more data points at different immersion time periods are neces-
sary and the oxidation rate law for the present test conditions is not
defined. Ziemniak and Hanson [52] studied the corrosion behavior
of 304 SS in a 10,000 h test conducted in hydrogenated water at
260 ◦ C, and suggested that the corrosion kinetics were parabolic.
Generally, the oxidation of austenitic alloys in high temperature fol-
lows the parabolic law [52–54], where the increasing rate of oxide
film thickness decreases with increasing immersion time. Although
the oxidation rate law for the alloy/environment combinations in
the present research is not determined, it is expected that fur-
ther increasing the oxidation duration time after 1194 h immersion
would produce only a slight increase of the film thickness.
It has been reported that austenitic stainless steels with high
Si contents exhibit high SCC growth rates in high temperature
water environments [12,13]. Andresen and Morra [12] suggested
that crack growth rates of stainless steels with elevated Si con-
centrations were insensitive to changes in both corrosion potential
and stress intensity. Addition of Si in austenitic stainless steels
would affect the oxidation process of the model austenitic alloys in
high-temperature water and therefore the stress corrosion cracking
behavior. The initial oxidation behavior of the crack tip is impor-
tant for SCC susceptibility and the crack growth rate [17,18]. The

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results in the present work imply that Si would significantly affect
the stress corrosion behavior through its strong effect on the initial
oxidation behavior. The results would be useful for understanding
irradiation assisted stress corrosion cracking where Si-enrichment
at the grain boundaries of reactor core internal alloys due to irradi-
ation is a great concern. It is noted that SCC growth is affected by the
oxidation behavior and the oxide film toughness in terms of film
rupture strain or film degradation strain, and the crack tip mechan-
ics [12,53,54]. Care should be taken when correlating oxidation
behavior directly to SCC growth behavior.
5. Conclusions
The morphology, chemical composition and microstructure
of the oxide film formed on 9Cr–26Ni–1.5Mo–5Si specimen are
significantly different from those on 316L and 9Cr–26Ni–1.5Mo
specimens exposed to a de-aerated, simulated PWR primary water
at 310 ◦ C.
(1) High reactivity of Si and high solubility of silicon oxides in
high temperature water contribute to the observed Si-depletion
in the outer oxide layer and the local Si-enrichment near the
metal/oxide interface for 9Cr–26Ni–1.5Mo–5Si alloy.
(2) High reactivity of Si in 9Cr–26Ni–1.5Mo–5Si with water
enhances the oxidation of other alloy elements to form a con-
tinuous iron-rich spinel outer layer even after a short term
immersion in high temperature water. The prior-oxidation of
Si and the subsequent dissolution of the Si-bearing oxides in
high temperature water contribute to the observed cavities in
the outer oxide layer.
(3) The inner layer formed on 316L SS with about 17 wt.%
Cr is thinner than those formed on 9Cr–26Ni–1.5Mo and
9Cr–26Ni–1.5Mo–5Si model alloys with about 9 wt.% Cr. The
Cr content in the inner oxide formed on 316L SS is higher than
that on 9Cr–26Ni–1.5Mo and 9Cr–26Ni–1.5Mo-5Si specimens.
A high Cr-content in the alloys favors the formation of a protec-
tive thin Cr-rich inner layer that hinders the further growth of
the inner layer. The effect of Si on the distribution of chromium
in the inner layer is not significant due to the strong tendency
of Cr to form oxides.
Ni enrichment near the oxide/metal interfaces is observed for
316L SS and 9Cr–26Ni–1.5Mo specimens but not observed for
9Cr–26Ni–1.5Mo–5Si specimen, indicating the effect of Si on the
oxidation kinetics of Ni.
Acknowledgments
This work has been supported by the International Cooperative
Project, sponsored by the Science and Technology Commission of
Shanghai Municipality No. 13520721200, the Ph.D. Programs Foun-
dation of the Ministry of Education of China No. 20123108110021,
and Shanghai Pujiang Project No. 12PJ1403600.
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