(Paperhub Ir) 10 1016@j Corsci 2016 02 001
(Paperhub Ir) 10 1016@j Corsci 2016 02 001
(Paperhub Ir) 10 1016@j Corsci 2016 02 001
Corrosion Science
journal homepage: www.elsevier.com/locate/corsci
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
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 P S Cr Ni Mo Fe
316L SS 0.020 0.54 1.28 0.014 0.004 17.21 12.46 2.45 Bal.
9Cr–26Ni–1.5Mo 0.026 0.35 0.65 0.020 0.013 9.29 26.12 1.54 Bal.
9Cr–26Ni–1.5Mo–5Si 0.023 4.54 0.60 0.021 0.018 9.15 26.41 1.47 Bal.
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. 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.
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 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.
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 Fig. 7 shows the morphologies of the oxide films formed
on 316L SS, 9Cr–26Ni–1.5Mo and 9Cr–26Ni–1.5Mo–5Si after
40 immersion in the simulated PWR primary water for 1194 h. The
oxide films formed on 316L SS and 9Cr–26Ni–1.5Mo specimens
20 were composed of polyhedral oxides, and the specimen surfaces
were not fully covered by the outer layer oxide particles. The
0 9Cr–26Ni–1.5Mo–5Si specimen surface was fully-covered by large
0 900 1800 2700 3600 4500 5400 6300
and continuously packed oxide particles with some cavities. The
Sputtering time (s)
average size of the outer oxide particles formed on 316L SS was
Fig. 5. Composition profiles in the depth of the oxide films formed on 316L SS and smaller than that of 9Cr–26Ni–1.5Mo, as shown in Figs. 3 and 7,
model alloys exposed to the simulated PWR primary water at 310 ◦ C for 114 h. (a) which was consistent with the observation on the surfaces of 316
316L SS, (b) 9Cr–26Ni–1.5Mo, (c) 9Cr–26Ni–1.5Mo–5Si. 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
specimen after 114 h immersion. In the Cr2p3/2 spectra (Fig. 6b), 316L SS, 9Cr–26Ni–1.5Mo and 9Cr–26Ni–1.5Mo–5Si after immer-
the peak at approximately 576.7 eV was assigned to Cr3+ [22,23]. sion for 1194 h. Table 4 shows the Raman shifts of Raman
In the Fe2p3/2 spectra (Fig. 6c), the main peak at approximately spectra peaks. Similar to the results of immersion for 114 h, the
711 eV was assigned to Fe3+ , and the peak at approximately 709 eV Raman spectra of the oxide film formed on the 316L SS and
was from Fe2+ [24]. Two different chemical states were detected in 9Cr–26Ni–1.5Mo–5Si specimens exhibited the strong signals of
the Ni2p3/2 spectra: the peak at 853 eV was assigned to metallic Ni0 Fe3 O4 and the oxide film formed on the 9Cr–26Ni–1.5Mo specimen
and the peak at 855.3 eV was assigned to Ni2+ [22,23]. After approx- exhibited the strong signals of NiFe2 O4 .
imately 600 s sputtering, no signals corresponding to Cr2p were Figs. 9–12 show the TEM results of the oxide films formed on
generated due to the lower Cr content in the outer layer. However, 316L SS exposed to the simulated PWR primary water for 1194 h.
strong signals corresponding to Ni0 were detected after 600 s sput- As mentioned previously, the high angle annular dark field (HAADF)
tering, and the peak decomposition of Ni2p3/2 was similar to that contrast is proportional to the average atomic number, and the
after 3600 s. Ni-containing oxides are stable in the de-aerated, sim- oxides are darker than the matrix in the STEM-HAADF images. Fig. 9
ulated PWR primary water according to the potential-pH diagram shows the duplex structure of the oxide film formed on 316L SS.
of Ni–H2 O at 300 ◦ C [25]. However, Ni-containing oxides is very sus- The outer layer was composed of discontinuous and large oxide
ceptible to reduction by ion bombardment during XPS profiling, so grains, whereas the inner layer was composed of dense and fine
the detected Ni0 might be reduced from Ni2+ during the argon ionic 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+
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
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
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.
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. 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.
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.
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.
Fig. 8. Raman spectra of the oxide films formed on 316L SS and model alloys exposed The TEM–EDS results of the outer oxide particles are shown in
to the simulated PWR primary water for 1194 h at 310 ◦ C. 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
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. 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).
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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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.
Fig. 13. STEM-HAADF image of the oxide film formed on 9Cr–26Ni–1.5Mo after The EDS mappings shown in Figs. 21 and 22 indicated that Fe and Ni
exposure to the simulated PWR primary water at 310 ◦ C for 1194 h.
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
consistent with the Raman result shown in Fig. 8. The EDS line scan shown in Fig. 23b. The TEM–EDS microanalysis, as shown in Table 6,
profiles of the oxide film indicated that the content of Cr was much indicated that the inner oxide film close to oxide/metal interface
higher than Fe and Ni, as shown in Fig. 11b. Ni was enriched near (region I) had higher contents of Si and O and lower contents of
the oxide/metal interface, which was confirmed in the EDS line scan Ni and Fe than the common oxide film, like region II. The electron
profiles of the oxide film. diffraction patterns shown in Fig. 24b and c indicated that both the
Figs. 13–19 show the TEM results of the oxide film formed on outer layer oxides and the inner layer oxides had the spinel-type
9Cr–26Ni–1.5Mo exposed to the simulated PWR primary water for Fex Niy Crz O4 crystal structure.
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.
4. Discussion
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
The oxide films formed on 316L SS, 9Cr–26Ni–1.5Mo and
Cr than that on the 316L SS specimen. The inner oxide film was inho-
9Cr–26Ni–1.5Mo–5Si after exposure to the simulated PWR primary
mogeneous, and its thickness, as determined by TEM, ranged from
water at 310 ◦ C for 1194 h have a duplex structure, as shown in
160 to 700 nm. There were some darker areas (such as area I shown
Figs. 9, 13 and 20. TEM analysis shows that the outer layer oxides
in Fig. 13) in the inner oxide film. Fig. 16a shows that the darker
formed on 316L S, 9Cr–26Ni–1.5Mo and 9Cr–26Ni–1.5Mo–5Si are
areas in the oxide film shown in the STEM-HAADF images were
(Ni, Fe) Fe2 O4 .
composed of porous granular oxide. High resolution TEM images
Si in the model alloy affects both the chemical composition
of the dark (granular) zones exhibited lattice fringes, as shown in
profile and the surface morphology of the oxide film. After expo-
Fig. 16c. Images of selected area electron diffraction exhibited poly-
sure to the simulated PWR primary water at 310 ◦ C for 114 h
crystalline characteristics, as shown in Fig. 16b, and the dark field
and 1194 h, the 316L SS and 9Cr–26Ni–1.5Mo specimen surfaces
images also indicated the presence of crystals.
are covered by dispersed faceted oxide particles, whereas the
There were several factors that could cause the occurrence of
9Cr–26Ni–1.5Mo–5Si surface is covered by large, continuously
the dark zones in the STEM-HAADF images, such as the chemical
packed oxide particles with cavities. The large oxide particles
compositions and the quantity of the existing oxides. TEM obser-
on 9Cr–26Ni–1.5Mo–5Si specimen may not mainly deposit from
vations show that the dark zones were typical granular regions, as
the metallic cations released from autoclave body corrosion
shown in Figs. 16 a and 19 a. Results of TEM–EDS line scan profiles
because they are not observed on the surfaces of 316L SS and
show that the Fe contents in the dark zones were lower than those
9Cr–26Ni–1.5Mo in the same immersion experiments. According
in the relatively bright zones, as shown in Fig. 15a. The contrast of
to the thermodynamic data from HSC software [32], the change
the TEM–EDS Cr mapping did not show any significant decrease in
of standard Gibbs free energy for the reaction of Si with water at
the dark zones, as shown in Fig. 14. These results indicated that the
310 ◦ C is calculated to be −415.69 kJ/mol (equivalent to standard
local chemical composition would contribute to the observed dark
electrode potential of −1.08 V(SHE)), taking G0 H2O (310 ◦ C) as
zones.
−193.99 kJ/mol and G0 SiO2 (310 ◦ C) as −803.67 kJ/mol, according
The EDS area mappings shown in Fig. 14 indicated that there was
to Eq. (1). Si in the model alloy tends to react with high tempera-
a Ni-enriched thin layer, which also was confirmed by the EDS line
ture water to form oxides and at the same time affects the oxidation
scan profiles of the oxide film cross-section shown in Fig. 15a. How-
behavior of other metals. The solubility of silicon oxides in water
ever, the Ni enrichment layer was not continuous. Fig. 13 shows that
increases with increasing temperature from 0 ◦ C to about 310 ◦ C,
the inner oxide film just beneath the Ni enrichment regions was
which is strongly affected by the forms of silicon oxides such as
thinner than that beneath the regions without Ni enrichment. The
amorphous silica quartz [33,34]. The solubility for amorphous sil-
EDS area mappings shown in Fig. 17 showed that Ni enriched adja-
ica in 310 ◦ C water varied in the range of about 1400 to 1800 mg/kg
cent to some oxide/metal interfaces, which was consistent with the
[33,34], which is about a half or lower for quartz. Even though the
results of the EDS line scan profiles of the oxide film cross-section
solubility of silicon oxide in PWR primary water could be different
shown in Fig. 18b.
from that in pure water, it is expected to be still high by referring the
Fig. 19 shows the micrograph and electron diffraction patterns
effect of composition of high temperature solutions on solubility of
of region II shown in Fig. 13. For the inner layer of the oxide film,
silicon oxide [33].
the atomic percents of Fe, Ni and Cr were not stoichiometric and
it was difficult to deduce the exact chemical formula of the oxide. Si + 2H2 O = SiO2 + 2H2 (1)
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 Due to the high solubility of silicon oxides in high temperature
diffraction patterns of the designated area in TEM image (Fig. 19a), water, the oxidized silicon on the alloy surface can be dissolved
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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 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.
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 The HAADF images (Fig. 20) show that the inner oxide film close
explains why silicon is depleted in the outer layer of the oxide film, to the interface between the oxide/matrix on 9Cr–26Ni–1.5Mo–5Si
which has been shown by XPS results in Fig. 6 and TEM results in is characterized by a lower average atomic number compared with
Tables 5 and 6. 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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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. 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%)
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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. 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 It has been reported that adding a certain amount of Si in
9Cr–26Ni–1.5Mo–5Si specimens, as shown in Figs. 9, 13 and 20. The austenitic alloys could improve the oxidation resistance in air by
effect of Si on the distribution of chromium in the inner layer is not forming protective oxide scales [43]. It has been found that addi-
significant due to the strong tendency of Cr to form oxides. tion of silicon had the potential of improving the formation of scales
Results in Figs. 3 and 7 show that the presence of Si in the model of Ni–Al and Ni–Cr–Al alloys in high temperature atmosphere envi-
alloy would facilitate the formation of other metallic oxides thus ronments [44–47]. The protectiveness of oxides in air and in high
favors the formation of a continuous iron-rich spinel outer layer temperature water could be significantly different due to different
even after a short term immersion in high temperature water. The oxidation mechanisms. Silicon oxides can act as a protective bar-
cavities in the outer-layer oxide particles on 9Cr–26Ni–1.5Mo–5Si rier mitigating further oxidation in high temperature atmospheric
specimen can be related to the oxidation of Si and the subsequent environments while silicon oxides would not provide adequate
dissolution of the Si-bearing oxides in the solution.
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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 of other alloying elements in the model alloy has been proved by
environments [12,33,34]. the results of the outer surface films, as shown in Figs. 3 and 7.
Local Ni-enrichment near the oxide/metal interface is observed Table 7 summarizes the experimental results of oxide films
for 316L SS and 9Cr–26Ni–1.5Mo specimens, as shown in formed on 316L SS and model alloys exposed to the simulated
Figs. 10, 14 and 17. Ni enrichment near the oxide/metal interface or PWR primary water at 310 ◦ C for 1194 h. In the present work,
ahead of the crack tip has been previously observed for austenitic the thickness of the inner layer determined by TEM of 316L
stainless steels in simulated PWR primary water [48–50]. Ni enrich- SS, 9Cr–26Ni–1.5Mo and 9Cr–26Ni–1.5Mo–5Si is about 100 nm,
ment near the oxide/metal interface could be related to its lower 160–700 nm and 100–420 nm after 1194 h immersion, respec-
oxidation rates compared with Fe and Cr during the formation of tively. The oxidation rate constants are not calculated because
the oxide film. Local depletion of iron in region I and almost uniform more data points at different immersion time periods are neces-
distribution of oxygen in Fig. 17 indicates that the inward diffusion sary and the oxidation rate law for the present test conditions is not
of oxygen would be more difficult than the outward diffusion of defined. Ziemniak and Hanson [52] studied the corrosion behavior
ferrous/ferric ions in the inner oxide film. Ni is the least likely to of 304 SS in a 10,000 h test conducted in hydrogenated water at
be oxidized due to the lower affinity for oxygen than for Cr and 260 ◦ C, and suggested that the corrosion kinetics were parabolic.
Fe; therefore the rate of incorporation of Ni in the oxide scale is Generally, the oxidation of austenitic alloys in high temperature fol-
lower than that of Cr and Fe, resulting in a high Ni concentration lows the parabolic law [52–54], where the increasing rate of oxide
between oxide and metal [41,51]. Das et al. [18] suggested that Fe film thickness decreases with increasing immersion time. Although
and Cr atoms segregated faster than Ni atoms at the surface, and Ni the oxidation rate law for the alloy/environment combinations in
enrichment occurred at the inner oxide layer on Fe–Cr–Ni ternary the present research is not determined, it is expected that fur-
alloys. Ni enrichment is not continuous, and no Ni enrichment is ther increasing the oxidation duration time after 1194 h immersion
observed beneath the porous oxides, as shown in Fig. 14, indicating would produce only a slight increase of the film thickness.
that the porous oxides have a negative influence on the Ni enrich- It has been reported that austenitic stainless steels with high
ment near the interface. The micro pores in the porous oxides are Si contents exhibit high SCC growth rates in high temperature
expected to provide more shortcuts for the inward diffusing oxygen water environments [12,13]. Andresen and Morra [12] suggested
and outward diffusing metal ions. The enhanced inward diffus- that crack growth rates of stainless steels with elevated Si con-
ing oxygen favors the formation of the Ni-oxides. Moreover, these centrations were insensitive to changes in both corrosion potential
shortcuts would contribute to the outward diffusion of nickel ions. and stress intensity. Addition of Si in austenitic stainless steels
Ni-enrichment near the oxide/metal interface was not observed on would affect the oxidation process of the model austenitic alloys in
9Cr–26Ni–1.5Mo–5Si specimen, which is likely due to the effect of high-temperature water and therefore the stress corrosion cracking
Si on the oxidation behavior of Ni. The effect of Si on the oxidation behavior. The initial oxidation behavior of the crack tip is impor-
tant for SCC susceptibility and the crack growth rate [17,18]. The
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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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