Accepted Manuscript

Corrosion behavior of Alloy 690 in aerated supercritical water Xiangyu Zhong, En-Hou Han, Xinqiang Wu PII: DOI: Reference: To appear in: Received Date: Accepted Date: S0010-938X(12)00484-2 http://dx.doi.org/10.1016/j.corsci.2012.10.001 CS 5108 Corrosion Science 3 August 2012 1 October 2012

Please cite this article as: X. Zhong, E-H. Han, X. Wu, Corrosion behavior of Alloy 690 in aerated supercritical water, Corrosion Science (2012), doi: http://dx.doi.org/10.1016/j.corsci.2012.10.001

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Corrosion behavior of Alloy 690 in aerated supercritical water

Xiangyu Zhong, En-Hou Han*, Xinqiang Wu* State key Laboratory for Corrosion and Protection, Liaoning Key Laboratory for Safety and Assessment Technique of Nuclear Materials, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, P. R. China

*Corresponding author: En-Hou Han, Xinqiang Wu State Key Laboratory for Corrosion and Protection Institute of Metal Research, Chinese Academy of Sciences 62 Wencui Road, Shenyang 110016, P.R. China Tel: +86-24-2384-1883 Fax: +86-24-2389-4149 E-mail: ehhan@imr.ac.cn (E-H. Han), xqwu@imr.ac.cn (X. Wu)

Abstract
The oxidation behavior of Alloy 690 exposed to aerated supercritical water at different temperatures was investigated using gravimetry, scanning electron microscopy/energy dispersive X-ray spectroscopy, X-ray diffraction, X-ray

photoelectron spectroscopy, Raman spectroscopy and electron probe micro-analyzer. The oxide films showed a duplex layer structure with Ni and Fe rich in the outer layer, and Cr rich in the inner layer. Some pits and nodules observed in the oxide films could be related to TiN inclusions in the alloy matrix. The oxidation mechanism and effects of TiN inclusions are discussed.

Key words: A: Alloy, B: SEM, B: XPS, C: High Temperature Corrosion, C:

Oxidation.

1. Introduction

Supercritical water cooled reactor (SCWR) is one of the most promising advanced reactor concepts for Generation IV nuclear reactors because of its high thermal efficiency and plant simplification [1, 2]. For the safety of the nuclear power plant, the corrosion behavior of candidate materials used in such an aggressive environment needs to be understood. Nickel-based alloys have been considered as one kind of candidate materials for SCWR due to their combined good corrosion resistance and mechanical properties in high temperature and high pressure water [3-5]. Many nickel-based alloys such as Alloy 625, Alloy 617, Alloy 718 and Hastelloy C-276 have been investigated as candidate materials for SCW systems [5-9]. The corrosion behavior of Inconel 625 exposed to a deaerated SCW in a temperature range of 400-550 oC showed uctuations in weight change measurements and pitting as the predominant corrosion mode, and it was assumed that the fluctuations of weight change were related to the pitting and spalling [7, 10]. While other authors found that a weight gain appeared for Alloy 625 exposed to SCW contains H2O2 and C-276 exposed to deareated SCW [8, 9]. Microstructure often plays a leading role in corrosion resistance [10]. The -phase such as Ni3(Al, Ti) is a common intermetallic precipitate in Nickel-based alloys, the carbides M23C6 in the grain boundary have strong influence on the resistance to intergranular corrosion and stress corrosion cracking [11-13], and the TiN inclusions act as the initiation sites of pitting [14, 15], corrosion fatigue [16] and stress corrosion cracking [17]. The TiN inclusions oxidized
3

much faster than metal matrix and resulted in high shear strain in the oxide scales, leading to the shrinking and cracking of the oxide films [18]. Therefore, these inclusions have a strong influence on the corrosion behavior of nickel-based alloys in SCW, and the effects of the inclusions need to be further investigated. The present work is to investigate the corrosion behavior of Alloy 690 exposed to aerated SCW with different temperature and time, and to characterize the phase composition, morphologies and chemical composition of the oxide films formed on the surface of Alloy 690. The related corrosion mechanism and the effects of TiN inclusions are also discussed.

2. Experimental

2.1 Apparatus Exposure tests were performed with a continuous flowing SCW system consisting of an HPLC pump (Eldex Inc., AA-100-S), a preheater, a nickel-based Alloy 625 autoclave with a volume of 850 ml, a heat exchanger and a back-pressure regulator (BPR) (Fig. 1). The internal pressure was measured by a pressure sensor placed at the inlet of the reactor and controlled by an HPLC pump and a BPR. A computer with Labview 6.0 software was used to control the internal pressure and the temperature in autoclave and preheater was monitored by two thermocouples. The test solution was aerated pure water with 8 ppm (by weight) O2, and the flow rate was maintained at 5 ml/min.

2.2 Materials and Specimens Alloy 690 used in the present work was solution annealed at 1333 K for 0.5 h and then water quenched. Table 1 is the chemical composition of the alloy. Fig. 2a and 2b are the metallographic images of the as received alloy. The microstructure of the alloy is typical austenite with many annealing twins (Fig. 2a) and TiN inclusions were clearly observed in the alloy (Fig. 2b). Specimens (10 mm 12.5 mm 2 mm) for expose test in SCW were mechanically ground progressively with ne grit silicon-carbide paper up to 2000# grit, and final mechanical polished with 2.5 m diamond paste. Prior to each test, the specimens were cleaned with ethanol and ultrasonically rinsed with deionized water for 30 min.

2.3 Methodology The specimens were mounted on a rack and put into the autoclave. The testing conditions were maintained at 450 oC /25 MPa and 550 oC/25 MPa and the exposure time was up to 500 h. After exposure test, the specimens were cleaned with deionized water and dried. Then they were characterized by weight gain measurement, surface analysis and cross-section analysis. The weight of all specimens before and after exposure was measured using Sartorius BP211D microbalance with a resolution of 10-5 g. Corrosion products analysis were performed by D/Max 2400 X-ray
o

diffractometer (XRD) using copper radiation (=1.542 A ) and a BWS905 custom Raman system. The Raman system contains a powerful laser at 532 nm with a maximum power of 1.5 W. The Raman shift range is 175-2875 cm-1 and the spectral
5

resolution is 12 cm-1. The integration time used was 15 or 20 s depending on the signal intensity of the specimens. The surface and cross-section morphologies and compositions of oxide films were performed using scanning electron microscopy (SEM) (FEI INSPECT F50) equipped with an energy-dispersive X-ray spectroscopy (EDS) system. To investigate the cross-sections of the oxide films, some specimens were coated in Ni-P solution to protect the films. The coated specimens were mounted with epoxy resin and then polished. The corresponding cross-sections of the oxide films were examined using SEM and EDS. An electron probe micro-analyzer (EPMA-6010) was used to detect the distribution of O, Ni, Cr and Fe elements on cross-section under the operating condition of U = 15 kV and I = 100 nA. X-ray photoelectron spectroscopy (XPS) measurements were performed with

ESCALAB250 X-ray photoelectron spectrometer. Photoelectron emission was excited by monochromatic Al Ka source operated at 150 W with initial photo energy 1486.6 eV. The C1s peak from adventitious carbon at 285 eV was used as a reference to correct the charging shifts. Depth profile information was performed over an area of 2 2 mm2 under 2 keV Ar-ion sputtering and spectra were obtained over a 0.5 mm spot using a focusing X-ray monochromator. Sputtering rate was determined to be about 0.2 nm/s (vs. Ta2O5). The peak decomposition of the species in the oxide films was carried out with a commercial peak fitting software (XPSpeak4.1) using Gaussian-Lorentzian peak fitting after Savitzky-Golay smoothing and Shirley background subtraction, and the peak areas were converted to atomic concentrations as depending on sputtering depth.
6

3. Results

3.1 Gravimetry Fig. 3 shows the weight gain of Alloy 690 exposed to SCW at 450 oC/25 MPa and 550
o

C/25 MPa for different times. The weight gain of Alloy 690 at 550 oC is higher than

that at 450 oC, and the trend of the weight gain at 550 oC is different from that at 450
o

C. At 550 oC, the weight gain increases first, and reaches a peak after 100 h exposure,
o

and then decreases with further increasing exposure time. At 450

C, some

uctuations in weight gain are observed. The different trend of the weight gain may be caused by the competing processes of weight gain due to oxidation and weight loss due to pitting or oxide dissolution [7, 10, 19]. At 450 oC, the competing processes of oxidation and dissolution keep balance. Therefore, the weight gain of Alloy 690 fluctuated with the increasing of exposure time. At 550 oC, the oxidation rate increased, and it is easy to form a compact Cr2O3 layer, this layer can hinder the inward diffusion of oxygen and the oxidation rate can be decreased. On the other hand, the dissolution rate of the oxide film increased quickly. As a result, the weight gain exhibited decreasing phenomenon. 3.2 XRD analysis Fig. 4 shows the XRD spectra of Alloy 690 after exposure tests at different temperatures (Fig. 4a) and for different time (Fig. 4b). The major phases in the oxide films are spinel (PDF card NO. 23-1271 and 10-0325), Cr2O3 (PDF card NO.
7

38-1479), NiO (PDF card NO. 44-1159) and Ni(OH)2 (PDF card NO. 03-0177). Since XRD patterns for spinels concerning the three alloying constituents (Fe, Cr, Ni) are very similar, the spinel type cannot be claried right now. A further analysis is needed to identify the composition of the oxide film. The intensity of the Cr2O3 peak increase with increasing exposure temperature and time. The intensity of the peak relates to the content of phases in the oxide films, indicating that the Cr2O3 in the oxide film increase with increasing temperature and time.

3.3 Raman spectra Fig. 5 shows the Raman spectra of the oxide films on Alloy 690 after exposure tests in SCW at 450 oC and 550 oC. The peaks on the spectra show no obvious change with increasing exposure temperature and time. Spinel structure is responsible for the Raman peaks at 693 cm-1 [20, 21]. Due to the limited detecting depth of Raman spectroscopy, only the outmost surface of the oxide films can be detected. The present results indicate that the outmost layer of the oxide film is spinel.

3.4 Surface morphology Fig. 6 and Fig. 7 show the effects of exposure temperature and time on the surface morphologies of the Alloy 690 exposed to 450 oC and 550 oC SCW. It can be seen that the oxide films present as layered oxide under all test conditions. The outer layer consists of large sparsely distributed, discrete polyhedral crystallites and some slide-shaped oxide particles, and the inner layer contains fine and uniform oxide
8

particles (Fig. 6 and Fig. 7). The size of polyhedral crystallites increases with the increasing exposure temperature and time (Fig. 6 and Fig. 7). After exposing to the SCW for 50h, there are some large polyhedral crystallites sparsely distributed on the surface (Fig. 7a). With increasing exposure time, the surface cover rate of the large polyhedral crystallites increased (Fig. 7b), corresponding to the increasing of the weight gain. After exposure in the SCW for 500 h, the size of the large polyhedral crystallites increased, but the cover rate decreased (Fig. 7c), and the pitting was also observed (Fig. 7d). The pitting and the decrease of the polyhedral crystallites may be the reasons for the decrease of the weight gain. The growth process of the oxide films during exposure tests can be described as an initial oxide nucleation on selected sites followed by a uniform growth of oxide particles until they connect with each other and result in a compact layer. On the oxide surface, the grain boundaries were outlined by topographically elevated oxides (Fig. 8b), similar to the work of Ren et al. [7]. They found that O and Cr were enriched at grain boundaries and Ni was depleted. This indicates that Cr was segregated at the grain boundaries and the chromium carbide formed in the grain boundaries of the alloy was oxidized faster than the grains [22]. The oxidation morphologies at the grain boundaries are different from that in the bulk grains. In the grains, there are some large polyhedral particles (as shown label 1 in Fig. 8b) and slide-shape oxide particles (as shown label 3 in Fig. 8b). But at the grain boundaries, the polyhedral oxides are much smaller (particle 2 in Fig. 8b). Some quadrate-like holes and cauliflower-like oxides are observed on the surface of oxide films (Fig. 8c
9

and Fig. 8d). EDS analysis indicate that Ti content is enriched in the hole and the center of the cauliflower, while Ni and Cr content are depleted (Table 2). Same results are also obtained for the specimens exposed to 450 oC SCW (Fig. 6c and Fig. 6d). As shown Fig. 6c and Fig. 6d, there are many large oxides in the TiN inclusions, while few oxides are observed around the inclusions. The above results indicate that the selective oxidation of the TiN inclusions has occurred, the holes and nodules in the oxide films originate from local attack at the TiN inclusions.

3.5 Structure of the oxide film Fig. 9 shows the cross-sectional morphologies of oxide films and composition depth profiles for the Alloy 690 specimens exposed to 450 oC and 550 oC SCW for 500 h. A typical duplex oxide structure is detected, consisting of a Ni-rich outer layer and a Cr-rich inner layer. The number 1, 2, 3, 4 present the metal matrix, the inner layer, the outer layer and the Ni coating layer respectively. Since the oxide layer is plated with Ni, the Ni composition of the oxide layer measured by EDS is not reliable, especially considering the very thin oxidation layer (0.25 to 1m), but the evolution trend of the concentration of Ni and Cr can be observed from the EDS result. Some polyhedral crystallites in the outer oxide layer are rich in Ni and Fe (Fig. 9d). Combined with the results of XRD and Raman spectroscopy, the polyhedral crystallites may be NiFe2O4 spinel. Fig. 10 shows the EPMA results of O, Ni, Cr and Fe elements distribution in the oxide film on Alloy 690 after 500 h exposure test in 550 oC SCW. Coinciding with the
10

previous results of EDS line scan, Ni and Fe are rich in the outer layer and Cr is rich in the inner layer. Ni and Cr maps complement each other since Cr-rich regions are Ni-depleted and vice-versa. The O map shows strong enhancement at the location of Cr-rich zones. Fig. 11 shows the cross-sectional morphologies of inclusion-involved oxide films. Corresponding to the surface morphologies of inclusion-involved oxide films (Fig. 6 to Fig. 8), the TiN inclusions which are located at or close to the metal surface are selectively oxidized, and the oxide shrinks due to the high shear strain at the interface between the oxide and TiN inclusions when the oxidation proceed (Fig. 11a). In Fig. 11b, there are two TiN inclusions on the cross section close to the metal/oxide interface. The inclusion 2 is closer to the metal/oxide interface than the inclusion 3, EDS results (Table 3) show that the element N is detected in the inclusion 3, while no N is detected in the inclusion 2. The above results seem to indicate that the inclusion 2 oxidizes faster than the inclusion 3 during exposure tests in SCW.

3.6 XPS analysis Fig. 12 shows the XPS depth profiles of the oxide film formed on Alloy 690 exposed to 450 oC SCW for 100 h. It is obvious that Cr content first increases from the outermost surface and then decreases gradually, while Ni content first decreases from the outermost surface and then increases gradually, O content decreases from the outermost surface to the inner layer, and Fe content keeps at a low level. Before sputtering, the atomic ratio O/Ni=2:1, and after 180 s sputtering, the atomic ratio
11

Ni/Cr=1:2, indicating that the outermost layer contains Ni(OH)2 and the inner layer contains spinel NiCr2O4 [23]. Fig. 13 shows the Ni 2p3/2 core level spectra recorded after different sputtering time. At the specimen surface (0 s sputtering time), Ni 2p3/2 spectrum consists of the intense peak at the binding energy (BE) of 856.3 0.5 eV, and its satellite peak at about 860.5 0.3 eV. These two features originate from Ni(OH)2 [8, 23-25]. And the intensity of the peak decreases with increasing sputtering time, and disappears finally after 60 s sputtering. After 30 s sputtering, the peak at 852.4 0.2 eV appears and become dominant. And the peak at 853.2 0.3 eV springs out and increases first and then decreases after 390 s sputtering. The BE of 853.2 0.3 eV, corresponding to NiO or NiCr2O4, and the other one located at BEs of 852.4 0.2 eV corresponding to metallic Ni0 [8, 23, 24]. As XPS identies the chemical composition on surface within only several tens of nanometers, this information indicates that a Ni(OH)2 layer was formed in the outermost layer in contact with SCW. The above results suggest that the out layer of the oxide film mainly contains Ni(OH)2, and the inner layer consists of NiCr2O4. Metallic Ni0 can be detected after 30 s sputtering. The metallic Ni0 becomes the dominant peak after 180 s sputtering (Fig. 12). Machet et al. [23, 26] thought that the detected Ni0 most probably resulted from chemical reduction during ion sputtering while Liu et al. [27] believed Ni was not oxidized during exposure tests. In the present work, considering the signicant intensity ratio of Ni0, it is believed that the signal of metallic Ni0 detected after 30 s and 180s sputtering result from the reduction during sputtering, and the metallic Ni0 detected after 360 s and 690 s sputtering come from
12

the metal matrix. Fig. 14 shows the Cr 2p3/2 core level spectra recorded after different sputtering time. The Cr 2p3/2 peaks have been systematically decomposed into up to two components: one located at a BE of 573.8 0.2 eV, corresponding to metallic Cr, and the other one located at BE of 576.2 0.3 eV, corresponding to Cr2O3 or NiCr2O4 [23, 26]. With increasing sputtering time, the intensity of the signal at BE of 576.2 0.3 eV increases first and then decreases. After 360 s sputtering, the peak of metallic Cr0 springs out and becomes dominant, indicating the oxide/matrix interface. Fig. 15 shows the Fe 2p3/2 core lever spectra after different sputtering time. The peak located at BE of 711.0 0.1 eV corresponding to Fe3+ and 709.6 0.1 eV corresponding to Fe2+ [26]. After 360 s sputtering, the peak at BE of 711.0 0.1 eV and 709.6 0.1 eV disappears, and the peak at the BE of 707 0.2 eV and its satellite peak at the BE of 711.6 0.2 eV corresponding to metallic Fe0 become dominant. The Fe0 peak appears after sputtering 360 s, the signal of Fe0 comes from the metal matrix. Fig. 16 shows the O 1s core lever spectra recorded after different sputtering time. The O 1s peaks have been systematically decomposed into up to two components: one located at a BE of 530.3 0.3 eV, corresponding to O2- [23, 28] and the other one located at BE of 531.7 0.5 eV, corresponding to OH- [23, 28]. With increasing sputtering time, the intensity of the signal at BE of 531.7 0.5 eV decreases and that at BE of 530.3 0.3 eV increases, indicating that the outmost layer of the oxide film contains hydroxide.

13

4. Discussion
4.1 The fluctuation of weight change In the present work, it is found that the weight change of Alloy 690 is fluctuated (Fig. 3), coinciding with the corrosion behavior of Inconel 625 and Hastelloy C-276 exposed to SCW reported by Allen et al. [10], Was et al. [19] and Cook et al. [29]. They assumed that the fluctuation of weight change is due to the competition between the oxidation and pitting or spalling of the oxide films. But Sun et al. [8] and Zhang et al. [9] reported that the Alloy 625 and C-276 exhibited weight gain with increasing exposure time without fluctuations. Chang et al. [30] found that the weight change of Alloy 625 were slight and fluctuated in 400 oC and 500 oC SCW with 8.3 ppm (by weight) O2, and the weight gain followed a parabolic law in 600 oC SCW. Kuang et al. [31] investigated the corrosion behavior of Alloy 690 in 290 oC oxygenated high temperature water, they found that the oxide film dissolved with increasing exposure time due to the release of Cr in the oxide into the solution as CrO42-. In the present work, the dissolution of the oxide particles and some pits were also observed at the surface of the oxide film (Fig. 7 and Fig. 8). Therefore, the fluctuation of the weight change may be caused by the competing processes of weight gain due to oxidation and weight loss due to pitting or oxide dissolution during exposure tests [7, 10, 19]. At 450 oC, the competing processes of oxidation and dissolution keep balance. Therefore, the weight gain of Alloy 690 fluctuated with the increasing of exposure time. But at 550 oC, after exposure for 100 h, the surface cover rate of the large polyhedral crystallites increased than that for 50 h (Fig. 7a and b), the oxidation rate
14

increased. And it is easy to form a compact Cr2O3 layer at initial stage, this layer can hinder the inward diffusion of oxygen and the oxidation rate can be decreased in the later oxidation stage. On the other hand, the pitting caused by the selective oxidation of TiN inclusions and the dissolution rate of the oxide film are more severe than that at 450 oC (Fig. 6 to Fig. 8). As a result, the weight gain showed a decrease phenomenon.

4.2 Effects of inclusions In addition to the general oxidation, some selective oxidation of the inclusions (Fig. 6c and Fig. 6d) and some pits and nodules are also observed on the surface of Alloy 690 (Fig. 8c and Fig. 8d). The EDS analysis results indicated that these pits and nodules are related to the TiN inclusions in the alloy (Table 2). Ren et al. [7] and Tan et al. [10] have observed several pits formed on Alloy 625 and Alloy 718 exposed to 500 oC SCW with 25 ppb O2 (by weight). They believed that the pits maybe associated with the Nb- and/or Ti-rich precipitates (likely -phase) leading to galvanic corrosion due to the difference of electrochemical potential between the matrix and -phase. Zhang et al. [32] also found some nodules and cauliflower-like oxides originated from the local attack of the -phase precipitates and scattered on the uniform scale formed on Alloy 625, C-276 and X-750 in 500 oC SCW. Lim et al. [15] also found that some pits initiated at TiN inclusions in Alloy 600. (Mg, Ca)S and angular TiN particles acted as a preferential site for the film breakdown for pitting corrosion, and the micro-crevice formed at the angular TiN/matrix interface facilitated
15

the formation of an occluded cell for pitting corrosion. Chang et al. [30] investigated the corrosion behavior of Alloy 625 in 400-600 oC aerated SCW. They found that some pits initiated from the (Nb, Ti)C inclusions in the substrate. The TiN or TiC inclusions were selectively oxidized if they were located at or close to the metal surface. Moreover, the inclusions oxidized faster than the metal matrix [18], the volume increased when the oxidation proceeded (the ratio of molar volume TiO2/TiC=1.28 [18]), resulting in high shear strain at the interface between the oxide film and TiN inclusion, and the oxide shrank with development of the oxidation, as shown in Fig. 10a. As a result, some cracks could be generated in the shrunk oxide films with continuous oxidation. These cracks may promote the short circuit diffusion of aggressive components such as oxygen penetrating into the metal matrix, thereby causing internal oxidation processes around the TiN inclusions [18].

4.3 Multi-layer oxide structure In the present work, the oxide films formed on Alloy 690 in aerated SCW is a duplex structure, consisting of a loose outer layer with large polyhedral crystallites and a dense inner layer with fine oxide particles (Fig. 6 and Fig. 7). The outer layer is Ni-rich and the inner layer consists of Cr-rich oxides (Fig. 9, Fig. 10 and Fig. 12). The outer layer is composed of polyhedral nickel ferrite crystallites with sizes of micrometric scale (Fig. 6 and Fig. 7). Besides the outer polyhedral oxide particles, some plate-like oxides (particle 3 in Fig. 8b) and faceted oxide particles (particle 2 in Fig. 8b) are growing up on the surface layer. The plate-like oxides are also observed
16

around the TiN inclusions (Fig. 6c, Fig. 6d and Fig. 8c). According to the XPS analyses in the present work (Fig. 12), the Ni2+ signal at BE of 856.3 0.5 eV and O 1s signal at BE of 531.7 0.5 eV can be assigned to Ni(OH)2 [23, 25]. The results of XRD (Fig. 4) also reveal that the oxide films consist of Ni(OH)2. Angeliu and Was [25] have also found plate-like oxide formed on Nickel-based alloy had a hexagonal crystal structure corresponding to Ni(OH)2. The presence of nickel hydroxide in the external layer of oxide film was identified using XPS by several other authors [8, 23, 24]. In the present work, it is believed that the plate-like oxides are Ni(OH)2. Carrete and Machet [26] found that some iron hydroxide also existed as intermediate precipitates in the external layer formed on Alloy 690. However, the iron hydroxide is not stable, it would react with nickel hydroxide, and then the spinel NiFe2O4 formed in the external layer according to reaction (1) [33]. This mechanism results from the precipitation phenomenon due to the local saturation of Ni and Fe.

Ni(OH)2 +2Fe(OH)2 NiFe2O4 +2H2O+H2

(1)

The Ni2+ signal at BE of 853.2 0.3 eV and O 1s signal at BE of 530.3 0.3 eV are assigned to NiO [23], the Cr signal at BE of 576.2 0.3 eV and O 1s single at BE of 530.3 0.3 eV correspond to Cr2O3 [23, 26]. The E-pH diagrams of Ni and Cr in SCW at 400 oC proposed by Cook et al. [34-38] reveal that, NiO and Cr2O3 are chemical stable phases in such an environment. However, they just consider the pure metal, if taking the elements into account, the oxides maybe more complicate. The E-pH diagrams of Alloy 690 in PWR primary condition proposed by Huang et al. [39] revealed that NiCr2O4 and NiFe2O4 were the thermodynamic stable oxides. Sennour et
17

al. [33] calculated the thermodynamic stability of some oxides in PWR primary conditions and found that the stability of oxides as a decreasing rank Cr2O3>FeCr2O4>NiCr2O4>NiFe2O4>NiO. These results mean that the NiCr2O4 is more stable than NiO in high temperature water. The XRD results in the present work (Fig. 4) indicate that the intensity of NiO is weaker than that of spinel, suggesting that the content of NiO in the oxide film is less than spinel. This could be explained by considering the solid-state reaction between NiO and Cr2O3. With the development of oxidation, a part of NiO react with Fe3+ and OH- to form NiFe2O4 according reaction (2) [39], and a part of NiO react with Cr2O3 to form spinel NiCr2O4 by the reaction (3) [40]. As a result, the outer layer formed on Alloy 690 consists of Ni(OH)2, NiO and NiFe2O4. And the inner layer of the oxide film formed on Alloy 690 mainly contains Cr2O3 and NiCr2O4 after long-term exposure test in SCW.
NiO+2Fe3+ +6OH- NiFe2O4 +3H2O

(2) (3)

NiO+Cr2O3 NiCr2O4

Machet et al. [23] and Mclntyre et al. [41] proposed that the oxide films formed on Alloy 600 consist of an outer layer of Ni(OH)2/NiO and an inner of Cr2O3. However, both of them did not consider the transport of Fe ions in the oxide during long-term oxidation. The transport of Fe through Cr oxide at high temperatures has been observed in dry oxidation experiments [42]. If considering the transport of Fe through the oxide film, a more complicate spinel (Ni, Fe)(Cr, Fe)2O4 may be formed in the oxide lms after long-term oxidation. Combined with the results of XRD, Raman spectra and XPS, the outer layer consist of NiO, Ni(OH)2 and NiFe 2O4, and the inner
18

layer consists of Cr2O3 and NiCr2O4. This type of oxide film has been observed by many other authors in nickel-based alloys in sub-critical water and SCW [7-10, 24, 25, 33, 43].

4.4 Oxidation mechanism Several mechanisms have been proposed to explain the duplex oxide layer formed on metals in SCW [8, 9, 33, 43-45], in which the solid-stated growth mechanism [44] and metal dissolution/oxide precipitation mechanism [45] are generally accepted. In the present work, the experimental results and related analyses indicate that the oxides grew via a mixed mechanism. The porous outer layer grows via metal dissolution and oxide precipitation mechanism, and the compact inner layer grows via solid-state growth mechanism. Fig. 17 shows a schematic of the oxidation process of Alloy 690 in aerated SCW. At the beginning of exposure test, Cr oxidized preferentially by reacting with dissolved oxygen to form Cr2O3. Simultaneously, Fe and Ni can selectively dissolve into SCW at the active sites. With an increase in dissolved metal ions concentrations, the metal cations may combine with anions to form oxides or hydroxides and precipitate on the surface of the specimen. Ni(OH)2 and Fe(OH)2 precipitated on the surface (Fig. 17a), and then the outer layer of NiFe2O4 spinel is formed according to the reaction (1). Cr diffuses more slowly than Ni and Fe in the oxide, the lattice diffusion coefcient of the Cr ions in the Cr2O3 layer were two orders of magnitude lower than that of Ni ions [46], so Cr is retained and enriched in the inner layer. The anion (O2-) diffuses inward to the oxide/metal interface through
19

the short circuit paths such as micro-pores and grain boundaries [40, 47], and reacts with the enriched Cr in the inner layer. As a result, a continuous compact inner layer is formed (Fig. 17b). Oxidation can continue by outward diffusion of cation (Ni2+) to the oxide/water interface and reaction with oxygen or high temperature water, resulting in a NiO layer. With the development of oxidation, some NiO react with Fe3+ and OH- to form NiFe2O4 in the outer layer according reaction (2). And some NiO react with Cr2O3 to form spinel NiCr2O4 according to the reaction (3), as shown in Fig. 17c. With the outwards diffusion of Fe and Ni through the oxide layers, the process of oxide precipitation and solid-state reactions continue. As a result, a thicker oxide lm was formed.

5. Conclusions

The weight gain, phase compositions, surface and cross-section morphologies and elements distribution of the oxide films formed on Alloy 690 exposed to 450 oC and 550 oC aerated SCW has been investigated. The growth mechanism of the oxide films is also discussed. The following conclusions can be drawn. (1) General corrosion, pitting corrosion and nodule corrosion are observed on Alloy 690 exposed to aerated SCW. The weight change is fluctuated and a weight loss is observed with increasing exposure time, which could be attributed to the pitting. (2) The corrosion of TiN inclusions is faster than that of alloy matrix, resulting in high shear strain in the oxide films, followed by scale shrinking and cracking.
20

These inclusions play an important role in the pitting and nodule corrosion. (3) The oxide films formed on Alloy 690 in SCW show a duplex layer structure with a Cr-rich compact inner layer grown via solid-state growth mechanism and Ni-rich porous outer layer grown via metal dissolution/oxide precipitation mechanism. The outer layer consists of NiFe2O4 spinel, NiO and Ni(OH)2, and the inner layer contains Cr2O3 and NiCr2O4 spinel.

Acknowledgments
This study was jointly supported by National Basic Research Program of China (2011CB610501), National Science and Technology Major Project (2011ZX06004009) and Innovation Fund of Institute of Metal Research (IMR), Chinese Academy of Sciences (CAS).

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Figure Captions
Fig. 1 Schematic diagram of supercritical water experimental apparatus. Fig.2 (a) The metallographic image of as received Alloy 690, (b) Light optical morphologies of the TiN on Alloy 690 surface. Fig. 3 The weight change of Alloy 690 exposed to SCW at 450 oC and 550 oC. Fig. 4 (a) XRD patterns of the oxide films formed on Alloy 690 exposed to SCW at 450 oC and 550 oC. (b) XRD patterns of the oxide films formed on Alloy 690 exposed to SCW at 550 oC for different time. Fig. 5 (a) Raman spectroscopy of the oxide films formed on Alloy 690 exposed to SCW at 450 oC and 550 oC. (b) Raman spectroscopy of the oxide films formed on Alloy 690 exposed to SCW at 550 oC for different time. Fig. 6 SEM morphologies of the oxide film formed on Alloy 690 surface exposed to SCW at 450 oC for different time. (a, c) 450 oC for 100 h, (b, d) 450 oC for 500 h, Fig. 7 SEM morphologies of the oxide film formed on Alloy 690 surface exposed to SCW at 550 oC for different time. (a) 50 h, (b) 100 h, (c, d) 500 h. Fig. 8 Details of SEM morphologies of the oxide films formed at 550 oC for 100 h. (a) low amplification image, (b) high amplification image of area A in Fig. 8a, (c) cauliflower-like oxide on the oxide surface area B in Fig. 8a, (d) quadrate-like hole on the oxide surface. Fig. 9 SEM morphologies and EDS line scan of cross-section of the oxide films formed on Alloy 690 surface exposed to SCW at 450 oC and 550 oC for about 500 h. (a, b) 450 oC, (c, d) 550 oC.
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Fig. 10 The distribution of O, Fe, Ni, Cr in the oxide film formed on Alloy 690 surface exposed to SCW at 550 oC for 500 h. Fig. 11 The cross-section morphologies of oxidized TiN beneath the oxide film formed on Alloy 690 exposed to SCW at 550 oC for different time. (a) 100 h and (b) 500 h. Fig. 12 XPS depth proles of the oxide lms formed on Alloy 690 exposed to 450 oC SCW for 100 h. Fig. 13 XPS Ni 2p3/2 core level spectra (and their decomposition) of the oxide films formed on Alloy 690 exposed to 450 oC SCW for 100 h. Fig. 14 Cr 2p3/2 core level spectra (and their decomposition) of the oxide films formed on Alloy 690 exposed to 450 oC SCW for 100 h. Fig. 15 Fe 2p3/2 core level spectra (and their decomposition) of the oxide films formed on Alloy 690 exposed to 450 oC SCW for 100 h. Fig. 16 O 1s core level spectra (and their decomposition) of the oxide films formed on Alloy 690 exposed to 450 oC SCW for 100 h. Fig. 17 Schematics of oxidation process of Alloy 690 exposed to aerated SCW.

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Table Captions
Table 1 Chemical compositions of Alloy 690 (wt.%). Table 2 EDS results of site 1 to 5 in Fig. 8c and Fig. 8d (at.%). Table 3 EDS results of site 1 to 3 in Fig. 11 (at.%).

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Table 1 Chemical compositions of Alloy 690 (wt%).

C 0.013 N 0.01 Cr 29.15 Fe 9.19 Mn 0.21 P 0.01 Si 0.02 Al 0.26 Ti 0.305 Cu 0.01 Nb 0.01 Co 0.01 Ni Bal

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Table 2 EDS results of site 1 to 5 in Fig. 8c and Fig. 8d (at%).

Elements O Ti Cr Fe Ni 1 75.27 15.77 7.60 0.40 0.97 2 48.20 1.62 21.23 4.28 24.68 3 51.90 0.65 19.18 4.81 23.45 4 60.77 19.82 7.30 1.72 10.38 5 32.82 0.80 21.47 5.75 39.17

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Table 3 EDS results of site 1 to 3 in Fig. 11 (at%).

Elements O Ti Cr Fe Ni N 1 63.33 20.48 10.67 0.85 4.67 2 68.27 23.51 3.21 5.01 3 45.89 2.22 1.85 50.04

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Figure1

Figure2a

Figure2b

Figure3

Figure4a

Figure4b

Figure5a

Figure5b

Figure6a

Figure6b

Figure6c

Figure6d

Figure7a

Figure7b

Figure7c

Figure7d

Figure8a

Figure8b

Figure8c

Figure8d

Figure9a

Figure9b

Figure9c

Figure9d

Figure10

Figure11a

Figure11b

Figure12

Figure13

Figure14

Figure15

Figure16

Figure17

Highlights:

Weight gain of Alloy 690 fluctuated in aerated SCW. Ni and Fe are rich in outer layer of oxide scale, and Cr is rich in inner layer. Pits and nodules observed in oxide scales could be related to TiN inclusions.