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Corrosion Science 52 (2010) 10981101

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

Short Communication

Effect of hydrogen in Inconel Alloy 600 on corrosion in high temperature


oxygenated water
J. Hou a,b, Q.J. Peng a,*, K. Sakaguchi a, Y. Takeda a, J. Kuniya a, T. Shoji a
a b

Fracture and Reliability Research Institute, Graduate School of Engineering, Tohoku University, 6-6-01, Aramaki Aoba, Aoba-ku, Sendai 980-8579, Japan State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, 62 Wencui Road, Shenyang 110016, China

a r t i c l e

i n f o

a b s t r a c t
Corrosion test on hydrogen charged and uncharged coupons of Inconel Alloy 600 in high temperature oxygenated water showed more weight loss of charged coupon. Observation of the oxide lm by transmission electron microscopy (TEM) showed a defective, thicker oxide layer on charged coupon. Analyses of the oxide lm by TEM-energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy indicated enrichment of Ni but depletion of Cr in the oxide lm on charged coupon. The changes in corrosion behavior and microstructure of the oxide lm were most likely due to the hydrogen enhanced preferential dissolution of Cr cations in the water. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 8 October 2009 Accepted 25 November 2009 Available online 3 December 2009 Keywords: A. Inconel Alloy 600 B. XPS B. TEM C. Hydrogen enhanced corrosion C. Corrosion in high temperature water C. Oxide lm

1. Introduction The corrosion of structural alloys in light water reactors has been one of the main concerns to the materials degradation management in nuclear power plants. While hydrogen dissolved in water and from metal oxidation in water can dissolve into the metal, little attentions have been paid to the role of hydrogen in metal in the corrosion in high temperature water. Most efforts relating to hydrogen effects have been focused on a mechanism of hydrogen facilitated cracking [13]. Since an amount of hydrogen is expected to enter and accumulate in the metal during a long-term operation of light water reactors, it is necessary to understand the role of hydrogen in metal in the corrosion behavior in high temperature water. Dissolved hydrogen in metals has shown to increase the anodic dissolution of an austenitic stainless steel and chromium in chloride and sulfate containing solution at room temperature [4,5], and the oxidation rate of iron, chromium and chromium ferritic steels in oxygen or steam at high temperatures [69]. It has been suggested that hydrogen could decrease the lm stability [813]. While these works have been done, to date the effect of hydrogen in metal on the corrosion behavior in high temperature water had remained unknown. Further, direct observation and analysis of the oxide lm are required to clarify the effect of hydrogen on the lm microstructure.
* Corresponding author. Tel.: +81 22 7957520; fax: +81 22 7957543. E-mail address: qpeng@rift.mech.tohoku.ac.jp (Q.J. Peng). 0010-938X/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2009.11.037

In the present work, the effect of hydrogen in Inconel Alloy 600 on corrosion in high temperature oxygenated water was studied by employing an exposure test, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses in an effort to develop the understanding of the role of hydrogen in metal in the corrosion behavior in high temperature water. The Alloy 600 was selected for the study because it has been used extensively in light water reactors as structural materials. 2. Experimental method The material used for the experiment is mill-annealed Alloy 600 with a chemical composition (wt.%): 0.07 C, 0.37 Mn, 9.46 Fe, 0.34 Si, 0.20 Cu, 15.41 Cr and 74.15 Ni. The corrosion test employed coupons of the alloy with the size of 30 mm 20 mm 0.5 mm, which were ground using emery papers up to 4000 grit. Hydrogen was charged into the coupon cathodically with a current density of 1 mA/cm2 in sulfuric acid solution at 50 C and pH 3.03.5 [2]. A charging time of 1680 h was used to obtain a high and uniform hydrogen concentration in the coupon. The time needed to achieve a near-uniform hydrogen concentration is determined when Dt/ L2 > 1.5 [14], where D: diffusivity (cm2/s), t: time and L: half thickness of the sample. Suppose the hydrogen diffusivity in Alloy 600 at 50 C is 1.7 1010 cm2/s [15], the time needed is about 1560 h. Following hydrogen charging, the coupon was ground again using the emery papers of 1500 and 4000 grits, in order to remove any surface damage by the cathodic charging. Then the charged

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coupon and an uncharged coupon were weighted, and hung into a refreshed autoclave equipped with a recirculation loop. The autoclave loop was then lled with high-purity water, pressurized to 8.5 MPa and heated to 288 C. Dissolved oxygen (DO) in the inlet water was kept at 8 ppm by purging the mixture of N2 and O2 into the water tank of the loop. Water purity was controlled by using ultra-high-purity water at the inlet and by purifying the outlet water using ion-exchangers. During the exposure, the water conductivity at inlet was 0.06 ls/cm and < 0.2 ls/cm at outlet. The coupons were exposed in the water for a period of 100 h. Post-test analyses conducted include weigh gain measurements and microstructural and compositional analyses of the oxide using XPS, SEM, TEM and TEM-energy dispersive X-ray spectroscopy (EDX). The XPS analysis was done by sequential sputtering of the oxide scale with a rate of 4.2 nm/min using a 2 kV argon ion beam rastering an area of 2 mm diameter. Samples for the TEM analysis were prepared by focus ion beam technique after coated the oxide by carbon and platinum.

3. Results and discussion Both charged and uncharged coupons showed weight loss following the exposure, Fig. 1. However, the charged coupon has a weight loss of 1.7 times of the uncharged coupon, indicating the enhanced dissolution of Alloy 600 in high temperature oxygenated water by hydrogen. Depth prole analysis of the oxide by XPS

0.00

-0.01

-0.02

-0.03

-0.04

Fig. 1. Weight gain of the hydrogen charged and uncharged coupons of Alloy 600 after the exposure in 288 C, oxygenated water.

showed a thicker lm on the charged coupon, Fig. 2(a) and (b). The thickness of the oxide lm estimated by the half height of oxygen is about 70 nm on charged coupon and 40 nm on uncharged coupon. Further, the gures also show that the oxide lm on charged coupon has a higher Ni concentration but lower Cr concentration throughout the thickness of the lm than the oxide lm on uncharged coupon, indicating that hydrogen increased Ni concentration but decreased Cr concentration in the lm. The maximum concentrations of Ni and Cr in the lm on the charged coupon is 32 at.% and 17.5 at.%, respectively, which changed to 23.5 at.% and 23 at.% in the lm on the uncharged coupon. The concentration of Fe, however, did not show difference in the two oxide lms. The difference in the corrosion behavior and concentrations of Ni and Cr in the oxide lm are most likely indications that hydrogen inuences the cation transport behavior in the oxide, which will be discussed later. Surface morphologies of the oxide lms were observed by SEM, Fig. 3. An amount of white, irregular networks of oxide was observed on the uniform oxide layer on the charged coupon (Fig. 3a), but few on uncharged coupon (Fig. 3b). Cross-sections of the oxide lms were analyzed by TEM. On the charged coupon, a layer of loose, defective oxide was observed with a thickness of about 30100 nm, Fig. 4(a). Scattered, needle- and pyramid-like oxides were observed on this layer, which should correspond to the white oxides on the outmost surface shown in Fig. 3(a). It is worthwhile to note that the oxide layer has a high density of defectiveness, suggesting it is unprotective. The diffraction pattern reveals that the defective layer is a spinel-type oxide, shown in Fig. 4(a) as an inset. The oxide scale on the uncharged coupon has a typical double-layer structure that consists of an inner thin, compact layer and an outer thick, continuous layer of needle- and pyramid-like oxides with a total thickness of about 2050 nm, Fig. 4(b). The numbered points 1 and 2 in both Fig. 4(a) and (b) designate the locations for the TEMEDX analyses of the oxides in inner and outer layers. The concentrations of Ni, Fe, Cr, O and the ratio of the concentration of Ni to Cr obtained from the analyses are listed in Table 1. Concentrations of Ni and Cr as well as their ratio clearly indicate the enrichment of Ni but depletion of Cr in the oxide on the charged coupon. Further, it is noted that the enrichment of Ni is more in the outer layer than that in the inner layer. The depletion of Cr, however, is more in the inner layer than that in the outer layer. It should be mentioned that while the element concentrations shown in Fig. 2 and Table 1 follow similar dependence on dissolved hydrogen, there are also discrepancies in the lm thickness and element concentration between Fig. 2 and Table 1. A main cause for the discrepancy may lie in the large area of the XPS analysis

Weight gain ( g/cm )

Charged coupon

80 70 60 50

Ni Cr as oxide Cr as metal Fe O

Uncharged coupon

80 70 60 50

Ni Cr as oxide Cr as metal Fe O

oxide

oxide

at%

40 30 20 10 0 0 5 10 15 20 25 30 35

at%

40 30 20 10 0 0 5 10 15 20 25 30 35

Sputtering time (min)

Sputtering time (min)

Fig. 2. Depth prole of the oxide lm on hydrogen charged coupon (a) and uncharged coupon (b) of Alloy 600 analyzed by XPS.

1100

J. Hou et al. / Corrosion Science 52 (2010) 10981101

Fig. 3. SEM observation of the surface morphology of the oxide on hydrogen charged coupon (a) and uncharged coupon (b) of Alloy 600.

Fig. 4. TEM observation of the cross section of the oxide lm on hydrogen charged coupon (a) and uncharged coupon (b) of Alloy 600.

(2 mm in diameter) that incorporated scatters in the concentration generated by the unevenness of the surface, the interface between the inner and outer layers of the oxide lm, and the interface between the oxide lm and the substrate. In addition, certain errors may have been generated by the EDX analysis of the light element (oxygen). The results of the experimental works described above showed that both the corrosion behavior and the microstructure of the oxide lm were affected by hydrogen dissolved in the alloy. In addition to the higher weight loss, hydrogen also resulted in a thicker, defective inner layer and a discontinuous outer layer of the oxide, in conjunction with the enrichment of Ni and depletion of Cr. One possible cause for the enhanced corrosion by hydrogen is the interactions of hydrogen with defects in the alloy and with the lattice of the alloy [4]. Defects in the alloy trapped hydrogen can become to the active sites. On the other hand, hydrogen may de-

Table 1 Concentrations of Ni, Cr, Fe, O and the ratio of the concentration of Ni to Cr in the oxide lms on hydrogen charged and uncharged coupons of Alloy 600 analyzed by TEMEDX. at.% Ni Charged Uncharged 1 (inner layer) 2 (outer layer) 1 (inner layer) 2 (outer layer) 19.1 16.5 18.0 11.6 Cr 10 7.4 14.3 9. 9 Fe 6.2 5.9 4.7 6.1 O 64.6 70.2 63.0 72.8 Ni/Cr 1.9 2.3 1.3 1.2

crease the interatomic cohesion, increase the activity and consequently the corrosion propensity. The simulation of quantum chemical molecular dynamics on the interaction of hydrogen with metal also suggested that hydrogen diffusing into the metal could be negatively charged, which weakened metal atomic bond strength and accelerated the oxidation [16,17]. While the interactions of hydrogen with the defects and lattice of the alloy can generally interpret the enhanced corrosion by hydrogen, the change in the microstructure and composition of the oxide lm by hydrogen can not be claried by this mechanism since details of the interactions remain unknown. The most possible cause for the effect of hydrogen is the hydrogen enhanced preferential dissolution of Cr cations in the water. Hydrogen in metals dissolves in the oxide lm as interstitial protons [5,9]. The protons at the metaloxide interface or in the oxide lm are commonly bonded to oxygen ions, forming substitutional hydroxide point defects, which are nally compensated by the metal vacancies in the lm [5,9,1820]. Therefore, the increase of dissolved interstitial protons in the lm resulted from the diffusion of hydrogen in the metal to the lm can increase the concentration of metal vacancies in the lm. This is the cause for the defective nature of the oxide shown in Fig. 4(a). Although it is difcult to demonstrate directly the enhanced transport of cations in the oxide by the presence of hydrogen-related defects, it is possible the increased concentration of metal vacancies enhance the diffusivity of metal cations [9,1820]. In fact, the enhanced transport of Cr cations in chromia due to the presence of dissolved hydrogen has been reported [9]. Depending on the solubility of the metal cations in the water, the enhanced

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cation transport will result in the difference in the cation concentration in the oxide. At high electrochemical corrosion potential associated with oxidizing species, the solubility of Cr is higher than that of Fe and Ni since Cr tends to go into solution as chromate (CrO42), and hence, the Cr-decient oxide is expected to be formed by the preferential dissolution of Cr cation [21]:

  3 2 Ni; FeCr2 O4 O2 H2 O ! Ni ; Fe2 2CrO2 2H 4 2

3. Analyses of the oxide by XPS and TEM indicated a thicker oxide lm on hydrogen charged coupon of Alloy 600. The enrichment of Ni and depletion of Cr in the lm on the hydrogen charged coupon were also revealed. 4. The enhanced corrosion of Alloy 600 by hydrogen is most likely the result of enhanced preferential dissolution of Cr cations in high temperature oxygenated water due to the hydrogen enhanced cation transport in the oxide lm.

It is therefore can be inferred that the enhanced cation transport in the lm will increase the concentration of Ni due to its relatively low solubility in the oxygenated water but will promote the dissolution of Cr cations in the outer layer of the oxide lm. In fact the results shown in Table 1 support the hypothesis on the hydrogen enhanced transport of cations. Suppose there are enhanced transports of the cation in the lm, it can be easily inferred that the enrichment of Ni cation would be more in the outer layer but the depletion of Cr cation will be more in the inner layer since the transport direction of the cation is from the inner layer to the outer layer. This is in consistence with the results of EDX analyses of the inner and outer layers shown in Table 1. As for Fe, its concentration showed little difference in the oxide lm on the charged and uncharged coupons. This likely implies that the transport of Fe cation is not dominant in the oxide due to the low Fe concentration in the alloy. However, the exact mechanism is not fully understood. The preferential dissolution of Cr cations in high temperature oxygenated water also suggests it dominates the enhanced dissolution of Alloy 600. On the other hand, the enhanced transport of Ni cation may promote the lm growth due to their low solubility and result in a thicker oxide lm on the charged coupon. As mentioned previously, there are difculties in obtaining direct proof of the hydrogen enhanced cation transport in the oxide lm. Further mechanistic study of the hydrogen enhanced corrosion of nickel-base alloys in high temperature water is required. 4. Conclusions

Acknowledgements This research has been supported by a joint research program on Prediction and Evaluation of Environmentally Assisted Cracking in LWR Structural Materials (PEACE-E program). The authors would thank Prof. T. Miyazaki for his support to the TEM analysis. One author (J. Hou) would also thank the support of the Special Funds for the Major State Basic Research Projects G2006CB605000 in China. References
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1. Exposure of hydrogen charged and uncharged coupons of Alloy 600 in 288 C, oxygenated water showed that hydrogen in Alloy 600 enhanced the dissolution of the alloy. 2. The defective nature of the oxide lm formed on the hydrogen charged coupon of Alloy 600 was shown directly by TEM observation.

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