Oxide Layers on (0001) Plane of Zircaloy-4 After Corrosion at 360 °C in Lithiated Aqueous Solution

doi:10.1007/s40195-015-0256-2

Abstract

Abstract:

The microstructures of the oxide layers formed on near (0001) plane of Zircaloy-4 were investigated by autoclave tests at 360 °C in lithiated aqueous solution. Oxygen-rich regions with hcp structure were observed at the undulating O/M interface, and the inner surface morphology of the oxide layers formed on (0001) was only concave-convex. Monoclinic, tetragonal and cubic phases and a kind of zirconium sub-oxide with bcc structure were detected in the oxide layer near the metal matrix. This zirconium sub-oxide layer had a coherent relationship with α-Zr matrix, and the growth direction of the zirconium sub-oxide layer was nearly parallel to the [0001] direction of α-Zr regardless of the orientation of metal matrix. The orientations scattering of columnar grains formed on near (0001) plane differ from that formed on near () plane.

Key words: Zircaloy-4, (0001), plane, Oxide/metal, interfaces, Microstructure, Oxygen-rich, regions, Zirconium, sub-oxide

Shao-Qiu Gou, Bang-Xin Zhou, Mei-Yi Yao, Jian-Chao Peng, Chuan-Ming Chen, Qiang Li, Jin-Long Zhang. Oxide Layers on (0001) Plane of Zircaloy-4 After Corrosion at 360 °C in Lithiated Aqueous Solution[J]. Acta Metallurgica Sinica (English Letters), 2015, 28(6): 748-757.

Figures/Tables 10

Fig. 1 TEM image of the whole thin foil sample showing the oxide layer and O/M interface

Fig. 2 a Bright-field image of metal matrix; b SAED pattern of the metal matrix; c bright-field image of the oxygen-rich region; d SAED pattern of the oxygen-rich region

Table 1 EDS results of the positions in Fig. 2a marked by the numbers

Position	Zr content (at%)	O content (at%)	Zr/O ratio
1	96.04	3.96	24.3
2	96.30	3.70	26.0
3	97.15	2.85	34.1
4	85.15	14.85	5.7
5	83.16	16.84	4.9
6	59.79	40.21	1.5
7	61.56	38.44	1.6
8	56.75	43.25	1.3

Fig. 3 Inner surface morphologies of the oxide layers formed on the grain surface with near (0001) plane: a the inner surface was concave-convex; b there were some relatively small concave-convex on the ridge strips observed at higher magnification

Fig. 4 HRTEM image of the type 1 O/M interface and FFT patterns for the areas marked by the letters (A α-Zr matrix, B bcc-ZrOx, C m-ZrO2, D c-ZrO2, E undefined structure)

Fig. 5 HRTEM image of the type 2 O/M interface and FFT patterns for the areas marked by the letters (A oxygen-rich region, B t-ZrO2, C m-ZrO2, D m-ZrO2)

Fig. 6 Reconstruction of the phase-contrast image of the area marked by “B” in Fig. 5

Fig. 7 HRTEM images of bcc-ZrO x that formed on metal grain with an orientation near ()

Fig. 8 HRTEM images of bcc-ZrO x that formed on metal grain with an orientation near (0001)

Fig. 9 SAED patterns of the oxide layers formed on near (0001) plane a, near () plane b, the corresponding dark-field TEM images obtained from the oxide layers on near (0001) plane c, near () plane d

References 32

[1]	H.J. Kim, T.H. Kim, Y.H. Jeong, J. Nucl. Mater. 306, 44(2002)
[2]	G. Bakradze, P.H. Jeurgens, J. Mittemeijer,Surf. Interface Anal. 42, 588(2010)
[3]	D. Charquet, R. Tricot, J.F. Wadier, paper present in: Zirconium in the Nuclear Industry, 8th International Symposium, West Conshohocken, ASTM STP 1023, (1989), pp. 374-388
[4]	G.C. Sun, B.X. Zhou, M.Y. Yao, S.J. Xie, Q. Li,Acta Metall. Sin. 48, 1103(2012). (in Chinese)
[5]	J. Favergeon, T. Montesin, G. Bertrand,Oxid. Met. 64, 253(2005)
[6]	C.S. Zhang, B.J. Flinn, I.V. Mitchell, P.R. Norton,Surf. Sci. 245, 373(1991)
[7]	B.X. Zhou, J.C. Peng, M.Y. Yao, Q. Li, S. Xia, C.X. Du, G. Xu, paper present in: Zirconium in the Nuclear Industry: 16th International Symposium, ASTM STP 1529, ASTM International, (2011), pp. 620-646
[8]	A. Yilmazbayhan, E. Breval, A.T. Motta, R.J. Comstock, J. Nucl. Mater. 349, 265(2006)
[9]	P. Bossis, G. Lelievre, P. Barberis, X. Iltis, F. Lefebvre, L. Thomas, M. Maguire, paper present in: Zirconium in the Nuclear Industry: Twelfth International Symposium, ASTM International, (2000), pp. 918-945
[10]	B. Wadman, Z. Lai, H.O. Nystrom, L.A. Nystrom, P. Rudling, H. Pettersson, paper present in: Zirconium in the Nuclear Industry: Tenth International Symposium, ASTM International, Baltimore, (1993), pp. 579-598
[11]	S. Abolhassania, G. Barta, A. Jakobb, J. Nucl. Mater. 399, 1(2009)
[12]	H. Anada, K. Takeda, paper present in: Zirconium in the Nuclear Industry: Eleventh International Symposium, American Society for Testing and Materials, Garmisch-Partenkirchen, Germany, (1995), pp. 35-54
[13]	Y. Dong, A.T. Motta, E.A. Marquis, J. Nucl. Mater. 442, 270(2013)
[14]	B.X. Zhou, Q. Li, M.Y. Yao, W.Q. Liu, Y.L. Chu,Corros. Prot. 30, 589(2009)
[15]	W.J. Gong, H.L. Zhang, Y. Qiao, H. Tian, X.D. Ni, Z.K. Li, X.T. Wang,Corros. Sci. 74, 323(2013)
[16]	J.C. Peng, MS Thesis, Shanghai University, 2009
[17]	S.Q. Gou, B.X. Zhou, C.M. Chen, M.Y. Yao, J.C. Peng, X. Liang, J.L. Zhang, Q. Li,Corros. Sci. 92, 237(2015)
[18]	M.Y. Yao, B.X. Zhou, Q. Li, W.Q. Liu, X. Geng, Y.P. Lu, J. Nucl. Mater. 374, 197(2008)
[19]	M. Paris, R. Foerch, G. Cailletaud, J. Phys. IV France 9, 311 (1999)
[20]	D.S. Balint, J.W. Hutchinson,Acta Mater. 51, 3965(2003)
[21]	V. Likhanskii, M. Kolesnik,Corros. Sci. 87, 416(2014)
[22]	B.X. Zhou, Q. Li, W.Q. Liu, M.Y. Yao, Y.L. Chu,Rare Met. Mater. Eng. 35, 1009(2006). (in Chinese)
[23]	D.J. Park, J.Y. Park, Y.H. Jeong, J. Nucl. Mater. 412, 233(2011)
[24]	H.J. Beie, A. Mitwalsky, F. Garzarolli, H. Ruhmann, H.J. Sell, paper present in: Zirconium in the Nuclear Industry: 10th International Symposium, ASTM STP 1245, ASTM International, (1994), pp. 615-643
[25]	H. Arashi, M. Ishigame, Phys. Stat. Solidi A 71, 313 (1982)
[26]	H.X. Zhang, D. Fruchart, E.K. Hill, L. Ortega, Z.K. Li, J.J. Zhang, J. Sun, L. Zhou, J. Nucl. Mater. 396, 65(2010)
[27]	E. Polatidis, P. Frankel, J. Wei, M. Klaus, R.J. Comstock, A. Ambard, S. Lyon, R.A. Cottis, M. Preuss, J. Nucl. Mater. 432, 102(2013)
[28]	W. Qin, C. Nam, H.L. Li, J.A. Szpunar,Acta Mater. 437, 280(2007)
[29]	R.C. Garvie, J. Phys. Chem. 69, 218(1965)
[30]	S. Fabris, A.T. Paxton, M.W. Finnis,Acta Mater. 50, 5171(2002)
[31]	P. Ghigna, G. Spinolo, U. Anselmi-Tamburini, F. Maglia, M. Dapiaggi, G. Spina, L. Cianchi, J. Am. Chem. Soc. 121, 301(1999)
[32]	C.X. Du, J.C. Peng, H. Li, B.X. Zhou,Acta Metall. Sin. 47, 887(2011). (in Chinese)