基于团簇模型设计的Cu-Cu12-[Mx/(12+x)Ni12/(12+x)]5 (M=Si, Cr, Cr+Fe) 合金抗高温氧化研究

李晓娜; 郑月红; 李震; 王苗; 张坤; 董闯

doi:10.7498/aps.63.028102

摘要

文章在稳定固溶体团簇模型的指导下，对白铜合金进行微合金化，将Cu元素在合金中的含量固定为72.22 at.%，改变Ni与 M（M 为Si，Cr，Cr+Fe）的比例，设计了系列合金成分，并对其抗高温氧化性能及其机制进行了研究. 同时加入基体中的Ni-Si元素可以从两方面提高合金的抗氧化性能：以团簇形式加入，形成稳定固溶体结构，可以降低Cu-Ni-Si合金的化学反应活性；Si/Ni比增大后，合金在少量固溶的基础上能析出抗氧化性能优于基体的析出相，且析出越多，抗高温氧化性能越好. 所以其抗氧化能力的来源并不是形成致密Si氧化物薄膜. Ni-Cr 的同时加入可以明显抑制Cu合金在800 ℃以下的中温氧化，但其抗高温氧化能力主要与外氧化层中是否形成连续的Cr 氧化层有关，因而该系列合金的抗高温氧化能力与Cr/Ni比有密切联系，合理选择团簇内Cr/Ni比例，才能够提高Cu合金的抗高温氧化能力. 第四组元Fe和第三组元Cr相比较，不能够起到优先氧化、生成保护性氧化皮的作用，所以Cr，Fe同时添加只能抑制Cu在800 ℃以下的中温氧化，却不能够提高Cu合金的抗高温氧化能力.

关键词:

Abstract

Based on the stable solid solution cluster model, cupronickel is microalloylized in this paper. Alloys with different Ni-M (M=Si, Cr, Cr+Fe) ratios are designed at constant atomic ration of Cu (72.22 at.%). The high temperature oxidation resistance and mechanism of alloy are also investigated. In the Cu-Ni-Si system, the addition of Ni-Si can enhance the oxidation resistance of the alloy from two aspects: firstly, the Ni-Si is in solid solution state when being added as a cluster, it can inhibit the chemical reactivity of Cu-Ni-Si alloy; secondly, anti-oxidation precipitation can be obtained with the increase of Si/Ni ratio. Therefore, the oxidation resistance of the alloy is not because of the formation of the compact silicon oxide film. In the Cu-Ni-Cr system, the oxidation is obviously inhibited at medium temperatures (lower than 800 ℃). But at higher temperatures, the oxidation resistance is relevant to the integrality of chrome oxide layer. The high temperature oxidation resistance is closely related to Cr/Ni ratio, hence an appropriate Cr/Ni ratio is necessary for the good high temperature oxidation resistance. Compared with the third element Cr, the forth element Fe cannot be oxidized first. Therefore, combined addition of Cr and Fe can only inhibit the medium temperature oxidation, but not high temperature oxidation.

Keywords:

作者及机构信息

1.
大连理工大学材料科学与工程学院, 三束材料改性教育部重点实验室, 大连 116024;

2.
大连理工常州研究院有限公司, 常州 213164;

3.
大连理工大学机械工程学院, 大连 116024

基金项目: 国家自然科学基金（批准号：51271045）和江苏省自然科学基金（批准号：BK20131138）资助的课题.

Authors and contacts

1.
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Ministry of Education, School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China;

2.
Changzhou Institute of Dalian University of Technology Corporation, Changzhou 213164, China;

3.
School of Mechanical Engineering, Dalian University of Technology, Dalian 116024, China

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 51271045) and the Natural Science Foundation of Jiangsu Province, China (Grant No. BK20131138).

参考文献

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[29]	Li X N, Liu L J, Zhang X Y, Chu J P, Wang Q, Dong C 2012 J. Electron. Mater. 41 3447
[30]	Cao Z Q, Shen Y, Liu W H, Xue Y 2006 Mater. Sci. Eng. A 425 138

施引文献

[1]	Wang Q, Ma M Z, Jing Q, Li G, Qi L, Zhang X Y, Wang W K, Liu R P 2008 Chin. Phys. Lett. 25 3808
[2]	《Engineering Materials Practical Handbook》Editorial Board 2002 Engineering Materials Practical Handbook (Version 2) (Beijing: Higher Education Press) (in Chinese) pp452–465 [《工程材料实用手册》编辑委员会 2002 工程材料实用手册 (第2版) (北京: 中国标准出版社) 第452–465页]
[3]	Bergmann W 1989 Werkstofftechnik (Vol. 1) (Munich: Hanser) p246, Vol. 2 p511
[4]	Kohlrausch F 1968 Praktische Physik (Vol. 3) (Stuttgart: Teubner) p84
[5]	Pan Q H 1996 The Chinese Journal of Nonferrous Metals 6 91 (in Chinese) [潘奇汉 1996 中国有色金属学报 6 91]
[6]	Beck T R 1995 in: J. Evans (ed) Light Metals, TMS, Warrendale, PA, USA p335
[7]	Suzuki S, Shibutani N, Mimura K, Isshiki M, Waseda Y 2006 J. Alloys Compd. 417 116
[8]	Yamamoto Y, Sasaki G, Yamakawa K, Ota M 2000 Hitachi Cable Review 19 65
[9]	Xiang J H, Li W K, Yang Q L, Zheng Y 2005 J. Yunnan Univ. 27 367 (in Chinese) [向军淮, 李文魁, 杨千兰, 郑勇 2005 云南大学学报 27 367]
[10]	Cao Z Q, Niu Y 2001 Corros. Sci. Protect. Technol. 13 408 (in Chinese) [曹中秋, 牛焱 2001 腐蚀科学与防腐技术 13 408]
[11]	Cao Z Q, Niu Y, Gesmundo F 2001 Oxid. Met. 56 287
[12]	Tomlinson W J, Yates J 1978 Oxid. Met. 12 323
[13]	Srivastava V C, Schneider A, Uhlenwinkel V, Ojha S N, Bauckhage K 2004 J. Mater. Process. Technol. 147 174
[14]	Qi N, Jia Y L, Liu H Q, Yi D Q, Chen Z Q 2012 Chin. Phys. Lett. 29 127803
[15]	Zhao D M, Dong Q M, Liu P, Kang B X, Huang J L, Jin Z H 2003 Mater. Chem. Phys. 79 81
[16]	Shao C W, Wang Z H, Li Y N, Zhao Q, Zhang L 2011 Acta Phys. Sin. 60 179 (in Chinese) [邵琛玮, 王振华, 李艳男,赵骞, 张林 2011 60 179]
[17]	Liu L, Dong Y D, He Y Z 1993 Acta Phys. Sin. (Overseas Edition) 2 731
[18]	Wen D D, Peng P, Jiang Y Q, Tian Z A, Liu R S 2013 Acta Phys. Sin. 62 196101 (in Chinese) [文大东, 彭平, 蒋元祺, 田泽安, 刘让苏 2013 62 196101]
[19]	Ding L P, Kuang X Y, Shao P, Zhao Y R, Li Y F 2012 Chin. Phys. B 21 043601
[20]	Qian S, Guo X L, Wang J J, Yu X Q, Wu S X, Yu J 2013 Acta Phys. Sin. 62 57803 (in Chinese) [钱帅, 郭新立, 王家佳, 余新泉, 吴三械, 于金 2013 62 57803]
[21]	Chen J X, Wang Q, Wang Y M, Dong C 2010 Phil. Mag. Lett. 90 683
[22]	Dong C, Wang Q, Qiang J B, Wang Y M, Jiang N, Han G, Li Y H, Wu J, Xia J H 2007 Phys. D: Appl. Phys. 40 R273
[23]	Dong C, Chen W R, Wang Y M, Qiang J B, Wang Q, Lei Y J 2007 Non-Cryst. Solids 353 3405
[24]	Hao C Q, Wang Q, Ma R T, Wang Y M, Qiang J B, Dong C 2011 Acta Phys. Sin. 60 116101 (in Chinese) [郝传璞, 王清, 马仁涛, 王英敏, 羌键兵, 董闯 2011 60 116101]
[25]	Takeuchi A, Inoue A 2005 Mater. Trans. 46 2817
[26]	Zhang J, Wang Q, Wang Y M, Wen L S, Dong C 2010 J. Alloys Compd. 505 179
[27]	Wang T C, Chen R Z, Tuan W H 2003 J. Europ. Ceram. Soc. 23 927
[28]	Liu G L, Yang J 2010 Acta Phys. Sin. 59 4939 (in Chinese) [刘贵立, 杨杰 2010 59 4939]
[29]	Li X N, Liu L J, Zhang X Y, Chu J P, Wang Q, Dong C 2012 J. Electron. Mater. 41 3447
[30]	Cao Z Q, Shen Y, Liu W H, Xue Y 2006 Mater. Sci. Eng. A 425 138

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