扩散路径分析模型及其在镍基合金高温水氧化研究中的应用
Diffusion Path Analysis Model and Its Application to the Oxidation of Nickel-based Alloys in High Temperature Water
摘 要
针对Inconel 600和Inconel 690合金在高温高压水环境中生成的腐蚀氧化膜, 提出了扩散路径分析模型, 阐明了氧化膜微观结构及其形成机理。基于氧化膜成分、合金成分、以及环境因素, 构建了Inconel 600及Inconel 690合金的Ni-Cr-H2O三元相图。Inconel 600合金高温高压水腐蚀的扩散路径表明, 其氧化膜由内层Cr2O3与外层FeCr2O4尖晶石构成。通过Inconel 690合金高温高压水腐蚀的扩散路径分析可知, 氧化膜由单一的Cr2O3构成。扩散路径分析结果表明, 在Inconel 600氧化膜中, O2-比Cr3+具有更高的扩散速率, 而在Inconel 690氧化膜中, O2-的迁移率较低, 所受阻力较大, 从而使得Inconel 600和Inconel 690合金氧化膜呈现出不同的微观结构。
镍基合金
高温水氧化
diffusion path analysis (DPA) model
nickel-based alloy
oxidation in high temperature water
Abstract
A model of diffusion path analysis (DPA) was proposed to describe the microstructure and formation mechanism of oxide films on Inconel 600 and Inconel 690 in high-temperature and high-pressure water. First, a Ni-Cr-H2O ternary phase diagram was plotted according to the known composition of the alloys and oxide films, along with the environment factors. The diffusion path describing the oxidation of Inconel 600 in high-temperature and high-pressure water indicated that the surface films consisted of Cr2O3 inner layer and FeCr2O4 outer layer. According to the DPA for Inconel 690, the surface film was composed of Cr2O3 entirely. The diffusivity of O2- was higher than that of Cr3+ in surface films on Inconel 600. The Cr2O3 film formed on Inconel 690 had a higher resistance to the transportation of oxygen through the film, and thus the mobility of oxygen was low. As a consequence, the surface films formed on Inconel 600 and Inconel 690 exhibited different microstructures.
中图分类号 TG172.82 DOI 10.11973/fsyfh-201606014
所属栏目 应用技术
基金项目 国家核电技术有限公司资助项目(2015SN010-006)
收稿日期 2016/1/16
修改稿日期
网络出版日期
作者单位点击查看
备注汪峰(1977-), 高级工程师, 博士, 主要从事核电材料腐蚀研究,
引用该论文: WANG Feng,Thomas M. Devine. Diffusion Path Analysis Model and Its Application to the Oxidation of Nickel-based Alloys in High Temperature Water[J]. Corrosion & Protection, 2016, 37(6): 498
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【3】郦晓慧, 王俭秋, 韩恩厚, 等. 核级商用690合金和800合金在模拟压水堆核电站一回路高温高压水中的腐蚀行为研究[J]. 金属学报, 2012, 48(8):941-950.
【4】KUANG W J, WU X Q, HAN E H, et al. The mechanism of oxide film formation on alloy 690 in oxygenated high temperature water[J]. Corrosion Science, 2011, 53(11):3853-3860.
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【6】MACHET A, GALTAYRIES A, ZANNA S, et al. XPS and STM study of the growth and structure of passive films in high temperature water on a nickel-base alloy[J]. Electro Acta, 2004, 49(22/23):3957-3962.
【7】SENNOUR M, MARCHETTI L, MARTIN F, et al. A detailed TEM and SEM study of Ni-base alloys oxide scales formed in primary conditions of pressurized water reactor[J]. J Nucl Mater, 2010, 402:147-156.
【8】HUANG F, WANG J Q, HAN E H, et al. Microstructural characteristics of the oxide films formed on alloy 690 TT in pure and primary water at 325 ℃[J]. Corrosion Science, 2013, 76:52-59.
【9】SENNOUR M, LAGHOUTARIS P, GUERRE C, et al. Advanced TEM characterization of stress corrosion cracking of alloy 600 in pressurized water reactor primary water environment[J]. J Nucl Mater, 2009, 393:254-266.
【10】DELABROUILLE F, LEGRAS L, VAILLANT F, et al. Effect of the chromium content and strain on the corrosion of nickel based alloys in primary water of pressurized water reactors[C]//Proceedings of the 12th International Conference on Environmental Degradation of Materials in Nuclear Power System-Water Reactors. Slat Lake City:TMS, 2005:903-911.
【11】DEFARIA D L A, SILVA S V, DEOLIVEIRA M T. Raman microspectroscopy of some iron oxides and oxyhydroxides[J]. J Raman Spec, 1997, 28(11):873-878.
【12】VERBLE J L. Temperature-dependent light-scattering studies of the Verwey transition and electronic disorder in magnetite[J]. Phys Rev B, 1974, 9(12):5236-5241.
【13】FROMHOLD J R A T, Kruger J. Space-charge and concentration-gradient effects on anodic oxide film formation[J]. J Electr Soc, 1973, 120(6):722-729.
【14】CABRERA N, MOTT N F. Theory of the oxidation of metals[J]. Rep Prog Phys, 1949, 12:163-171.
【15】DALVI A D, COATES D E. A review of the diffusion path concept and its application to the high-temperature oxidation of binary alloys[J]. Oxid Metal, 1972, 5(2):113-135.
【16】NIU Y, GESMUNDO F. Phase stability, kinetic diagrams and diffusion path in high temperature oxidation of binary solid-solution alloys[J]. J Mater Sci Technol, 2003, 19(6):545-552.
【17】MACDONALD D D. Passivity-the key to our metals-based civilization[J]. Pure & Appl Chem, 1999, 71(61):951-978.
【18】BOJINOV M, FABRICIUS G, LAITINEN T. Coupling between ionic defect structure and electronic conduction in passive films on iron, chromium and iron-chromium alloys[J]. Electro Acta, 2000, 45(13):2019-2164.
【19】KIRKALDY J S, BROWN L C. Diffusion behaviour in ternary, multiphase systems[J]. Canadian Metallurgical Quarterly, 1963, 2(1):89-115.
【20】PANTER J, VIGUIER B, CLOUE J M, et al. Influence of oxide films on primary water stress corrosion cracking initiation of alloy 600[J]. J Nucl Mater, 2006, 348:213-221.
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