Cr对Fe-Cr合金耐蚀性能影响的电子理论研究
收稿日期: 2016-07-01
网络出版日期: 2017-03-06
基金资助
国家高技术研究发展计划项目No.2006AA06A105和西南石油大学油气藏地质及开发工程国家重点实验室基金项目No.PLN0609
Electronic Theoretical Study of the Influence of Cr on Corrosion Resistance of Fe-Cr Alloy
Received date: 2016-07-01
Online published: 2017-03-06
Supported by
Supported by National High Technology Research and Development Program of China (No.2006AA06A105) and Fund of State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation (No.PLN0609)
基于固体与分子经验电子理论(EET),对Fe-Cr合金(Cr含量为0~30%,原子分数)的价电子结构进行了半定量分析,利用界面电子密度差Δρ的计算方法,计算了Fe-Cr合金与Cr2O3、Fe2O3钝化膜低指数晶面间的电子密度。结果表明,Fe-Cr合金固溶体的杂化原子轨道数σn、最强键共价电子数nA和最强键键能EA均大于纯Fe,Cr能提高Fe基体的稳定性。当Cr含量达到12.52%和24.3%时,Cr原子从低阶迁移到共价电子数少的高阶状态,不稳定性增加,此时Cr易偏离平衡位置与腐蚀介质作用形成钝化膜,造成Fe-12.52%Cr和Fe-24.3%Cr合金的耐腐蚀性能发生突变。Fe-Cr合金与Cr2O3、Fe2O3钝化膜的24个低指数界面中,只有Fe-Cr(112)/Cr2O3(0001)、Fe-Cr(112)/Cr2O3(10
王垚 , 李春福 , 林元华 . Cr对Fe-Cr合金耐蚀性能影响的电子理论研究[J]. 金属学报, 2017 , 53(5) : 622 -630 . DOI: 10.11900/0412.1961.2016.00269
Based on the empirical electron theory (EET) of solids and molecules, the valence electron structure caculation results of Fe-Cr alloy containing (0~30%)Cr were analyzed semi-quantitatively. The electron density differences of interface (Δρ) between Fe-Cr alloy and Cr2O3, Fe2O3 passivation films were calculated. According to the results, adding Cr to α-Fe matrix can strengthen the matrix by improving the number of hybid atomic orbitals σn, the number of the strongest bond covalent electron pairs nA and the strongest covalent bond energy EA of Fe-Cr alloy. Once the content of Cr rises up to 12.52% and 24.3%, the corrosion resistance of Fe-Cr alloy is improved because of Cr being changed to a higher hybrid level, where Cr becomes more unstable and easily reacts with environment to form a complete passivation layer of Cr2O3. Moreover, among the electronic density differences of 24 low-index faces between Fe-Cr and Cr2O3, Fe2O3, only the Δρ of Fe-Cr(112)/ Cr2O3(0001), Fe-Cr(112)/Cr2O3 (10
Key words： empirical; electron; theory,; corrosion; resistance,; passivation; film,; interfacial; electron; density; difference,; Tammann's; law
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