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金属学报  2017, Vol. 53 Issue (5): 622-630    DOI: 10.11900/0412.1961.2016.00269
  论文 本期目录 | 过刊浏览 |
Cr对Fe-Cr合金耐蚀性能影响的电子理论研究
王垚1,李春福1,林元华1,2()
1 西南石油大学材料科学与工程学院 成都 6105002
2 西南石油大学油气藏地质及开发工程国家重点实验室 成都 610500
Electronic Theoretical Study of the Influence of Cr on Corrosion Resistance of Fe-Cr Alloy
Yao WANG1,Chunfu LI1,Yuanhua LIN1,2()
1 School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500, China
2 State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation,
全文: PDF(1268 KB)   HTML
摘要: 

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(101?0)Cr、Fe-Cr(112)/Fe2O3(112?0)界面的Δρ <10%,对于同等Cr含量的基体,Fe-Cr(112)/Cr2O3(101?0)Cr界面Δρ最小,满足Δρ<10%的杂化原子轨道数σ最大。随着基体中Cr含量升高,Fe-Cr(112)/Cr2O3(0001)和Fe-Cr(112)/Fe2O3(112?0)界面Δρ降低,σ增加,Cr2O3、Fe2O3与基体的界面更加稳定牢固,因此Fe-24.3%Cr合金的耐腐蚀性可跃迁至更高水平。价电子结构对Fe-Cr合金耐蚀性能变化的分析结果基本符合Tammann定律的描述。

关键词 经验电子理论耐腐蚀性能钝化膜界面电子密度差Tammann定律    
Abstract

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 (101?0)Cr,Fe-Cr(112)/Fe2O3(112?0) are lower than 10%. For the matrix with same content of Cr, the Δρ between Fe-Cr(112) and Cr2O3(101?0)Cr is the lowest, but the number of hybid atomic orbitals σ satisfied Δρ<10% is the largest. Δρ (σ) of Fe-Cr(112)/Cr2O3(0001) and Fe-Cr(112)/Fe2O3(112?0) is decreased (increased) with the increase of Cr, therefore the interface bonding strength between Cr2O3, Fe2O3 and matrix will be enhanced, it has been found that the corrosion resistance of Fe-24.3%Cr is better. The calculation results of variation of Fe-Cr corrosion resistance with Cr content are in better agreement with Tammann's law.

Key wordsempirical    electron    theory,    corrosion    resistance,    passivation    film,    interfacial    electron    density    difference,    Tammann's    law
收稿日期: 2016-07-01      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

引用本文:

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.
Yao WANG,Chunfu LI,Yuanhua LIN. Electronic Theoretical Study of the Influence of Cr on Corrosion Resistance of Fe-Cr Alloy. Acta Metall Sin, 2017, 53(5): 622-630.

链接本文:

http://www.ams.org.cn/CN/10.11900/0412.1961.2016.00269      或      http://www.ams.org.cn/CN/Y2017/V53/I5/622

图1  M的晶体结构图(M为Fe、Cr 原子组成的平均原子;A、B为不可忽略的共价键)
图2  X2O3 (X=Cr、Fe)晶面原子分布
Crystal face Bond Ia na S / cm2 ρ / nm-2
(110) M-M 4 0.3875 0.1162 14.8559
M-M 2 0.0882
(100) M-M 4 0.0882 0.0822 4.2942
(112) M-M 27 0.3875 0.0503 2.2004
表1  Fe-5%Cr合金的界面电子密度
Crystal face Bond Ia na S / cm2 ρ / nm-2
Cr2O3 Fe2O3 Formula Cr2O3 Fe2O3 Cr2O3 Fe2O3
(0001) O1-O3 6 0.0261 0.0340 32a02 0.2123 0.2187 1.0930 1.2756
O1-O2 12 0.0063 0.0102
(101?0)Cr O1-O2 6 0.0063 0.0102 a0c 0.6736 0.6921 0.0560 0.0884
(101?0)X X1-X2 2 0.4076 0.2186 a0c 0.6736 0.6921 1.9754 1.0957
X1-X3 2 0.2327 0.1456
X1-X4 2 0.0201 0.0111
X1-X5 2 0.0049 0.0039
(112?0) X-O2 4 0.9528 1.1290 3a0c 1.1667 1.1988 6.2157 6.2597
X-O1 4 0.8024 0.6689
X-O3 4 0.0032 0.0033
O1-O3 6 0.0261 0.0340
O1-O4 6 0.0103 0.0160
表2  Cr2O3、Fe2O3的界面电子密度
Atomic fraction Atomic state σn nA EA
of Cr / % Hybridization ncFe Hybridization ncCr kJmol-1
level of Fe level of Cr
0 8 3.5955 - - 3 0.3835 59.8761
1 8 3.5955 1 4 54 0.3840 60.0479
2 8 3.5955 1 4 54 0.3844 60.2197
3 8 3.5955 1 4 54 0.3848 60.3926
4 8 3.5955 3 3.9515 54 0.3851 60.6105
5 8 3.5955 5 3.8779 54 0.3851 60.7721
6 8 3.5955 5 3.8779 54 0.3854 60.8624
7 8 3.5955 5 3.8779 54 0.3857 61.0289
8 7 3.5560 1 4 61 0.3831 60.1916
9 7 3.5560 1 4 65 0.3836 60.3758
10 7 3.5560 2 3.9851 65 0.3839 60.6539
11 7 3.5560 3 3.9515 67 0.3840 60.8699
12 7 3.5560 4 3.9360 67 0.3842 61.0611
12.50 7 3.5560 4 3.9360 68 0.3844 61.1598
12.52 9 3.7743 13 3.1290 68 0.3940 65.3692
13 9 3.7743 13 3.1290 68 0.3937 65.3777
14 7 3.5560 5 3.8779 65 0.3841 61.3981
15 7 3.5560 5 3.8779 64 0.3845 61.6811
16 7 3.5560 5 3.8779 64 0.3848 61.7875
17 9 3.7743 11 3.2932 60 0.3939 65.9435
18 9 3.7743 11 3.2932 58 0.3934 65.9905
19 9 3.7743 10 3.3538 61 0.3941 66.2459
20 9 3.7743 10 3.3538 63 0.3937 66.3043
21 9 3.7743 10 3.3538 64 0.3932 66.3630
22 9 3.7743 9 3.3972 65 0.3938 66.5806
23 9 3.7743 9 3.3972 69 0.3934 66.5781
24 9 3.7743 9 3.3972 71 0.3930 66.7128
24.3 10 3.9723 13 3.1290 71 0.4019 70.2113
25 10 3.9723 13 3.1290 73 0.4013 70.1827
26 10 3.9723 12 3.1635 72 0.4013 70.3102
27 10 3.9723 12 3.1635 70 0.4004 70.2761
28 8 3.5955 6 3.6807 75 0.3861 64.0870
29 8 3.5955 6 3.6807 76 0.3862 64.2539
30 8 3.5955 6 3.6807 78 0.3863 64.6460
表3  Fe-Cr合金的价电子结构
图3  不同Fe-Cr合金中杂化原子轨道数σn和最强键键能EA
图4  不同Fe-Cr合金的Fe、Cr原子杂阶
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