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Acta Metall Sin  2017, Vol. 53 Issue (5): 622-630    DOI: 10.11900/0412.1961.2016.00269
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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,
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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.

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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 words:  empirical      electron      theory,      corrosion      resistance,      passivation      film,      interfacial      electron      density      difference,      Tammann's      law     
Received:  01 July 2016     
Fund: 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)
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Yao WANG
Chunfu LI
Yuanhua LIN

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https://www.ams.org.cn/EN/10.11900/0412.1961.2016.00269     OR     https://www.ams.org.cn/EN/Y2017/V53/I5/622

Fig.1  Unit cell structure of M (M is considered to be an average atom of Fe and Cr; A, B are the

non-negligible covalent bonds)

Fig.2  Atomic arrangement of X2O3 (X=Cr, Fe) in different crystallographic faces(a) (0001) (b) (101?0)O (c) (101?0)X (d) (112?0)
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
Table 1  Interfacial electron densities of Fe-5%Cr (atomic fraction) alloy on the different crystal faces
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
Table 2  Interfacial electron densities (ρ) of Cr2O3 and Fe2O3
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
Table 3  Vanlance electron structures of Fe-Cr alloy
Fig.3  Number of hybrid atomic orbital σn and EA of different Fe-Cr alloys
Fig.4  Hybrid levels of Fe (a) and Cr (b) in different Fe-Cr alloys
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