稀土元素鈰對鋼中非金屬夾雜物改性和腐蝕影響的第一性原理研究

劉瀚澤; 張靜; 張繼; 張立峰; 蓋彥峰

doi:10.13374/j.issn2095-9389.2022.02.04.001

稀土元素鈰對鋼中非金屬夾雜物改性和腐蝕影響的第一性原理研究

doi: 10.13374/j.issn2095-9389.2022.02.04.001

劉瀚澤¹,
張靜^1, ,,
張繼²,
張立峰^3, ,,
蓋彥峰⁴

1.
燕山大學車輛與能源學院，秦皇島 066004
2.
北京科技大學冶金與生態工程學院，北京 100083
3.
北方工業大學機械與材料工程學院，北京 100144
4.
燕山大學理學院，秦皇島 066004

基金項目: 河北省科技計劃資助項目（20311004D，20591001D，20311005D）；燕山大學高鋼中心（HSC）和北方工業大學高鋼中心（HSC）資助項目

詳細信息

通訊作者:
張靜，E-mail: zhangjing@ysu.edu.cn

張立峰，E-mail: zhanglifeng@ncut.edu.cn

中圖分類號: TG142.1
計量
- 文章訪問數: 2524
- HTML全文瀏覽量: 220
- PDF下載量: 105
- 被引次數: 0
出版歷程
- 收稿日期: 2022-02-04
- 網絡出版日期: 2022-05-05
- 刊出日期: 2022-09-01

First-principle study of the effect of cerium on the modification and corrosion of nonmetal inclusions in steel

LIU Han-ze¹,
ZHANG Jing^{1
, ,},
ZHANG Ji²,
ZHANG Li-feng^{3
, ,},
GE Yan-feng⁴

1.
School of Vehicle and Energy, Yanshan University, Qinhuangdao 066004, China
2.
School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing100083, China
3.
School of Mechanical and Materials Engineering, North China University of Technology, Beijing 100144, China
4.
School of Science, Yanshan University, Qinhuangdao 066004, China

More Information

Corresponding author: ZHANG Jing, E-mail: zhangjing@ysu.edu.cn; ZHANG Li-feng, E-mail: zhanglifeng@ncut.edu.cn

摘要

摘要: 通過原位腐蝕觀察和基于密度泛函理論的第一性原理計算方法，從微觀角度研究了稀土元素鈰（Ce）對J5不銹鋼中夾雜物的改性和夾雜物誘導腐蝕的機理。采用掃描電子顯微鏡與能譜分析了稀土元素Ce改性夾雜物的過程中夾雜物成分和類型的變化，觀察到的代表夾雜物為CeAlO₃?Ce₂O₂S、Ce₂O₃?Ce₂O₂S、MnS等。根據形成能計算，經稀土元素Ce處理后，生成了穩定的Ce₂O₃、Ce₂O₂S、CeAlO₃夾雜物。通過表面能判斷了晶面的穩定性，Fe(100)-2面的表面能經收斂測得為2.4374 J·m^?2，該晶面的功函數為4.7352 eV。通過對比夾雜物與鋼基體的功函數與計算電勢差，分析了不同含Ce夾雜物誘導點蝕的趨勢，探討了不同原子位置、原子數量和不同slab模型對功函數的影響。研究表明，與Fe (100)-2面的電子功函數相比，MnS以及改性后3種夾雜物CeS、Ce₂O₃和Ce₂O₂S電勢差大多小于0，CeAlO₃的電勢差在0 eV左右。夾雜物不同晶面對功函數影響很大，O、S等非金屬原子數量多的晶面功函數平均值較高，添加稀土元素Ce可以有效降低晶面功函數。5種夾雜物和鋼基體的平均功函數大小順序為CeAlO₃>Fe>MnS>CeS>Ce₂O₂S>Ce₂O₃。結合不銹鋼中復合夾雜物的實驗結果可知，Ce₂O₃誘導點蝕發生的概率最高，CeAlO₃可以有效提高鋼的耐腐蝕能。
- 第一性原理 /
- 局部腐蝕 /
- 夾雜物 /
- 電子功函數 /
- 原位觀察 /
- 稀土元素鈰
Abstract: Nonmetallic inclusions in steel significantly influence the steel life, quality, toughness, and corrosion resistance. Pitting corrosion is the most common type of localized corrosion in stainless steel. Rare-earth elements, which are key materials in the metallurgical sector, largely influence the modification of sulfur (S) and oxygen (O) inclusions in steel. Numerous experimental studies have been conducted on the corrosion of the rare-earth metal cerium (Ce); however, studies on the microscopic-scale mechanism are few. In this study, in situ corrosion observation and the first-principle calculations based on density functional theory were applied to investigate the effects of the rare-earth element cerium on inclusions in J5 stainless steel and the inclusion-induced corrosion process. The changes in the inclusion composition and the primary types of inclusions in the steel were investigated by scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The results show that CeAlO₃?Ce₂O₂S, Ce₂O₃?Ce₂O₂S, and MnS are representative inclusions. MnS and other oxide inclusions in stainless steel were treated with Ce to generate stable Ce₂O₃, Ce₂O₂S, and CeAlO₃ inclusions, according to formation energy calculations. The surface energy of the Fe (100)-2 plane is measured as 2.4374 J·m^?2, and the work function of this crystal plane is predicted to be 4.7352 eV. The crystal plane stability was examined according to the surface energy. The work functions and potential differences between the inclusion and the steel matrix were analyzed to compare the trend of pitting corrosion induced by different Ce-containing inclusions, and the influences of different atomic positions, atomic numbers, and different slab models on the work function were explored. Compared with the electronic work function of the Fe (100)-2 surface, the potential difference between MnS and the three modified inclusions CeS, Ce₂O₃, and Ce₂O₂S is typically less than zero, and the potential difference of CeAlO₃ is about 0 eV. The average work function of the crystal plane with a large number of nonmetal atoms such as O and S is higher. Ce addition reduces the work function of the crystal plane, and the molecular mechanism of pitting corrosion according to different crystal planes and termination planes of inclusions is revealed. The five types of inclusions and the steel matrix are in the following order: CeAlO₃>Fe>MnS>CeS>Ce₂O₂S>Ce₂O₃. The experimental findings on composite inclusions in stainless steel reveal that Ce₂O₃ has the highest chance of pitting corrosion, and CeAlO₃ can significantly improve steel corrosion resistance.
- first principles /
- pitting corrosion /
- inclusions /
- electron work function /
- in-situ observation /
- rare earth element cerium

HTML全文

圖 1 晶體結構. (a) bcc-Fe；(b) MnS；(c) CeS；(d) Ce₂O₃；(e) Ce₂O₂S；(f)CeAlO₃

Figure 1. Crystal structures: (a) bcc-Fe; (b) MnS; (c) CeS; (d) Ce₂O₃; (e) Ce₂O₂S; (f) CeAlO₃

下載: 全尺寸圖片幻燈片

圖 2 MnS夾雜物的形貌及元素分布

Figure 2. Morphology and element distribution of the MnS inclusions

下載: 全尺寸圖片幻燈片

圖 3 CeAlO₃?Ce₂O₂S夾雜物的形貌及元素分布

Figure 3. Morphology and element distribution of the CeAlO₃?Ce₂O₂S inclusions

下載: 全尺寸圖片幻燈片

圖 4 Ce₂O₃?Ce₂O₂S夾雜物的形貌及元素分布

Figure 4. Morphology and element distribution of the Ce₂O₃?Ce₂O₂S inclusions

下載: 全尺寸圖片幻燈片

圖 5 Fe(100)-2面靜電勢曲線(a)和slab模型(b)

Figure 5. Electrostatic potential curve (a) and slab model (b) of Fe (100)-2 surface

下載: 全尺寸圖片幻燈片

圖 6 MnS和CeS的slab模型

Figure 6. Slab model of MnS and CeS

下載: 全尺寸圖片幻燈片

圖 7 Ce₂O₃的slab模型

Figure 7. Slab model of Ce₂O₃

下載: 全尺寸圖片幻燈片

圖 8 Ce₂O₂S的slab模型

Figure 8. Slab model of Ce₂O₂S

下載: 全尺寸圖片幻燈片

圖 9 MnS夾雜物與鋼基體間的電勢差

Figure 9. Potential difference between MnS inclusions and steel matrix

下載: 全尺寸圖片幻燈片

圖 10 CeS夾雜物與鋼基體間的電勢差

Figure 10. Potential difference between CeS inclusions and steel matrix

下載: 全尺寸圖片幻燈片

圖 11 Ce₂O₃夾雜物與鋼基體間的電勢差

Figure 11. Potential difference between Ce₂O₃ inclusions and steel matrix

下載: 全尺寸圖片幻燈片

圖 12 Ce₂O₂S夾雜物與鋼基體間的電勢差

Figure 12. Potential difference between Ce₂O₂S inclusions and steel matrix

下載: 全尺寸圖片幻燈片

圖 13 CeAlO₃夾雜物與鋼基體間的電勢差

Figure 13. Potential difference between CeAlO₃ inclusions and steel matrix

下載: 全尺寸圖片幻燈片

圖 14 鋼中典型夾雜物在0、1和5 min浸泡后的形貌圖

Figure 14. Morphologies of typical inclusion in the Ce-bearing steel after 0, 1, and 5 min immersion

下載: 全尺寸圖片幻燈片

表 1 Fe與夾雜物晶體結構參數

Table 1. Inclusion crystal structure parameters

Material	Space ground	Atom positions	Lattice parameters
Fe	Im$\overline{3} $m (299)	Fe (0,0,0)	a=b=c=0.283 nm α=β=γ=90°
MnS	Fm$\overline{3} $m (225)	Mn (0,0,0) S (0.5,0.5,0.5)	a=b=c=0.522 nm α=β=γ=90°
CeS	Fm$\overline{3} $m (225)	Ce (0,0,0) S (0.5,0.5,0.5)	a=b=c=0.568 nm α=β=γ=90°
Ce₂O₃	P$\overline{3} $m1 (164)	Ce (0.33,0.67,0.25) O (0.33,0.67,0.64)	a=b=0.383 nm c=0.607 nm α=β=90°，γ=120°
Ce₂O₂S	P$\overline{3} $m1 (164)	Ce (0.33,0.67,0.28) O (0.33,0.67,0.63) S (0,0,0)	a=b=0.395 nm c=0.680 nm α=β=90°, γ=120
CeAlO₃	R$\overline{3} $c (164)	Ce (0,0,0.25) Al (0,0,0) O (0.519,0,0.25)	a=b=0.539 nm c=1.139 nm α=β=90°, γ=120°

下載: 導出CSV

表 2 J5不銹鋼化學成分(質量分數)

Table 2. Chemical composition of J5 stainless steel %

C	Si	Mn	P	S	Cr	Ni	N
0.13	0.51	10.05	0.045	0.0019	13.37	0.93	0.15

下載: 導出CSV

表 3 含Ce夾雜物的形成能

Table 3. Formation energy of inclusions eV·atom^?1

Ce₂O₃	Ce₂O₂S	CeAlO₃	CeS	Ce₂S₃	Ce₃S₄
?3.33192	?3.20334	?3.22015	?2.38639	?2.43052	?2.41476

下載: 導出CSV

表 4 Fe不同終止面的電子功函數與表面能

Table 4. Electronic work function and surface energy of different termination surfaces of Fe matrix

Surface	Terminated plane	Work function/eV			Surface energy/(J·m^?2)
Surface	Terminated plane	This work	Experiment	Calculation	This work	Experiment	Calculation
100	1	4.7433	4.67^[23]	4.65^[18]	2.7405	2.41^[24]	2.463^[25]
100	2	4.7352			2.4374
110	1	4.7367	4.5^{[23, 26]}		2.4443	2.41^[24]	2.48^[26]
110	2	4.7368			2.4431
111	1	3.8098	4.81^[23]		2.7111	2.41^[24]	2.658^[27]
	2	3.8105			2.7113
	3	3.8182			2.7111

下載: 導出CSV

表 5 MnS不同終止面的電子功函數

Table 5. Electronic work function of different termination surfaces of MnS

Surface	Terminated plane	Work function/eV
100	1	4.11
100	2	4.10
110	1	4.14
110	2	4.13
111	1	3.36
	2	5.82
	3	3.39
	4	5.82
	5	3.38
	6	5.81

下載: 導出CSV

表 6 CeS不同終止面的電子功函數

Table 6. Electronic work function of different termination surfaces of CeS

Surface	Terminated plane	Work function/eV
100	1	2.34
100	2	2.32
110	1	2.42
110	2	2.42
111	1	3.16
	2	5.33
	3	3.15
	4	5.34
	5	3.15
	6	5.34

下載: 導出CSV

表 7 Ce₂O₃不同終止面的電子功函數

Table 7. Electronic work function of different termination surfaces of Ce₂O₃

Surface	Terminated plane	Work function/eV
100	1	3.08
	2	2.05
	3	2.45
	4	3.09
	5	2.05
	6	2.44
110	1	1.87
110	2	1.85
111	1 upper plane	2.49
	1 lower plane	2.12
	2 upper plane	2.42
	2 lower plane	4.72
	3 upper plane	2.74
	3 lower plane	2.58
	4 upper plane	4.09
	4 lower plane	2.22
	5 upper plane	2.19
	5 lower plane	3.08
	6 upper plane	2.46
	6 lower plane	2.12
	7 upper plane	2.41
	7 lower plane	4.74
	8 upper plane	2.72
	8 lower plane	2.59
	9 upper plane	4.09
	9 lower plane	2.23
	10 upper plane	2.21
	10 lower plane	3.13

下載: 導出CSV

表 8 Ce₂O₂S不同終止面的電子功函數

Table 8. Electronic work function of different termination surfaces of Ce₂O₂S

Surface	Terminated plane	Work function/eV
100	1	4.52
	2	2.11
	3	2.52
	4	4.51
	5	2.14
	6	2.53
110	1	2.13
110	2	2.13
111	1 upper plane	3.44
	1 lower plane	2.00
	2 upper plane	2.35
	2 lower plane	4.72
	3 upper plane	2.42
	3 lower plane	2.75
	4 upper plane	3.84
	4 lower plane	2.17
	5 upper plane	2.11
	5 lower plane	3.53
	6 upper plane	3.56
	6 lower plane	2.03
	7 upper plane	2.33
	7 lower plane	4.69

下載: 導出CSV

表 9 CeAlO₃不同終止面的電子功函數

Table 9. Electronic work function of different termination surfaces of Ce₂O₃

Surface	Terminated plane	Work function/eV
100	1	4.20
	2	1.96
	3	1.96
	4	4.64
	5	6.50
110	1	3.89
	2	2.73
	3	1.28
	4	5.94
	5	6.42
111	1	4.19
	2	5.18
	3	4.19
	4	4.01

下載: 導出CSV

www.77susu.com

參考文獻(31)

[1]	Wang X H. Non-metallic inclusion control technology for high quality cold rolled steel sheets. Iron Steel, 2013, 48(9): 1 王新華. 高品質冷軋薄板鋼中非金屬夾雜物控制技術. 鋼鐵, 2013, 48(9):1
[2]	Zimer A M, De Carra M A S, Rios E C, et al. Initial stages of corrosion pits on AISI 1040 steel in sulfide solution analyzed by temporal series micrographs coupled with electrochemical techniques. Corros Sci, 2013, 76: 27 doi: 10.1016/j.corsci.2013.04.054
[3]	Frankel G S. Pitting corrosion of metals: A review of the critical factors. J Electrochem Soc, 1998, 145(6): 2186 doi: 10.1149/1.1838615
[4]	Zhang J, Zhang L F. Application and research progress of rare earth elements in stainless steels. J Yanshan Univ, 2020, 44(3): 267 doi: 10.3969/j.issn.1007-791X.2020.03.008 張繼, 張立峰. 稀土元素在不銹鋼中的應用及研究進展. 燕山大學學報, 2020, 44(3):267 doi: 10.3969/j.issn.1007-791X.2020.03.008
[5]	Ghahari S M, Davenport A J, Rayment T, et al. In situ synchrotron X-ray micro-tomography study of pitting corrosion in stainless steel. Corros Sci, 2011, 53(9): 2684 doi: 10.1016/j.corsci.2011.05.040
[6]	Liu C, Revilla R I, Liu Z Y, et al. Effect of inclusions modified by rare earth elements (Ce, La) on localized marine corrosion in Q460NH weathering steel. Corros Sci, 2017, 129: 82 doi: 10.1016/j.corsci.2017.10.001
[7]	Li Y B, Wang F M, Li C R, et al. Effect of cerium on pitting resistance of low sulphur ferritic stainless steels. Chin Rare Earths, 2010, 31(3): 30 doi: 10.3969/j.issn.1004-0277.2010.03.007 李亞波, 王福明, 李長榮, 等. 鈰對低硫鐵素體不銹鋼抗點蝕性能的影響. 稀土, 2010, 31(3):30 doi: 10.3969/j.issn.1004-0277.2010.03.007
[8]	Cai G J, Li C S. Effects of Ce on inclusions and corrosion resistance of low-nickel austenite stainless steel. Mater Corros, 2015, 66(12): 1445 doi: 10.1002/maco.201508380
[9]	Xi X J, Yang S F, Li J S, et al. Inclusion modification and corrosion resistance optimization of 304 stainless steel containing cerium. Iron Steel, 2020, 55(1): 20 習小軍, 楊樹峰, 李京社, 等. 含鈰304不銹鋼夾雜物改性及耐腐蝕性能優化. 鋼鐵, 2020, 55(1):20
[10]	Cai G J, Pang Y T, Huang Y R, et al. Roles of inclusion, texture and grain boundary in corrosion resistance of low-nickel austenite stainless steel containing Ce. ISIJ Int, 2019, 59(12): 2302 doi: 10.2355/isijinternational.ISIJINT-2019-248
[11]	Liu X, Wang L M. Effect of Ce on the inclusions and pitting resistance of 2Cr13 stainless steel. Adv Mater Res, 2012, 602-604: 376 doi: 10.4028/www.scientific.net/AMR.602-604.376
[12]	Zhang J, Su C M, Chen X P, et al. First-principles study on pitting corrosion of Al deoxidation stainless steel with rare earth element (La) treatment. Mater Today Commun, 2021, 27: 102204 doi: 10.1016/j.mtcomm.2021.102204
[13]	Li W, Li D Y. Variations of work function and corrosion behaviors of deformed copper surfaces. Appl Surf Sci, 2005, 240(1-4): 388 doi: 10.1016/j.apsusc.2004.07.017
[14]	Hou Y H, Liu L L, Li G Q, et al. The correlation between potential difference and galvanic corrosion of composite inclusions/steel matrix in steel // The 12th Proceedings of China Iron & Steel Annual Meeting. Beijing, 2019: 510 侯延輝, 劉林利, 李光強, 等. 鋼中復合夾雜物/鋼基體的電勢差與電偶腐蝕的關系 // 第十二屆中國鋼鐵年會論文集. 北京, 2019:510
[15]	Kresse C, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B Condens Matter, 1996, 54(16): 11169 doi: 10.1103/PhysRevB.54.11169
[16]	Sweeney J S, Heinz D L. Compression of α-MnS (alabandite) and a new high-pressure phase. Phys Chem Miner, 1993, 20(1): 63
[17]	Bl?chl P E. Projector augmented-wave method. Phys Rev B, 1994, 50(24): 17953 doi: 10.1103/PhysRevB.50.17953
[18]	Cao Y X, Li G Q, Hou Y H, et al. DFT study on the mechanism of inclusion-induced initial pitting corrosion of Al?Ti?Ca complex deoxidized steel with Ce treatment. Phys B Condens Matter, 2019, 558: 10 doi: 10.1016/j.physb.2019.01.027
[19]	?nmark N, Karasev A, J?nsson P G. The effect of different non-metallic inclusions on the machinability of steels. Mater (Basel Switz), 2015, 8(2): 751 doi: 10.3390/ma8020751
[20]	Wilson W G, Kay D A R, Vahed A. The use of thermodynamics and phase equilibria to predict the behavior of the rare earth elements in steel. JOM, 1974, 26(5): 14 doi: 10.1007/BF03355873
[21]	Mattsson T R, Mattsson A E. Calculating the vacancy formation energy in metals: Pt, Pd, and Mo. Phys Rev B, 2002, 66(21): 214110 doi: 10.1103/PhysRevB.66.214110
[22]	Liu X J, Yang J C, Zhang F, et al. Experimental and DFT study on cerium inclusions in clean steels. J Rare Earths, 2021, 39(4): 477 doi: 10.1016/j.jre.2020.07.021
[23]	Michaelson H B. The work function of the elements and its periodicity. J Appl Phys, 1977, 48(11): 4729 doi: 10.1063/1.323539
[24]	Tyson W R, Miller W A. Surface free energies of solid metals: Estimation from liquid surface tension measurements. Surf Sci, 1977, 62(1): 267 doi: 10.1016/0039-6028(77)90442-3
[25]	Hou Y H, Wang J R, Liu L L, et al. Mechanism of pitting corrosion induced by inclusions in Al-Ti-Mg deoxidized high strength pipeline steel. Micron, 2020, 138: 102898 doi: 10.1016/j.micron.2020.102898
[26]	Skriver H L, Rosengaard N M. Surface energy and work function of elemental metals. Phys Rev B Condens Matter, 1992, 46(11): 7157 doi: 10.1103/PhysRevB.46.7157
[27]	Chamati H, Papanicolaou N I, Mishin Y, et al. Embedded-atom potential for Fe and its application to self-diffusion on Fe(1 0 0). Surf Sci, 2006, 600(9): 1793 doi: 10.1016/j.susc.2006.02.010
[28]	Zhang B, Wang J, Wu B, et al. Quasi-in-situ ex-polarized TEM observation on dissolution of MnS inclusions and metastable pitting of austenitic stainless steel. Corros Sci, 2015, 100: 295 doi: 10.1016/j.corsci.2015.08.009
[29]	Jeon S H, Kim S T, Lee I S, et al. Effects of sulfur addition on pitting corrosion and machinability behavior of super duplex stainless steel containing rare earth metals: Part 2. Corros Sci, 2010, 52(10): 3537 doi: 10.1016/j.corsci.2010.07.002
[30]	Zhang X, Wei W Z, Cheng L, et al. Effects of niobium and rare earth elements on microstructure and initial marine corrosion behavior of low-alloy steels. Appl Surf Sci, 2019, 475: 83 doi: 10.1016/j.apsusc.2018.12.243
[31]	Wang C G, Ma R Y, Zhou Y T, et al. Effects of rare earth modifying inclusions on the pitting corrosion of 13Cr₄Ni martensitic stainless steel. J Mater Sci Technol, 2021, 93: 232 doi: 10.1016/j.jmst.2021.03.014