Al2O3夹杂物在CaO–MgO–SiO2–Al2O3–TiO2系精炼渣中的溶解行为

邓志银; 张小萌; 郝广御; 魏春新; 朱苗勇

doi:10.1007/s12613-023-2817-0

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文章导航 > 矿物冶金与材料学报（英文） > 2024 > 31(5): 977-987

Zhiyin Deng, Xiaomeng Zhang, Guangyu Hao, Chunxin Wei, and Miaoyong Zhu, Dissolution behavior of Al₂O₃ inclusions into CaO–MgO–SiO₂–Al₂O₃–TiO₂ system ladle slags, Int. J. Miner. Metall. Mater., 31(2024), No. 5, pp. 977-987. https://doi.org/10.1007/s12613-023-2817-0

Cite this article as:

Zhiyin Deng, Xiaomeng Zhang, Guangyu Hao, Chunxin Wei, and Miaoyong Zhu, Dissolution behavior of Al2O3 inclusions into CaO–MgO–SiO2–Al2O3–TiO2 system ladle slags, Int. J. Miner. Metall. Mater., 31(2024), No. 5, pp. 977-987. https://doi.org/10.1007/s12613-023-2817-0

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研究论文

Al₂O₃夹杂物在CaO–MgO–SiO₂–Al₂O₃–TiO₂系精炼渣中的溶解行为

1)
东北大学多金属共生矿生态化冶金教育部重点实验室, 沈阳 110819, 中国
2)
东北大学冶金学院, 沈阳 110819, 中国
3)
特变电工沈阳变压器集团有限公司, 沈阳 110141, 中国
4)
鞍钢股份有限公司, 鞍山 114021, 中国

通讯作者:
邓志银 E-mail: dengzy@smm.neu.edu.cn

朱苗勇 E-mail: myzhu@mail.neu.edu.cn

文章亮点

(1) 分析了Al₂O₃夹杂物在CaO–MgO–SiO₂–Al₂O₃–TiO₂系精炼渣中溶解的限制性环节。

(2) 计算了Al₂O₃在CaO–MgO–SiO₂–Al₂O₃–TiO₂系精炼渣中的扩散系数。

(3) 讨论了渣中TiO₂含量对Al₂O₃夹杂物溶解速率的影响机制。

中文摘要

在含钛铝镇静钢精炼过程中，钢液中的钛元素因钢–渣反应会向精炼渣中迁移，从而形成CaO–MgO–SiO₂–Al₂O₃–TiO₂系精炼渣，降低了钛的收得率。部分学者提出在精炼渣中添加少量TiO₂来提高钛收得率。为了揭示精炼渣中的TiO₂对夹杂物去除行为的影响规律，本文采用高温激光共聚焦显微镜观察了Al₂O₃夹杂物在含TiO₂精炼渣（w(TiO₂)= 0–10wt%）中的溶解行为，并利用扫描电子显微镜分析了Al₂O₃夹杂物与含TiO₂精炼渣的界面反应行为。研究表明，Al₂O₃夹杂物在溶解过程中，并不会在夹杂物与实验精炼渣的边界生成新的物相，且实验精炼渣中的TiO₂不会改变夹杂物的溶解机理，即边界层扩散是Al₂O₃夹杂物溶解的限制性环节。计算表明，在1450–1500°C时，边界层Al₂O₃的扩散系数在4.18 × 10⁻¹⁰和2.18 × 10⁻⁹ m²/s之间。当添加TiO₂后，精炼渣中Al₂O₃的溶解度降低。尽管如此，相比Al₂O₃的溶解度，精炼渣的黏度和温度对Al₂O₃夹杂物溶解速率的影响更大，即低黏度和低熔点的精炼渣更有利于Al₂O₃夹杂物溶解。添加适当的TiO₂（如5wt%）可以降低精炼渣的黏度和熔点，从而更有利于Al₂O₃夹杂物的溶解；而TiO₂添加过量时（如10wt%）则作用相反。

关键词:

Research Article

Dissolution behavior of Al₂O₃ inclusions into CaO–MgO–SiO₂–Al₂O₃–TiO₂ system ladle slags

+ Author Affiliations

1)
Key Laboratory for Ecological Metallurgy of Multimetallic Mineral (Ministry of Education), Northeastern University, Shenyang 110819, China
2)
School of Metallurgy, Northeastern University, Shenyang 110819, China
3)
TBEA Shenyang Transformer Group Co., Ltd., Shenyang 110141, China
4)
Angang Steel Co., Ltd., Anshan 114021, China

Miaoyong Zhu is an editorial board member of this journal and was not involved in the editorial review or the decision to publish this article. The author states that there is no conflict of interest.

Corresponding authors:
Zhiyin Deng E-mail: dengzy@smm.neu.edu.cn

Miaoyong Zhu E-mail: myzhu@mail.neu.edu.cn
Received: 9 September 2023; Revised: 23 November 2023; Accepted: 26 December 2023; Available online: 27 December 2023

Abstract

Abstract

To investigate the dissolution behaviors of Al₂O₃ inclusions in CaO–5wt%MgO–SiO₂–30wt%Al₂O₃–TiO₂ system ladle slags, confocal scanning laser microscopy was conducted on the slags with different TiO₂ contents (0–10wt%), and scanning electron microscopy was performed to study the interfacial reaction between Al₂O₃ and this slag system. The results disclose that the dissolution of Al₂O₃ inclusions does not result in the formation of new phases at the boundary between the slag and the inclusions. In TiO₂-bearing and TiO₂-free ladle slags, there is no difference in the dissolution mechanism of Al₂O₃ inclusions at steelmaking temperatures. Boundary layer diffusion is found as the controlling step of the dissolution of Al₂O₃, and the diffusion coefficient is in the range of 4.18 × 10⁻¹⁰ to 2.18 × 10⁻⁹ m²/s at 1450–1500°C. Compared with the solubility of Al₂O₃ in the slags, slag viscosity and temperature play a more profound role in the dissolution of Al₂O₃ inclusions. A lower viscosity and a lower melting point of the slags are beneficial for the dissolution. Suitable addition of TiO₂ (e.g., 5wt%) in ladle slags can enhance the dissolution of Al₂O₃ inclusions because of the low viscosity and melting point of the slags, while excessive addition of TiO₂ (e.g., 10wt%) shows the opposite trend.
- inclusions;
- dissolution;
- ladle refining slag;
- titanium dioxide;
- confocal scanning laser microscopy

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References

[1]	L.X. Zhang, M. Chen, M.Y. Huang, N. Wang, and C. Wang, Dissolution kinetics of SiO₂ in FeO–SiO₂–V₂O₃–CaO–MnO–Cr₂O₃–TiO₂ system with different FeO contents, Metall. Mater. Trans. B, 52(2021), No. 4, p. 2703. doi: 10.1007/s11663-021-02214-6
[2]	G.J. Chen, S.P. He, and Q. Wang, Dissolution behavior of Al₂O₃ into tundish slag for high-Al steel, J. Mater. Res. Technol., 9(2020), No. 5, p. 11311. doi: 10.1016/j.jmrt.2020.07.107
[3]	Z.R. Li, B.R. Jia, Y.B. Zhang, S.P. He, Q.Q. Wang, and Q. Wang, Dissolution behaviour of Al₂O₃ in mould fluxes with low SiO₂ content, Ceram. Int., 45(2019), No. 3, p. 4035. doi: 10.1016/j.ceramint.2018.11.082
[4]	B.N. Samaddar, W.D. Kingery, and A.R. Cooper JR, Dissolution in ceramic systems: 11, Dissolution of aluminu, mullite, anorthite, and silica in a calcium–aluminum–silicate slag, J. Am. Ceram. Soc., 47(1964), No. 5, p. 249. doi: 10.1111/j.1151-2916.1964.tb14405.x
[5]	K.H. Sandhage and G.J. Yurek, Indirect dissolution of sapphire into calcia–magnesia–alumina–silica melts: Electron microprobe analysis of the dissolution process, J. Am. Ceram. Soc., 73(1990), No. 12, p. 3643. doi: 10.1111/j.1151-2916.1990.tb04270.x
[6]	Y.J. Park, Y.M. Cho, W.Y. Cha, and Y.B. Kang, Dissolution kinetics of alumina in molten CaO–Al₂O₃–Fe_tO–MgO–SiO₂ oxide representing the RH slag in steelmaking process, J. Am. Ceram. Soc., 103(2020), No. 3, p. 2210. doi: 10.1111/jace.16879
[7]	S. Sridhar and A.W. Cramb, Kinetics of Al₂O₃ dissolution in CaO–MgO–SiO₂–Al₂O₃ slags: In Situ observations and analysis, Metall. Mater. Trans. B, 31(2000), No. 2, p. 406. doi: 10.1007/s11663-000-0059-2
[8]	J. Liu, M. Guo, P.T. Jones, F. Verhaeghe, B. Blanpain, and P. Wollants, In situ observation of the direct and indirect dissolution of MgO particles in CaO–Al₂O₃–SiO₂-based slags, J. Eur. Ceram. Soc., 27(2007), No. 4, p. 1961. doi: 10.1016/j.jeurceramsoc.2006.05.107
[9]	J.H. Park, J.G. Park, D.J. Min, Y.E. Lee, and Y.B. Kang, In situ observation of the dissolution phenomena of SiC particle in CaO–SiO₂–MnO slag, J. Eur. Ceram. Soc., 30(2010), No. 15, p. 3181. doi: 10.1016/j.jeurceramsoc.2010.07.020
[10]	Y.M. Lee, J.K. Yang, D.J. Min, and J.H. Park, Mechanism of MgO dissolution in MgF₂–CaF₂–MF (M = Li or Na) melts: Kinetic analysis via in situ high temperature confocal scanning laser microscopy (HT-CSLM), Ceram. Int., 45(2019), No. 16, p. 20251. doi: 10.1016/j.ceramint.2019.06.298
[11]	M. Sharma and N. Dogan, Dissolution behavior of aluminum titanate inclusions in steelmaking slags, Metall. Mater. Trans. B, 51(2020), No. 2, p. 570. doi: 10.1007/s11663-019-01762-2
[12]	K.Y. Miao, A. Haas, M. Sharma, W.Z. Mu, and N. Dogan, In situ observation of calcium aluminate inclusions dissolution into steelmaking slag, Metall. Mater. Trans. B, 49(2018), No. 4, p. 1612. doi: 10.1007/s11663-018-1303-y
[13]	T.L. Tian, Y.Z. Zhang, H.H. Zhang, K.X. Zhang, J. Li, and H. Wang, Dissolution behavior of SiO₂ in the molten blast furnace slags, Int. J. Appl. Ceram. Technol., 16(2019), No. 3, p. 1078. doi: 10.1111/ijac.13120
[14]	L. Zhang, W.L. Wang, L. Zhang, J. Zeng, and X. Gao, A comparison study on the dissolution mechanism of Al₂O₃ inclusion on fluorine-bearing and fluorine-free molten mold fluxes, Ceram. Int., 49(2023), No. 16, p. 27176. doi: 10.1016/j.ceramint.2023.05.262
[15]	L. Gou, H. Liu, Y. Ren, and L.F. Zhang, Concept of inclusion capacity of slag and its application on the dissolution of Al₂O₃, ZrO₂ and SiO₂ inclusions in CaO–Al₂O₃–SiO₂ slag, Metall. Mater. Trans. B, 54(2023), No. 3, p. 1314. doi: 10.1007/s11663-023-02763-y
[16]	C.Y. Ren, C.D. Huang, L.F. Zhang, and Y. Ren, In situ observation of the dissolution kinetics of Al₂O₃ particles in CaO–Al₂O₃–SiO₂ slags using laser confocal scanning microscopy, Int. J. Miner. Metall. Mater., 30(2023), No. 2, p. 345. doi: 10.1007/s12613-021-2347-6
[17]	Y. Kim, Y. Kashiwaya, and Y. Chung, Effect of varying Al₂O₃ contents of CaO–Al₂O₃–SiO₂ slags on lumped MgO dissolution, Ceram. Int., 46(2020), No. 5, p. 6205. doi: 10.1016/j.ceramint.2019.11.088
[18]	W.Z. Mu and C.J. Xuan, Phase-field study of dissolution behaviors of different oxide particles into oxide melts, Ceram. Int., 46(2020), No. 10, p. 14949. doi: 10.1016/j.ceramint.2020.03.023
[19]	C.J. Xuan and W.Z. Mu, A phase-field model for the study of isothermal dissolution behavior of alumina particles into molten silicates, J. Am. Ceram. Soc., 102(2019), No. 11, p. 6480. doi: 10.1111/jace.16509
[20]	J.J. Liu, J. Zou, M.X. Guo, and N. Moelans, Phase field simulation study of the dissolution behavior of Al₂O₃ into CaO–Al₂O₃–SiO₂ slags, Comput. Mater. Sci., 119(2016), p. 9. doi: 10.1016/j.commatsci.2016.03.034
[21]	J. Heulens, B. Blanpain, and N. Moelans, A phase field model for isothermal crystallization of oxide melts, Acta Mater., 59(2011), No. 5, p. 2156. doi: 10.1016/j.actamat.2010.12.016
[22]	Z.J. Wang and I. Sohn, A review of in situ observations of crystallization and growth in high temperature oxide melts, JOM, 70(2018), No. 7, p. 1210. doi: 10.1007/s11837-018-2887-z
[23]	I. Sohn and R. Dippenaar, In-situ observation of crystallization and growth in high-temperature melts using the confocal laser microscope, Metall. Mater. Trans. B, 47(2016), No. 4, p. 2083. doi: 10.1007/s11663-016-0675-0
[24]	D.C. Fu, G.H. Wen, X.Q. Zhu, J.L. Guo, and P. Tang, Modification for prediction model of austenite grain size at surface of microalloyed steel slabs based on in situ observation, J. Iron Steel Res. Int., 28(2021), No. 9, p. 1133. doi: 10.1007/s42243-020-00513-x
[25]	Q.R. Tian, G.C. Wang, D.L. Shang, et al. , In situ observation of the precipitation, aggregation, and dissolution behaviors of TiN inclusion on the surface of liquid GCr15 bearing steel, Metall. Mater. Trans. B, 49(2018), No. 6, p. 3137. doi: 10.1007/s11663-018-1411-8
[26]	Y.G. Wang and C.J. Liu, Agglomeration characteristics of various oxide inclusions in molten steel containing rare earth element under different deoxidation conditions, ISIJ Int., 61(2021), No. 5, p. 1396. doi: 10.2355/isijinternational.ISIJINT-2020-684
[27]	W.Z. Mu and C.J. Xuan, Agglomeration mechanism of complex Ti–Al oxides in liquid ferrous alloys considering high-temperature interfacial phenomenon, Metall. Mater. Trans. B, 50(2019), No. 6, p. 2694. doi: 10.1007/s11663-019-01686-x
[28]	X.J. Zhao, Z.N. Yang, and F.C. Zhang, In situ observation of the effect of AIN particles on bainitic transformation in a carbide-free medium carbon steel, Int. J. Miner. Metall. Mater., 27(2020), No. 5, p. 620. doi: 10.1007/s12613-019-1911-9
[29]	J. Guo, X.R. Chen, S.W. Han, Y. Yan, and H.J. Guo, Evolution of plasticized MnO–Al₂O₃–SiO₂-based nonmetallic inclusion in 18wt%Cr–8wt%Ni stainless steel and its properties during soaking process, Int. J. Miner. Metall. Mater., 27(2020), No. 3, p. 328. doi: 10.1007/s12613-019-1945-z
[30]	M. Valdez, K. Prapakorn, A.W. Cramb, and S. Sridhar, Dissolution of alumina particles in CaO–Al₂O₃–SiO₂–MgO slags, Ironmaking Steelmaking, 29(2002), No. 1, p. 47. doi: 10.1179/030192302225001965
[31]	M. Sharma, W.Z. Mu, and N. Dogan, In situ observation of dissolution of oxide inclusions in steelmaking slags, JOM, 70(2018), No. 7, p. 1220. doi: 10.1007/s11837-018-2908-y
[32]	S. Taira, K. Nakashima, and K. Mori, Kinetic behavior of dissolution of sintered alumina into CaO–SiO₂–Al₂O₃ slags, ISIJ Int., 33(1993), No. 1, p. 116. doi: 10.2355/isijinternational.33.116
[33]	W.D. Cho and P. Fan, Diffusional dissolution of alumina in various steelmaking slags, ISIJ Int., 44(2004), No. 2, p. 229. doi: 10.2355/isijinternational.44.229
[34]	F. Verhaeghe, J. Liu, M. Guo, S. Arnout, B. Blanpain, and P. Wollants, Dissolution and diffusion behavior of Al₂O₃ in a CaO–Al₂O₃–SiO₂ liquid: An experimental-numerical approach, Appl. Phys. Lett., 91(2007), No. 12, art. No. 124104.
[35]	C.Y. Ren, L.F. Zhang, J. Zhang, S.J. Wu, P. Zhu, and Y. Ren, In situ observation of the dissolution of Al₂O₃ particles in CaO–Al₂O₃–SiO₂ slags, Metall. Mater. Trans. B, 52(2021), No. 5, p. 3288. doi: 10.1007/s11663-021-02256-w
[36]	K.W. Yi, C. Tse, J.H. Park, M. Valdez, A.W. Cramb, and S. Sridhar, Determination of dissolution time of Al₂O₃ and MgO inclusions in synthetic Al₂O₃–CaO–MgO slags, Scand. J. Metall., 32(2003), No. 4, p. 177. doi: 10.1034/j.1600-0692.2003.20631.x
[37]	A.B. Fox, M.E. Valdez, J. Gisby, R.C. Atwood, P.D. Lee, and S. Sridhar, Dissolution of ZrO₂, Al₂O₃, MgO and MgAl₂O₄ particles in a B₂O₃ containing commercial fluoride-free mould slag, ISIJ Int., 44(2004), No. 5, p. 836. doi: 10.2355/isijinternational.44.836
[38]	B.J. Monaghan and L. Chen, Effect of changing slag composition on spinel inclusion dissolution, Ironmaking Steelmaking, 33(2006), No. 4, p. 323. doi: 10.1179/174328106X101547
[39]	Y. Ren, P. Zhu, C.Y. Ren, N. Liu, and L.F. Zhang, Dissolution of SiO₂ inclusions in CaO–SiO₂-based slags in situ observed using high-temperature confocal scanning laser microscopy, Metall. Mater. Trans. B, 53(2022), No. 2, p. 682. doi: 10.1007/s11663-021-02401-5
[40]	B.J. Monaghan and L. Chen, Dissolution behavior of alumina micro-particles in CaO–SiO₂–Al₂O₃ liquid oxide, J. Non Cryst. Solids, 347(2004), No. 1-3, p. 254. doi: 10.1016/j.jnoncrysol.2004.09.011
[41]	G.Y. Hao, Z.Y. Deng, C.X. Wei, and M.Y. Zhu, Degradation behavior of MgO-based refractory by CaO–SiO₂–Al₂O₃–MgO–TiO₂ system ladle slags, Metall. Mater. Trans. B, 54(2023), No. 6, p. 3203. doi: 10.1007/s11663-023-02901-6
[42]	Y. Wang, J.H. Cho, T.S. Jeong, et al., Evolution of the non-metallic inclusions influenced by slag–metal reactions in Ti-containing ferritic stainless steel, Metall. Mater. Trans. B, 52(2021), No. 6, p. 3986. doi: 10.1007/s11663-021-02314-3
[43]	Z.D. Pang, X.W. Lü, Z.M. Yan, C.G. Bai, H.E. Xie, and C. Pan, Viscosity and free running temperature of ultra-high TiO₂ bearing blast furnace slag, Iron Steel, 55(2020), No. 8, p. 181.
[44]	X.M. Zhang, Z.W. Yan, Z.Y. Deng, and M.Y. Zhu, Effect of TiO₂ addition on the melting behaviors of CaO-SiO₂-30%Al₂O₃-5%MgO system refining slags, Metals, 13(2023), No. 2, art. No. 431. doi: 10.3390/met13020431
[45]	X.M. Zhang, Z.Y. Deng, Z.W. Yan, C.X. Wei and M.Y. Zhu; Effect of TiO₂ addition on the viscosity of ladle refining slags, Metall. Mater. Trans. B, (2024). Doi: 10.1007/s11663-024-03055-9.
[46]	M.J. Whelan, On the kinetics of precipitate dissolution, Met. Sci. J., 3(1969), No. 1, p. 95. doi: 10.1179/msc.1969.3.1.95
[47]	K.C. Mills and B.J. Keene, Physical properties of BOS slags, Int. Mater. Rev., 32(1987), No. 1, p. 1. doi: 10.1179/095066087790150296
[48]	S. Feichtinger, S.K. Michelic, Y.B. Kang, and C. Bernhard, In situ observation of the dissolution of SiO₂ particles in CaO–Al₂O₃–SiO₂ slags and mathematical analysis of its dissolution pattern, J. Am. Ceram. Soc., 97(2014), No. 1, p. 316. doi: 10.1111/jace.12665