含氟連鑄保護渣黏度檢測與預測模型

趙忠宇; 趙俊學; 譚澤馨; 屈波樵; 崔雅茹

doi:10.13374/j.issn2095-9389.2020.05.03.002

含氟連鑄保護渣黏度檢測與預測模型

doi: 10.13374/j.issn2095-9389.2020.05.03.002

趙忠宇^{1, 2},
趙俊學^1, ,,
譚澤馨¹,
屈波樵¹,
崔雅茹¹

1.
西安建筑科技大學冶金工程學院，西安 710055
2.
中冶賽迪技術研究中心有限公司，重慶 401120

基金項目: 國家自然科學基金資助項目（51674185，51674186）

詳細信息

通訊作者:
E-mail：zhaojunxue1962@126.com

中圖分類號: F407.3
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出版歷程
- 收稿日期: 2020-05-03
- 刊出日期: 2021-04-26

Viscosity detection and the estimation model of fluorine-containing mold flux for continuous casting

1.
School of Metallurgical Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China
2.
CISDI R&D Co. Ltd, Chongqing 401120, China

More Information

Corresponding author: E-mail: zhaojunxue1962@126.com

摘要

摘要: 采用旋轉柱體法對不同類型的含氟連鑄保護渣黏度進行檢測，并基于Arrhenius方程通過非線性回歸分析建立了新的黏度預測模型，分析了組分變化對黏度的影響。結合模型計算和實驗檢測，建立了CaF₂?Na₂O?Al₂O₃?CaO?SiO₂?MgO渣系的等黏度圖。結果表明，與傳統的含氟連鑄保護渣黏度預測模型相比，該模型計算的偏差在10%以內，當渣中w（CaF₂）超過20%時，偏差逐漸增大，主要由于氟化物揮發造成爐渣成分變化，最終黏度實測值與爐渣初始成分不符，造成模型無法對黏度有效預測。此外，研究發現，CaF₂的增加能顯著降低爐渣黏度，而Al₂O₃和Na₂O對黏度的影響受CaF₂含量的限制。當w(CaF₂)>17%，爐渣黏度隨Al₂O₃含量增加而減小，當w(CaF₂)<17%，Al₂O₃的增加使爐渣黏度顯著增大；當w(CaF₂)>11.5%，爐渣黏度隨Na₂O含量增加顯著下降，當w(CaF₂)<11.5%，Na₂O含量變化對黏度的影響并不明顯。此外，該等黏度圖表明低黏度區w(CaF₂)接近14%。通過調整等黏度圖中各組分比例，可以改善保護渣的黏度和流動性，供鋼鐵工業應用。
- 連鑄保護渣 /
- CaF₂ /
- 黏度模型 /
- 非線性回歸分析 /
- 等黏度圖
Abstract: Mold flux plays a significant role in the continuous casting of steel. Especially, the viscosity (or its inverse, fluidity) of mold flux is a key parameter for industrial applications to aid in product quality. In this paper, viscosities of different types of fluorine-containing continuous casting mold fluxes were first measured by the rotating cylinder method, and then a new viscosity estimation model was established based on the Arrhenius equation combined with nonlinear regression analysis to analyze the influence of component changes on the viscosity. Combining model calculation and experimental measurement, an iso-viscosity diagram of the CaF₂–Na₂O–Al₂O₃–CaO–SiO₂–MgO slag system was also created. It is found that deviation within 10% is calculated using the model in this study compared with the traditional viscosity estimation models of different types of fluorine-containing continuous casting mold fluxes but gradually increases when the w(CaF₂) of slag exceeds 20%, mainly due to the change of slag composition caused by fluoride volatilization. Finally, the measured value cannot correspond to the composition of the initial slag, and the model cannot give an accurate estimated value. It is also found that an increase of CaF₂ can significantly reduce viscosity, whereas, the effect of Al₂O₃ and Na₂O on viscosity is restricted by CaF₂ content. When w(CaF₂) > 17%, the viscosity of slag decreases with increasing w(Al₂O₃), and when w(CaF₂) < 17%, the viscosity of slag increases significantly with increasing w(Al₂O₃). When w(CaF₂) > 11.5%, the viscosity of the slag system decreases significantly with increasing w(Na₂O) mass. When w(CaF₂) < 11.5%, the effect of Na₂O on viscosity is not obvious. In addition, the diagram shows that the mass fraction of CaF₂ in the low viscosity area is nearly 14%. This shows that the viscosity and fluidity of mold flux can be improved by adjusting the component ratio in this iso-viscosity diagram for applications in the steel industry.
- continuous casting mold flux /
- CaF₂ /
- viscosity estimation model /
- nonlinear regression analysis /
- iso-viscosity diagram

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圖 1 黏度?溫度線性分析

Figure 1. Linear analysis of lnη to 1/T

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圖 2 黏度參數擬合數值變化。（a）lnA；（b）B

Figure 2. Viscosity parameter fitting value: (a) lnA; (b) B

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圖 3 含氟保護渣黏度預測值與檢測值對比。（a）Riboud模型；（b）Iida模型；（c）Mills模型；（d）本研究模型

Figure 3. Estimated and measured viscosities of fluorine-containing mold flux: (a) Riboud model; (b) Iida model; (c) Mills model; (d) studied model

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圖 4 CaF₂?CaO?SiO₂三元渣黏度預測值與檢測值對比。（a）Mills模型；（b）本研究模型

Figure 4. Estimated and measured viscosities of CaF₂?CaO?SiO₂: (a) Mills model; (b) studied model

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圖 5 CaF₂，Na₂O和Al₂O₃成分變化對保護渣黏度影響

Figure 5. Effect of CaF₂, Na₂O, and Al₂O₃ on the viscosity of mold flux

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圖 6 CaF₂?Na₂O?Al₂O₃?CaO?SiO₂?MgO等黏度圖（M=0.9, w(MgO)=6.5%，1500 ℃）

Figure 6. CaF₂–Na₂O–Al₂O₃–CaO–SiO₂–MgO iso-viscosity diagram (M=0.9, w(MgO)=6.5%, 1500 °C)

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表 1 含氟保護渣成分范圍（質量分數）

Table 1. Composition of fluorine-containing mold flux %

CaF₂	M	Na₂O	Al₂O₃	MgO
4–20	0.6–1.2	3–12	2–12	0–12

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表 2 連鑄保護渣組成（質量分數）

Table 2. Components of mold fluxes for continuous casting %

Slag	CaO	SiO₂	Al₂O₃	CaF₂	Na₂O	MgO	M	Slag	CaO	SiO₂	Al₂O₃	CaF₂	Na₂O	MgO	M
C1	24.6	22.3	11.2	19	11.7	11.2	1.1	C24	33.7	37.4	7.2	12.4	3.1	6.2	0.9
C2	34.0	30.9	10.5	17.8	4.7	2.1	1.1	C25	27.6	30.7	7.6	13	8.1	13	0.9
C3	35.1	32.0	11.2	7.8	11.7	2.2	1.1	C26	33.8	37.5	7.6	13	8.1	0	0.9
C4	35.1	31.9	10.5	7.3	4.7	10.5	1.1	C27	30.7	34.1	7.6	13	8.1	6.5	0.9
C5	32.8	29.8	4.5	19	11.7	2.2	1.1	M1	23.4	38.3	6.2	12.9	18.8	0.5	0.6
C6	32.9	29.9	4.2	17.8	4.7	10.5	1.1	M2	17.5	40.0	5.2	14.5	21.5	1.3	0.4
C7	33.9	30.9	4.5	7.8	11.7	11.2	1.1	M3	20.1	34.4	4.8	14.3	26.4	0	0.6
C8	42.8	38.9	4.2	7.3	4.7	2.1	1.1	M4	19.4	36.6	18.0	17.2	8.8	0	0.5
C9	23.0	32.9	11.2	19	11.7	2.2	0.7	M5	32.6	31.2	5.3	8.0	22.9	0	1.0
C10	23.3	33.2	10.5	17.8	4.7	10.5	0.7	M6	22.5	42.2	10.4	10.7	13.0	1.3	0.5
C11	23.9	34.2	11.2	7.8	11.7	11.2	0.7	M7	21.5	33.2	3.7	15.4	25.7	0.5	0.6
C12	31.0	44.4	10.5	7.3	4.7	2.1	0.7	M8	22.7	38.6	6.3	13.5	18.9	0	0.6
C13	22.1	31.5	4.5	19	11.7	11.2	0.7	M9	22.3	35.0	8.9	16.5	17.3	0	0.6
C14	29.3	41.9	4.2	17.8	4.7	2.1	0.7	M10	20.4	34.0	4.3	17.9	23.4	0	0.6
C15	30.4	43.4	4.5	7.8	11.7	2.2	0.7	M11	13.8	32.0	3.5	20.2	27.1	3.5	0.4
C16	30.2	43.1	4.2	7.3	4.7	10.5	0.7	P1	39	39	0	13	8.4	1.6	1.0
C17	35.3	29.5	7.6	13	8.1	6.5	1.2	P2	39	39	0	13	3.6	6.4	1.0
C18	24.3	40.5	7.6	13	8.1	6.5	0.6	P3	41	41	0	13	3.6	1.6	1.0
C19	28.1	31.3	13	13	8.1	6.5	0.9	P4	39	39	0	7	8.4	6.4	1.0
C20	33.3	36.9	2.2	13	8.1	6.5	0.9	P5	42	42	0	7	8.4	1.6	1.0
C21	26.6	29.6	7.6	21.6	8.1	6.5	0.9	P6	42	42	0	7	3.6	6.4	1.0
C22	34.8	38.7	7.6	4.3	8.1	6.5	0.9	P7	44	44	0	7	3.6	1.6	1.0
C23	27.5	30.5	8.0	13.6	13.6	6.8	0.9	P8	30	42	0	13	8.4	6.4	0.7
P9	34	48	—	13	3.6	1.6	0.7	S1	33.5	53.0	—	13.5	—	—	0.6
P10	34	41	—	15	6	4	0.85	S2	32.9	47.8	—	19.3	—	—	0.7
P11	35	41	—	10	10	4	0.85	S3	33.1	46.9	—	20.0	—	—	0.7
P12	39	45	—	10	6	0	0.85	S4	30.8	37.8	—	31.4	—	—	0.8
P13	35	41	—	10	6	8	0.85	S5	27.0	30.4	—	42.6	—	—	0.9
P14	37	43	—	10	6	4	0.85	S6	33.0	39.6	—	27.4	—	—	0.8
P15	42	38	—	10	6	4	1.1	S7	33.2	38.6	—	28.2	—	—	0.9

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表 3 黏度參數分析

Table 3. Viscosity controlling parameters

Slag	lnA	B	Slag	lnA	B	Slag	lnA	B
C1	?12.1166	16750.76	C10	?11.1663	15523.76	C19	?11.6419	16899.20
C2	?11.1521	15331.25	C11	?11.4069	16399.51	C20	?10.5736	14696.67
C3	?11.4827	16323.80	C12	?11.9045	19019.28	C21	?9.26063	11473.14
C4	?11.2338	16106.31	C13	?10.7114	13670.59	C22	?11.3388	18048.45
C5	?10.9666	13904.19	C14	?11.1896	15932.56	C23	?10.4814	13697.65
C6	?11.1806	14859.89	C15	?11.4391	17000.89	C24	?17.2362	25991.79
C7	?11.3522	15328.48	C16	?11.1312	16491.46	C25	?10.5812	14320.87
C8	?11.3635	16421.96	C17	?14.9610	21103.44	C26	?13.0682	18316.60
C9	?10.9992	14722.03	C18	?12.8972	19711.71	C27	?10.7828	13602.93

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參考文獻(27)

[1]	Wang X H. Metallurgy of Iron and Steel: Steelmaking. Beijing: Higher Education Press, 2007 王新華. 鋼鐵冶金: 煉鋼學. 北京: 高等教育出版社, 2007
[2]	Anisimov K N, Longinov A M, Toptygin A M, et al. Investigation of the mold powder film structure and its influence on the developed surface in continuous casting. Steel Transl, 2016, 46(7): 489 doi: 10.3103/S0967091216070032
[3]	Viswanathan N N, Fatemeh S, Du S C, et al. Estimation of escape rate of volatile components SiF₄ and HF from slags containing CaF₂ during viscosity measurement. Steel Res, 1999, 70(2): 53 doi: 10.1002/srin.199905600
[4]	Cho J W, Yoo S, Park M S, et al. Improvement of castability and surface quality of continuously cast TWIP slabs by molten mold flux feeding technology. Metall Mater Trans B, 2017, 48(1): 187 doi: 10.1007/s11663-016-0818-3
[5]	Susa M, Sakamaki T, Kojima R. Chemical states of fluorine in CaF₂?CaO?SiO₂ and NaF?Na₂O?SiO₂ glassy slags from the perspective of electronic polarisability. Ironmaking Steelmaking, 2005, 32(1): 13 doi: 10.1179/174328105X15841
[6]	Zhao J X, Zhao Z Y, Shang N, et al. Analysis on influence of fluoride in mold powder of continuous casting. Iron Steel, 2018, 53(10): 8 趙俊學, 趙忠宇, 尚南, 等. 連鑄保護渣中氟化物作用及影響分析. 鋼鐵, 2018, 53(10):8
[7]	Li J Y, Zhang L, Tan Y, et al. Research of boron removal from polysilicon using CaO–Al₂O₃–SiO₂–CaF₂ slags. Vacuum, 2014, 103: 33 doi: 10.1016/j.vacuum.2013.12.002
[8]	Wang Q, He S P, Li Y G, et al. Status and developing needs of mould fluxes for continuous casting in China. Continuous Cast, 2014(5): 1 王謙, 何生平, 李玉剛, 等. 中國連鑄保護渣技術現狀及發展需求. 連鑄, 2014(5):1
[9]	Arefpour A R, Monshi A, Saidi A, et al. Effect of CaF₂ and MnO on mold powder viscosity and solidification during high-speed continuous casting. Refract Ind Ceram, 2013, 54(3): 203 doi: 10.1007/s11148-013-9575-x
[10]	Persson M, Seetharaman S, Seetharaman S. Kinetic studies of fluoride evaporation from slags. ISIJ Int, 2007, 47(12): 1711 doi: 10.2355/isijinternational.47.1711
[11]	Haverkamp R G. An XPS study of the fluorination of carbon anodes in molten NaF–AlF₃–CaF₂. J Mater Sci, 2012, 47(3): 1262 doi: 10.1007/s10853-011-5772-5
[12]	Shi C B, Cho J W, Zheng D L, et al. Fluoride evaporation and crystallization behavior of CaF₂–CaO–Al₂O₃–(TiO₂) slag for electroslag remelting of Ti-containing steels. Int J Miner Metall Mater, 2016, 23(6): 627 doi: 10.1007/s12613-016-1275-3
[13]	Park H S, Kim H, Sohn I. Influence of CaF₂ and Li₂O on the viscous behavior of calcium silicate melts containing 12 wt pct Na₂O. Metall Mater Trans B, 2011, 42(2): 324 doi: 10.1007/s11663-011-9474-9
[14]	Tong Z F, Qiao J L, Jiang X Y. Kinetics of Na₂O evaporation from CaO?Al₂O₃?SiO₂?MgO?TiO₂?Na₂O slags. Ironmaking Steelmaking, 2017, 44(4): 237 doi: 10.1080/03019233.2016.1210354
[15]	Park J Y, Ryu J W, Sohn I. In-situ crystallization of highly volatile commercial mold flux using an isolated observation system in the confocal laser scanning microscope. Metall Mater Trans B, 2014, 45(4): 1186 doi: 10.1007/s11663-014-0087-y
[16]	Shin S H, Cho J W, Kim S H. Structural investigations of CaO–CaF₂–SiO₂–Si₃N₄ based glasses by Raman spectroscopy and XPS considering its application to continuous casting of steels. Mater Des, 2015, 76: 1 doi: 10.1016/j.matdes.2015.03.035
[17]	Guo J M, Peng K W, Yi L, et al. Study on properties of Al₂O₃?CaO?SiO₂?CaF₂?MgO slag system. Appl Mech Mater, 2014, 513-517: 24 doi: 10.4028/www.scientific.net/AMM.513-517.24
[18]	Zhao J X, Ge B L, Cui Y R, et al. High temperature properties measurement of slag with higher volatile content. Ind Heat, 2016, 45(2): 12 趙俊學, 葛蓓蕾, 崔雅茹, 等. 含易揮發組元爐渣的高溫性能檢測. 工業加熱, 2016, 45(2):12
[19]	Han X L, Li P. Effect of alkalinity, F’s content and Na₂O content in steel slag film crystals. J Hebei United Univ Nat Sci Ed, 2014, 36(1): 18 韓秀麗, 李沛. 堿度值R、F-含量和Na₂O含量對中碳鋼保護渣渣膜結晶體的影響規律. 河北聯合大學學報(自然科學版), 2014, 36(1):18
[20]	Zhao X J, Wen H Q, Zhang J Y. The phase properties of mold flux in continuous casting mold flux. Mod Metall, 2019, 47(3): 46 趙顯久, 溫宏權, 張捷宇. 連鑄結晶器保護渣物相性能研究. 現代冶金, 2019, 47(3):46
[21]	Riboud P V, Roux Y, Lucas L D, et al. Improvement of continuous casting powders. Fachber Hiittenprax Metallweiterverarb, 1981(19): 859
[22]	Iida T, Sakai H, Kita Y, et al. An equation for accurate prediction of the viscosities of blast furnace type slags from chemical composition. ISIJ Int, 2000, 40(Suppl): S110 doi: 10.2355/isijinternational.40.Suppl_S110
[23]	Mills K C, Fox A B, Li Z, et al. Performance and properties of mould fluxes. Ironmaking Steelmaking, 2005, 32(1): 26 doi: 10.1179/174328105X15788
[24]	Liu Z X, Wang L. Experimental Design and Data Processing. 2nd Ed. Beijing: Chemical Industry Press, 2015 劉振學, 王力. 實驗設計與數據處理. 2版. 北京: 化學工業出版社, 2015
[25]	Mills K C, Sridhar S. Viscosities of ironmaking and steelmaking slags. Ironmaking Steelmaking, 1999, 26(4): 262 doi: 10.1179/030192399677121
[26]	Pan Z S, Wang Q, He S P, et al. Effect of viscosity components on mould fluxes. Spec Steel Technol, 2010, 16(2): 18 潘志勝, 王謙, 何生平, 等. 連鑄保護渣組分對黏度的影響. 特鋼技術, 2010, 16(2):18
[27]	Mills K C, Fox A B. The role of mould fluxes in continuous casting-so simple yet so complex. ISIJ Int, 2003, 43(10): 1479 doi: 10.2355/isijinternational.43.1479