Review on research progress of properties and application of titanium-containing continuous casting mold flux
HAN Xiu-li1, LIU Ying-ying2, LIU Lei1, YAN Xiao-peng2, LIU Zi-yao2
1. College of Mining Engineering, North China University of Science and Technology, Tangshan 063210, Hebei, China; 2. College of Metallurgy and Energy, North China University of Science and Technology, Tangshan 063210, Hebei, China
Abstract：With the advancement of iron and steel technology and the needs of social development,iron and steel enterprises are developing and producing various types of high-quality special steel grades with high strength,good toughness and strong corrosion resistance. How to effectively control the stability of the continuous casting production process for special steel grades is a common problem faced by the current mold flux development. Designing and developing reasonable chemical composition of mold slag,stabilizing its physical and chemical properties,and ensuring good slab quality of special steel grades are hot issues concerned by researchers in the field of iron and steel metallurgy. To this end,relevant researchers have carried out a large number of basic theoretical and applied researches on mold slag,and achieved certain results. Most scholars believe that adding a certain amount of TiO2 to the traditional mold slag can improve the physical and chemical properties of the mold slag,improve the ability to adsorb inclusions, prevent the steel-slag interface reaction,and reduce the occurrence of slab quality problems. When the TiO2 content in the mold slag is in the range of 4% to 8%,the alkalinity is controlled between 1.1 and 1.3,which can effectively improve the physical and chemical properties of the mold slag such as melting temperature,viscosity and heat flux density,and can also promote the crystallization of the slag film. It can basically meet the requirements of special steel grades such as high-titanium steel and high-alumina steel;the perovskite in the titanium-containing mold slag film can replace the gun spar in the traditional mold slag film,which has a great effect on the heat transfer of the mold slag. It plays a decisive role;after the titanium-containing mold slag absorbs the inclusions in the molten steel,the physical properties of the mold slag remain stable,and can prevent the "fishing" on the surface of the slab caused by the interface reaction between the titanium in the special molten steel and the mold slag. The occurrence of titanium-containing mold slag has been initially explored and applied in some special steel grades and staged results have been achieved. About the influence mechanism of perovskite and other minerals in the slag film on the heat transfer of titanium-containing mold powder,how to better coordinate the contradiction between the basic performance of mold powder and the lubricating heat transfer mechanism,and realize the continuous connection of titanium-containing mold powder. The wide application in the casting process to meet the high-quality,high-efficiency and stable production needs of the continuous casting process is still the main subject of further research by metallurgical workers.
韩秀丽, 刘盈盈, 刘磊, 闫晓鹏, 刘子瑶. 含钛型连铸保护渣性能及应用研究进展[J]. 钢铁, 2022, 57(10): 10-18.
HAN Xiu-li, LIU Ying-ying, LIU Lei, YAN Xiao-peng, LIU Zi-yao. Review on research progress of properties and application of titanium-containing continuous casting mold flux[J]. Iron and Steel, 2022, 57(10): 10-18.
[1] Matsuura H,Yang X,Li G,et al. Recycling of ironmaking and steelmaking slags in Japan and China[J]. International Journal of Minerals,Metallurgy and Materials,2022,29(4):739. [2] 王杏娟,曲硕,刘然,等. 高钛钢专用连铸保护渣研究现状及展望[J]. 材料导报,2021,35(s1):467.(WANG Xing-juan,QU Shuo,LIU Ran,et al. Research status and prospect of continuous casting mold flux for high titanium steel[J]. Materials Review,2021,35(s1):467.) [3] 梁雪,杨树峰,李京社, 等. 高品质含钛焊丝钢生产过程中夹杂物的行为演变[J]. 中国冶金,2020,30(2):19.(LIANG Xue,YANG Shu-feng,LI Jing-she,et al. Behavior evolution of inclusions in the production process of high-quality titanium-containing wire steel[J]. China Metallurgy,2020,30(2):19.) [4] 靳贺斌,吉俊德,王时松,等. 钢渣反应对高钛钢保护渣物化特性的影响[J]. 连铸,2021(6):59.(JIN He-bin,JI Jun-de,WANG Shi-song,et al. Effect of slag reaction on physicochemical properties of high titanium steel mold slag[J]. Continuous Casting,2021(6):59.) [5] CHEN Y,HE S,LI Z,et al. Properties and structure of a new non-reactive mold flux for high-Al steel[J]. Journal of Iron and Steel Research,International,2022,29(1):61. [6] YAN W,HAO Z,CHEN W,et al. Mixing effect of slag compositions and additives on crystallization of mold fluxes for Ti-bearing steels[J]. Journal of Materials Research and Technology,2021(10):882. [7] LI J L,SHU Q F,CHOU K C. Effect of TiO2 addition on viscosity and structure of CaO-Al2O3 based mould fluxes for high Al steel casting[J]. Canadian Metallurgical Quarterly,2015,54(1):85. [8] 何宇明,何生平. 结晶器保护渣的润滑与传热控制功能剖析[J]. 连铸,2021(2):2.(HE Yu-ming,HE Sheng-ping. Analysis of the lubrication and heat transfer control function of mold powder[J]. Continuous Casting,2021(2):2.) [9] Mills K C. Structure and properties of slags used in the continuous casting of steel:Part 1 conventional mould powders[J]. ISIJ International,2016,56(1):1. [10] Jalali P N,SjÖstrÖm U,Jonsson P,et al. Key lubrication concepts to understand the role of flow,heat transfer and solidification for modelling defect formation during continuous casting[J]. ISIJ International,2018,58(2):201. [11] Shi C B,Seo M D,Cho J W,et al. Based mold flux and their effects on in-mold performance during high-aluminum TRIP steels continuous casting[J]. Metallurgical and Materials Transactions B,2014,45(3):1081. [12] 王杏娟,田阔,樊亚鹏,等. TiO2对连铸三元无氟CaO-SiO2-TiO2渣系特性的影响[J]. 材料导报,2018,32(12):2100.(WANG Xing-juan,TIAN Kuo,FAN Ya-peng,et al. Effect of TiO2 on the properties of continuous casting ternary fluorine-free CaO-SiO2-TiO2 slag system[J]. Materials Review,2018,32(12):2100.) [13] 冀成庆,谢兵,雷云,等. TiO2对连铸保护渣非等温结晶过程的影响[J]. 北京科技大学学报,2010,32(3):306.(JI Cheng-qing,XIE Bing,LEI Yun,et al. Effect of TiO2 on non-isothermal crystallization process of continuous casting mold flux[J]. Journal of University of Science and Technology Beijing,2010,32(3):306.) [14] 苗胜田,文光华,唐萍,等. 无氟连铸结晶器保护渣的结晶性能[J]. 钢铁研究学报,2006,18(10):20.(MIAO Sheng-tian,WEN Guang-hua,TANG Ping,et al. Study on crystallographic ore phase of mold slag for fluorine-free continuous casting[J]. Journal of Iron and Steel Research,2006,18(10):20.) [15] 翟冰钰,张磊,王万林. CSP包晶钢连铸用保护渣综合理化性能的优化[J]. 连铸,2020(5):30.(ZHAI Bing-yu,ZHANG Lei,WANG Wan-lin. Optimization of comprehensive physical and chemical properties of mold flux for CSP peritectic steel continuous casting[J]. Continuous Casting,2020(5):30.) [16] 张翼飞,韩秀丽,刘磊,等. 连铸结晶器保护渣物化性能的研究进展[J]. 钢铁研究,2016,44(1):58.(ZHANG Yi-fei,HAN Xiu-li,LIU Lei,et al. Research progress on physical and chemical properties of mold slag for continuous casting[J]. Research on Iron and Steel,2016,44(1):58.) [17] QI Xin,WEN Guang-hua,TANG Ping. Investigation on heat transfer performance of fluoride-free and titanium-bearing mold fluxes[J]. Journal of Non-Crystalline Solids,2008,354(52):5444. [18] JU J T,AN J,JI G H. Effect of CaF2 substitution with TiO2 on the crystallization characteristics of low-fluoride slag for electroslag remelting[J]. Journal of Mining and Metallurgy B:Metallurgy,2019,55(3):397. [19] 孙丽枫,王宏坡,姜茂发. TiO2对连铸保护渣结晶性能的影响[J]. 工业加热,2009,38(1):3.(SUN Li-feng,WANG Hong-po,JIANG Mao-fa. Influence of TiO2 on crystallization properties of continuous casting molding powder[J]. Industrial Heating,2009,38(1):3.) [20] 孙丽枫,刘承军,姜茂发. 含二氧化钛连铸保护渣的黏性特征[J]. 硅酸盐学报,2008(3):395.(SUN Li-feng,LIU Cheng-jun,JIANG Mao-fa. Viscosity characteristics of continuous casting mold flux containing titanium dioxide[J]. Journal of the Chinese Ceramic Society,2008(3):395.) [21] SUN Li-feng,WANG Hong-po,JIANG Mao-fa,et al. Effects of TiO2 on the viscocity and solidification temperature of mold fluxes for the stainless steel[J]. Advanced Materials Research,2011,1165(189):107. [22] SUN L F,WANG H P,JIANG M F,et al. The crystalline phases of mold fluxes containing TiO2[J]. Advanced Materials Research,2011,287:227. [23] 苗胜田,岳杰,文光华,等. 无氟连铸结晶器保护渣结晶矿相研究[J]. 山西冶金,2017,40(5):21.(MIAO Sheng-tian,YUE Jie,WEN Guang-hua,et al. Study on crystallographic ore phase of mold slag for fluorine-free continuous casting[J]. Shanxi Metallurgy,2017,40(5):21.) [24] 苗胜田,文光华,唐萍. 无氟含钛保护渣表面粗糙度研究[J]. 山西冶金,2017,40(6):21.(MIAO Sheng-tian,WEN Guang-hua,TANG Ping. Study on the surface roughness of fluorine-free titanium-containing mold powder[J]. Shanxi Metallurgy,2017,40(6):21.) [25] 束奇峰,王珍,Klug J,等. TiO2和B2O3对Al2O3-CaO-MgO-Na2O-SiO2渣系结晶行为的作用[C]//2012年全国冶金物理化学学术会议论文集. 昆明:中国金属学会,2012:152.(Shu Qi-feng,Wang Zhen,Klug J,et al. Effects of TiO2 and B2O3 on the crystallization behavior of Al2O3-CaO-MgO-Na2O-SiO2 slag system[C]//Proceedings of the 2012 National Conference on Metallurgical Physical Chemistry. Kunming:The Chinese Society for Metals,2012:152.) [26] 王珍,束奇峰,周国治. TiO2替代含钛不锈钢保护渣中SiO2对渣系结晶性能的影响[C]// 2012年全国冶金物理化学学术会议论文集. 昆明:中国金属学会,2012:208.(WANG Zhen,SHU Qi-feng,ZHOU Guo-zhi. Effect of TiO2 substituting SiO2 in titanium-containing stainless steel molding slag on crystallization properties of slag system[C]//Proceedings of the 2012 National Metallurgical Physical Chemistry Conference. Kunming:The Chinese Society for Metals,2012:208.) [27] XU R H,GUO J,ZHANG M,et al. Effect of SiO2 and TiO2 on the crystal morphology of CaF2 Al2O3 CaO-Based electroslag remelting slag[J]. Steel Research International,2022,93(3):2100191. [28] LI J,SHU Q,HOU X,et al. Effect of TiO2 addition on crystallization characteristics of CaO-Al2O3-based mould fluxes for high Al steel casting[J]. ISIJ International,2015,55(4):830. [29] WANG Z,SHU Q F,CHOU K C. Crystallization characteristics of B2O3 and TiO2-bearing glassy fluoride-free mold fluxes[J]. Journal of Mining and Metallurgy B:Metallurgy,2020,56(2):279. [30] HE S P,LONG X,XU J F et al. Effects of crystallisation behaviour of mould fluxes on properties of liquid slag film[J]. Ironmaking and Steelmaking,2012,39(8):593. [31] Shu Q,Wang Z,Klug J L,et al. Effects of B2O3 and TiO2 on crystallization behavior of slags in Al2O3-CaO-MgO-Na2O-SiO2 system[J]. Steel Research International,2013,84(11):1138. [32] 邱斌,袁守谦,曹余良,等. MgO和Li2O对预熔型无氟连铸保护渣熔化温度的影响[J]. 连铸,2009(2):44.(QIU Bin,YUAN Shou-qian,CAO Yu-liang,et al. Effects of MgO and Li2O on the melting temperature of premelted fluorine-free continuous casting mold flux[J]. Continuous Casting,2009(2):44.) [33] Mills K,Fox A,Li Z,et al. Performance and properties of mould fluxes[J]. Ironmaking and Steelmaking,2005,32(1):26. [34] 刘永庆,唐萍,文光华,等. 结晶器含钛无氟保护渣的粘度和熔化特性[J]. 中国有色金属学报,2006(3):550.(LIU Yong-qing,TANG Ping,WEN Guang-hua,et al. Viscosity and melting characteristics of titanium-containing fluorine-free mold flux for molds[J]. The Chinese Journal of Nonferrous Metals,2006(3):550.) [35] 王杏娟,武宾宾,朱立光,等. 无氟连铸保护渣流变特性的研究[J]. 钢铁钒钛,2017,38(4):135.(WANG Xing-juan,WU Bin-bin,ZHU Li-guang,et al. Study on rheological properties of fluorine-free continuous casting mold flux[J]. Iron Steel Vanadium Titanium,2017,38(4):135.) [36] 郝占全,陈伟庆,Carsten Lippold,等. 氧化钛对含钛不锈钢连铸保护渣性能的影响[J]. 过程工程学报,2009,9(3):514.(Hao Zhan-quan,Chen Wei-qing,Carsten Lippold,et al. Effect of titanium oxide on properties of titanium-containing stainless steel continuous casting mold[J]. The Chinese Journal of Process Engineering,2009,9(3):514.) [37] MA J,LI W,FU G,et al. Effect of B2O3 on the melting temperature and viscosity of CaO-SiO2-MgO-Al2O3-TiO2-Cr2O3 slag[J]. Journal of Sustainable Metallurgy,2021,7(3):1190. [38] CHEN Z,ZHANG Y B,HE S P,et al. Reaction performances of mould slags with different SiO2 contents for 321 stainless steel[J]. Canadian Metallurgical Quarterly,2019,58(4):464. [39] Shu Q,Klug J L,Medeiros S L S,et al. Crystallization control for fluorine-free mold fluxes:Effect of Na2O content on non-isothermal melt crystallization kinetics[J]. ISIJ International,2020,60(11):2425. [40] WANG Z,SHU Q,CHOU K. Viscosity of fluoride-free mold fluxes containing B2O3 and TiO2[J]. Steel Research International,2013,84(8):766. [41] 于雄,文光华,唐萍,等. 连铸结晶器保护渣渣膜结晶特性的研究进展[J]. 材料导报,2010,24(5):101.(YU Xiong,WEN Guang-hua,TANG Ping,et al. Research progress on crystallization characteristics of mold slag film in continuous casting molds[J]. Materials Review,2010,24(5):101.) [42] XIN Q,WEN G,PING T. Viscosity and viscosity estimate model of fluoride-free and titanium-bearing mold fluxes[J]. Journal of Iron and Steel Research,International,2010,17(6):6. [43] WANG W L,CAI D,ZHANG L,et al. Effect of TiO2 and TiN on the viscosity,fluidity,and crystallization of fluorine-free mold fluxes for casting Ti-bearing steels[J]. Steel Research International,2021,92(2):2000314. [44] Shu Q,Wang Z,Klug J L,et al. Effects of B2O3 and TiO2 on crystallization behavior of slags in Al2O3-CaO-MgO-Na2O-SiO2 system[J]. Steel Research International,2013,84(11):1138. [45] WANG Z,SHU Q,CHOU K. Study on structure characteristics of B2O3 and TiO2-bearing F-free mold flux by Raman spectroscopy[J]. High Temperature Materials and Processes,2013,32(3):265. [46] 肖建平,谢兵,刁江. 碱度和TiO2对连铸保护渣辐射传热特性的影响[J]. 连铸,2009(5):42.(XIAO Jian-ping,XIE Bing,DIAO Jiang. Effects of basicity and TiO2 on radiation heat transfer characteristics of continuous casting mold flux[J]. Continuous Casting,2009(5):42.) [47] DIAO J,XIE B,XIAO J P. Experimental investigation into radiative heat transfer characteristics for mould fluxes containing transition oxides[J]. Ironmaking and Steelmaking,2009,36(8):610. [48] 韩文殿,仇圣桃,张兴中,等. 结晶器无氟保护渣渣膜的传热性和矿物结构[J]. 钢铁研究学报,2007(3):14.(HAN Wen-dian,QIU Sheng-tao,ZHANG Xing-zhong,et al. Heat transfer and mineral structure of fluorine-free mold slag film on molds[J]. Journal of Iron and Steel Research,2007(3):14.) [49] Wen G H,Sridhar S,Tang P,et al. Development of fluoride-free mold powders for peritectic steel slab casting[J]. ISIJ International,2007,47(8):1117. [50] Bothma J A,Pistorius P C. Heat transfer through mould flux with titanium oxide additions[J]. Ironmaking and Steelmaking,2007,34(6):513. [51] 青雪梅,谢兵,刁江,等. TiO2对连铸保护渣导热性能的影响[J]. 钢铁研究学报,2011,23(11):10.(QING Xue-mei,XIE Bing,DIAO Jiang,et al. Effect of TiO2 on thermal conductivity of continuous casting mold flux[J]. Journal of Iron and Steel Research,2011,23(11):10.) [52] 魏国立,朱青德,胡绍岩. MiDa 超高拉速连铸结晶器保护渣初步设计[J]. 连铸,2020,45(5):16.(WEI Guo-li,ZHU Qing-de,HU Shao-yan. Preliminary design of mold slag for MiDa ultra-high-speed continuous casting[J]. Continuous Casting,2020,45(5):16.) [53] Ni P,Tanaka T,Suzuki M,et al. Mathematical modelling study of dynamic composition change of steel and mold flux in continuous casting of steel[J]. ISIJ International,2019,59(11):2024. [54] LI J,SHU Q,CHOU K. Structural study of glassy CaO-SiO2-CaF2-TiO2 slags by Raman spectroscopy and MAS-NMR[J]. ISIJ International,2014,54(4):721. [55] WANG Z,SHU Q F,HOU X M,et al. Effect of substituting SiO2 with TiO2 on viscosity and crystallisation of mould flux for casting titanium stabilised stainless steel[J]. Ironmaking and Steelmaking,2012,39(3):210. [56] ZHOU L J,PAN Z,WANG W,et al. Interfacial interactions between inclusions comprising TiO2 or TiN and the mold flux during the casting of titanium-stabilized stainless steel[J]. Metallurgical and Materials Transactions B,2020,51(1):85. [57] Wang Z,Sohn I. Review on the high-temperature thermophysical properties of continuous casting mold fluxes for highly alloyed steels[J]. ISIJ International,2020,60(12):2705. [58] PIAO Z,ZHU L,WANG X,et al. Effects of BaO on the viscosity and structure of a new fluorine-free CaO-Al2O3-TiO2-based mold flux for high titanium steel[J]. Metallurgical and Materials Transactions B,2020,51(5):2119. [59] 王谦,何生平,解丹,等. 低碳钢板坯连铸用无氟保护渣生成区域的研究[J]. 北京科技大学学报,2008(5):487.(WANG Qian,HE Sheng-ping,XIE Dan,et al. Research on the generation area of fluorine-free mold flux for continuous casting of low carbon steel billets[J]. Journal of Beijing University of Science and Technology,2008(5):487.) [60] ZHANG J,LÜ X,YAN Z,et al. Desulphurisation ability of blast furnace slag containing high Al2O3 and 5 mass% TiO2 at 1 773 K[J]. Ironmaking and Steelmaking,2016,43(5):378. [61] 王万林,黄道远,高尔卓,等. 一种含TiO2高铝钢保护渣及其应用:中国,CN107498013A[P]. 2017-12-22 [2022-04-06].(WANG Wan-lin,HUANG Dao-yuan,GAO Er-zhuo,et al. A TiO2-Containing High-Alumina Steel Mold Powder and Its Application:China,CN107498013A[P]. 2017-12-22[2022-04-06].) [62] 刘志明,尚德礼,朱晓雷,等. 一种适用于高钛钢的连铸保护渣:中国,CN113751681A[P]. 2021-12-07 [2022-04-06].(LIU Zhi-ming,SHANG De-li,ZHU Xiao-lei,et al. A Continuous Casting Mold Suitable for High Titanium Steel:China,CN113751681A[P]. 2021-12-07[2022-04-06].) [63] 朱立光,张晓仕,王杏娟,等. 高钛焊丝钢CaO-Al2O3基专用保护渣熔化特性分析[J]. 中国冶金,2020,30(10):9.(ZHU Li-guang,ZHANG Xiao-shi,WANG Xing-juan,el al. Analysis of melting characteristics of CaO-Al2O3-based special mold flux for high titanium welding wire steel[J]. China Metallurgy,2020,30(10):9.) [64] 朴占龙,王杏娟,张彩军,等. 高钛钢连铸结晶器内钢-渣界面反应行为[J]. 钢铁,2022,57(3):61.(PU Zhan-long,WANG Xing-juan,ZHANG Cai-jun,et al. Reaction behavior of steel-slag interface in continuous casting mold of high titanium steel[J]. Iron and Steel,2022,57(3):61.) [65] Nathalie K. New mold slag compositions for the continuous casting of soft steels[J]. Steel Research International,2021,93:1.
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