Shear-thinning behavior of the CaO-SiO2-CaF2-Si3N4 system mold flux and its practical application

Satisfying the mold-flux performance requirements for high-speed continuous casting necessitates the development of a new non-Newtonian-fluid mold flux with shear-thinning behavior, i.e., a mold flux whose viscosity is relatively high under lower shear rates and relatively low under higher shear rates. In this work, a mold flux that exhibits shear-thinning behavior was developed by adding different amounts of Si₃N₄ to the CaO-SiO₂-CaF₂ mold flux. The shear-thinning behavior was investigated using a rotational viscometer. In addition, the microstructure of the newly prepared slags was studied by high-temperature Raman spectroscopy and X-ray photoelectron spectroscopy. The results showed that the mechanism of shear-thinning was attributable to a temporary viscosity loss caused by the one-way shear stress, whereas the corresponding magnitude of shear-thinning was closely related to the degree of polymerization (DP). Finally, the non-Newtonian fluid mold flux was used for laboratory casting tests, which revealed that the mold flux could reduce slag entrapment and positively affect the continuous casting optimization.     

FeO影响CaO-SiO_2-MgO-Al_2O_3-Cr_2O_3体系中含铬尖晶石晶体析出的热力学分析

不锈钢渣中的铬以尖晶石矿物相状态赋存时不易溶出,有利于钢渣的资源化利用。本文基于熔体非平衡凝固理论,采用热力学数据库FactSage 7.0研究了FeO添加量对CaO-SiO_2-MgO-Al_2O_3-Cr_2O_3不锈钢渣体系中尖晶石晶体析出温度、析出量、化学组成及铬元素赋存状态的影响规律。模拟计算结果表明,尖晶石晶体为高温析出相,主要由MgCr_2O_4和FeCr_2O_4组成;随着FeO添加量不断增多,尖晶石晶体的析出温度逐渐降低,其最终析出量逐渐增加,析出物中FeCr_2O_4所占比例增加而MgCr_2O_4相对减少;铬元素的赋存状态未受FeO添加量变化影响,仍以尖晶石固溶体形式存在。     

Shear-thinning behavior of the CaO-SiO2-CaF2-Si3N4 system mold flux and its practical application

Satisfying the mold-flux performance requirements for high-speed continuous casting necessitates the development of a new non-Newtonian-fluid mold flux with shear-thinning behavior, i.e., a mold flux whose viscosity is relatively high under lower shear rates and relatively low under higher shear rates. In this work, a mold flux that exhibits shear-thinning behavior was developed by adding different amounts of Si3N4 to the CaO-SiO2-CaF2 mold flux. The shear-thinning behavior was investigated using a rotational viscometer. In addition, the microstructure of the newly prepared slags was studied by high-temperature Raman spectroscopy and X-ray photoelectron spectroscopy. The results showed that the mechanism of shear-thinning was attributable to a temporary viscosity loss caused by the one-way shear stress, whereas the corresponding magnitude of shear-thinning was closely related to the degree of polymerization (DP). Finally, the non-Newtonian fluid mold flux was used for laboratory casting tests, which revealed that the mold flux could reduce slag entrapment and positively affect the continuous casting optimization.     

Effect of CeO_2 on heat transfer and crystallization behavior of rare earth alloy steel mold fluxes

To improve the heat transfer capability and the crystallization property of the traditional mold flux, CaF_2 was replaced with B_2O_3. Then, the influences of CeO_2 on the heat transfer and the crystallization of the CaF_2-bearing mold flux and the new mold flux with 10 wt% B_2O_3 were studied using a slag film heat flux simulator and X-ray diffraction(XRD). The results revealed that the addition of CeO2 reduced the heat transfer by increasing the solid slag thickness and the crystallization of two mold fluxes. However, CeO_2 had less effect on the B_2O_3-containing mold flux compared with the CaF_2-bearing mold flux. According to the analyses, the CeO_2 contents in the CaF_2-bearing mold flux and the B_2O_3-containing mold flux should not exceed 8 wt% and 12 wt%, respectively. Therefore, these experimental results are beneficial to improve and develop the mold flux for casting rare earth alloy steels.     

基于热丝法对CaO-SiO_2-Al_2O_3保护渣结晶性能与凝固分数的研究

针对髙铝包晶钢连铸设计了Ca O-Si O2-Al2O3系保护渣.采用单丝法研究w(Ca O)/w(Al2O3)对保护渣结晶性能的影响;采用双丝法模拟了保护渣渣膜形成及凝固过程,研究了w(Ca O)/w(Al2O3)对保护渣固相体积分数φ的影响.结果表明:实验保护渣系结晶能力随w(Ca O)/w(Al2O3)增大而增强,按结晶能力分为两个区间,w(Ca O)/w(Al2O3)1.30时保护渣结晶能力强于w(Ca O)/w(Al2O3)≤1.30的保护渣;在等温结晶过程中,w(Ca O)/w(Al2O3)=1.00的实验保护渣中析出枪晶石,w(Ca O)/w(Al2O3)=2.50时渣中析出硅酸二钙;w(Ca O)/w(Al2O3)增大使保护渣渣膜双丝间固相体积分数增大,结晶层增厚,不利于保证结晶器内润滑.与浇注常规包晶钢的Ca O-Si O2系保护渣性能对比表明,Ca O-Si O2-Al2O3系保护渣在w(Ca O)/w(Al2O3)≤1.30时的结晶能力和固相体积分数都与对照渣相近,设计的Ca O-Si O2-Al2O3系保护渣适用于高铝包晶钢连铸.     

超低碳钢新型连铸保护渣的开发

采用BN替代碳质材料 ,作为连铸保护渣的骨架粒子 ,研究开发出一种新型的超低碳钢连铸保护渣·新型连铸保护渣在绝热保温性能、熔化特性、粘性特征、夹杂物吸收能力和结晶性能等方面与传统连铸保护渣十分接近·新型连铸保护渣 ,可以彻底解决超低碳钢结晶器内钢液增碳和铸坯表面渗碳问题 ,而且不会发生超低碳钢结晶器内钢液增硼和铸坯表面渗硼问题·新型骨架粒子BN可以使连铸保护渣JRBW增大、熔化速度降低、粘度减小、Al2 O3 吸收速率增大、熔化温度降低、凝固温度降低、结晶温度降低     

Non-catalytic nucleation coating for undercooled Cu50Ni50 melt

A non-catalytic nucleation coating (B-F3) was prepared by the high temperature curing process of the sol-gel glass film based on the viscous flow mechanism of the coating. X-ray diffraction technology was adopted to study the crystallization behavior of the coating as a function of treating temperature. It was evident that no crystallization phenomenon happened on the coating which kept stable after the heat treatment of 60 min at 1773 K. The purified melt of Cu₅₀Ni₅₀ was selected to evaluate the effectiveness of undercooling heredity of the coating in the undercooling experiments. The maximum undercooling of the melt solidified in the coated mold could reach 236 K. Based on the solidified microstructural evolution at different undercoolings, a single crystal of the alloy Cu₅₀Ni₅₀ was achieved with no aid of the selection process of the crystal in the mold with the B-F3 coating by means of undercooling technology.     

结晶器内连铸坯凝固过程的有限元数值模拟

建立了结晶器内连铸坯凝固过程的有限元数学模型，在坯壳面表面边界条件中引入与气隙相关的传热模型修正平均热流量方程，研究了铸坯角部气隙对坯壳凝固行为的影响，模拟结果表明，铸坯角部形成的气隙流量显著地长低了坯壳表面的换热，使得铸坯偏角区成的为热节区，此热节区是铸坯凹陷，裂纹等缺陷乃至漏钢事故发生的诱因。     

Non-uniform heat transfer behavior during shell solidification in a wide and thick slab continuous casting mold

By employing a two-dimensional transient thermo-mechanical coupled finite element model for simulating shell heat transfer behaviors within a slab continuous casting mold, we predicted the evolution of shell deformation and the thermal behaviors, including the mold flux film dynamical distribution, the air gap formation, as well as the shell temperature field and the growth of carbon steel solidification, in a 2120 mm × 266 mm slab continuous casting mold. The results show that the shell server deformation occurs in the off-corners in the middle and lower parts of the mold and thus causes the thick mold flux film and air gap to distribute primarily in the regions of 0–140 mm and 0–124 mm and 0–18 mm and 0–10 mm, respectively, from the corners of the wide and narrow faces of the shell under typical casting conditions. As a result, the hot spots, which result from the thick mold flux film filling the shell/mold gap, form in the regions of 20–100 mm from the corners of the wide and narrow faces of the shell and tend to expand as the shell moves downward.     

TiO_2对连铸保护渣非等温结晶过程的影响

采用热丝法、X射线衍射(XRD)以及矿相方法研究TiO2对保护渣非等温结晶过程的影响.结果表明:枪晶石是含钛保护渣的主要物相.在综合碱度为1.3的基础渣中加入质量分数2%～8%TiO2后,随着TiO2的加入,渣样开始析出了少量的Ca2SiO4、Ca2Al(AlSi7O7)、Ca2SiO2F2和CaTiO3晶体.虽然加入TiO2,促进了析晶种类的增加,但保护渣的结晶过程的时间延长,且保护渣的结晶速率和结晶率降低.因此,加入TiO2后,抑制了保护渣的析晶,从而保证在控制渣膜热流的前提下,提高玻璃态的比例以改善润滑.     

基于Pt-Au-MoS2-ITO传感器对于H2O2的还原检测

实验探究了二硫化钼（MoS₂）作为一种新型材料与贵金属纳米粒子金（Au）、铂（Pt）的复合基底对于过氧化氢（H₂O₂）的还原性检测,采用氧化铟锡导电玻璃（ITO）作为电极,制备出了基于Pt-Au-MoS₂-ITO的生物传感器,为H₂O₂还原性检测的便携性操作打下了基础.实验采用电化学沉积的方法制备材料,同时使用循环伏安（CV）法、计时电流法等传统电化学手段表征了传感器电化学性能,采用场发射扫描电子显微镜（FE-SEM）来表征传感器表面形貌.建立了用于H₂O₂还原检测的、具有高检测限、高灵敏度和宽检测范围的传感器.     

连铸保护渣渣膜润滑的研究现状

连铸中，特别是高速连铸条件下，渗入结晶器与凝固坯壳之间的保护渣渣膜的润滑状态对连铸过程有着重要的影响，本文介绍了国内外对渣膜润滑的主要研究成果。     

基于反算热流的结晶器内流动--传热--凝固耦合模拟

基于Navier-Stokes动量方程和湍流低雷诺数k-ε方程,综合考虑能量守恒和钢液凝固与糊状区对流动过程的影响,建立了描述结晶器内钢液流动、传热及凝固过程的三维耦合数学模型。以实测温度和结晶器反问题模型计算出的热流为边界条件,模拟计算了结晶器内钢水的流动、传热和凝固行为。钢液流动决定结晶器内的温度和热流分布,铸坯凝固受钢液流动和结晶器热流双重因素的影响。建立的模型以及由此得到的铸坯凝固非均匀特征可为进一步考察浇铸过程中纵裂和其他表面缺陷提供借鉴和参考。     

Effect of continuous casting speed on mold surface flow and the related near-surface distribution of non-metallic inclusions

For the control of surface defects in interstitial-free(IF) steel, quantitative metallographic analyses of near-surface inclusions and surface liquid flow detection via the nail-board tipping method were conducted. The results show that, at casting speeds of 0.8 and 1.0 m/min, a thin liquid mold flux layer forms and non-uniform floating of argon bubbles occurs, inducing the entrainment and subsequent entrapment of the liquid flux; fine inclusion particles of Al_2O_3 can also aggregate at the solidification front. At higher casting speeds of 1.4 and 1.6 m/min, the liquid mold flux can be entrained and carried deeper into the liquid steel pool because of strong level fluctuations of the liquid steel and the flux. The optimal casting speed is approximately 1.2 m/min, with the most favorable surface flow status and, correspondingly, the lowest number of inclusions near the slab surface.     

连铸结晶器中坯壳生长有限元分析

为了预测结晶器出口铸坯坯壳的厚度与均匀性,考虑气隙对连铸坯的边界换热条件的影响,建立了铸坯传热凝固有限元计算分析的数学模型。采用热通量系数法反映实际的坯壳角部凝固特征现象。在方坯结果验证基础上,通过对新型H型连铸坯凝固过程进行模拟,计算得出了结晶器出口处坯壳的厚度。计算结果表明:H型铸坯坯壳的厚度随着拉速的增加而变小;铸坯在腹板和翼板交接处最薄,应适当增加水量,以保证坯壳在结晶器出口处具有足够的厚度。     

热型连铸工艺凝固过程的数值模拟

采用直接差分的方法对热型连铸工艺凝固过程的稳定温度场进行了模拟,绘制了热型连铸工艺凝固过程的温度曲线,分析了铸型出口温度、冷却条件、连铸速度和型内金属液温度对凝固温度曲线的影响．铸型出口温度、冷却条件、连铸速度依次为影响液固界面的主要因素,型内金属液温度对液固界面的影响很小．     

宽厚板包晶钢的保护渣

针对包晶钢的凝固特性,研发了高碱度、高结晶速率、低结晶温度及低热流密度保护渣,并在宝钢3#连铸机上进行了试验研究.现场试验四个浇次的结果表明,使用改进渣的试验流铸坯无纵裂发生,而使用原渣的对比流铸坯裂纹率达到5%.优化保护渣有效防止了铸坯表面纵裂的发生.     

CSP结晶器内钢液流动及凝固的数值模拟

应用数值模拟方法,建立CSP漏斗型结晶器内钢液流动及凝固传热耦合模型。针对结晶器内铸坯角部受到强冷的特点,对结晶器内热流密度采用修正方程进行计算,分析热流密度修正系数对铸坯凝固坯壳表面温度计算精度的影响。通过比较不同拉坯速率下结晶器内钢液凝固的特点,研究凝固坯壳对结晶器内钢液流动行为的影响。结果表明,采用热流密度修正系数后,铸坯凝固坯壳角部温度的计算值与实际情况更相符;提高拉坯速率可使铸坯凝固坯壳厚度减小;拉坯速率较大时凝固坯壳厚度随铸坯距弯月面距离的增大基本呈线性增长,拉坯速率为3m/min时,凝固坯壳在生长过程中厚度的增长有短暂的停滞现象;凝固坯壳对钢液流动的影响较大,主要是由钢液有效流动区域减少及两相区额外动量阻损造成的。     

恒稳磁场控制连铸结晶器内钢液流场热模拟实验

采用BiPbSn低熔点合金和硅油分别模拟钢液和保护渣,在实验连铸机上,对全幅双条恒稳磁场作用下的连铸结晶器水口区域的流场进行了热模拟实验研究·结果表明:电磁场对结晶器水口区域流场和水口出流流股的控制能力取决于磁感应强度和拉坯速度·磁感应强度大,拉坯速度高,控制效果好;反之,控制效果差·因此,结晶器流动控制技术更适合于高拉速的场合,而且磁感应强度不应低于某一定值     

Bi_2Se_3、Bi_2Te_3和Sb_2Te_3的声子和热力学性质的第一性原理研究

基于第一性原理的密度泛函理论,在未考虑和考虑自旋-轨道耦合(SOC)的情况下分别优化拓扑绝缘体Bi2Se3、Bi2Te3和Sb2Te3的结构,计算它们的声子谱及热力学性质.基于广义梯度交换相关泛函及SOC效应,计算得到三种物质的声子频率比不考虑SOC时更吻合实验数据.最后计算出三种物质的赫尔姆赫兹自由能F,内能E,等体热容CV和熵S随温度的变化趋势.