Mass Exchange at the Metal‐Mould Flux Interface

Mass exchange between liquid steel and the mould flux leads to the oxidation of some elements in the steel and the reduction of slag components. In the continuous casting process, where metal initially solidifies at the metal‐slag interface, reaction products generated there can be cached by the growing solidification front. The disruptions of the interface promote the entrapment of flux particles additionally. They can cause surface defects with quality damages of the cast products as a consequence. These investigations are focused on the contact area between liquid mould flux and metal. The samples were taken from the mould during the continuous casting process. The results show that layers up to approximately 300 nm from the slag/metal interface represent a specific reaction space. The transport of oxygen near the interface and the charge transfer is explained on the basis of the ionic character of the slag. Sodium in this layer on the slag side plays a special role in the oxygen transport besides of the iron ions. The mass transfer rate of oxygen crossing the interface is calculated from measured data and conclusions concerning the stability of the interfacial tension are made.     

TiO2含量对CaO-Al2O3-TiO2基连铸保护渣界面性质的影响

采用热丝法对不同TiO₂含量的CaO-Al₂O₃-TiO₂基保护渣进行接触角试验,计算出保护渣表面张力和钢渣界面张力,分析TiO₂含量对保护渣接触角、表面张力、界面张力的影响规律。结合拉曼光谱,分析TiO₂在微观结构上对钢渣界面张力的影响机理。研究结果表明,1 723 K温度下,保护渣中TiO₂质量分数为4%~12%时,接触角为15.3°~38.5°,保护渣表面张力为523~541 mN/m;在保护渣TiO₂质量分数为4%~10%和10%~12%时,钢渣界面张力变化量分别为4 mN/m和82 mN/m。TiO₂质量分数为4%~10%时,界面张力基本保持不变,钢渣间界面反应变弱,钢渣易分离,更符合高钛钢连铸生产的需求。随着TiO₂含量的增加,离子半径增加,阴阳离子间距增大,熔体内主要阴离子为TiO₄4-单体和Ti₂O₄6-链单元,复合阴离子被排挤到熔体表面,阴阳离子间结合力降低,进一步导致表面张力降低。     

TiO2含量对CaO-Al2O3-TiO2基连铸保护渣界面性质的影响

采用热丝法对不同TiO₂含量的CaO-Al₂O₃-TiO₂基保护渣进行接触角试验,计算出保护渣表面张力和钢渣界面张力,分析TiO₂含量对保护渣接触角、表面张力、界面张力的影响规律。结合拉曼光谱,分析TiO₂在微观结构上对钢渣界面张力的影响机理。研究结果表明,1 723 K温度下,保护渣中TiO₂质量分数为4%~12%时,接触角为15.3°~38.5°,保护渣表面张力为523~541 mN/m;在保护渣TiO₂质量分数为4%~10%和10%~12%时,钢渣界面张力变化量分别为4 mN/m和82 mN/m。TiO₂质量分数为4%~10%时,界面张力基本保持不变,钢渣间界面反应变弱,钢渣易分离,更符合高钛钢连铸生产的需求。随着TiO₂含量的增加,离子半径增加,阴阳离子间距增大,熔体内主要阴离子为TiO₄4-单体和Ti₂O₄6-链单元,复合阴离子被排挤到熔体表面,阴阳离子间结合力降低,进一步导致表面张力降低。     

Study of Interfacial Tension between Molten Steel and Na_2O-Li_2O-SiO_ 2-B_2O_3 Slag

Ｔｈｅｒｅａｒｅｍａｎｙｃａｓｅｓｗｈｅｒｅｔｈｅｉｎｔｅｒｆａｃｅｂｅ ｔｗｅｅｎｍｏｌｔｅｎｍｅｔａｌａｎｄｓｌａｇｐｌａｙａｎｉｍｐｏｒｔａｎｔｒｏｌｅｉｎｔｈｅｓｔｅｅｌｍａｋｉｎｇ ｐｒｏｃｅｓｓｓｕｃｈａｓｔｈｅｆｏｒｍａｔｉｏｎ ,ａｇｇｒｅｇａｔｉｏｎ ,ｄｉｓｔｒｉｂｕｔｉｏｎａｎｄｓｉｚｅｏｆｎｏｎ ｍｅｔａｌｌｉｃｉｎ ｃｌｕｓｉｏｎｓｉｎｓｔｅｅｌ ,ｆｏｒｍａｔｉｏｎｏｆｍｅｔａｌ ｉｎ ｓｌａｇｅｍｕｌｓｉｏｎｉｎｔｈｅＢＯＦｐｒｏｃｅｓｓａｎｄｓｌａｇ ｍｅｔａｌｒｅａｃｔｉｏ…     

表面张力对保护渣设计及选用的影响

通过对结晶器保护渣性能影响钢液面裹渣的理论分析、试验研究，提出通过提高液渣表面张力及钢渣界面张力，在实际生产中达到减少结晶器钢液面裹渣的目的。通过降低渣中SiO2、Na2O，提高MgO，减少FeO、Fe2O3改进了原保护渣，批量应用表明，铸坯粘渣现象大大减轻，夹渣协议板率由6％降为0．61％。     

Interfacial Convection and Mass Transport in Thin Liquid Layer

Investigations into the phenomenology of convection flows next to the interface between two liquids have been carried out in laboratory experiments using various liquids. Then convection flows have been observed in industrial tests during continuous casting. The results show that the motional velocity of volume elements next to the interface due to disturbances of interfacial tension (produced by mass and charge transfer) depends on liquid layer thickness and on liquid properties. A new dimensionless number is introduced to describe this manner of convective flow; it is also suitable for evaluation of experimental results. Furthermore, a dimensionless function is theoretically developed to describe the relation between convective flows near the interface in the slag layer and mass transport. Casting powders melt on the surface of the liquid metal forming a liquid slag layer. Samples taken during casting have revealed convective flows in the flux layer and mass exchange with the liquid metal. Coefficients of the developed dimensionless function have been determined empirically for Ti‐transport from the interface into the flux layer.     

Rupture Strength of some Mould Flux Slag Films relevant to Swedish Continuous Casting Practice

In this paper, the high temperature rupture strengths of some solid mould flux slag films in Swedish continuous casting processes are presented. The apparatus, designed and constructed in the present laboratory is based on the principle that the solidified film of the mould flux slag is subjected to elongation stress at temperatures below the solidus points of the fluxes. The rupture strength tests were conducted in air. The results indicate that the rupture strength is dependent on the extent of polymerization of the silicate network. The results of Raman spectra studies of the mould flux slags used in the present work were corroborated by estimations of the NBO/T ratios of the slags. It was found that lower NBO/T ratios in the slag led to higher rupture strengths. Earlier measurements of the viscosities, thermal diffusivities as well as stress relaxation results for the same slags followed a similar trend indicating the dependency of these properties on the slag structure and a clear link between thermophysical and mechanical properties of slags. The results are expected to provide some basic guidelines to develop the next‐generation mould flux and modelling of the continuous casting process.     

稀土处理钢连铸结晶器保护渣的研制

研究了稀土氧化物(RE_xO_y)对连铸保护渣理化性能的影响,分析了RE_xO_y在液体保护渣中的扩散熔解过程,确定了稀土处理钢连铸保护渣的化学成分。应用新型的稀土处理钢用保护渣没有发生拉漏事故,并提高了铸坯表面质量。     

Relation between steel/slag interfacial tension and the sulphur absorption rate in dependence of the Si and Mo concentration

The relation between the interfacial tension at the steel/slag interface and the sulphur transport through the phase boundary has been investigated. The experiments have been carried out at 1550°C. The steel/slag system consisted of Armco iron in combination with a synthetic slag containing 40% CaO, 40% SiO₂ and 20% Al₂O₃. The controlled change of the interfacial tension was performed by additional alloying of the surface active element silicon and surface inactive molybdenum. The different influences of silicon and molybdenum on interfacial tension are directly reflected by the sulphur transport rate. Higher interfacial tensions generally cause a lower sulphur transport rate. A linear relationship was only obtained in presence of silicon.     

Interfacial tensions of liquid Fe-Ni alloys and stainless steels in contact with CaO-SiO2″AI2O3-based slags at 1550 °C

In the present work, the interfacial tensions of Fe-Ni alloys in contact with slags of the CaO-Al2O3-SiO2 system were measured at 1550 °C. Nickel additions to the alloy were found to decrease interfacial tension. The effects of alumina and titania additions to the slag on the interfacial tension of the Fe-20 wt pct Ni alloy were determined: alumina was found to increase the interfacial tension by a small amount, while titania was found to decrease it drastically. Using the present interfacial tension data for the CaO-Al2O3-SiO2 system and the ones measured by Jimbo and Cramb, Girifalco and Good’s interaction coefficient (ϕ) was determined as a function of the slag composition using regression analysis and was found to be a useful means of correlating interfacial tension data. The interfacial tension of an Fe-20 wt pct Ni-2.39 wt pct Al alloy in contact with a CaO-Al2O3-SiO2 slag was found to decrease drastically in the first 60 to 75 minutes of the experiment due to the dynamic effects of mass transfer. Slight lowering of interfacial tensions of industrial stainless steels due to sulfur transfer from liquid metal to slag was also observed. The equilibrium interfacial tensions of type 304 stainless steels were found to be more dependent on the slag chemistry than on the nickel and chromium content of the alloy. Formerly Graduate Student, Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, PA     

FTSC薄板坯连铸中碳钢保护渣研究及开发

针对唐钢FTSC薄板坯连铸所产生的板坯裂纹、表面夹渣、卷渣及漏钢现象进行保护渣生产试验研究与理论分析。研究结果表明,组分变化对保护渣熔化温度和粘度等指标有着重要的影响。通过实验室对保护渣组份及其变化对其性能影响的研究,结合唐钢FTSC薄板坯连铸自身特点,设计出保护渣基本配方,且在不断试验改进中,最终开发出适合唐钢薄板坯连铸用中碳钢保护渣C2.     

Effect of Al2O3 and MgO on Interfacial Tension Between Calcium Silicate‐Based Melts and a Solid Steel Substrate

The effect of Al₂O₃ and MgO on the interfacial tension between the molten CaO–SiO₂‐based slag and solid steel at 1773 K was studied. The interfacial tension of molten slags slightly increased with increasing Al₂O₃, but no significant change of interfacial tension was observed with higher MgO. Fourier transform infrared (FTIR) of as‐quenched slag samples indicated the slag structure to polymerize with Al₂O₃ additions, but depolymerize with MgO additions. Further detailed studies of the slag surface using X‐ray photoelectron spectroscopy (XPS) showed the fraction of free oxygen ions to decrease with higher Al₂O₃ but remained constant at higher MgO. The results suggested that interfacial tension decreases not only with the depolymerization of the melt, but also with an increase in the free oxygen ions at the molten slag/solid steel interface.     

连铸保护渣与氧化铝的交互作用研究现状

保护渣中Al2O3质量分数变化是渣钢交互作用的结果,包括吸附钢液中Al2O3夹杂和渣金反应产物。氧化铝对保护渣成分与性能稳定性影响突出,进而影响铸坯质量。分析指出,影响保护渣吸附Al2O3夹杂的因素包括接触角、润湿速率和界面张力、熔渣成分和性能等。熔渣与夹杂物的交互作用行为决定了其对上浮夹杂的去除率。高铝钢连铸过程渣金反应尤为突出,保护渣的工作性能将发生明显改变。基于近年关于Al2O3夹杂的吸附溶解试验研究,以及高铝钢浇铸渣金反应及其保护渣性能变化的研究结果,探讨了通过合理设计保护渣成分或更换渣系等措施来实现该类钢种保护渣工作性能的相对稳定性。     

GCrl5轴承钢精炼渣对夹杂物祛除行为的研究

通过建立的夹杂物穿越钢渣界面运动模型,研究了精炼渣对夹杂物的吸附现象。结果表明,夹杂物 粒径、表面张力和熔渣粘度是影响夹杂物冲破钢渣界面的重要参数,大型夹杂物中粒径和熔渣粘度起决定作用,而 ≤ 20㎛ 级别的小型夹杂物中仅表面张力起决定作用;大型夹杂物冲破钢渣界面的能力远大于小型夹杂物。针对 小型夹杂物难以吸附的问题,运用了夹杂物运动模型和熔渣、钢液表面张力模型,研究了表面张力对吸附过程的影 响。结果表明,直径≤ 122.9 ㎛尺寸的夹杂物均无法穿越钢渣界面,回弹至钢液一侧,由此得出：无法通过调整精 炼渣用以吸附≤ 122.9 ㎛夹杂物以达到进一步降低钢中氧含量的目的。     

Fluorine‐Free Mould Powders for Billet Casting – Technological Parameters and Industrial Tests

There is a clear trend in industry to eliminate fluorine from metallurgical slags. Regarding the continuous casting process, fluorine in mould powders is undesirable due to the following reasons: (i) evolves easily from slags producing health‐injurious gaseous substances like hydrofluoric acid, (ii) creates problems for storage and utilization of solid waste, and (iii) causes machinery corrosion. A collaboration among universities, mould powder supplier, and steel producer was established, aiming for the development of a new F‐free mould powder for billet casting. Firstly, technological parameters for a particular composition were determined: melting characteristics, viscosity, melting behavior, and crystallization tendency. Afterwards, industrial trials were performed in a Brazilian steelworks, doing some evaluations during the continuous casting process, such as ΔT between water cooling inlet and outlet, slag pool thickness, melting performance, powder consumption, Al₂O₃ pick‐up, and effect on SEN erosion. Comparable surface quality for the billets was obtained when using the F‐free mould powder, since the amount of scrap produced during the rolling process was not critical.     

板坯结晶器内钢/渣界面流态的水模拟

通过在全比例水模型上进行模拟,研究了结晶器宽度、拉坯速度、浸入式水口结构及水口浸入深度等工艺参数对板坯结晶器内钢/渣界面波动和界面最大流速的影响。结果表明:单独增大结晶器宽度或拉坯速度,结晶器内钢/渣界面波动和界面最大流速都将增大;而浸入式水口结构和水口浸入深度对钢/渣界面波动和界面最大流速的影响较复杂,其中,15°凸型水口通用性较好。     

Influence of carbon,silicon and molybdenum on the separating and emulsifying behaviour of steel and slag

The influence of C, Si, and Mo on the surface tension of Armco iron, and on the interfacial tension between Armco iron and a 40%CaO/40%SiO₂/20%Al₂O₃ slag at 1550°C has been investigated. Surface tension was determined according to the drop weight method, and the interfacial tension by the drop detachment method. Based on these measurements, ternary interfacial tension diagrams are set up, which enable the separating and emulsifying tendencies of the related steel/slag/gas systems to be predicted. This is followed by the calculation of the meniscus radius as a function of interfacial tension in continuous casting, together with the assessment of its effect on lubrication.     

Prediction model for steel/slag interfacial instability in continuous casting process

In a continuous casting process, mould powder is typically adopted to cover molten steel, which prevents liquid steel from oxidation by air, preserves heat for the top layer of liquid steel, lubricates the initial shell and so on. However, mould powder may deteriorate the quality of the final product if the entrapment of mould powder forms, which is usually caused by the instability of the steel/slag interface. In the current work, a model to predict the critical point of interfacial instability for liquid–liquid stratified flow was developed based on the Kelvin–Helmholtz instability. To prove the validity of the prediction model, a water model experiment was carried out in a rectangular container. In this experiment, oil and water were used to simulate slag and molten steel respectively. The results of the water model prove that the prediction model is correct. Applying the prediction model to a steel–slag system, the critical velocity of molten steel for mould powder entrapment is 0.463–0.541?m?s^??1. When considering the most severe chemical reaction, the critical velocity decreases to 0.29?m?s^??1. The lowest critical velocity of molten steel is 0.264?m?s^??1 when the viscosity of the slag and steel/slag interfacial tension is extremely low.     

Interfacial phenomena between fluxes for continuous casting and liquid stainless steel

Abstract

Casting powders melt on the surface of the liquid metal forming a liquid slag layer. Samples taken during casting revealed convective flows in the flux layer and mass exchange with the liquid metal. It is demonstrated that concentrations of certain elements are considerably higher at the phase boundary than in the bulk of the metal and slag phase. Disturbances of interfacial tension produced by mass and charge transfer evidently cause strong shearing forces which act in parallel with the phase boundary. These forces induce convective movements in the flow boundary layer. Convective flows next to the interface between two liquids have been studied in laboratory experiments using various liquids. The results show that the movement velocity of volume elements next to the interface (due to disturbances of interfacial tension) are dependent on liquid layer thickness and on liquid properties. A new dimensionless number describing this manner of convective flow and suitable for evaluation of experimental results is introduced. Its contribution to the total mass transfer will be shown. A dimensionless function describing the relation between convective flows in the slag layer and mass transport is theoretically developed. Coefficients of this function for Ti transfer into the flux layer have been determined empirically.     

Mould Flux Film between Mould and Steel Shell – Effect on Heat Flux and Defect Formation

This work desrcibes the occurence of the so called slag defect in industrial continuous casting of stainless steel slabs. When liquid casting powder infiltrates into the gap between mould and shell, a part of it solidifies on the mould surface. This layer of the powder slag can grow in thickness and can change in its structure during hours of casting, leading to a reduction in heat flux and an increase in frequency of the defect type.