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.     

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.     

Mass Transfer in Slag Refining of Silicon with Mechanical Stirring: Transient Interfacial Phenomena

Experiments have been carried out to study the rates of mass transfer between liquid silicon and CaO-SiO₂ slag with impeller stirring at 1823 K (1550 °C). The occurrence of transient interfacial phenomena related to the mass transfer of calcium has been observed; the evidence suggests that the reduction of calcium oxide at the interface leads to a rapid, temporary drop in the apparent interfacial tension. At low apparent interfacial tension, mechanical agitation facilitates the dispersion of metal into the slag phase, which dramatically increases the interfacial area; here, it has been estimated to increase by at least one order of magnitude. As the reaction rate slows down, the apparent interfacial tension increases and the metal recoalesces. The incidental transfer of calcium very likely promotes the transfer of boron by increasing the interfacial area. Mechanical mixing appears to be an extremely effective means to increase the reaction rate of boron extraction and could feasibly be implemented in the industrial slag refining of silicon to improve reaction rates.     

Interfacial phenomena and mass transfer in extractive metallurgy

Interfacial phenomena play an important role in pyrometallurgical processes and knowledge of them and of physical properties involved is necessary for understanding the mechanisms and the kinetics of such reactions. A large number of measurements, performed at Irsid under equilibrium conditions, are presented in this review. Several experimental techniques were used and more particularly: – Sessile drop method for measurement of liquid metals surface tension and contact angle liquid metal/solid oxide; – measurement of the contact angle between a liquid slag drop and its liquid metal substrate from which the interfacial tension can be derived; – direct determination of the interfacial tension from X-ray pictures of metal drops immersed in the slag. The systems studied consisted, for the metal phase, of binary and ternary Fe alloys containing C, Mn, Si, O, S and, for the slag phase, binary and ternary mixtures made from CaO, SiO₂, Al₂O₃, MnO, iron oxides, CaF₂ and Na₂O. A strong effect of O and S potentials was observed. For non-equilibrium conditions, however, the dynamic interfacial tension between liquid metal and slag decreases sharply when an intense mass transfer occurs through the interface. The potential consideration of interfacial turbulence phenomena (Marangoni effect) in metallurgical reactions is also discussed.     

Physical modeling of liquid/liquid mass transfer in gas stirred ladles

Several of the metallurgical reactions occurring in gas stirred steel ladles are controlled by liquid phase mass transfer between the metal and slag. In order to calculate the rate of these reactions, information about the two phase mass transfer parameter is necessary. The mass transfer between two immiscible liquids, oil and water simulating slag and steel, respectively, was measured in a scale model of a ladle. The mass transferred species was thymol which has an equilibrium partition ratio between oil and water similar to that for sulfur between slag and metal. The mass transfer rate was measured as a function of gas flow rate, tuyere position and size, method of injection, oil viscosity, and oil/water volume ratio. In addition, mixing times in the presence of the oil layer and mass transfer coefficient for the dissolution of solid benzoic acid rods were measured. The results show that there are three gas flow rate regimes in which the dependence of mass transfer on gas flow rate is different. At a critical gas flow rate, the oil layer breaks into droplets which are entrained into the water, resulting in an increase in the two phase interfacial area. This critical gas flow rate was found to be a function of tuyere position, oil volume, densities of two phases, and interfacial tension. Two phase mass transfer for a lance and a tuyere was found to be the same for the same stirring energy in low energy regions regardless of lance depth. Mass transfer is faster for a center tuyere as compared to an offcenter tuyere, but mixing times are smaller for the offcenter tuyere. From the results obtained, the optimum stirring conditions for metallurgical reactions are qualitatively discussed. SEON-HYO Kim, formerly Graduate Student in the Department of Metallurgical Engineering and Materials Science, Carnegie Mellon University.     

Measurements and Calculation of Interfacial Tension between Commercial Steels and Mould Flux Slags

Surface quality of continuously cast is strongly influenced by the interfacial tension between steel and mould flux slag. The meniscus shape and the inclusion entrapment are directly determined by interfacial tension. To achieve a better understanding of the continuous casting process, the interface between four commercial steels and the mould fluxes used at the continuous casting of each steel grade have been investigated. The situation at this interface is determined by the surface tension of steel and slag respectively and also by the mass transfer occurring across the interface. The surface tensions of the mould flux slags have been measured by sessile drop method. The results indicate that the surface tension of mould flux slags decreases with increasing temperature but does not vary so much within the present composition range. Interfacial tensions between steel samples and mould flux slags have been measured in the same way with the aid of X‐ray unit. Estimation of interfacial tension from the steel and slag composition was done by applying empirical models. The measured and the calculated values were in agreement. The interfacial tension was lower for higher alloyed steel grades according to both experiments and calculations though the influence of surface active elements is significant.     

The Rate of the Phosphorous Reaction Between Liquid Iron and Slag

In the current study, the rates of dephosphorization and rephosphorization of liquid iron with simulated steelmaking slags were investigated at 1873 K (1600° C). The experiments were conducted in an induction furnace with supplemental heating to maintain a consistent temperature within both the metal and slag phases. An integrated form of the rate equation was used to evaluate the results, assuming mass transfer in both the slag and metal was rate controlling. The results of the current and previous studies indicate that the mass transfer parameter, the slag-metal surface area, and the overall mass transfer coefficient (A*k ₀), decreased as the reaction proceeded. It is proposed that initially when the rate and oxygen flux are high, the interfacial energy decreases, and the interfacial fluid velocity increases causing disruption of the slag metal interface. The consequent increases in interfacial area and interfacial fluid flow cause A*k ₀ to be high initially and then decrease as the oxygen flux decreases.     

Flow of molten slag and iron at 1500 °C to 1600 °C through packed coke beds

The blast furnace dripping zone is of great importance to the mass transfer of elements such as sulfur, carbon, and silicon, to and from the liquid metal phase. To understand mass transfer in the dripping zone, not only mass-transfer reactions and kinetics should be known, but the flow phenomena and process dynamics should be understood as well. The flow of hot metal and slag in the dripping zone was studied in experiments, in which liquid slag and metal trickled through a packed coke bed at 1500 °C to 1600 °C. The results indicate that slag and iron flow concurrently in a funicular type of flow. The iron flows through the core of the voids in the bed and is enveloped by slag, which flows filmwise in between the coke and the iron. This mode of flow allows for a large contact area between slag and iron, through which mass can be transferred. While flowing, the liquid can only pass and access a void, if and when the fluid capillary pressure at the void neck can be overcome. As a result, liquid droplets collect into rivulets. These rivulets flow down, along the accessible voids, using only a part of the available volume. The residence times of the fluids in the bed depend partly on the length of the pathway and are a function of the bed structure, the void neck distribution, and the stochastics of the flow. During flow, slag may react with coke, thus changing the distribution of the slag composition, and its sulfur capacity. In addition, the residence time distribution of the slag and the liquid holdup change as a result of these reactions. Holdup and residence time distribution of the liquids as measured in the experimental setup could not be modeled quantitatively, most likely due to the doubly distributed nature (in space and in time) of the model parameters, induced by reactions between slag, coke, and liquid metal.     

Influence of alloying elements and metalloids on the emulsion and separation behaviour of steel and slag

With the aid of surface and interfacial tension data it has been possible to clarify the effect of the elements nickel, titanium and sulphur in steel and titanium oxide and sulphur in slag on the emulsifying or separating tendencies of liquid steel/molten slag phases. This has been related to the tendency of (scattered) liquid steel films to adhere to gas bubbles crossing the interface, which in turn leads to the formation of metal droplets in the slag phase. Nickel containing steels tend to form emulsions, whereas titanium, both dissolved in the steel and as titanium oxide in the slag, tends to suppress adherence of the steel to the bubbles and promotes steel/slag separation. Sulphur containing steels show also an emulsifying tendency in contact with both sulphur containing and sulphur free slags. With sulphur present in the slag, however, the opposite effect is observed, so that, as sulphur transfer proceeds between the steel and the slag during desulphurization, the emulsifying tendency is markedly reduced, leading to steel/slag separation.     

Kinetics of iron oxide reduction from CaO-MgO-FeOn-SiO2 slags by silicon dissolved in liquid iron

At steelmaking temperatures, the kinetics of slag-metal reactions is usually determined by mass transfer. This occurs in two ways: normal mass transfer which is induced by stirring, and mass transfer by interfacial convection induced by interfacially active elements like oxygen and sulphur. In the present work, mass transfer during the reduction of iron oxide from a basic slag by silicon dissolved in liquid iron was studied under defined conditions of gas stirring by argon in MgO crucibles with 1500 g iron and 250 g slag. The variations of the FeO content in the slag and the silicon content in the iron during the reaction were measured by sampling. Trials were carried out with stirring gas flow rates between 1 and 20.4 l/h(STP). The experimental data were evaluated with the multi-component transport model in order to determine the mass transfer coefficients of the reaction components. Simultaneously, the coefficients of normal mass transfer were calculated with the boundary layer theory of liquid-liquid mass transfer for non-turbulent flow conditions. The measured mass transfer coefficients were by a factor 2.5 larger than the theoretically calculated. The difference indicates the presence of mass transfer by interfacial convection. Mass transfer by interfacial convection is superimposed to normal mass transfer.     

Mass transfer of sulfur from liquid iron into lime-saturated CaO-Al2O3-MgO-SiO2 slags

Laboratory experiments on the kinetics of sulfur transfer from aluminium-deoxidized liquid iron into lime-saturated CaO-Al₂O₃-MgO-SiO₂ slags were carried out at 1600°C in MgO crucibles with 1500 g iron and 180 to 250 g slag. The mass-transfer coefficients of sulfur were determined under defined flow conditions of liquid metal induced by gas stirring. A square-root dependence of measured rate constants on flow velocity of metal was found. This is interpreted as normal liquid-liquid mass transfer caused by the forced convection of gas stirring. It could be described by boundary-layer theory applied to the metal-slag interface. With increasing sulfur contents of metal mass-transfer coefficients became larger. This is interpreted as mass transfer by interfacial convection superimposed to normal mass transfer. Interfacial convection was confirmed by microscopic observation of quenched metal-slag interface samples. If the sulfur content in liquid iron exceeds a critical value, calcium sulfide crystals precipitate in slag at the slag-metal interface. The precipitation inhibits generation of interfacial convection.     

Investigation of inclusion re-entrainment from the steel-slag interface

The mechanism of inclusion elimination from continuous steel casting is investigated at the steelslag interface. Inclusion impact at the interface is considered under the concept of energy balance, with buoyancy forces, fluid dynamic forces, interfacial adhesion, and rebound forces determining whether the particle will pass through the interface or be retained by it. The effects of the inclusion, slag, and steel properties, as well as the effect of inclusion impact velocity, are considered at the interface. The interfacial tension between the slag and the inclusion should be smaller than that between the steel and the inclusion (negative wettability), so that the inclusions can pass into the slag layer and avoid re-entrainment. The inclusion particles that reach an equilibrium state at the steel-slag interface are subject to re-entrainment back into the steel, due to lift forces applied to them by the turbulent boundary layer at the interface. A removal criterion dependent upon the shear stress is introduced, and then the removal rates are calculated from the turbulent burst theory. It is found that the smaller diameter inclusions are trapped at the interface. Of the particles that remain at the interface, it is the larger ones that are more easily removed by the lift forces due to the turbulent shear stress. High slag viscosity is desirable, since it makes inclusion re-entrainment into the casting product more difficult.     

Influence of the Physical Properties of Liquids and Diameter of Bubble on the Formation of Liquid Column at the Interface of Two Liquid Phases by the Rising Bubble

The formation of metal emulsion in a steel-making process enhances the reaction between metal and slag. A part of the metal emulsion is formed by a bubble passing through the interface between the metal and slag phases. In a previous study, it was determined that the formation of metal column by the bubble is related to the formation of metal droplets. In this research, the effects of bubble particle size, interfacial tension, viscosity of upper layer, and lower layer density on the formation of lower liquid column were investigated. In order to conduct an in situ observation of gas and liquid behaviors, aqueous solution and silicon oil systems were employed. It was determined that a narrow and elongated column forms liquid droplets in the upper liquid layer and contributes to the formation of droplets. The height of the column and the volume of droplets increase with the increase in bubble size. The influence of interfacial tension of the two liquid phases on the column height and the formation of droplet is slight. The height of the formed column decreases with the increase in the density of lower liquid.     

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。     

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。     

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     

Model Investigations on the Stability of the Steel-Slag Interface in Continuous-Casting Process

In the continuous-casting mold, the mold powder in contact with the liquid steel surface forms a liquid slag layer. The flow along the steel-slag interface generates shear stress at the interface, waves, and leads to fingerlike protrusions of liquid slag into steel. Reaching a critical flow velocity and thereby shear stress, the protrusions can disintegrate into slag droplets following the flow in the liquid steel pool. These entrained droplets can form finally nonmetallic inclusions in steel material, cause defects in the final product, and therefore, should be avoided. In the current work, the stability of a liquid-liquid interface without mass transfer between phases was investigated in cold model study using a single-roller driven flow in oil-water systems with various oil properties. Applying the similarity theory, two dimensionless numbers were identified, viz. capillary number Ca and the ratio of kinematic viscosities ν ₁/ν ₂, which are suitable to describe the force balance for the problem treated. The critical values of the dimensionless capillary number Ca^* marking the start of lighter phase entrainment into the heavier fluid, are determined over a wide range of fluid properties. The dimensionless number ν ₁/ν ₂ was defined as the ratio of kinematic viscosities of the lighter phase ν ₁ and heavier phase ν ₂. The ratios of kinematic viscosities of different steel-slag systems were calculated using measured thermophysical properties. With the knowledge of thermophysical properties of steel-slag systems, Ca^* for slag entrainment as a function of v ₁/v ₂ is derived. Assuming no reaction between the phases and no interfacial flow, slag entrainment should not occur under the usual casting conditions.     

A New Insight to Interfacial Phenomena Occurring at Slag‐Metal Interfaces

Interfacial dilatational modulus was evaluated for slag‐metal systems using oxygen and sulfur as tracers at 1823 K. The high values of the dilatational modulus (5–10 times that obtained for surfactant adsorption) was directly related to the higher change in apparent interfacial tension prevailing at the slag‐metal interface. The variation in the dilatational modulus was attributed to the non‐uniform distribution of surface active elements at the interface and also due to the varying surface pressure. Further, experiments were designed to estimate the surface shear viscosity. A relationship was established to find the surface/interfacial shear viscosity from the Newton's law of viscosity. The order of magnitude of the interfacial shear viscosity at the slag‐metal interface was estimated from the values obtained earlier for the interfacial velocity. The order of magnitude obtained for slag‐metal systems was roughly 10–100 times that usually occurring in colloidal systems. The same could be attributed to the high bulk viscosities of the individual phases in slag‐metal systems. The order of magnitude of the interfacial velocity was verified from the equation generated earlier by dimension analysis to be similar to those obtained from experiments.