Fumitaka Tsukihashi

A Kinetic Study of the Effect of Basicity on the Mold Fluxes Crystallization

The effect of basicity on the mold fluxes crystallization was investigated in this article. The time-temperature-transformation (TTT) diagrams and continuous-cooling-transformation (CCT) diagrams of mold fluxes with different basicity were constructed by using single, hot thermocouple technology (SHTT). The results showed that with the increase of basicity, the incubation time of isothermal crystallization became shorter, the crystallization temperature was getting higher, and the critical cooling rate of continuous cooling crystallization became faster. The X-ray diffraction analysis suggested that calcium silicate (CaO·SiO2) was precipitated at the upper part of the TTT diagram and cuspidine (Ca4Si2O7F2) was formed at the lower part, when the basicity of mold fluxes was within 1.0 to 1.2. However, when basicity was 0.8, only the cuspidine phase was formed. A kinetic study of isothermal crystallization process indicated that the increase of the basicity tended to enhance the mold flux crystallization, and the crystallization activation energy became smaller. The crystallization mechanism of cupsidine was changing from one-dimensional growth to three-dimensional growth with a constant number of nuclei, when the basicity of mold fluxes varied from 0.8 to 1.2.

Thermodynamics of boron in a silicon melt

The activity coefficient of B in a Si melt and the interaction parameters of boron and nitrogen in molten silicon were determined by equilibrating solid BN and liquid Si in a nitrogen atmosphere from 1723 to 1923 K. The standard Gibbs free energy change of the nitrogen dissolution into silicon is also obtained. The activities of BO1.5 in the CaO-CaF2-SiO2 and CaO-MgO-SiO2 systems are estimated in relation to the removal of boron from silicon by these fluxes.

Effect of Inclusions’ Behavior on the Microstructure in Al-Ti Deoxidized and Magnesium-Treated Steel with Different Aluminum Contents

To clarify the precipitation behavior of beneficial inclusions and mechanism of their effects on microstructure, the effect of aluminum content on inclusion’s characteristics and their influence on the refinement of microstructure in Al-Ti complex deoxidized magnesium-treated steels were systematically investigated based on experiment and calculation. The results showed that due to the dual effects of Ti and Mg deoxidation, a large amount of finely dispersed Al2O3-TiOx-MgO inclusions in low aluminum steel with a complex multilayer or mosaic structure were formed, whereas a relatively smaller amount of Al2O3-MgO inclusions with the simple bundle structure were observed in high aluminum steel. The Al2O3-TiOx-MgO core oxides are more conducive to the precipitation of multiple manganese sulfides with thinner thickness on their local surfaces. Thus, the inclusion deformation, which mainly depends on the surface manganese sulfides layer, is smaller in low aluminum steel than that in high aluminum steel. Complex inclusions in low aluminum steel can pin austenite grain boundaries and induce interlocking acicular ferrite effectively. In addition to the small size and chemical composition of inclusions, the complex structure of oxides and the precipitation of multiple MnS on their surface are important to the nucleation of interlocking AFs on inclusions in Ti-deoxidized Mg-treated steel. The AFs quantity is much more, and the grain size is more uniform in low aluminum steel than that in high aluminum steel.

Deoxidation equilibrium of solid titanium, zirconium and niobium with calcium

Abstract In a study of the deoxidation equilibria of β-Ti, β-Zr and niobium using calcium, solid samples of titanium, zirconium or niobium were equilibrated with liquid calcium in a CaO crucible at temperatures ranging from 1323 to 1723 K. After equilibration the oxygen contents of titanium, zirconium and niobium were analysed. Values for the standard Gibbs energies were determined and the deoxidation behaviour of these refractory metals by calcium is discussed.

Modeling of Electromagnetic Field and Liquid Metal Pool Shape in an Electroslag Remelting Process with Two Series-Connected Electrodes

A three-dimensional finite-element model has been developed to understand the electromagnetic field and liquid metal pool shape in an electroslag remelting (ESR) process with two series-connected electrodes. The magnetic vector potential is introduced into the Maxwell’s equations, and the nodal-based method is used to solve a three-dimensional harmonic electromagnetic field. The heat transfer of the solidifying processes of ingot is modeled by a source-based enthalpy method, and the Joule heating is included in an inner source. The results show the main part of the current flows through the slag cap and a little enters into ingot in a two-series-connected electrode ESR system. As the interaction of self-induced and mutual-induced of two electrodes occurs, the skin effect is significantly suppressed by the neighbor effect. A symmetrical pattern of magnetic flux density in a two-series-connected electrode ESR system is displayed. The magnetic flux density between two electrodes is reinforced and reduced at the outside of two electrodes. The maximum Joule heat power density is located at the interface of slag and electrodes, and it decreases with an increase of the electrode immersion depth. The averaged Joule heat power density increases when slag cap thickness is reduced. With the increase of ingot height, the liquid metal pool shape changes from arc shaped to “V” shaped. When the ingot height is more than the diameter in the ESR processes, the liquid metal pool shape is constant.

Population Balance Modeling of Polydispersed Bubbly Flow in Continuous-Casting Using Multiple-Size-Group Approach

A population balance model based on the multiple-size-group (MUSIG) approach has been developed to investigate the polydispersed bubbly flow inside the slab continuous-casting mold and bubble behavior including volume fraction, breakup, coalescence, and size distribution. The Eulerian–Eulerian approach is used to describe the equations of motion of the two-phase flow. All the non-drag forces (lift force, virtual mass force, wall lubrication force, and turbulent dispersion force) and drag force are incorporated in this model. Sato and Sekiguchi model is used to account for the bubble-induced turbulence. Luo and Svendsen model and Prince and Blanch model are used to describe the bubbles breakup and coalescence behavior, respectively. A 1/4th water model of the slab continuous-casting mold was applied to investigate the distribution and size of bubbles by injecting air through a circumferential inlet chamber which was made of the specially-coated samples of mullite porous brick, which is used for the actual upper nozzle. Against experimental data, numerical results showed good agreement for the gas volume fraction and local bubble Sauter mean diameter. The bubble Sauter mean diameter in the upper recirculation zone decreases with increasing water flow rate and increases with increasing gas flow rate. The distribution of bubble Sauter mean diameter along the width direction of the upper mold increases first, and then gradually decreases from the SEN to the narrow wall. Close agreements between the predictions and measurements demonstrate the capability of the MUSIG model in modeling bubbly flow inside the continuous-casting mold.

Heat-Transfer Phenomena Across Mold Flux by Using the Inferred Emitter Technique

An investigation was carried out to study the heat-transfer phenomena across mold flux film by using infrared emitter technique (IET). With IET, it is possible to develop the mold fluxes with a liquid layer at the top and a solid layer in contact with copper mold with the degree of varying crystallization. The dynamic crystallization and melting process of the mold fluxes as well as their effects on the overall heat-transfer rate in the mold were successfully conducted. The single hot thermocouple technique (SHTT) was also employed in this investigation to study the melting and crystallization behaviors of mold fluxes for the interpretation of IET results. The results suggested that the interfacial thermal resistance between the solidified mold flux and copper mold would significantly influence the heat-transfer rate in continuous casting and the melting of the mold flux tends to enhance the overall heat-transfer rate. The technique established in this article by utilizing the IET can be well applied to the investigation of mold flux thermal properties, which in turn gives guidelines for the design of new mold flux for continuous casting.

The thermodynamic behavior of sulfur in BaO-BaF2 slags

A gas-slag-metal equilibration technique was used to determine the sulfide capacity of the BaO-BaF2 system at 1473 and 1573 K. The dependence of carbonate capacity on the slag composition was also measured at these temperatures. It was found that the BaO-BaF2 system has the highest sulfide capacities among the fluxes which are of metallurgical interest. The dependence of sulfide and carbonate capacities on the partial pressure of O2 and CO2 was also investigated. The partial pressure of CO2 proved to have a strong effect on these values at the investigated temperatures. The influence of temperature on the sulfide and carbonate capacities was studied in the temperature range between 1423 and 1623 K. The data for sulfide and carbonate capacities were correlated in order to check if the carbonate capacity can be used as a measure of basicity of slags. It was found that the carbonate capacity can be used as a representative measure of the slag basicity at low contents of BaO and at temperatures higher than 1623 K when the carbonate dissolution into the slag is low and the ratio of the activity coefficient of a sulfide ion to that of a carbonate ion is independent of slag composition.

Thermodynamic properties of the BaO-MnO flux system

Although a great number of works on BaO-bearing fluxes for refining Fe-Cr and Fe-Mn alloys have been carried out, there still remain several unresolved problems on using them in the refining process. The principal aim of the present study is to understand the thermodynamic properties of the BaO-MnO system, which has been shown to be very effective for dephosphorization of Fe-Mn alloys. The activity of manganese oxide in the BaO-MnO flux was measured at 1573 and 1673 K by equilibrating the flux, a Ag-Mn alloy, and a gas mixture of CO and CO2 as functions of the flux composition and temperature. The influence of BaF2, which is an effective additive for lowering the melting temperature of the flux, on the thermodynamics of the BaO-MnO system, including the solubility of MnO in the BaO-BaF2 system, was also investigated.

Determination of standard Gibbs energies of formation of CaC2, SrC2, and BaC2

The standard Gibbs energies of formation of CaC2, SrC2, and BaC2 were determined by an equilibration technique at temperatures ranging from 1223 to 1673 K, yielding the following results: Ca (l)+ 2C (s)= CaC2\GDG\dg = -90,100(\+-500)- 11.0(\+-1.1)T [J/mol]Sr (l) + 2C (s) = SrC2 (s)\GDG\dg = -104,000(\+-1000) - 8.04(\+-2.76)T [J/mol]BA (l) + 2C(s) = BaC2 (s)\GDG\dg = -115,000(\+-1000) + 3.53 (\+-1.69)T [J/mol]