Showing papers in "Metallurgical and Materials Transactions B-process Metallurgy and Materials Processing Science in 2012"

Thermal Conductivity of Copper-Graphene Composite Films Synthesized by Electrochemical Deposition with Exfoliated Graphene Platelets

Abstract: Samples of graphene composites with matrix of copper were prepared by electrochemical codeposition from CuSO4 solution with graphene oxide suspension. The thermal conductivity of the composite samples with different thickness and that of electrodeposited copper was determined by the three-omega method. Copper-graphene composite films with thickness greater than 200 μm showed an improvement in thermal conductivity over that of electrolytic copper from 380 W/m.K to 460 W/m.K at 300 K (27 °C). The thermal conductivity of copper-graphene films decreased from 510 W/m.K at 250 K (–23 °C) to 440 W/m.K at 350 K (77 °C). Effective medium approximation (EMA) was used to model the thermal conductivity of the composite samples and determine the interfacial thermal conductance between copper and graphene. The values of interface thermal conductance greater than 1.2 GW/m2.K obtained from the acoustic and the diffuse mismatch models and from the EMA modeling of the experimental results indicate that the interface thermal resistance is not a limiting factor to improve the thermal conductivity of the copper-graphene composites.

Formation and Modification of MgO·Al2O3-Based Inclusions in Alloy Steels

Abstract: The current study performed thermadynamic calculation, laboratory experiments, and industrial trials for the formation and modification of MgO-Al2O3 spinel inclusions in alloy steels. The stability Mg-Al-O diagram was obtained using the thermodymanic study. The resulting MgO-Al2O3-CaO inclusions from MgO-Al2O3 spinel inclusions after the calcium treatment were spherical, and > 5 μm MgO-Al2O3-CaO inclusions have a two-layer structure: an outside CaO-Al2O3 layer and a MgO-Al2O3 core. The modification of > 5 μm MgO·Al2O3 spinel inclusions by calcium treatment includes two steps: (1) reducing MgO in the inclusion into the dissolved magnesium by the dissolved calcium in the steel and (2) generating a liquid xCaO·yAl2O3 layer at the outside of the spinel inclusion. For <2 μm MgO·Al2O3 spinel inclusions, they can possibly be modified into a xCaO·yAl2O3 inclusion by reducing all MgO component in the spinel inclusions with the added calcium.

Silico-ferrite of Calcium and Aluminum (SFCA) Iron Ore Sinter Bonding Phases: New Insights into Their Formation During Heating and Cooling

Abstract: The formation of silico-ferrite of calcium and aluminum (SFCA) and SFCA-I iron ore sinter phases during heating and cooling of synthetic iron ore sinter mixtures in the range 298 K to 1623 K (25 °C to 1350 °C) and at oxygen partial pressure of 5 × 10−3 atm has been characterized using in situ synchrotron X-ray diffraction. SFCA and SFCA-I are the key bonding phases in iron ore sinter, and an improved understanding of their formation mechanisms may lead to improved efficiency of industrial sintering processes. During heating, SFCA-I formation at 1327 K to 1392 K (1054 °C to 1119 °C) (depending on composition) was associated with the reaction of Fe2O3, 2CaO·Fe2O3, and SiO2. SFCA formation (1380 K to 1437 K [1107 °C to 1164 °C]) was associated with the reaction of CaO·Fe2O3, SiO2, and a phase with average composition 49.60, 9.09, 0.14, 7.93, and 32.15 wt pct Fe, Ca, Si, Al, and O, respectively. Increasing Al2O3 concentration in the starting sinter mixture increased the temperature range over which SFCA-I was stable before the formation of SFCA, and it stabilized SFCA to a higher temperature before it melted to form a Fe3O4 + melt phase assemblage (1486 K to 1581 K [1213 °C to 1308 °C]). During cooling, the first phase to crystallize from the melt (1452 K to 1561 K [1179 °C to 1288 °C]) was an Fe-rich phase, similar in composition to SFCA-I, and it had an average composition 58.88, 6.89, 0.82, 3.00, and 31.68 wt pct Fe, Ca, Si, Al, and O, respectively. At lower temperatures (1418 K to 1543 K [1145 °C to 1270 °C]), this phase reacted with melt to form SFCA. Increasing Al2O3 increased the temperature at which crystallization of the Fe-rich phase occurred, increased the temperature at which crystallization of SFCA occurred, and suppressed the formation of Fe2O3 (1358 K to 1418 K [1085 °C to 1145 °C]) to lower temperatures.

Calcium Modification of Spinel Inclusions in Aluminum-Killed Steel: Reaction Steps

Abstract: Calcium treatment is a well-established way to modify solid alumina inclusions to liquid or partially liquid calcium aluminates. Spinels (Al2O3·xMgO) can also form in liquid steel after aluminum deoxidation. Like alumina, the spinels can be modified readily to liquid inclusions by a calcium treatment. The modification of spinels was studied by observing the transient evolution of inclusions, in laboratory and industrial heats. Spinel modification involves the preferential reduction of MgO from the spinel, with Mg dissolving in the steel, and it proceeds through transient calcium sulfide formation, just like in the case of alumina inclusions. Because magnesium dissolves in steel after the calcium treatment of spinels, the reoxidation of the melt will produce new spinels.

Vacuum Refining of Molten Silicon

Abstract: Metallurgical fundamentals for vacuum refining of molten silicon and the behavior of different impurities in this process are studied. A novel mass transfer model for the removal of volatile impurities from silicon in vacuum induction refining is developed. The boundary conditions for vacuum refining system—the equilibrium partial pressures of the dissolved elements and their actual partial pressures under vacuum—are determined through thermodynamic and kinetic approaches. It is indicated that the vacuum removal kinetics of the impurities is different, and it is controlled by one, two, or all the three subsequent reaction mechanisms—mass transfer in a melt boundary layer, chemical evaporation on the melt surface, and mass transfer in the gas phase. Vacuum refining experimental results of this study and literature data are used to study the model validation. The model provides reliable results and shows correlation with the experimental data for many volatile elements. Kinetics of phosphorus removal, which is an important impurity in the production of solar grade silicon, is properly predicted by the model, and it is observed that phosphorus elimination from silicon is significantly increased with increasing process temperature.

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

Abstract: 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.

Au-Sn SLID Bonding—Properties and Possibilities

Abstract: Au-Sn solid–liquid interdiffusion (SLID) bonding is a novel and promising interconnect technology for high-temperature applications. This article gives a review over previously published work on Au-Sn SLID bonding. An overview of the crystal phases and the thermomechanical properties of the Au-Sn phases relevant for Au-Sn SLID bonding is given. A summary of the bonding conditions used during Au-Sn SLID bonding is presented together with results from reliability tests. Additional challenges, possibilities, and recommendations for how a reliable high-temperature Au-Sn SLID bonding should be constructed are also discussed.

Effect of Electromagnetic Ruler Braking (EMBr) on Transient Turbulent Flow in Continuous Slab Casting using Large Eddy Simulations

Abstract: Static electromagnetic braking (EMBr) fields affect greatly the turbulent flow pattern in steel continuous casting, which leads to potential benefits such as decreasing flow instability, surface defects, and inclusion entrapment if applied correctly. To gain a fundamental understanding of how EMBr affects transient turbulent flow, the current work applies large eddy simulations (LES) to investigate the effect of three EMBr ruler brake configurations on transient turbulent flow through the bifurcated nozzle and mold of a liquid-metal GaInSn model of a typical steel slab-casting process, but with deep nozzle submergence and insulated walls with no solidifying shell. The LES calculations are performed using an in-house graphic-processing-unit-based computational-fluid-dynamics code (LES-CU-FLOW) on a mesh of ~7 million brick cells. The LES model is validated first via ultrasonic velocimetry measurements in this system. It is then applied to quantify the mean and instantaneous flow structures, Reynolds stresses, turbulent kinetic energy and its budgets, and proper orthogonal modes of four cases. Positioning the strongest part of the ruler magnetic field over the nozzle bottom suppresses turbulence in this region, thus reducing nozzle well swirl and its alternation. This process leads to strong and focused jets entering the mold cavity making large-scale and low-frequency (<0.02 Hz) flow variations in the mold with detrimental surface velocity variations. Lowering the ruler below nozzle deflects the jets upward, leading to faster surface velocities than the other cases. The double-ruler and no-EMBr cases have the most stable flow. The magnetic field generates large-scale vortical structures tending toward two-dimensional (2-D) turbulence. To avoid detrimental large-scale, low-frequency flow variations, it is recommended to avoid strong magnetic fields across the nozzle well and port regions.

Numerical Simulation of Fluid Flow in a Round Bloom Mold with In-Mold Rotary Electromagnetic Stirring

Abstract: In this article, an electromagnetic field simulation and a flow analysis model are performed to describe the three-dimensional electromagnetic field distribution and the electromagnetically driven flow characteristics in a round-bloom mold with a low-frequency in-mold rotary electromagnetic stirrer. The interaction between the induced flow and the inertial impinging jet from a straight-through submerged entry nozzle (SEN) of the caster is considered. The effects of stirrer current and frequency on the electromagnetic field and the flow in the round-bloom mold are investigated, and a strategy to optimize the stirring parameters is proposed. The results show that the distributions of magnetic flux density and electromagnetic force magnitude are nonuniform in a three-dimensional electromagnetic stirring (EMS) configuration. There exists a significant axial induced component of electromagnetic force. The flow in the in-mold EMS system is characterized by a dominant swirling movement at the transverse sections, coupled with the recirculating flows in the axial direction. An upper recirculation zone and a lower recirculation zone with the reverse melt flowing are found near the strand wall at the axial location close to the middle of the stirrer, and another recirculation zone is formed due to the interference of the induced flow with the jet from SEN. The meniscus surface has a swirl flow, and the meniscus level rises near the bloom strand wall and sinks around the SEN wall. All of these flow features are closely associated with metallurgical performances of the in-mold rotary stirrer. With the increase of stirring current and the decrease of frequency, the magnetic flux magnitude increases. There is an optimum frequency to obtain a peak of electromagnetic force magnitude and maximum tangential velocity. For a mold rotary EMS system, to determine the optimum stirring intensity, it is necessary to make a compromise between a larger tangential velocity and a relatively quiescent meniscus surface.

Effect of Activated Flux on the Microstructure, Mechanical Properties, and Residual Stresses of Modified 9Cr-1Mo Steel Weld Joints

Abstract: A novel variant of tungsten inert gas (TIG) welding called activated-TIG (A-TIG) welding, which uses a thin layer of activated flux coating applied on the joint area prior to welding, is known to enhance the depth of penetration during autogenous TIG welding and overcomes the limitation associated with TIG welding of modified 9Cr-1Mo steels. Therefore, it is necessary to develop a specific activated flux for enhancing the depth of penetration during autogeneous TIG welding of modified 9Cr-1Mo steel. In the current work, activated flux composition is optimized to achieve 6 mm depth of penetration in single-pass TIG welding at minimum heat input possible. Then square butt weld joints are made for 6-mm-thick and 10-mm-thick plates using the optimized flux. The effect of flux on the microstructure, mechanical properties, and residual stresses of the A-TIG weld joint is studied by comparing it with that of the weld joints made by conventional multipass TIG welding process using matching filler wire. Welded microstructure in the A-TIG weld joint is coarser because of the higher peak temperature in A-TIG welding process compared with that of multipass TIG weld joint made by a conventional TIG welding process. Transverse strength properties of the modified 9Cr-1Mo steel weld produced by A-TIG welding exceeded the minimum specified strength values of the base materials. The average toughness values of A-TIG weld joints are lower compared with that of the base metal and multipass weld joints due to the presence of δ-ferrite and inclusions in the weld metal caused by the flux. Compressive residual stresses are observed in the fusion zone of A-TIG weld joint, whereas tensile residual stresses are observed in the multipass TIG weld joint.

Modeling Viscosities of CaO-MgO-FeO-MnO-SiO 2 Molten Slags

Abstract: A model for estimating the viscosity of silicate melts is proposed in this article. The structural characteristics of a silicate slag can be described by the numbers of the bridging oxygen, nonbridging oxygen, and free oxygen present in the slag. A method of calculating the numbers of the different types of oxygen ions is presented in this article, which involves a simple approximation of “complete bridge breaking.” With just a few parameters, the model provides both the temperature and composition dependencies of viscosity for the pure component: SiO2; the binary systems: MgO-SiO2, CaO-SiO2, FeO-SiO2, and MnO-SiO2; the ternary systems: CaO-MgO-SiO2, CaO-FeO-SiO2, MgO-FeO-SiO2, and CaO-MnO-SiO2; and the quaternary systems: CaO-MgO-MnO-SiO2 and CaO-FeO-MnO-SiO2. It was found that the ability of different basic metal oxides to decrease viscosity varies and is in the following hierarchy: FeO > MnO > CaO > MgO. Two factors influence the viscosity: The first is related to the mutual interaction among different ions, and the stronger the interaction, the higher the viscosity. The second factor is the size (radius) of basic oxide cation, with viscous flow becoming increasingly more difficult (i.e., viscosity increases) as the cation size increases. However, there is a paradox in the effect of cation radius (of the basic oxide) on the two factors. Thus, varying cation size causes competitive effects; smaller cationic radii give stronger interactions among ions but less hindrance to viscous flow (and vice versa for large cation radii).

Investigation of Leaching Kinetics of Copper from Malachite Ore in Ammonium Nitrate Solutions

Abstract: The production of metallic copper from low-grade copper ores is generally carried out by hydrometallurgical methods Leaching is the first prerequisite of any hydrometallurgical process Solutions containing ammonia may allow for selective leaching of the copper from the ore In this study, the leaching kinetics of malachite, which is an oxidized copper ore, in ammonium nitrate solutions was examined The effects of some experimental parameters on the leaching process were investigated, and a kinetic model to represent the effects of these parameters on the leaching rate was developed It was determined that the leaching rate increased with increasing solution concentration, temperature, and agitation speed, as well as decreasing particle size It was found that the leaching reaction followed the mixed kinetic controlled model, which includes two different leaching processes including the surface chemical reaction (303 K to 323 K [30 °C to 50 °C]) and diffusion through a porous product layer (323 K to 343 K [50 °C to 70 °C]) The activation energies of these sequential steps were determined to be 9510 and 2950 kJ/mol, respectively

A Unified Mechanism for the Formation of Oscillation Marks

Abstract: Oscillation marks (OMs) are regular, transverse indentations formed on the surface of continuously cast (CC) steel products. OMs are widely considered defects because these are associated with segregation and transverse cracking. A variety of mechanisms for their formation has been proposed (e.g., overflow, folding, and meniscus freezing), whereas different mark types have also been described (e.g., folded, hooks, and depressions). The current work uses numerical modeling to formulate a unified theory for the onset of OMs. The initial formation mechanism is demonstrated to be caused by fluctuations in the metal and slag flow near the meniscus, which in turn causes thermal fluctuations and successive thickening and thinning of the shell, matching the thermal fluctuations observed experimentally in a mold simulator. This multiphysics modeling of the transient shell growth and explicit prediction of OMs morphology was possible for the first time through a model for heat transfer, fluid flow, and solidification coupled with mold oscillation, including the slag phase. Strategies for reducing OMs in the industrial practice fit with the proposed mechanism. Furthermore, the model provides quantitative results regarding the influence of slag infiltration on shell solidification and OM morphology. Control of the precise moment when infiltration occurs during the cycle could lead to enhanced mold powder consumption and decreased OM depth, thereby reducing the probability for transverse cracking and related casting problems.

Some New Observations on Freckle Formation in Directionally Solidified Superalloy Components

Abstract: To improve the understanding of freckle formation in superalloys, several directional solidification experiments were carried out in a production-scale Bridgman furnace. During the careful inspections of the many cast specimens, several interesting phenomena were observed, indicating new aspects of freckle formation. Accordingly, several new factors influencing the freckle formation, such as the shadow effect, the edge effect, the step effect, and the crystal orientation effect, are proposed. This will contribute to our current understanding of freckle formation and the future development of new measures to minimize freckle defects in directionally solidified components of superalloys.

Effect of Complex Inclusion Particles on the Solidification Structure of Fe-Ni-Mn-Mo Alloy

Abstract: The effect of combinations of several deoxidizers, i.e., Mg-Al, Mg-Ti, Al-Ti, and Ce-Al, on the solidification structure of Fe-2 mass pct Ni-1 mass pct Mn-1 mass pct Mo alloy melt was investigated using a melt sampling and quenching method. Using this method, we evaluated the catalytic potency of several complex inclusion particles by taking the inclusion evolution process into account. Fine equiaxed crystals were obtained in the Mg-Ti-deoxidized steel wherein the MgO(MgAl2O4)-TiN complex compounds formed. However, the longer the holding time at high temperatures, the larger the fraction of Ti2O3, and very fine TiN formed because of microsegregation during solidification, resulting in poor equiaxed crystals. When the steel was deoxidized with Mg-Al, the initial structure was dominantly columnar. However, the longer the holding time, the larger the fraction of MgAl2O4 spinel, resulting in the formation of fine equiaxed crystals. Ce-Al complex deoxidation provided a relatively small portion of equiaxed crystals, whereas Ti-Al deoxidation produced the fewest equiaxed crystals because of the formation of alumina. The effectiveness of each inoculant particle for the crystallization of the primary δ-iron was explained well by the lattice disregistry concept.

Investigation of Oxide Inclusions and Primary Carbonitrides in Inconel 718 Superalloy Refined through Electroslag Remelting Process

Abstract: The effect of remelting atmosphere and calcium treatment during electroslag remelting (ESR) of Inconel 718 superalloy on the oxide inclusions and primary carbonitrides was investigated. The results show that after ESR refining combined with calcium treatment, the original oxide inclusions in the electrode, mainly MgO·Al2O3 spinels and some MgO inclusions, were modified to CaO-Al2O3 system inclusions or the inclusions of MgO·Al2O3 spinel core surrounded by CaO-MgO-Al2O3 system inclusion layer. Without the calcium treatment in ESR process, all the oxide inclusions in superalloy ingots are MgO·Al2O3 spinels. All the oxide inclusions in ESR ingots act as the nucleation site for carbonitride (Nb,Ti)CN with two-layer structure precipitation, except for those with a single (Nb,Ti)CN layer containing a small amount of Ti and N in the ingot refined by a proper amount of calcium addition in ESR process. The carbonitrides (Nb,Ti)CN formed directly on the oxide inclusion have a small amount of Nb and C as well as a relatively fixed atomic ratio of Nb/Ti (about 0.6:1). There is a Nb-rich and C-rich (Nb,Ti)CN layer on the pre-existing (Nb,Ti)CN formed on the oxide inclusion. The size of the observed carbonitrides is in the range of 5 μm to 15 μm. The calcium treatment in the ESR process has a significant effect on the morphology of carbonitrides in superalloy ingot due to modification of oxide inclusions by Ca-treatment resulting in the change of precipitation and growth conditions for carbonitrides. The morphologies of carbonitrides were changed from clustered block or single octahedral to skeleton-like after calcium treatment.

Dendrite-Free Aluminum Electrodeposition from AlCl 3 -1-Ethyl-3-Methyl-Imidazolium Chloride Ionic Liquid Electrolytes

Abstract: A novel, dendrite-free electrorefining of aluminum scrap alloys (A360) was investigated by using a low-temperature AlCl3-1-ethyl-3-methyl-imidazolium chloride (EMIC) ionic liquid electrolyte on copper/aluminum cathodes. The bulk electrodeposition of aluminum was carried out at a fixed voltage of 1.5 V, temperatures 323 K to 383 K (50 °C to 110 °C), stirring rate (0 to 120 rpm), concentration (molar ratio AlCl3:EMIC = 1.25 to 2.0), and electrode surface modification (modified/unmodified). The study investigated the effect of electrode surface modification, cathode materials, temperature, stirring rate, electrolyte concentration, and deposition time on the deposit morphology of aluminum, cathode current density, and their role in production of dendrite-free aluminum deposit, which is essential for decreasing the production cost. The deposits were characterized using scanning electron microscope (SEM), energy-dispersive spectroscopy (EDS), and X-ray diffraction (XRD). It was shown that electrode surface modification, cathode overpotential, and stirring rate play an important role in dendrite-free deposit. Modified electrodes and stirring (60 rpm) eliminate dendritic deposition by reducing cathode overpotential below critical overpotential (\( \eta_{\text{crt}} \approx - 0.53V \)) for dendrite formation. Pure aluminum (>99 pct) was deposited for all experiments with a current efficiency of 84 to 99 pct and energy consumption of 4.51 to 5.32 kWh/kg Al.

A Water Model Study of Impinging Gas Jets on Liquid Surfaces

Abstract: Water modeling experiments were designed to observe the deformation of a liquid surface by impinging the gas jet. Video images were taken and processed in a systematic way. The important surface cavity parameters, such as depth, width, and their frequency of oscillation, were obtained. The relation between surface depression depth and the supplied gas momentum were consistent with previous findings and were extended to higher flow rates. The surface instability and the onset of splashing were observed and interpreted with the Blowing number. The wave behaviors were described qualitatively with a combination of photographic evidence and power spectral density analysis to extract the characteristic wave numbers for each gas flow rate. The analysis of the time series of the surface variables showed a connection to the attenuation of turbulence gas pressure fluctuation and the surface deformation by the gas impingement. Bath velocities were measured with a particle image velocimetry (PIV) technique. To quantify the transfer of kinetic energy from the gas to the liquid, an energy transfer index was defined and calculated with the PIV data. The index was insensitive to gas flow rate but increased with cavity width. The momentum transfer across the interface was also analyzed, and a similar cavity width dependence was found. A correlation between the cavity shape and momentum transfer was proposed.

Interfacial Reaction Between CaO-SiO2-MgO-Al2O3 Flux and Fe-xMn-yAl (x = 10 and 20 mass pct, y = 1, 3, and 6 mass pct) Steel at 1873 K (1600 °C)

Abstract: This study investigated the interfacial reaction kinetics and related phenomena between CaO-SiO2-MgO-Al2O3 flux and Fe-xMn-yAl (x = 10 and 20 mass pct, y = 1, 3, and 6 mass pct) steel, which simulates transformation-induced plasticity (TRIP) and twinning-induced plasticity (TWIP) steels at 1873 K (1600 °C). It also examines the effect of changes in the composition of the steel and slag phases on the interfacial reaction rate and the reaction mechanisms. The content of Al and Si in the 1 mass pct Al-containing steel was found to change rapidly within the first 15 minutes of the reaction, but then it remained relatively constant. The content of Al and Si in the 3 to 6 mass pct Al-containing steels, in contrast, changed continuously throughout the entire reaction time. In addition, the content of Mn in the 1 mass pct Al-containing steels initially decreased with increasing time, but the content did not change in the 3 to 6 mass pct Al-containing steels. Furthermore, the mass transfer coefficient of Al, kAl, in the 1 mass pct Al-containing systems was significantly higher than that in other systems; i.e., the kAl can be arranged such that 1 mass pct Al systems >> 3 mass pct Al systems ≥ 6 mass pct Al systems. The compositions of the final slags were close to the saturation lines of the [Mg,Mn]Al2O4 and MgAl2O4 spinels when the slags reacted with 1 mass pct Al and 3 to 6 mass pct Al-containing steels, respectively. These results, which show the effect of Al content on the reaction phenomena, can be explained by the significant increase in the apparent viscosity of the slags that reacted with the 3 to 6 mass pct Al-containing steels. This reaction was likely caused by the precipitation of solid compounds such as MgAl2O4 spinel and CaAl4O7 grossite at locally alumina-enriched areas in the slag phase. This analysis is in good accordance with the combination of Higbie’s surface renewal model and the Eyring equation.

Green Electrochemical Process Solid-Oxide Oxygen-Ion-Conducting Membrane (SOM): Direct Extraction of Ti-Fe Alloys from Natural Ilmenite

Abstract: The direct electrochemical extraction of Ti-Fe alloys from natural ilmenite (FeTiO3) in molten CaCl2 is reported in this article. The sintered porous pellet of natural ilmenite acted as the cathode of the electrochemical system, and the carbon-saturated liquid tin contained in a solid-oxide oxygen-ion-conducting membrane (SOM) tube served as the anode of the electrolytic cell. The electrochemical process was carried out at 3.8 V, under 1223 K and 1273 K (950 °C and 1000 °C). Oxygen was ionized continuously from the cathode and discharged at the anode; solid porous Ti-Fe alloys were obtained at the cathode. The electro-deoxidation procedure of the ilmenite was characterized by analyzing partially electro-deoxidized samples taken periodically throughout the electro-deoxidation process. The findings of this study are as follows: (1) The electro-deoxidation process followed these steps: Fe2TiO5 → FeTiO3 → Fe2TiO4 → Fe, Ti (and/or Ti-Fe alloys); and TiO2 → CaTiO3 → Ti; and (2) two types of particle growth pattern are observed in the experiments. The first pattern is characterized with particle fusion and second pattern is interconnection of particles to form porous structure. A microhole oxygen-ion-migration model is suggested based on the experimental evidence.

Upgrading of Low-Grade Manganese Ore by Selective Reduction of Iron Oxide and Magnetic Separation

Abstract: The utilization of low-grade manganese ores has become necessary due to the intensive mining of high-grade ores for a long time. In this study, calcined ferruginous low-grade manganese ore was selectively reduced by CO, which converted hematite to magnetite, while manganese oxide was reduced to MnO. The iron-rich component was then separated by magnetic separation. The effects of the various reduction parameters such as particle size, reduction time, temperature, and CO content on the efficiency of magnetic separation were studied by single-factor experiments and by a comprehensive full factorial experiment. Under the best experimental conditions tested, the manganese content in the ore increased from around 36 wt pct to more than 44 wt pct, and almost 50 wt pct of iron was removed at a Mn loss of around 5 pct. The results of the full factorial experiments allowed the identification of the significant effects and yielded regression equations for pct Fe removed, Mn/Fe, and pct Mn loss that characterize the efficiency of the upgrading process.

Dissimilar Friction-Stir Lap Joining of 5083 Aluminum Alloy to CuZn34 Brass

Abstract: In this research, lap joining of Al-Mg aluminum alloy and CuZn34 brass was produced by friction-stir welding during which the aluminum alloy sheet was placed on the CuZn34. Optical microscopy, scanning electron microscopy (SEM), X-ray diffraction analysis, and energy-dispersive X-ray spectroscopy (EDS) analysis were used to probe the microstructures and chemical compositions. In addition, the mechanical properties of each sample are characterized using both shear and hardness tests. The optimum parameters resulted in no visible welding cracks and defects. A dark area in the Al/CuZn34 interface contained intermetallic compounds Al2Cu, Al4Cu9, and CuZn. In addition, the results show that using high rotational speeds or low traverse speeds causes the growth of the interfacial intermetallic area.

Effect of Mn, Si, and Cooling Rate on the Formation of Iron-Rich Intermetallics in 206 Al-Cu Cast Alloys

Abstract: The solidification structures of commercial 206 Al-Cu cast alloys with 0.15 pct Fe have been studied using thermal analysis (TA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and electron backscattered diffraction (EBSD). The EBSD results have shown that there are two iron-rich intermetallics: Chinese script α-Fe and platelet-like β-Fe. The addition of either Mn or Si has helped to promote the formation of α-Fe and hinder the precipitate of β-Fe. The combined addition of both Mn and Si is even more effective than the individual addition of either Mn or Si. The full solidification sequence of the 206 cast alloy has been established. The volume percent and formation temperature increase for α-Fe but decrease for β-Fe with increasing cooling rate. The platelet β-Fe can be effectively suppressed in 206 cast alloys by controlling the alloy chemistry and cooling rate. A casting process map is proposed to correlate the Mn and Si contents with cooling rates for the 206 cast alloys.

Effect of an Electromagnetic Brake on the Turbulent Melt Flow in a Continuous-Casting Mold

Abstract: This article presents numerical and experimental investigations with respect to the fluid flow in the continuous-casting process under the influence of an external direct current (DC) magnetic field. Numerical calculations were performed by means of the software package CFX (Ansys, Inc., Canonsburg, PA) with an implemented Reynolds-averaged Navier–Stokes (RANS)-SST turbulence model. The nonisotropic nature of the magnetohydrodynamic (MHD) turbulence was taken into account by specific modifications of the turbulence model. The numerical results were validated by flow measurements carried out in a small-scale mockup using the eutectic alloy GaInSn. The jet flow discharging from the submerged entry nozzle was exposed to a level magnetic field spanning across the entire wide side of the mold. The comparison between our numerical calculations and the experimental results displays a good agreement; in particular, we reconstructed the peculiar phenomenon of an excitation of nonsteady, nonisotropic, large-scale flow perturbations caused by the application of the DC magnetic field. Another important result of our study is the feature that the electrical boundary conditions, namely the wall conductivity ratio, have a serious influence on the mold flow while it is exposed to an external magnetic field.

State of the Art in Control of Inclusions, Their Characterization, and Future Requirements

Abstract: Because of the growing demand of cleaner and defect-free steels, faster and more reliable offline steel cleanliness determination methods combined with online techniques are finding increasing usage to study steel refining and casting issues. Because a single-steel characterization technique is not sufficient to provide answers to all process problems, a combination of these techniques is often used to find a customized solution of the problem. This article reviews the past experiences on steel cleanliness examination to standardize the inclusion-characterization techniques and their applications for both experienced and novice researchers. The article also proposes a suite of techniques as a reference tool to facilitate clean steelmaking research at ArcelorMittal Group more effectively in the future. Examples of use of automated scanning electron microscopy and pulse discrimination analysis are provided.

In Situ Observation and Investigation of Mold Flux Crystallization by Using Double Hot Thermocouple Technology

Abstract: The crystallization processes of mold fluxes for casting low-carbon (LC) and medium-carbon (MC) steels were investigated by using double hot thermocouple technology (DHTT) in this article. The results showed that the glass phase was first formed at the cold side thermocouple (CH-2), when the LC mold flux (mold flux for casting low-carbon steel) was exposed to the temperature gradient of 1773 K (1500 °C) to 1073 K (800 °C); then, the fine crystals were precipitated at the liquid/glass interface and grew toward glass and later on to liquid phase. However, the crystals were directly formed at CH-2 when MC flux (mold flux for casting medium-carbon steel) was under the same thermal gradient. The growth rate of MC flux crystals was much faster than that of LC ones. Scanning electron microscope (SEM) and X-ray energy dispersive spectroscopy (EDS) analyses suggested that the crystals formed in LC mold flux were mainly dendritic cuspidine Ca4Si2O7F2, and the crystals formed from the liquid phase were larger than those from the glass. For MC mold flux, the earlier precipitated crystals were large dendritic Ca4Si2O7F2, whereas the later ones were composed of equiaxed Ca2Al2SiO7 crystals. The results of DHTT measurements were consistent with the time-temperature-transformation (TTT) diagrams and X-ray diffraction (XRD) analysis.

Processing, Microstructure, and Residual Stress Effects on Strength and Fatigue Crack Growth Properties in Friction Stir Welding: A Review

Abstract: The purpose of this review is to provide a comprehensive overview of friction stir welding (FSW), as well as to introduce current research and applications involving this relatively new process. FSW is a new, efficient way of joining metal alloys that are considered unsuitable for welding via conventional fusion joining methods, and is capable of welding dissimilar metals with ease. This process also has the benefit of being solid-state, which mitigates the need for liquid filler metals that are common with conventional fusion welding techniques. This review will examine different facets of the FSW process, exploring the resulting static and dynamic properties and factors that influence these properties including weld zone boundaries, grain refinement, residual stress, and addition of reinforcing particles. Highlights of current research in this area and applications of this process in various industries will also be presented and discussed.

Extraction of Rare Earth Elements as Oxides from a Neodymium Magnetic Sludge

Abstract: We propose a simple method for separating rare earth elements as oxides from a neodymium magnetic sludge by focusing on the affinity of oxygen for the rare earth elements (Nd, Dy, and Pr) and Fe. We have conducted separation experiments with a carbon crucible as contact material to confirm that carbon maintains the oxygen potential in the coexistence region of rare earth oxides and metallic Fe. In this work, the oxide phase of the rare earth elements and the alloy phase that primarily consists of Fe were separated clearly when the magnetic sludge in the carbon crucible was kept at 1823 K (1550 °C) under an Ar atmosphere. The purity of the rare earth oxide phase was high and only a small amount of rare earth elements were contained in the alloy phase. We found that the melting temperature of the rare earth oxides is a crucial factor for separation efficiency in our proposed method.

Addition of Titanium Oxide Inclusions into Liquid Steel to Control Nonmetallic Inclusions

Abstract: Titanium oxide inclusions in steel are well known to inhibit grain growth and act as nucleation sites for acicular ferrite because of absorbing manganese from the surrounding steel resulting in a manganese depleted zone around the inclusion. In this article, the inclusions resulting from TiO2 additions to low-alloyed C-Mn-Cr steel were studied. Different types of TiO2 containing materials were added to liquid steel before or during casting to get small titanium-oxide–rich inclusions in steel. The main goals were to find out what happens to TiO2 in liquid steel after addition and during cooling and to study further what type of inclusions are formed in the steel as a result of the TiO2 addition. Based on the thermodynamic calculations and the results of scanning electron microscope (SEM)-energy dispersive spectroscope (EDS) and SEM-electron backscatter diffraction (EBSD) analysis, TiO2 is first reduced to Ti3O5 in liquid steel at high temperatures and then to Ti2O3 during cooling at around 1573 K (1300 °C). Both reactions liberate oxygen, which reacts with Ti, Mn, and Al forming complex Ti2O3-rich inclusions. The results also show that TiO2 additions result in more TiOx + MnO inclusions compared with experiments with Ti addition and that the absolute amount of manganese present in the inclusions is much higher in experiments with TiO2 addition than in experiments with Ti additions.

Crystallization Behavior of the CaO-Al2O3-MgO System Studied with a Confocal Laser Scanning Microscope

Abstract: The crystallization behavior of a calcium-aluminate system with various MgO content from 2.5 to 7.5 wt pct and CaO/Al2O3 ratios between 0.8 and 1.2 has been examined using a confocal laser scanning microscope (CLSM). CCT (continuous cooling transformation) and time temperature transformation (TTT) diagrams were constructed to identify the primary crystal phase of slag at different compositions and at cooling rates between 25 and 800 K/minutes. In the slag at a CaO/Al2O3 ratio of 1.0, crystallization temperature increased during isothermal and continuous cooling with higher MgO content, and the shortest incubation time was observed at 5 wt pct MgO. When MgO content was fixed to be 5 wt pct, crystallization temperature increased with lower CaO/Al2O3 ratio. According to the slag composition, cooling rates and temperature, the primary phase could be CA, or C5A3, or C3A, or C3MA2, or MgO, and the crystal morphology changes from dendrites to faceted crystals to columnar crystals in this composition range.