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By Gordon Irons, Kevin Graham, Krishnakumar Krishnapisharody

Ladle or secondary metallurgy in steelmaking is an essential process step for the production of high-quality steel. Professor David Robertson was a pioneer in the modeling of these processes, in particular gas-metal fluid dynamic interactions and the rates of slag-metal reactions. This is now a highly active area of research, and some of the recent developments in this area will be reviewed.

Jan 1, 2014

By Suswnu Makino

Sumitomo Metal Mining developed a new nickel refining process ( Matte Chlorine Leach Electrowinning process) based on chlorine leach and electrowinning technologies. After the pilot plant study, the commercial plant with design capacity of 24,000 tonnes per year was constructed and has been successfully operated since August, 1992. During the practice of the past three years, great deals of improvement have been achieved. Through these operations the MCLE process has been demonstrated to be one of the most superior processes in the world with nickel recovery, productivity, cathode quality and working environment. Today the refinery product capacity is increased to 30,000 tonnes per year. This paper describes the equipments and operation of the Sumitomo MCLE process.

Jan 1, 1996

By M. Shevchenko

Integrated experimental and modelling research program on the phase equilibria and development of thermodynamic databases of the lead and copper metallurgical gas/ slag-matte-metal-solids systems (PbO-“Cu2O”-FeO-Fe2O3- ZnO-CaO-SiO2) is being undertaken to support improvements in the pyrometallurgical smelting and recycling processes. This is the first systematic investigation of phase equilibria of slag systems in equilibrium with Pb metal, providing information for systems in which copper coexists in slag with lead or zinc as major components. The experimental studies involve high-temperature equilibration of synthetic samples, rapid quenching, and measurement of the compositions of equilibrium phases using electron probe X-ray microanalysis (EPMA). FactSage-based thermodynamic database development is integrated with experimental research. Initial thermodynamic assessments are used to identify priority compositions and conditions for experiments, which are planned to provide specific data to assist thermodynamic optimisation. Significant improvement in the accuracy of the phase equilibria description is achieved. Continuous database improvement and extension to include new elements are targeted. Example of industrial application is given.

By Dajian Wang

To obtain the thermodynamic properties of a multicomponent liquid alloy system over the whole range of concentration at an arbitrary temperature, the free volume cell theory has been applied to derive the formula of activity coefficients of liquid solutions based on the infinitely dilute solutions at some temperature. The linear logarithmic relationship between activity coefficients of binary dilute solutions and reciprocal of absolute temperature have been verified, and are in good agreement with the experimental values from the literature. The Monte-Carlo algorithm was used to calculate the nonlinear end value equations of binary systems, then the free volume parameters obtained were correlated with the activity coefficients of liquid binary, ternary, and quaternary systems at an arbitrary temperature. Three dimensional a-X-T diagrams of some binary systems representing the temperature and concentration dependence of activities were plotted. The calculated results regarding non-ferrous alloy systems have been statistically examined with the experimental values from the literature. Hence, this simple approach could be useful for analyzing thermodynamic properties of liquid alloy systems.

Jan 1, 2000

By Du Sichen, S. Seetharaman, J. A. Bustnes

"The present study deals with the kinetic studies of reduction of some selected transition metal tungstates with hydrogen. The measurements were carried out by the isothermal thermogravimetric method. Shallow powder beds were employed in order to avoid the effects due to transport phenomena affecting the reaction rate. In this way, the chemical reaction rates could be selectively studied. The experiments were carried out in the temperature range 873 - 1173 K. From the experimental data, the activation energies were evaluated and were found to be around 88 kJ / mol in the case of both iron as well as cobalt tungstates indicating the similarities in W-O bonds in both cases. The activation energies obtained are discussed in the light of the position of the transition metal in the periodic table as well as the thermodynamic stabilities of the various tungstates.IntroductionThe tungsten containing hard metals, characterized by high density, belong to a class of two-phase metal matrix composites. While these types of materials have traditionally found their applications within the defence industry as armour-piercing projectiles, counterbalance in helicopters and military aircrafts, outer casings of hand-grenades, etc., commercial applications for this class of alloys also exist, including radiation shields, penetrators for the oil industry, turbines for turbo-jet engines and a wide range of sports related parts. A possible route to the production of these alloys is to reduce the tungstates such as FeW04, Co W04 and NiW04 using a reductant like hydrogen or carbon monoxide. In order to have a better understanding of the processes involved in the production, it is important to have a knowledge of the reduction kinetics for these tungstates. According to the knowledge of the present authors, while the reduction ofNiW04 by hydrogen gas has been investigated earlier in the present laboratorypl no systematic reduction study has been carried out previously for the tungstates of iron, cobalt."

Jan 1, 1996

By cheng Peng-fei, TANG Hai-yan, guo Xiao-chen, LI Jing-she, Liang Yong-cang, Zhao Baojun

The origin and evolution of non-metallic inclusions for Al-killed casing steel during EAF-LFVD- CC process were studied by industrial tracer experiments. The formations of Al2O3 and MgO·Al2O3 micro- and macro-inclusions from ladle slag were analyzed by theoretical calculations. The results show that micro-inclusions were formed during deoxidation and temperature decreasing in the process of casting, most of the macro-inclusions come from entrapped ladle and mold slags. In addition, most of the Al2O3 formed were modified into 12CaO·7Al2O3 and 3CaO·Al2O3 inclusions which are liquid at steelmaking temperature. MnS cannot be fully modified to CaS and it was only wrapped outside the alumina or calcium aluminate in the form of (Ca,Mn)S with the amount of Ca-Si wire fed during the test.

Jan 1, 2016

By Xinlei Jia, Wenming Guo, Yanling Zhang

A large amount of stainless steel dust rich in Fe, Cr, and Ni has been being generated in China. Smelting treatment is accepted as a practical method for the recovery/reutilization of these second resources, during which Fe, Cr, and Ni is reduced into one metal phase and then separated from the residue slag. Based on the typical compositions of stainless steel dust, the residual slag can be termed as CaO-SiO2-MgO-Al2O3 system. In this paper, the activity coefficients of Cr in Fe-Cr-Ni-C (-Si/Al) melt and the properties of CaO-SiO2-MgO-Al2O3- 1%CrO system thermodynamically approached. Then, in laboratory experiments, the recovery ratios of Cr and its distribution behaviors between Fe-Cr-Ni-C melt and CaO-SiO2-MgO-Al2O3 slag system were examined.

Jan 1, 2015

By Deepak Gupta, R. Kageyamat, J. W. Evans

"In electromagnetic casting, a liquid metal pool is partly supported by electromagnetic forces resulting from the interaction between induced currents and an alternating magnetic field. Stability of the metal surface is of paramount importance if the cast ingot is to be free from surface defects. Prior work by Garnier and Moreau had suggested that the magnetic field has no influence on the surface stability, but a more complete analysis at Berkeley suggested that surface perturbations are destabilized by the magnetic field once a critical magnetic field is exceeded. More recently we have employed a modified version of the software SOLA to compute the behaviour of a melt surface in the presence of an alternating field. The computed results support the theoretical analysis in predicting an unstable surface. Experimental work is now in progress to examine the stability of a mercury pool in the presence of an alternating field. Introduction and Previous InvestigationsElectromagnetic casting (EMC) is a technique widely employed in the aluminum industry to produce ingot for subsequent rolling. It is a ""continuous"" casting technique (illustrated in Fig. 1) producing ingots several meters high (and perhaps 1m by 2m in horizontal dimensions) at a casting speed of one or two mm. per second. The technology has gained acceptance because the metal is solidified without contact with a mold. Consequently the surface finish of the ingot is usually smooth and the ingot can be fed directly to rolling without machining, the surface (""scalping""). Scalping is necessary with alternative technologies (e.g., DC casting) where a mold is used. Consequently any disturbances that result in surface imperfections of EMC ingot are a serious matter. One type of imperfection is waviness on the surface of the ingot; a line drawn along the crest of a wave would run horizontally around the ingot. This imperfection may be caused by waves on the surface of the metal pool. As the waves reach the solidification line at the periphery of the metal they cause alternate outward and inward bowing of the meniscus at that point with attendant small (but significant) changes in ingot width. Elimination of building vibrations and similar disturbances minimize the occurrence of these surface waves but it is interesting to speculate whether there are disturbances of the metal pool that arise from the electromagnetic forces supporting the liquid metal. These forces are generated by the interaction of currents induced in the melt and the magnetic field produced by the current imposed on the inductor surrounding the melt. The present investigation has been concerned with whether the alternating magnetic field destabilizes the melt surface."

Jan 1, 1994

By C. Isaac Garcia, Sihai Jiao, Anthony J. DeArdo

"A practical model based on the Hill analysis has been developed to calculate the Lankford value of interstitial free (IF) steels and its distribution in different rolling directions, by considering only a few selected texture components. The Texture Intensity Ratio (TIR), i.e. (111 ) /(100), was used in the model to describe texture. By using the new TIR parameter, the texture-based prediction models can be used more easily to predict the Lankford value in a rather straightforward way.IntroductionThe deep drawing capacity of sheet steels is generally indicated by the Lankford value, which is mainly determined by the texture in steels1. Traditionally, various models derived from the Taylor model are employed to calculate the Lankford value from the texture2-4. In such models, the plastic deformation of steel is assumed to be the result of the slip of dislocations in certain slip systems, i.e., by either pencil glide or restraint glide. The slip direction is the <111> direction. In the case of pencil glide, the slip is thought to be possible in all crystal planes with the <111> crystal direction. Assuming the material is elongated in the X1-direction by d n and compressed in the X2 and x3-direction by qd n and (l-q)d n, respectively, corresponding to a deformation tensor"

Jan 1, 2001

A new technology for the treatment of copper nickel-containing concentrate after high-grade matte flotation to blister copper with the production of liquid silicate slags in a vertical autogenous unit with upper oxygen blow has been considered. The copper and nickel behavior in the process of sulphide copper concentrate interaction with silicate melt containing oxide copper has been studied. The general mechanisms of such interaction are found.

Jan 1, 2003

By Shengli Wu, Wei Huang, Xinliang Liu, Kaifa Zhang

The slagging behavior, the phase of primary blast furnace slag and its transformation law of structure for the single furnace burden were studied in this paper. The results showed that the formation of primary slag was controlled by CaO/SiO2, Al2O3 content, MgO content, reducibility, iron content and porosity of the furnace burden. Fayalite (2FeO•SiO2) was easily formed from acid ferrous furnace burden while kirschsteinite (2(Fe,Ca)O•SiO2) was produced from alkaline ferrous furnace burden

Jan 1, 2015

By Yong Hack Lee

Nonferrous smelting processes have been through a rapid transformation since the beginning of 1980. The copper smelting technology has changed from the conventional Blast Furnace process to the Flash Smelting and MIB process. In the field of lead smelting, the technology has changed from the Blast Furnace Smelting to the Direct Smelting such as QSL and KIVCET. In 1992, Onsan Refinery successfully commissioned Direct Smelting QSL technology for lead. The QSL could produce more than 160,000 ton per year of lead bullion from lead concentrate and various residues. Moreover, since the year 2000, the TSL (Top Submerged Lance) Technology utilizing the same Direct Smelting process has been successfully commissioned to treat lead concentrate as well as lead sulfate residue produced from a hydrometallurgical zinc plant. This paper presents and compares the energy flows of lead smelting processes such as a conventional process and the Direct Smelting Processes plotted on the Pb-O-S phase diagram. The oxygen potential diagram suggests how to control the oxygen potential in the fum ace. Also, it describes the recent operational experience in the TSL plant of Onsan Refinery with necessary mass balance of key elements.

Jan 1, 2003

By J. K. Brimacombe, I. V. Samarasekera, B. G. Thomas

"Mathematical models have been developed for the processing of static cast steel ingots and are app1ied to investigate the mechanisms for the formation of panel cracks. Panel cracking is an intermittent but persistent defect that causes affected steel ingots to be scrapped. A two-dimensional, finite-element, heat-transfer model was formulated and employed to calculate the temperature distribution in both large and small steel ingots during the various processing stages from initial casting to the start of rolling, including solidification, cooling in the mold and in air, reheating in the soaking pit, and subsequent air cooling. The stress state in the ingot arising from the calculated temperature variations was then determined. This involved the development of a transient, elasto-visco-plastic, finite element, thermal stress model, including the effects of phase transformation volume changes and kinetics creep, and temperature-dependent, mechanical properties. The results of the mathematical model predictions of temperature and stress were then used to determine the mechanisms and to suggest solutions for two different types of panel crack formation. Mid-face panel cracks apparently form during air cooling when the mid-face surface temperature is between the Arl and 500~C. Off-corner panel cracks appear to initiate internally during the early stages of reheating but do not propagate to the surface until much later. IntroductionPanel crack formation in static-cast steel ingots is a defect that has been plaguing the steel industry for several decades. Although the problem is intermittent, it is also serious since affected ingots must be scrapped. Panel cracks are manifested as two distinct types of cracking problems. ""Mid-face"" panel cracks are found exclusively in small, 2 to 6 ton, medium carbon steel (0.3 to 0.7% C) ingots and usually exhibit a single, continuous, longitudinal crack down the center of one of the ingot faces as shown in Fig. l (l). ""Off-corner"" panel cracks often form roughly oval, discontinuous crack patterns on the wide faces of large, 20 to 30 ton ingots as seen in Fig. 2 (2). They affect only low carbon steels (0. l to 0.2% C) with high manganese content. Both defects affect only aluminum-treated steels and are caused by a combination of intermediate temperature ductility loss involving aluminum-nitride precipitation and thermal stress generation. The ductility problem has received a good deal of attention which was the subject of a recent review (3). The present study was undertaken to investigate the thermal stress aspects of the problem through the development of mathematical models of heat transfer and stress generation in static-cast steel ingots. The ultimate objective was to elucidate the mechanisms of formation for both types of panel crack and to evaluate possible solutions to the problem."

Jan 1, 1986

By Yoshinao Kobayashi

he removal of oxygen from titanium and zirconium is important for use in application because it significantly affects the mechanical and physical properties such as ductility and toughness. However, thermodynamic properties of oxygen in molten titanium and zirconium have not been clarified and the effective deoxidation process of molten titanium and zirconium has not been established. In this study, the standard Gibbs energy of reaction of oxygen and yttrium in molten titanium and zirconium have been measured by a chemical equilibrium technique. Molten titanium, zirconium, and their alloys with aluminum were equilibrated with a Y2O3, A12O3, or Zr02 pellet in a cold crucible. The results are summarized as follows:

Jan 1, 2000

By Robert H. Hsu

Palladium finely dispersed in a substrate of kieselguhr, Pd/k for short, has been successfully used for hydrogen storage, separation and pumping for a number of years at the Savannah River Site (SRS). Recently SRS has developed a new pd/k flow through bed (FTB) prototype for separating hydrogen from other gases and simultaneously storing the hydrogen on palladium. The FTB uses single-pass liquid nitrogen cooling during hydrogen absorption/separation/storage and electrical heating for desorption/unloading of hydrogen. Fourteen absorption-desorption or loading/unloading cycles using hydrogen have been conducted with the new FTB prototype. Test results show that all design performance objectives have been successfully achieved: recover 295% of hydrogen gas from feed gas, produce 99.9% hydrogen product gas and < 5% hydrogen in discharge gas. This paper will discuss characteristics of the palladium-coated kieselguhr or diatomaceous earth, design and operation of the FTB, and results of performance tests such as separation efficiency, hydrogen storage capacity and system heat transfer characteristics.

Jan 1, 2002

By G. Upadhya

Of late, solidification modeling has progressed considerably to emerge as a viable simulation tool for the foundry engineer. A wide variety of tools exist in the commercial market to cater to the various needs of the design/ foundry engineer. In fact, recent developments in the area of solidification modeling have been so rapid that a comprehensive review of the state-of-the-art is very much needed. In this paper, an attempt is made to summarize the various issues of solidification modeling, at the same time addressing the historical evolution of the subject. The various phenomenological issues covered in this paper include: heat transfer, fluid flow during mold-filling, solidification kinetics and microstructural evolution, quick-analysis schemes for approximations, porosity prediction models, and the phenomena of fluid flow in the mushy zone. Modeling issues related to the development of solidification stresses which lead to defects such as hot tears and the development of artificial intelligence concepts in the area of rigging design are also discussed. Due emphasis is given to the various phenomena which add to the complexity of the whole subject, and the various alternatives available for solving a particular problem. For example, the heat transfer problem can be approached by the use of simple modulus schemes or by solving the conduction equation to obtain a more accurate temperature distribution. Similarly the microstructural evolution can be handled in a deterministic way by use of nucleation and growth models, or in a probabilistic way by use of empirical models. The main goal of this paper is to put the multi-faceted problem of solidification modeling in proper perspective so that it can serve as a guide for future developments in this area.

Jan 1, 1994

By Xiaobing Yang, Abhishek Lahiri, Animesh Jha

"In the FFC-Cambridge process, the cathodic dissociation of oxide and CO/CO2 production on carbon anode is the basis for metal production in a CaCl2 bath. By using an inert intermetallic anode, the CO2 evolution can be eliminated altogether with acceleration in the electro-reduction kinetics. At present the process suffers from slow reduction kinetics of TiO2 to Ti metal, which can be enhanced significantly by the incorporation of alkali species in the TiO2 pellet at the cathode and in the CaCl2 bath in the presence of an intermetallic inert anode. Nearly full metallization with greater than 99% of Ti metal containing 1500 ppm of oxygen is possible to achieve in less than 16 hours of electro-reduction. Analyses of phase composition and the microstructures morphology in fully metallized pellets revealed the presence of localized solidified Ti layer, indicating that fast reduction process also involved formation of liquid phase as middle stage reaction. In addition, in situ creation of porosity and maintain higher current level during electrolysis process were two key factors to fully reduction of TiO2.IntroductionDuring cathodic dissociation of TiO2 in a CaCl2 bath and anodic evolution of CO2 on a carbon anode, which is the basis for the FFC Cambridge process [1], the rate of metallization slows down due to the formation of CaTiO3 at the reaction interface. Calcium and alkaline earth perovskites are known for their poor electrical conductivity which adversely affects the overall electro-reduction. One of the ways to increase the porosity is via the addition of polyethylene precursors in the pellet or by directly starting from perovskite [2, 3]. The experimental evidences shown in the literature confirm although the speed of reaction increases, but a complete or near complete metallization is not possible by enhancing the in-situ porosity alone, as the insulating perovskite is very slow to decompose under the equilibrium that prevails in the cell. Plethoric evidences on carbon anode show with the current decrease gradually, and finally stabilize at a very low value between 0.2 and 0.4 A, which is a testimony of the presence of perovskite insulating barrier in the current path. Our aim in this paper is to demonstrate the mechanism of enhanced electro-reduction when alkali ions are present in the oxide pellet at cathode and in the bath. We also show for the first time the use of an intermetallic anode for Ti-metal production using the FFC Cambridge process."

Jan 1, 2009

By K. Sarveswara Rao

The present paper firstly describes some recent trends from literature on energy management via process intensification to arrive at sustainable technologies for aqueous processing of minerals, metals and materials. Secondly, the energy saving measures practiced in leaching, solid-solution separation, solution purification, metal and material winning and environmental aspects have been discussed. The emerging importance of interdisciplinary nature of hydrometallurgy for practical applications is also highlighted. With the above background, the present paper describes an overview of energy conservation and autoclave processes with a special reference to hydrometallurgical research activities of our Laboratory.

Jan 1, 2008

By L. Sh. Tsemekhman

A new technology for the treatment of copper nickel-containing concentrate after high-grade matte flotation to blister copper with the production of liquid silicate slags in a vertical autogenous unit with upper oxygen blow has been considered. The copper and nickel behavior in the process of sulphide copper concentrate interaction with silicate melt containing oxide copper has been studied. The general mechanisms of such interaction are found.

Jan 1, 2003

By Nicole de Jager, Michael J. Nicol

"In order to liberate gold from refractory gold ores and concentrates it is generally necessary to oxidise the surrounding sulphide minerals, typically pyrite and arsenopyrite. Traditional methods of oxidation include pressure leaching, roasting and bacterial oxidation. In recent years, bacterial and pressure oxidation have found increasing favour, although these methods are by no means completely satisfactory and each is subject to particular disadvantages.A novel process has been developed as an alternative to the traditional methods whereby electro-generated ferrate(VI) ions in alkaline solution are used to oxidise a pyrite concentrate. This process has been observed to proceed fairly rapidly and could prove to be a more economically viable process, as well as being more environmentally acceptable. As an added benefit, operating in an alkaline environment is advantageous for downstream cyanidation processes.Ferrate(VI) is a relatively unknown species, due mainly to its instability in acidic solutions. However, in alkaline solution it has been observed to be sufficiently stable for use as an oxidant when used under favourable conditions. Ferrate(VI) is most conveniently manufactured electrolytically via the dissolution of high-carbon anodes in strongly alkaline solutions. Some literature has been published on the electrolytic generation of ferrate(VI) and relatively high efficiencies have been observed by both the authors and other researchers.This study utilises both electrochemical techniques and leaching experiments to examine the kinetics of the oxidation of pyrite by ferrate(VI), which is produced electrolytically. Cyclic voltammetry, rotating disk voltammetry and potential step experiments have been used to investigate the kinetics and mechanism of the oxidation process."

Jan 1, 1997