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By Frederic Pineau

Semisolid metal alloys have a special microstructure of globular grains suspended in a liquid metal matrix. This particular physical state of the matter can be exploited to produce near-net- shape parts with improved mechanical properties. However, the behavior of the slurry is strongly influenced by the local solid fraction and state of agglomeration. Different flow instabilities ·associated with the combined flow and solidification process result, which make difficult the application of semi-solid processing in the casting industry. Moreover, the rheology of semisolid materials is not well understood. Most of the theory has been derived from experimental data, which are somewhat difficult to measure. A model that accounts for the multiphase nature of semisolid slurries is required to get more insight into such complex flows. This paper describes a mixture model for semisolid slurries. It assumes that the mixture of liquid-solid components behaves as a single fluid as far as overall mass and momentum balances are concerned. The coupling force between the phases is derived on the assumption that the slurry is a fluid saturated isotropic media. The proposed methodology is implemented in a finite element code. The model is then applied to the the filling of an industrial-scale capillary flow viscometer. Segregation patterns are obtained and discussed.

Jan 1, 2001

By S. C. Flood, J. D. Hunt

"The columnar-equiaxed transition (CET) has been studied numerically under unsteady-state conditions using mathematical models that: (i) include a non-equilibrium undercooling at the columnar front;and(ii) describe the simultaneous evolution of the columnar and equiaxed zones.The results are discussed and compared with those produced by a steady-state analysis.IntroductionThe majority of the previous work on the columnar-equiaxed transition (CET) has concentrated on the production of equiaxed nuclei, regarding this as being the critical step in the formation of an equiaxed zone. Recently, the growth of equiaxed grains has been considered and this is not unreasonable because, for an equiaxed zone to be present, the grains must grow as well as nucleate. Since the growth rate of the grains will be determined by the thermal environment at and ahead of the columnar tips, it was decided to model the liberation and flow of heat during solidification to discover whether the various trends in the columnar range might be explained by their effect on the temperature profile throughout the casting. The models presented here for the solidification of a casting are the first to include the latent heat liberated ahead of the columnar front. Burden and Hunt (1) consider its effect only qualitatively, and although Lipton et al (2) adopt a criterion for the CET which is based on the thermal interaction of the columnar and equiaxed grains, they do not actually include the latent heat in their calculations.It can be argued that the latent heat liberated by the equiaxed grains in the bulk will retard the columnar dendrites in a casting: once the equiaxed grains are sufficiently well-established, the latent heat that they evolve could slow down the columnar growth to such an extent that the equi axed would dominate. Alternatively, the latent heat produced by the equiaxed grains might suppress further equiaxed solidification by raising the bulk temperature. The nature of the thermal interaction between columnar and equiaxed growth is not obvious, and because it is dependent on the material parameters and the dimensions of the system, it cannot be considered effectively in a qualitative way but has to be studied quantitatively: hence the need for the mathematical models discussed in the following pages. The results of the models are discussed in the light of a steady state analysis."

Jan 1, 1986

By Kenneth N. Ham

Hydrometallurgy covers a wide spectrum of areas and its knowledge base is enlarged and enhanced by contributions from many other fields. Dissolution of metals and alloys in aqueous media will be used to illustrate how rich the field of metal extraction can be. Comprehensive understanding of the fundamentals of metal and alloy dissolution in aqueous systems requires creative application of thermodynamic principles, solutions chemistry, ligand complexation theory, electrochemistry, transport phenomena and heterogeneous kinetics. In addition, recent developments in instrumentation in the fields of interfacial phenomena and corrosion have tremendously advanced the field of metal extraction in aqueous system. The close relationship between metal extraction in aqueous systems and various physicochemical phenomena occurring in corrosion and interfacial systems will be discussed and illustrated with examples.

Jan 1, 2002

By Toshihiko Emi

The quest for cleaner steel is driven by increasingly stringent requirements from the manufacturing and construction industries. Key issues are the occurrence and removal of inclusions; These are discussed in the context of the unit processes of deoxidation, refining, transfer and casting of molten steel. Process thermodynamics and kinetics are also discussed. Recent progresses achieved and problems yet to be solved are elaborated, and an integration of the unit processes into a system to produce extra clean, steels with better performance is presented.

Jan 1, 1999

By R. G. Robins

Metal separations based on the selective precipitation of phosphates have a potential application in many hydrometallurgical processes. This paper reviews the literature on the solubility of a number of both divalent and trivalent metal phosphates and presents the result of some additional experimental measurements. The systems examined have been modelled to obtain free energy of formation data for the various species. Computer generated solubility diagrams which are described can be useful in predicting a variety of metal separations.

Jan 1, 1991

By Derek J. Fray

"A need exists for fast and accurate analysis of species in various phases at elevated temperatures. Although modern analytical techniques are very efficient, the equipment is usually situated some distance from the industrial operation and time is spent taking the sample and sending it to the analytical facility. Several minutes can easily lapse and, during this time, heat must be supplied in order to keep the system molten and, if the composition is changing rapidly due to a refining process or reaction with the environment, the information may only be of retrospective use. Perhaps more important reasons for the use of on-line sensors are that instantaneous analysis gives better control, process optimisation and the minimisation of energy losses and pollution. To date oxygen has been the only element which is measured widely using solid electrolytes. However, the analysis of many more elements is required and possible electrolytes for other species are discussed. For some elements, ~here is no suitable conducting electrolyte and, therefore, a different approach is adopted where the electrolyte, in which one species is mobile, comes to equilibrium with another species. IntroductionThere is an ever increasing demand for the development of sensors for on-line measurements in most areas of technology and, in particular, metal processing. This is especially relevant in situations where greater control can be achieved by monitoring the chemical composition of the melt during processing and where a minor constituent in the melt can have a major effect on the properties of the finished alloy. Although modern analytical techniques are fast and reliable, the equipment due to its complexity, is frequently situated away from the process area and valuable time may be spent in sampling and transportation. During this period, heat may have to be supplied to prevent solidification and the refining reactions may be continuing, and, therefore, the analytical information may not be of direct use."

Jan 1, 1988

By G. Mark Aylmore

Various processes have been developed using a combination of elevated temperature and chemical treatment processing to recover Li from silicate minerals. To facilitate further process development, a comprehensive understanding of the deportment of Li and associated minerals in ore bodies is essential to allow the industry to predict the response of ore reserves to metallurgical treatment options. This paper describes results from the integrated use of the John de Laeter Centre’s state of the art analytical and mass spectrometry techniques to characterise a selection of Li bearing ore bodies and determine their amenability to potential processing options for the extraction of Li. The mineralogy, mineral associations, and liberation characteristics of ore-bearing and gangue minerals were characterised using a combination of the TIMA and XRPD studies. The Li content and distribution within minerals were defined using LA-ICPMS and field emission scanning electron microscopy techniques (EBSD, ToF-SIMS) and atomic probe microscopy.

By P. R. Taylor

Titanium carbide and titanium diboride powders have been successfully synthesized by direct treatment of ilmenite concentrates in a non-transferred arc thermal plasma reactor. Methane gas was used as the reducing agent and boron oxide was used as the boron source in these processes. Free energy minimization plots were used to predict the behavior of each system under different molar ratios and operating conditions. Products were characterized by XRD, SEM and chemical analytical techniques. The average size of the ceramic product is in the submicron range. Metallic iron apparently is finely deposited on the surface of the titanium carbide or titanium diboride particles. Minor impurities such as silica, manganese and zircon were converted to the carbide form.

Jan 1, 1995

By Yi Tan, Kazuki Morita, Yaqiong Li

Molten Si-Al alloy, with the addition of Sn, was used for metallurgical grade Si purification by a low-temperature solidification method, with the aim of improving the recovery rate of Si. In this ternary melt, bulk Si was grown with a planar front by a directional solidification process under a well-controlled thermal gradient and growth rate conditions, thereby reducing the contamination of solvent metals. Effects of cooling rate, amount of Sn addition, and temperature gradient on the quality of bulk Si were determined. The criterion for constitutional supercooling for single-phase growth from multicomponent melts was employed to evaluate the growth process.

Jan 1, 2015

Physical and chemical properties of the salt flux phase play a significant role in the recycling of UBC in Aluminum melting processes. Particularly knowledge of several properties such as salt vapor pressure, melting temperature, loss of aluminum, corrosion of refractories are useful for the process control decisions in order to attain a good quality of aluminum produced. A literature review and analysis of several salt flux systems for the selection of a flux for the Aluminum melter (low temperature natural gas bath melting) process were made. Based on these analysis two salt flux systems are recommended for further studies. These are NaCl?KCl?LiF system and NaF?LiF?KCl system with small amounts of other salt additives. Application of these fluxes to Al industrial processes are discussed.

Jan 1, 1996

By Guojun Qi

This work relates to wafer bumping technologies for flip chip packaging applications in the electronics industry. Nickel and its alloys are alternative under bump metallization (UBM) materials because of their slower reaction rates with Sn-based solder as compared to Cu-based UBMs. In this study, we compared the morphologies of the intermetallic compounds (IMC) formed between Sn-bearing solders (Sn3.5Ag and eutectic Sn-Pb) and two types of nickel- based UBMs, electroless Ni-P (EN) and sputtered nickel. Both chunky-type and needle-type of intermetallics were observed between the EN UBM and the solders. In the case of sputtered Ni UBM, there is only a layer of scallop-type intermetallics formed. The morphology change and growth kinetics of the IMC in thermal aging process were analysed. Kirkendall voids were noticed from samples of Sn3.5Ag solder vs Ni-P UBM that have undergone prolonged thermal aging at high temperature.

Jan 1, 2003

By Guojun Qi

This work relates to wafer bumping technologies for flip chip packaging applications in the electronics industry. Nickel and its alloys are alternative under bump metallization (UBM) materials because of their slower reaction rates with Sn-based solder as compared to Cu-based UBMs. In this study, we compared the morphologies of the intermetallic compounds (IMC) formed between Sn-bearing solders (Sn3.5Ag and eutectie Sn-Pb) and two types of nickel- based UBMs, electro less Ni-P (EN) and sputtered nickel. Both chunky-type and needle-type of intermetallics were observed between the EN UBM and the solders. In the case 'of sputtered Ni UBM, there is only a layer of scallop-type intermetallics formed, The morphology change and growth kinetics of the IMC in thermal aging process were analysed. Kirkendall voids were noticed from samples ofSn3.5Ag solder vs Ni-P UBM that have undergone prolonged thermal aging at high temperature.

Jan 1, 2003

By T. -M. Guo, M. J. Braun

"This paper presents an experimental and numerical study of melt flow near the solid-liquid interface and its effect on the interface curvature in a horizontal unidirectional solidification system with succinonitrile. Melt flow is introduced by increasing the ampoule channel thickness. Visualization techniques are employed to observe the flow field and the solid-liquid interface curvature. A numerical model is also developed to simulate the heat transfer, melt flow and phase change in the system. Quantitative information on the flow and temperature fields is generated. A good agreement is achieved between the experimental observations and model predictions. The results could be used for the study of the effect of the melt flow on interface morphology during solidification.IntroductionClassic unidirectional solidification experiments of transparent alloys are conducted with thin film samples sandwiched between two glass slides to investigate the development of interface morphology during solidification [1]. Samples with small channel thickness are usually used to suppress any melt flow due to natural convection and solidification in the channel would then be in the diffusive regime so that the solidification theory can be significantly simplified [2, 3]. Effects of melt flow, in particular due to natural convection, on solidification have also been studied extensively in those systems with large geometrical dimensions [4-6]. These studies indicate a strong effect of the melt flow on interface curvature during solidification [5, 6]. Only limited efforts were made to address the effect of the melt flow on interface morphology in horizontal unidirectional solidification, in particular for the cases when the channel thickness is not thin enough to suppress completely the natural convection [7]."

Jan 1, 2004

By Albert F. S. Seboukens

A 5;6 MVA pyrometallurgical demonstration-scale pilot plant was commissioned at Mintek, South Africa, in 1994, using lead blast-furnace slag and coke as raw materials. The plant included a.d.c. power. supply, two plasma-arc furnaces' and an ISP lead-splash condenser. Slags containing typically 12 per cent zinc oxide and 3 per cent lead oxide are produced as a waste during the smelting of lead in a blast furnace. These slags are a potential: resource for the recovery of lead and zinc. During 1994, about 600 t of lead blast-furnace, slag was proceced through the pilot plant using the Enviroplas process. Zinc and lead oxides were reduced to their respective metals, volatilized, and collected in an. ISP lead splash condenser. Prime Western grade zinc and slags disposable in accordance with current US legislation, were produced. Zinc condensation efficiencies of about 80 per cent were achieved.

Jan 1, 1995

By Taufiq Hidayat

Accurate description of complex phase equilibria provide the foundations for the improvement of non-ferrous pyrometallurgical smelting and recycling processes. Recent advances in microanalysis and experimental techniques enable accurate phase equilibria characterisation. Quantitative microanalytical techniques including Electron Probe X-ray Microanalysis and Laser Ablation ICP-MS enable the concentrations of major and minor elements present in different phases in samples to be accurately measured providing data that cannot be obtained using bulk chemical analysis techniques. High-temperature equilibration experiments coupled with the subsequent analysis of elementary reactions at micro- and macro-scales ensure the attainment of equilibrium conditions, and therefore, ensure true phase equilibria information is obtained. Examples of the application of the improved methodology on the investigation of phase equilibria of low-order and complex, multi-component gas/slag/matte/metal/solids Cu2O–PbO–ZnO–Al2O3–CaO–MgO– FeO–Fe2O3–SiO2–S systems and the distribution of minor element are provided. The experimental study is closely integrated with thermodynamic database development for the above system. Example of implementation of the research outcomes into industrial operations is demonstrated.

By O. Forsén

In the first part of this paper is studied the behaviour of small amounts of impurity elements? in the solidification of copper anodes. In the second part the dissolution of these impure anodes in sulphate based electrolysis is discussed. The first part is introduced with practical examples, the .model of solidification of impurities during the solidification of anode copper. According to this model the solidification structures of anode copper are strongly influenced by both thermodynamic and kinetic factors. Thermodynamics determine the microstructure of anode copper, but kinetics can alter the composition of melt to such that there is formed unequilibrium structures during the solidification, especially when the residual melt is solidified. The electrolysis experiments have clarified the behaviour of impuririties in the electrochemical dissolution in sulphate. Based copper electrolysis. In this study it is widely investigated to what extent any impurity elements or oxides will dissolve. In copper electrorefining. With the aid of the electrochemtcal experiments it was possible to fulfil quantitatively the qualitative results accomplished by microstructure studies.

Jan 1, 1985

By Petrus Christiaan Pistorius, Ming Tang

Magnetite concentrate is pelletized and then hardened by elevated-temperature oxidation to hematite, to produce pellets for ironmaking. Previous work showed that the rate of oxidation is under mixed control of gaseous mass transfer of molecular oxygen through the pellet pores, and solid-state diffusion into the oxidizing grains. Because of the partially limiting role of solid-state diffusion, concentrate size distribution strongly affects pellet oxidation. Previously, a simple mixed-control model was formulated to describe isothermal oxidation. In that model, the main effect of concentrate size distribution was on the plateau level of oxidation which is reached at a given temperature. However, the extent of plateau oxidation increases with increased temperature, requiring a more complex model for non-isothermal oxidation. In this paper, predictions of the non-isothermal model confirm the strong effects of concentrate size distribution and oxygen enrichment. In particular, a greater fraction of coarse magnetite particles would be beneficial, decreasing the size of the macroscopic unoxidized pellet core.

Jan 1, 2015

By Antoine Allanore, Luis A. Ortiz, Donald R. Sadoway

"The steelmaking industry has drastically reduced its energy consumption in the last fifty years, and today’s technologies are considered to operate at their optimal efficiency with respect to energy needs. To cope with new constraints related to greenhouse gas (GHG) emissions, a change of paradigm is necessary. One of the promising technologies that could be deployed to help reach CO2 mitigation targets relies on the intensive use of electricity: molten oxide electrolysis (MOE). This paper presents the key process parameters that need to be tuned to address the practical needs for both high productivity in a steelmaking reactor and for an energy efficient process. Herein we show that contrary to common perception, the electrolysis process for ironmaking requires less energy than today’s chemical reduction route. Furthermore, we prove that most of the energy that must be provided to operate the electrolytic iron production cell is thermal energy which is readily generated by joule heating during electrolysis due to large currents being passed through the electrolyte. The energy consumption of the electrolysis cell is therefore shown to be highly dependent on the cell configuration and the chemistry of the electrolyte. As a consequence, the CO2-impact of the technology strongly depends on both the power production mode and the technological choices for design of the process, including cell configuration. Surprisingly enough, even when the electricity generation is not carbon-free, MOE still appears to be viable from the perspective of reducing GHG emissions providing sound reactor design considerations are made.IntroductionIn the context of greenhouse gas (GHG) emissions mitigation, the steelmaking industry is considering several techniques that could sustain the efforts and progress achieved by this sector in the last decades [1]. A recent report [2] on potential routes for low-CO2 steelmaking highlighted for all techniques both the strong dependency of CO2 emissions on electric power production mode and the need for a decrease in energy consumption per tonne of steel. Incited to innovate with respect to this last criterion, the steel industry considers electrolysis to be a promising technological solution, and in particular the molten oxide electrolysis (MOE) process. This process conducts electrolysis in a mixture of oxides that dissolve the iron oxide feed, which by the action of electric current is decomposed into liquid iron and oxygen gas. The opportunity for reduction in energy consumption during steelmaking by MOE is commonly attributed to the “direct” pathway from iron oxide to liquid metal offered by the use of a molten oxide melt and operation at a temperature above the melting point of iron, ideally 1600°C, to provide enough superheat for tapping the molten iron product:"

Jan 1, 2011

By Zhihong Liu

Monodisperse micron size nickel oxalate particles with rhombohedron morphology were prepared from condensed Ni(OH)2 suspension by a novel gel-sol process proposed by one of the authors. Firstly, condensed nickel hydroxide gel was formed by fast adding 1 mol dm-3 NaOH solution into 0.2 mol dm-3 nickel chloride solution, and then oxalic acid solution with a concentration of 0.25 mol dm-3 was dropped into the gel drop wise through a pump equiped with a pH controller under preset pH value, and in this process, Ni(OH)2 gel was converted gradually into monodisperse nickel oxalate sol. The formation of the nickel oxalate particles was found to proceed through a dissolution-recrystallization mechanism from the nickel hydroxide gel. The product particles exhibited rhombohedron like shape with micron size long axis and sub-micron size short axis. The effects of such factors, as temperature, surfactants, et al, were evaluated experimentally on the particles sizes and morphologies.

Jan 1, 2006

By Hebi Yin

A coupled cellular automaton (CA) - finite element (FE) model was developed to calculate the growth of dendrites during the solidification of cubic and hexagonal metals. The model solves the conservation equations of mass, energy and solutes in order to calculate the temperature field, solute concentration and the growth morphology of dendrites, including the grain structure and the dendritic microstructure. Validation of the model was performed by comparing the simulation results with calculation results from previously published works, showing qualitatively good agreement in the dendritic morphology. Application to magnesium alloy AZ91 illustrates the difficulty of modeling dendrite growth in hexagonal systems, observed as deviations in growth direction caused by mesh-induced anisotropy. The model was applied to the simulation of small specimens with single- and multiple- equiaxed grain growths and columnar grain growth in directional solidification. The influence of cooling rate and some kinetics parameters on the grain morphology are also discussed.

Jan 1, 2009