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By J. A. Sekhar

Solidification processing/casting is increasingly being adopted as the preferred manufacturing technique for the fabrication of net shaped complex geometry components. Modeling of solidification processes is important both for design purposes as well as for understanding the physics of morphological evolution of the solidification microstructure. A fundamental aspect of such modeling involves the precise understanding? of heat transfer through the two phase solid/liquid region. A scheme to do this will be presented where the nonlinearity of the fraction liquid with change in temperature can be incorporated into the numerical calculations. The importance of properly accounting for the non-linear mushy zone will be discussed. Typical processes like squeeze casting and electromagnetic stirring will be discussed to illustrate how precise modeling of the solid/liquid region can aid in the calculation of accurate heat transfer coefficients for these processes.

Jan 1, 1990

By J. R. Bhamidipati, Nagy EI-Kaddah

"Over the years, mathematical modeling has been established as a viable tool for design and analysis of melting and solidification processes. Modeling of electromagnetic casting and melting systems involves three coupled problems -- determination of the containment field, the shape of the meniscus, and the temperature field -- which have to be solved simultaneously. One of the difficulties in numerical simulation of these systems is in defining and gridding the solution domain as the meniscus shape of the liquid region is not known a priori. This paper describes a methodology for solving these coupled problems in a two-dimensional electromagnetic containment field. This method is based on the solution of the electromagnetic, free surface dynamic, and heat transfer equations in a fixed domain in computational space by mapping the physical space into an invariant computational space during the search for the equilibrium shape using a variable non-orthogonal coordinate transformation. This approach, also, eliminates the need for regridding the liquid and solid regions during phase change. This methodology is demonstrated for two electromagnetic confinement systems -- the Magnetic Suspension Melting process and the electromagnetic casting of aluminum. The model predictions are in good agreement with available data for these systems. It is suggested that the methodology presented here is likely to provide a useful tool in the design, analysis, and optimization of electromagnetic confinement systems. IntroductionDuring the past decade, mathematical modeling has emerged as a viable tool for the design, analysis, and optimization of casting and melting processes /1-2/. It is generally recognized that the usefulness of modeling to study the interplay between the various process parameters without resorting to extensive experimentation relies heavily on accurate representation of the physical phenomena in these systems. In modeling electromagnetic confinement casting and melting systems, it is important that the model address all aspects of electromagnetic field interaction with the metal, if accurate predictions are to be obtained /3/. The electromagnetic field affects the heat transfer phenomena primarily through joule heating. In addition, the electromagnetic forces play a key role in heat redistribution in the molten pool via melt stirring, and, in confinement systems, support the molten metal pool."

Jan 1, 1994

By Tetsuya Uda

Our recent achievements of rare earth separation technique[1,2] and new process idea for rare earth magnet recycling[3] are reviewed, (1) Binary chloride mixtures of rare earths were separated by a new selective reduction-vacuum distillation process. According to our experimental results, apparent separation factors were 8.1 for the Pr-Nd chloride mixture and 570 for the Nd-Sm chloride mixture. These values are much higher than conventional solvent extraction methods. (2) A study of recycling process of magnet sludge was carried out. The rare earths in the neodymium magnet sludge were extracted by chlorination with FeCI2, An activated carbon was used as a de-oxidation reagent Metallic iron in the sludge was not chlorinated because the iron monochloride is not stable, The extracted rare earth chlorides were easily separated from Fe-alloy and the excess of FeCh by vacuum distillation, 96 % of neodymium and 94 % of dysprosium in the sludge were extraeted into chloride phase, By the vacuum distillation, a mixture of neodymium and dysprosium trichlorides of 99.2 % purity was recovered, On the other hand, the rare earth chlorides can be converted to the corresponding oxides by a pyrohydrolysis reaction accompanied by a formation of HCl gas, The HCI gas can chlorinate metallic iron to FeCh, Therefore, a new recycling process for rare earth magnet waste can be realized as a chlorine circulation type process. During the process, only carbon and water are consumed and there are no toxic pollutants, Moreover, the obtained rare earth oxide can be directly used as raw material in the conventional oxide electrolysis process,

Jan 1, 2003

By Duclerc Fernandes Parra, Luis Filipe Carvalho Pedroso de Lima, Washington Luiz Oliani, Danilo Marin Fermino, Ademar Benevolo Lugao

The modified polypropylene was obtained from isotactic polypropylene (iPP) in spheres by irradiation with gamma rays in the presence of acetylene. A new morphology with distinct rheology is obtained by this process in which occurs: degradation, branching and/or crosslinking. The objective of this study was to investigate the effects of thermal aging on the crystallinity and morphology of the modified polypropylene, High Melt Strength Polypropylene (HMS-PP). The thermal stability was evaluated after aging of samples using a stove at temperature of 90 °C, in presence of air at different periods of time. Aging effects were characterized by: Thermogravimetry analysis (TG), Differential scanning calorimetry (DSC), Infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM). In thermooxidative conditions, the formation of oxidation products essentially involves a hydrogen abstraction by the peroxyl radical, leading to hydroperoxides as primary products and chemical degradation in the immediate crack tips. The effect of thermal degradation (chain scission and oxygen diffusion) on iPP was a more intense crack formation. Surface cracks increased with the aging time. In comparison of iPP, the modified PP samples had a morphological barrier inhibiting the penetration of oxygen into the sample and in consequence limit the propagation of degradation

Jan 1, 2015

By Dean Ilievski

Mathematical modelling of the precipitation process requires that the kinetics of crystal growth, nucleation and agglomeration be known: This paper reviews the current state of knowledge on these precipitation sub-processes (ie. growth, nucleation and agglomeration) and describes a number of experimental techniques for estimating their kinetics. The experimental methods used to generate the precipitation data and the data analysis techniques used to extract the kinetics information from the data are discussed separately. There is no universal "best" technique for determining the kinetics. However, studies on multi-crystal systems are more reliable for modelling purposes than are single crystal studies. The selection of a technique will depend on which sub-processes are present. A problem with all kinetics studies is that there is generally a large uncertainty in the estimated kinetic parameters. This stems from the scatter in the experimental data being further propagated by the mathematical techniques used to extract the kinetic parameters.

Jan 1, 1996

By N. Y. Ma

Solid wastes produced in ironmaking and steelmaking off-gas cleaning systems often contain zinc. The zinc level in these solid wastes is generally too high to recycle the wastes for iron through blast furnaces, but too low to economically treat the wastes for zinc through zincrecovery facilities. The behavior, status, and distribution of zinc in the ironmaking and steelmaking off-gas cleaning systems have been analyzed from three aspects: thermodynamics of zinc condensation, oxidation and deposition, correlation of zinc concentration with particle size and density, and aerodynamics of dust particles in the off-gas cleaning systems. Theory and supporting data show that spontaneous separation of zinc from iron-bearing dust occurs in the ironmaking and steelmaking off-gas cleaning systems. Dry off-gas cleaning systems provide the most favorable conditions and environments for zinc to separate from the dust. If highefficiency dry separators were applied and appropriately arranged in the off-gas cleaning systems, zinc would be concentrated, and the majority of the solid wastes could be recycled for iron recovery through blast furnaces.

Jan 1, 2008

By Paul C. Turner

In 1998, approximately 57,000 tons of titanium metal was consumed in the form of mill products (1). Only about 5% of the 4 million tons of titanium minerals consumed each year is used to produce titanium metal, with the remainder primarily used to produce titanium dioxide pigment. Titanium metal production is primarily based on the direct chlorination of rutile to produce titanium tetrachloride, which is then reduced to metal using the Kroll magnesium reduction process. The use of titanium is tied to its high strength-to-weight ratio and corrosion resistance. Aerospace is the largest application for titanium, and titanium cost has prevented its use in non-aerospace applications including the automotive and heavy vehicle industries.

Jan 1, 2001

By C. A. Silva

Ladle change-over, during continuous casting of steel, initiates transient flow in the tundish which influences the inclusion content and degree of mixing between two consecutive batches of steel. The mixing behavior in the tundish during this period is determined by the casting rate and the ratios of: inflow to outflow during the refilling period; and, the low liquid level relative to the nominal level in the tundish during the transiency. A 3:10 scale water-model of a typical one strand slab caster was operated in conjunction with a tracer technique to characterize the velocity fields for several combinations of these parameters. Steady operation, a limiting case of the transiency, provided a basis for comparison. High-order moments -- skewness and kurtosis -- of the residence time density function have been utilized as signature elements associated with a particular residence-time distribution for the system. A simple mathematical model incorporating the above parameters as well as a characteristic Peclet Number was successful in simulating the features of the transient period.

Jan 1, 1993

By M. J. Adam

The U.S. Bureau of Mines has investigated the partitioning of complex minerals to simpler phases using sulfidation reactions for selective extraction of mineral values. This report describes research in which thermal processing of the complex Ti-bearing mineral ilmenite (FeTi03) resulted in partitioning of the valuable Ti metal to the simpler compound rutile (TiO2). Samples of ilmenite were blended with elemental S for thermal treatment at various temperatures under controlled atmospheres in an effort to dissociate the Fe from the ilmenite complex. Product characterization revealed that the Fe was partitioned 'from the ilmenite, forming a rim of pyrrhotite/pyrite (FeS/FeS2) on a rut il e core. The products were agate milled and then subjected to cursory magnetic and flotation techniques in an attempt to physically separate the partitioned phases. Partitioning results and phase concentration data are reported relative to thermal treatment variables and physical separation techniques.

Jan 1, 1991

By Milton Blander

"A review of concepts and theories for predicting thermodynamic solution properties of multicomponent high temperature liquid solutions is reviewed. During the last 50 years the ability to predict such properties for molten salts, silicates and metals based on the generally known properties of the lower order (often binary) systems has been developed and shown to provide predictions which are quite useful in science and technology. There are many gaps in our understanding of these high temperature solutions, especially for metals, and considerably more work is needed.INTRODUCTIONA number of solution theories and concepts have been developed which reliably predict the properties of multicomponent solutions from those of the lower order systems (often only the binaries). Because there is available data for a large fraction of the important binaries, the capability for making predictions for many multicomponent systems used in metallurgical separation processes is broad and potentially very useful. At the very least, the theories greatly minimize the data necessary for predicting properties of complex multicomponent solutions of molten salts, silicates and metals. It is the purpose of this paper to discuss the concepts which are demonstrably useful. We will discuss simple forms of the theories to make the concepts clear but we will refer to the publications which contain the more complex equations needed to treat the large majority of systems.A simple framework for understanding what we need to know in order to make technologically useful predictions is based on well known thermodynamic principles. In technologies and sciences where molten salts, slags magmas or molten metals are used or studied, one must often calculate the extent of a chemical reaction (or separation) or of phase changes. To do this, one must first write an equilibrium constant, K, for the reaction in terms of the standard free energy change of the reaction, ?G°."

Jan 1, 1996

By D. Van Dooren

The final goal of the research project is to develop a 3D FEM model that is able to predict the kinetics and micro-structural evolution during the bainitic transformation. The input parameters consist of thermodynamic and atomic mobility data obtained from the ThermoCalc and mCTRA databases combined with structural mechanics data extracted from the stress-strain curves of the fcc and bee phases. In this paper the general principles of the model are outlined and some interesting preliminary results are shown and commented. The full implementation of the model has presently not been achieved yet. In the model the bainitic transformation is considered as a sequence of martensitic (re)nucleation and growth of a ferritic subunit followed by the carbon rejection into the surrounding austenite. The (re)nucleation of the subunits will be described through a non-classical martensitic nucleation criterion. Once a nucleus has been activated at a specific location in the material, a full-sized subunit is instantaneously formed through a displacive mechanism. The stress state in the system that arises due to the transformation strain can be calculated by a 3D FEM programming code. Immediately after the formation of the subunit, another 3D FEM programming code calculates the carbon diffusion from the supersaturated ferrite into the surrounding austenite. The resulting stress state and carbon profiles will be used to determine where and when a new subunit will nucleate based on a renucleation criterion. Keywords: Bainitic Transformation, Modeling, Eshelby, Carbon Diffusion

Jan 1, 2003

By Kexin Jiao, Zhijia Zhang, Jianliang Zhang, Zhengjian Liu

Carburization behavior of molten iron in blast furnace is an essential part of BF long campaign technology. Maintaining carbon content stable is an important prerequisite to ensure the high production of the blast furnace. In this paper, the important aspects of the research progress which mainly including the study of iron carburization at the upper and the lower parts of the blast furnace was reviewed. Indirect carburizing is the main way at the top of the blast furnace. The content of carbon in metallic iron increases with the reducibility of iron ore improved. The thermodynamics and kinetics conditions are good for carburization reaction to take place at the bottom of the blast furnace. Carbon content of molten iron increased by coke carburizing. Meanwhile, the drawbacks of the existing literature on iron carburization behavior were analyzed and new research directions of iron carburization were proposed in the future.

Jan 1, 2015

By Filiz Sahin

This paper presents a synthesis of TiB2 via carbothermal reduction method using a mixture of TiO2, B4C and C prepared in molar ratio of 2:1:3. Reduction experiments were carried out in a high temperature graphite furnace in a graphite crucible under argon atmosphere at different time (0, 15, 30 and 60 min.) and temperatures (1400, 1500 and 1600 °C). The products obtained were investigated using XRD technique.

Jan 1, 2008

By Mike Trovant, Stavros A. Argyropoulos

"A fixed grid numerical model for phase change problems is proposed. The model solves for heat transfer and fluid flow, via the coupled solution of the energy, continuity and momentum equations. In addition, the numerical scheme accounts for temperature varying thermophysical properties and determines the shrinkage profile resulting from phase and density change. Simulations are run to determine the effect of varying model parameters and wall cooling rates on the location and shape of the shrinkage void formation in cylindrical casts. Results are shown for both aluminum and magnesium.IntroductionThe mathematical modeling of phase change processes (be they solidification or melting problems) entails solving for many interrelated phenomena. A comprehensive numerical simulation of the casting of a metal, for example, would have to account for: (a) heat transfer in both the solid and liquid portions of the metal and in the mold, (b) the release of latent heat during phase change, (c) fluid flow behavior in the liquid portion of the metal, (d) temperature induced shrinkage caused by liquid contraction and solidification contraction, and (e) the development of thermal stresses with accompanying shrinkage in the solid portion of the cast and mold. A schematic of the relationships that exist between the coupled equations which govern solidification is shown in Figure 1."

Jan 1, 1994

By Hu Long

In this, the first systematic study of the oxidation of orpiment (As2S3) in sulfuric acid solution under oxygen pressure at temperatures above 170°C, the effects of retention time, temperature, particle size, oxygen partial pressure, the concentration of sulfuric acid and pulp density were evaluated. The effects of cupric and ferric ions on the oxidation rate of As(III) to As(V) were also examined. The products of oxidation are As(III), As(V), SO42- and elemental sulfur. At temperatures ranging from 170 to 230°C, most of the arsenic was found to be in the trivalent state, and oxidation to As(V) with oxygen was very slow. This was confirmed by attempting to oxidize a synthetic arsenious solution. However, the rate of oxidation of As(III) to As(V) is rapid in the presence of ferric ion. Elemental sulfur was found at all temperatures investigated, which can be further oxidized to sulfate at high temperature.

Jan 1, 1999

By R. G. Reddy

To better understand the behavior of bacterial-mineral interfacial reactions, a thermodynamic model based on the- studies of bacteria adhesion on mineral surfaces has been evaluated. The bacteria adhesion to the mineral surface would be increased by l ' d1;1creasing the change in Gibbs free energy of adhesion and it would be reduced if the change in Gibbs free energy of adhesion of the system is increased. From the combination -of Young's equation and equation of state, the change in Gibbs free energy of adhesion -for bacterium-mineral system- was calculated. Influence of liquid surface tension, mineral surface tension on the change in Gibbs free energy of adhesion and consequently bacteria behavior on mineral systems- has been discussed.

Jan 1, 1991

By A. H. Castillejos E., F. A. Acosta G.

Filtration is widely used as a terminal refining step for metals, particularly for the casting of aluminum alloys, but still more knowledge is required to understand how several factors affect the efficiency of removal of inclusions. In this study, both, initial and long term filtration efficiencies of a ceramic foam filter have been obtained from the computed trajectories of solid particles suspended in molten aluminum. The complex structure of the foam filters is represented by a unit cell which is formed by a pair of pores with average dimensions. The fluid flow field was determined from the numerical solution of the Navier-Stokes equation, and periodic fully developed flow was assumed at the inlet of the calculation domain, as a boundary condition. This flow field corresponds to laminar flow as that found in ceramic filters operating under normal conditions. Computed initial filtration efficiencies showed that filtration efficiency decreases sharply with fluid velocity for particles larger than 30 µm, but smaller particles are better trapped at higher fluid velocities. Finally, it was found that long term filtration efficiency for particles of 8 µm decreased with time, in spite that perfect particle-wall attachment was assumed. Filter aging was considered in this study, and it was found that the distorted flow field, around the already trapped small inclusions prevented further collection.

Jan 1, 1999

By A. Andreas Hejja

Flow of slag and settling of matte in slag resistance electric furnaces are discussed in conjunction with furnace geometries, stirring action of the electrodes, buoyancy and electromagnetic effects. The rectangular electric furnace was regarded as a channel reactor and the mode of slag flow as a channel flow. The flow is affected both by buoyancy and electromagnetic forces, however the effect of electromagnetic forces is minimal. The flow velocity is made up of two components; (i) that developed by the action of the electrodes, and (ii) the bulk flow velocity determined by the smelting rate and the volume of the reactor. Slag samples were taken from various depths of the molten bath and were analyzed microscopically to determine the size and distribution of matte particles, The action of the electrodes was described by a simple mathematical formula indicating a balanced settling rate in the area of electrode action.

Jan 1, 1996

By Edgar Peek

Lixiviant regeneration is by definition a precondition for any hydrometallurgical process. In chloride hydrometallurgy either HCl or Cl2 has to be regenerated in order to establish an economically viable metallurgical process. One such regeneration process is widely used with steel pickling where HC1 is regenerated through the thermal decomposition of ferrous chloride in either spray roasters or fluid bed pyrohydrolyzers. This standard HC1 regeneration process deserves to be considered as a potential separation process, since thermodynamic calculations show that a fluid bed pyrohydrolyzer can function as a ferrous-nonferrous separator. Several nonferrous,metals such as zinc, lead and cadmium can be volatilized as a chloride under ferrous chloride pyrohydrolysis conditions. If such a nonferrous metal volatilization could be achieved in the case of slurry feeding of "contaminated" iron oxides, then this would increase the Fe/H2O ratio of the (process) feed and thus save on fuel per ton of iron, while yielding a marketable iron oxide product. Previous test work on synthetic materials revealed that the near-complete separation of zinc, lead and cadmium from iron oxide was possible in a pyrohydrolytic atmosphere, even if zinc was present as zinc ferrite (more than 99.5%). This investigation, which was carried out in a tube furnace at 1100 K has now been extended to treat synthetic zinc minerals and also franklinite ore. For the latter, it was found that 85% zinc volatilization could be achieved in 4 hours at 1300 K. It is postulated that complete zinc volatilization could not be attained due to the formation and/or presence of gahnite and hardystonite, which might be stable in HCl/H2O atmospheres at 1100 K. The effect of adding small amounts of calcium chloride to react with gahnite and hardystonite to give zinc chloride and both calcium aluminates and silicates is being discussed. Test work on slurry feeding of this complex ore in a recently constructed 4-inch diameter fluid bed pilot unit has been planned for the near future.

Jan 1, 1995

By E. T. White, Dean Ilievski

"Mathematical modelling of the precipitation process requires that the kinetics of crystal growth, nucleation and agglomeration be known. This paper reviews the current state of knowledge on these precipitation sub-processes (ie. growth, nucleation and agglomeration) and describes a number of experimental techniques for estimating their kinetics. The experimental methods used to generate the precipitation data and the data analysis techniques used to extract the kinetics information from the data are discussed separately. There is no universal ""best"" technique for determining the kinetics. However, studies on multi-crystal systems are more reliable for modelling purposes than are single crystal studies. The selection of a technique will depend on which sub-processes are present. A problem with all kinetics studies is that there is generally a large uncertainty in the estimated kinetic parameters. This stems from the scatter in the experimental data being further propagated by the mathematical techniques used to extract the kinetic parameters.IntroductionCrystallisation operations, including precipitation, are widely used in a number of hydrometallurgical processes to recover a desired component or to remove an undesired impurity. The goals of industrial precipitation processes are to maximise the recovery while maintaining product quality (generally product crystal size distribution, purity and morphology and product handling properties). Knowledge of the precipitation mechanisms and kinetics is invaluable for designing new precipitators or for improving existing units. The mechanistic and kinetic information is generally incorporated into mathematical precipitator models, which are then used for process design and optimisation."

Jan 1, 1996