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By A. Kar, J. Mazumder

"Laser ablation is a process that can be used to synthesize novel nanoscale particles as well as to deposit thin films of various materials. Usually, nanoscale particles and thin films are formed at relatively high and low pressures, respectively, inside the ablation chamber. This paper presents a mathematical model to predict the particle size distribution in the plasma generated during laser ablation. The model is developed by considering the effects of the laser-matter and laser-plasma interactions, the Stefan condition, and the discontinuity across the Knudsen layer. The nanoscale particles are found to be located at the central region of the plasma near the target. The particles have very high velocity and temperature. A good qualitative agreement is observed between the results of this model and experimental data. IntroductionRapid solidification produces novel microstructures whose atomic arrangements and/or chemical compositions are different from those of conventional materials. The conventional materials are either crystalline or amorphous. The crystalline materials have both short- and long-range orders, whereas the amorphous materials have only the shortrange order. The nanocrystalline materials have neither short- nor long-range orders, and for this reason, they exhibit novel properties which are important for synthesizing new materials. The atoms of a nanocrystal can be classified as ""crystal atoms"" and ""boundary atoms"", where the ""crystal atoms"" have the nearest-neighbor configurations similar to the lattice configuration, whereas the nearest-neighbor configurations of the ""boundary atoms"" differ from the lattice configurations 1. Various aspects of the nanoscale materials have been discussed in Refs. [1-7]."

Jan 1, 1994

By Jan Vrestal, Josef Tomiska, Pavel Broz

"Thermodynamic investigations on fcc solid ternary Fe-Ni-Cr alloys have been performed by means of the computer-aided Knudsen cell mass spectrometry. Ternary T.AP.-series (Thermodynamically adapted power series) are used for the algebraic representation of the thermodynamic excess properties. At 1650 K the molar excess Gibbs energy GE is negative over the whole field of stable fcc phase. The molar heat of mixing HE is exothermic in the predominant part of the fcc phase field. Only between the section with a constant ratio of mole fraction Xcr/XNi = 0.64 and the fcc phase field boundary the HE values are slightly endothermic. The results of this work can be used successfully for phase diagram calculations.IntroductionThermodynamic investigations on multicomponent alloy systems such as the Fe-Ni-Cr ternary system including the three binary boundary systems are very time-wasting and usually beset with considerable experimental difficulties. Additionally, the required experimental equipment is very expansive and the obtained results are not always satistying. Therefore it is understandable that many phase diagram calculations are based only on few experimental values of the molar excess free Gibbs energy GE. Consequently, Kundrat and Elliott [1] as well as Hillert and Qiu [2] used in their reassessments of the phase diagram of the Fe-Ni-Cr system thermodynamic data mainly assumed and/or optimized by means of various reasoning.Lee [3] reported recently, a revision of the used thermodynamic description of the Fe-Ni liquid phase is necessary to obtain a better agreement with the experimental data on the bcc/liquid or fcc/liquid tie lines and liquidus temperatures in the Fe-rich region of the Fe-Ni-Cr ternary system than in the previous assessments. This is 'in full agreement with mass spectrometric investigations of Fe-Ni alloys in the liquid and in the fcc solid phase, published earlier [4,5]. Indeed, phase diagram calculations based upon the molar excess free Gibbs energies GE obtained in these studies yield liquidus and solidus lines in excellent agreement with experimental phase diagram data [5]. Nevertheless, these experimental data have not been considered later on any more, not even in the revision by Lee [3]."

Jan 1, 1996

By A. McLean, Y. Uchida, M. Iwase, M. Myochin, K. Wiikimoto

"Phase diagrams of FeO-containing ternary systems could be derived from experimental data for the activities of FeO. The systems investigated are CaO-CaF2-FeO, SrO-SrF2-FeO; BaO-BaF2-FeO, CaO-CaCl2-FeO, SrO-SrC12-FeO, BaO-BaC12-FeO, CaO-A12O3-FeO and BaO-SiO2-FeO.IntroductionThe importance of phase diagram cannot be overemphasized. In a book, ""Alloy Phase Equilibria""[l], the author, Professor A Prince, states, ""A metallurgist has been defined as a person who thinks in terms of phase diagram"". Whether one accepts this statement or not, it is self-evident that an ability to interpret phase equilibria is essential to the professional metallurgists.The physical chemistry studies of iron and steelmaking process often require phase diagrams of FeO-containing slags. Iso-thermal section of the phase· diagrams of such systems can be derived from experimental data for chemical potentials of FeO. Due to the recent developments in the area of solid state electrochemistry, rapid determinations of the FeO activities have become possible. The present paper is aimed at documenting the derivation of the phase diagrams of FeO containing slags.Experimental AspectsAn electrochemical method incorporating stabilized zirconia can be used for the measurements of the activities of FeO in various slags and fluxes[2]. For the details of the experimental technique, reference should be made to reference 2"

Jan 1, 2000

By SM Rao

Nuclear Fuel Complex (NFC ) , Hyderabad (IN DIA ) , is engaged in the manufacture of nuclear fuel assemblies and zircaloy structural components required for the Indian nuclear power reactors. The production of zirconium oxide, sponge and zircaloy materials through chemical and hydro - metallurgical processes generates many effluents containing valuable zirconium and hafnium . This paper deals with the various processes such as multiple crystalization, phosphate precipitation, ion-exchanges amine solvent extraction etc, for the treatment of these effluents and subsequent recovery of valuable zirconium and hafnium .

Jan 1, 1992

By Fujio Ishii

The deoxidation of liquid nickel and nickel binary alloys with silicon has been determined at temperatures between 1500°C and 1650°C using quartz crucibles in order to investigate the deoxidation of nickel based alloys. The equilibrium constant of the deoxidation reaction in liquid nickel and the effects of the different alloying elements such as chromium, molybdenum, tungsten, iron, cobalt and coppcr on the activity coefficient of oxygen in liquid nickel have been established.

Jan 1, 1993

By M. Girgis

The behavior of arsenic III during electrolytic refining of copper in acidic copper ?sulphate electrolytes was studied by different electrochemical methods such as, linear potential sweep, cyclic voltammetry, chronoamperometry and chronopotentiometry. The study showed that arsenic behaves as a depolarizing ion and has a deleterious effect on copper deposit. Three substrates; Pb, Cu and Ag were used during the refining process and the electrode kinetics were found similar for both Cu and Pb electrodes while a little difference was found for the Ag electrode. A microscopic study by scanning electron microscope was undertaken to show the influence of arsenic on deposit's morphology. Surface analyses of the deposit were carried out by some electronspectroscopic techniques such as Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The results showed that arsenic coexists with copper deposit at potential?~ -0.25 V.

Jan 1, 1987

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly. subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fumeless fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003

By Wenzhou Yu, Cong Zhang, Wenhui Ma, Gang Wang, Kuixian Wei

"A novel technique was successfully developed for nickel further purification by vacuum directional solidification. The removal effect of impurities in nickel was studied based on theoretical analysis and experiments. High removal efficiency of impurities in nickel can be realized according to theoretical analysis. The experimental results show that the vacuum directional solidification treatment could increase the nickel purity from 99.96% to 99.996%. Since vacuum directional solidification could effectively remove the impurities from nickel with low contamination and low cost, it is a potential route to obtain high-purity nickel for commercial application.IntroductionNickel is widely used in metallurgy, machinery, petroleum industry, chemical industry, construction industry, light industry, and other industries for its ductility, medium hardness, ferromagnetism and high chemical activity. Nickel-based alloy is an important material for the key parts of aircraft, tanks, submarines, radars, nuclear reactors and aerospace fields [1-5]. Generally, nickel contains Si, P, S, Fe, Cu, Zn, As, Cd, Sn, Sb, Pb, Bi, Al, Mn, Mg and other impurity elements, which may hinder the commercial application of nickel. Therefore, it is necessary to refine the crude nickel for the high purity nickel."

Jan 1, 2014

By T. R. A. Davey

The technologies of lead, zinc and tin extraction have made varying degrees of progress over the past twenty years. Producers of all metals have faced increasing demands for reduction of pollution and environmental degradation, and the level of public concern is rising rather than abating. New processing techniques must therefore be not only economically feasible, but politically acceptable, even when the demands of "conservationists" and ?environmentalists? are unreasonable. A new generation of processing techniques has come into being, which do not rely on an expensive sintering stage, nor use metallurgical coke, which is difficult to make without serious pollution. They utilise intense reactors, conveying materials from one stage to the next preferably within an enclosed space, obviating fume emissions, and avoiding heat losses as far as possible. The acceptability of the new techniques? is increased if lowgrade or complex materials can be treated, along with a variety of returns and wastes. In addition, a good selling and servicing organisation seems to be as important as good process technology in determining the spread of the new processes. In the field of pyrometallurgical refining the need is for more general application of several recently developed techniques rather than a search for alternatives to the existing process technologies. However, there is a need for fundamental work investigating the phenomenon of oxygen anode overvoltage in the electrolytic zinc process, in order to make progress in the further reduction of energy consumption. There is also scope for further development and application of vacuum distillation to up-grade thermally produced zinc. This paper presents a personal view of processes which should be developed to overcome existing problems, as we approach the turn of the century,

Jan 1, 1990

By Teixeira

An experimental investigation on the kinetics of oxidation of As(III) with H202 in synthetic effluent solutions followed by precipitation of Fe/As (V) compounds was carried out. The variables investigated were: As concentration (200 -3000 mg/l) , oxidation pH (2.0 -11.0), oxidation temperature (25 -800C) , H202 stoichiometric excess (50% -100%), precipitation pH (5.0 -7.0), precipitation agent (Fe2+ -Fe3+). Fixed conditions were, Fe/As molar ratio (6:1) and stirring speed (560 rpm). The results were empirically modelled. The precipitates obtained were amorphous. The precipitates were checked upon their environmental stability according to the United States Environmental Protection Agency (U.S.E.P.A.) Toxicity Test, and were considered to be adequate for deposition in impermeable waste dumps. The combined Fe/H202 detoxification process, in selected conditions, was able to reduce the As contents of effluents containing 1600 mg/l As to 0.1 mg/l, in about 2 1/2 hours of total processing time.

Jan 1, 1990

By Graham J. C. Carpenter, Marc Charest, Jason Lo

"The method of producing magnesium-based composites with silicon carbide (SiC) particulates embedded in the matrix of magnesium AZ9I D alloy by the squeeze-casting technique are described. This method involves the fabrication of a SiC particulate preform and the subsequent squeezing of molten magnesium into the preform. In this study, alumina, aluminum phosphate and a proprietary binder were used for the fabrication of SiC particulate preforms. The procedures employed in the fabrication of SiC! AZ9ID composites are presented, together with the results of characterization of the composites using optical and transmission electron microscopy. Special attention is given to the reaction products in the bulk alloy and at the interfaces between SiC particles and the AZ9ID matrix alloy.1. IntroductionInterfacial, microstructural and metallurgical characteristics play an important role in determining the mechanical properties of a composite. In theory, reinforcing magnesium with SiC particulates should provide an improvement in strength and modulus of the composite over the unreinforced counterpart. However, many factors resulting from the fabrication process can cause degradation rather than improvements to the mechanical properties. In particular, the interfacial characteristics are known to critically influence the properties of composites [1]. Before evaluating the mechanical properties of a composite, it is always useful to examine the microstructure, which is closely related to the mechanical behavior. This helps to reduce the labor-intensive steps of sample preparation for mechanical property evaluation, which can be particularly difficult as a result of the high hardness of composite materials, as well as providing a wealth of information on the microstructural and interfacial characteristics, particularly the reaction products caused by processing. This information is also pertinent in understanding the factors governing the mechanical properties of the composites.There are many factors which determine the nature of the interfacial characteristics of a SiClMg composites. Qualitative estimations of the interfacial bonding have been performed based on thermodynamics, electronic and electrostatic concepts. In addition, the kinetic conditions during the fabrication play an important role. From an interfacial energy standpoint, the driving force for the formation of a metal/ceramic interface is the decrease in free energy that occurs when intimate contact is established between metal and ceramic surfaces. The simple representation of the energy change per unit area of interface formed (~G) is given by Dupre equation [2]:"

Jan 1, 1996

By Richard S. Kunter

Artech Recovery Systems, Inc has developed a low pressure and temperature? leach process called the "Cashman Process" to extract metals from arsenical flue dusts and residues and fix the arsenic in an environmentally stable form as ferric arsenate (scorodite). The process was pilot tested at Hazen Research in an integrated plant including continuous recycle from August 1989 to October 1989 during which several tons of flue dust were processed. Based on this pilot program, the process was deemed technically feasible and produced commercially salable products. Residues from this pilot program were subjected to a long-term stability test jointly designed by PTI environmental services and the USEPA. The process, its versatility, and the nature of the products is discussed in some detail.

Jan 1, 1992

By Yoichi Takeda

The CaO-FeO,-Cu20 slag has been practically applied to continuous converting of copper, and also has potential for refining of copper. Liquidus lines of the slag system and phase stability diagram for the liquid slag and the existing solid compounds under copper saturation are presented. Liquidus composition was determined by chemical analysis of slag sample saturated primary solid. The temperatures of invariant equilibria were investigated by thermal analyses. Oxygen potentials on the liquidus lines, the univariant and invariant equilibria were estimated from the relation slag composition and oxygen potential that relation was confirmed in separate experiments.

Jan 1, 2003

By Yoichi Takeda

The CaO-FeOx-Cu20 slag has been practically applied to continuous converting of copper, and also has potential for refining of copper. Liquidus lines of the slag system and phase stability diagram for the liquid slag and the existing solid compounds under copper saturation are presented. Liquidus composition was determined by chemical analysis of slag sample saturated primary solid. The temperatures of invariant equilibria were investigated by thermal analyses. Oxygen potentials on the liquidus lines, the univariant and invariant equilibria were estimated from the relation slag composition and oxygen potential that relation was confirmed in separate experiments.

Jan 1, 2003

By Christoph Zschiesche

Managing complex material streams within a lead smelting/reduction process has a long history at Aurubis. After modernization of the secondary lead smelter in 1991, Aurubis operates an electric furnace and a Peirce Smith converter to process complex secondary materials. This process links the copper and the lead metallurgy allowing Aurubis to properly combine primary and secondary process lines to optimize the processing of complex raw materials and smelter intermediates. However, combination of copper and lead metallurgy processing requires a continuous evaluation as raw material quality and composition varies. This paper describes Aurubis lead smelter processing and provides some fundamental considerations to optimize the lead processing, in particular with aspects related to speiss formation

By H. C. Roland Kammel

Stannous sulfate electrolytes are widely used nowadays in electrolytic tin production. Characteristic features of this electrolysis process are that dense cathode deposits can only be obtained by additions of organic additives and that so called ?black mud is formed on the anode surface which leads to an increase in cell-voltage. In order to prevent excessive cell-voltages or oxygen evolution the black mud has to be removed periodically. Studies in laboratory scale have been performed about the effect of different organic additives on electrolytic tin deposition and the formation of surface layers on pure and industrial tin anodes. Results reveal that organic addition agents are effective in reducing cathode roughening as well as extending the covering time of the anode ?by black muds.

Jan 1, 1985

Halide media are considered as suitable alternatives to cyanide for extracting gold and have received much attention lately. The extraction of gold by iodide-iodine mixture has been patented and briefly studied without much attention given to the fundamental aspects of this process. This paper reports recent studies on the kinetics of gold extraction in iodide media, using hypochlorite, iodine and hydrogen peroxide oxidants. The kinetics of dissolution was found to be dependent on the solution pH, reagent concentration and most importantly the iodide- oxidant molar ratio. Without proper control, the gold surface can be passivated due to the formation of solid products. Thermodynamic modelling was carried out to determine the equilibria governing the dissolution process. The formation of AuI solid was also identified as a possible product during the dissolution.

Jan 1, 1992

By Binxu Zeng, Mark Jolly, Xiaojun Dai

"The traditional investment casting foundries use batch melting and chunky running systems to produce casting components. This method leaves the energy saving issue as subsidiary one. In our research project, one of the partners, the AEROMET international PLC provides the thin wall aluminium component ""filter housing"" for test. The AERO MET uses traditional casting route to produce the filter housing, which only gives 5% --10% yield. In this paper, numerical simulation method is used to analyse filling and solidification of the casting running system. The CRIMSON running system of the filter housing is designed by using casting simulation software, MAGMAS and Flow3D. By working with AEROMET, various configurations of the casting running systems were tested and analysed. Using them ultiple life cycle approach, the energy content of new process is compared with traditional one. It indicates that the CRIMSON process only uses 36% of energy consumed by the traditional route.IntroductionThe investrnent casting is a metal for ming process using expendable patterns, which is a standard casting technique and is widely used to produce quality parts. Its accuracy, versatility and integrity tie itself to important and precious engineering components in Aerospace industry. However, traditional investrnent casting process usually uses chunky runner system and gravity filling method. It not only reduces the casting yield of the product but also causes the pouring defect during the casting. As author's previous research showed that gravity filling method pouring basin and down sprue are two main resources of entraimnent defects generation. No matter how good the running system is, entraimnent defects such as double oxide films (DOF) and bubbles will I get into the casting to cause problem."

Jan 1, 2013

By Michael L. Sorokin

The behaviour of cobalt during processing of nickel raw material is analysed within the Ni-Co-Fe-S-O-SiO2 system using the computer model. For this purpose the thermodynamic parameters for "three-suffix" Margules's equations in Co-Fe-S and Co-Fe¬Ni-O-S1O2 systems were computed! Phase and iso-activity diagrams for Co-Fe-S system, and phase diagrams for the systems Co-O, Co-Fe-O, Co-Ni-O, C-oO=SiO2 and Co-Fe-O¬SiO2 are calculated using the developed computer programs and identified parameters. The diagrams are used to analyze cobalt behaviour at smelting and converting.

Jan 1, 1995

By B. G. Thomas

"Mathematical process models can be applied in several different ways to serve industry by inducing beneficial changes to process operation. This paper attempts to summarize the different uses, types, and attributes of these models, and to offer some ideas to consider when developing, using, and reporting on them. Process models range from empirical to mechanistic in nature and vary in complexity from simple analytical solutions to coupled, 3-D transient numerical simulations. They are classified here according to the way in which they are implemented in practice, viz. fully-online models, semi-online models, off-line models, and literature models. The purpose of the model should dictate how choices are made during its development. Ways to validate and compare the model with experiments are suggested. Examples are taken in the context of the author's experience in modeling the continuous casting of steel.IntroductionThe objective of this paper is to provide a partial introduction for this symposium by discussing some basic aspects of the application of mathematical process models in industry. Essentially, the aim is to explore how process models are used to benefit industry, and to offer some general comments and suggestions, based on the experience of the author, on how models can best meet this goal.This work is concerned with process models, which consist of systems of mathematical equations and constants that are solved on a computer to make quantitative predictions about some aspect(s) of the process. The specific variables required as input data and generated as output data are important features of the model. The equations often derive from a numerical solution to one or more differential equations and their boundary conditions. The model also includes the constants, which represent material properties, empirical relationships, and other knowledge about the process, and usually require considerable effort to obtain. Thus, general purpose commercial software packages, (ie. finite-element or finite-difference based codes), are not models in this context. They are useful tools, however, serving as frameworks for the development of process models."

Jan 1, 1994