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By S. R. Reddy

Thennodynamic properties of several quaternary systems are calculated using our recently modified Margules equations. The modified Margules equations are expressed up to infinite order in the vicinity of solvent. Quaternary system of one solvent and three,solute partials are derived. First order interaction coefficients of binary, ternary and cross -interaction parameters of quaternary system are used to'evaluate the partial functions. In the original fonn of Margules equations,derived partial functions are convergent and same 'as Unified ,Interaction Parameter Fonnalism. But considering up to infinite order of the Margules coefficients, the functions are divergent, in order to overcome this restriction, Margules equations are modified to get consistent equations. Derived partial functions are thennodynamica Hy consistent with Maxwell and Gibbs Duhem relations. The derived logarithmic activity coefficient of the solvent and solutes are consistent with the ternary systems. The calculated data, ie., activity coefficient values of nitrogen and interaction coefficients are in good agreement with the data of Fe-Cr-V -N. Fe-Ni-V -N, Fe-Cr-Ta-N and Fe-Ni-Ta-N systems.

Jan 1, 1999

By H. L. Fraser

A review of the possibilities of performing microchemical analysis in thin sections using a combination of scanning transmission electron microscopy and energy dispersive spectroscopy of x-rays is given. Particular attention is paid to the factors that limit accurate analysis at the highest spatial resolution. As an example of the use of these techniques applied to a potential problem in minerals processing, the identification of iron pyrite and pyrrhotite particles in Illinois, Herrin #6 coal is presented.

Jan 1, 1981

By I-Min Lu

An electric field was applied to a metal-bearing kaolinite specimen to investigate the efficiency of electro-osmosis in removing heavy metals from contaminated soils. The electric field induces a flow of water through the porous medium, called electro-osmosis, which is superimposed on the hydraulic flow. Because the electro-osmotic flow is relatively stronger in smaller pores, it can enhance the displacement of contaminated solution by fluid convection. Furthermore local changes in pH caused by the electrode reactions can affect adsorption equilibria and the distribution of solutes between the solution and the solid surfaces. The electro-osmosis experiments were conducted by applying either a constant current or a constant voltage across 8-cm inside diameter, 25 to 30-cm long specimens of kaolinite clay with graphite electrodes. Samples of the pore fluid and of the clay were analyzed to determine metal content, pH, and conductivity as functions of time and position. Results show that removal of heavy metals from soil can be accomplished effectively by electrokinetic treatment of sufficient duration. Approximately 95% of the lead was removed after 189 days.

Jan 1, 1996

By R. E. Sundell, S. M. Correa

"A mathematical model is developed for the fluid flow in tungsten-inert gas weld pools. The fluid is taken to be incompressible, viscous, electrically conducting, and confined within a pool of specified shape. The flow is driven by surface-tension gradient (thermocapillary), electromagnetic, and buoyancy forces generally in this order of importance. Analysis indicates that the electromagnetic field may be calculated a priori and so decoupled from the nonlinear fluid mechanics and heat-transfer problem. The resulting set of equations is solved numerically by a line relaxation process. Computational errors caused by truncation in finite-difference schemes and by inadequate grid distributions are considered. The model is used to study several cases of differing heat and current input to the pool with and without surfactant-induced thermocapillary forces. The principal conclusions are that the thermocapillary flow, when present, is dominant with surface velocities on the order of 1 m/s. The heat transfer, as deduced from isotherms within the pool, is crucially dependent on the flow. Also, flow velocities and weld-pool surface temperatures were measuredand agree well with the model.2. IntroductionThe requirements of improved control and of automation in the TIG (tungsten-inert gas) welding process have led to the development of mathematical models for the heat transfer to the workpiece. It is now widely recognized that the fluid flow in weld pools sufficiently distorts the conduction heat transfer pattern to warrant inclusion in a process model. The experiments of Woods and Milner (1), among others, demonstrated that TIG weld pools could be driven by the electromagnetic J x B body forces present, J being the current distribution and B the induced magnetic field. Atthey (2) calculated that in typical pools the buoyancy force was about an order of magnitude less important - despite the large temperature gradients present - and neglected it in a computational study of the magnetohydrodynamic (MHD) flow. This work also reviewed many earlier studies of MHD flow caused by a source of current at a fluid surface, including analytical studies by Shercliffe (3), Sozou (4), and Sozou and Pickering (5), and a numerical study by Andrews and Craine (6). These works establish the importance of the electromagnetic force in the weld-pool flow."

Jan 1, 1986

By Timothy W. Ellis

This paper presents the basic theory of operation, physical chemistry and phase equilibria which allow the development of liquid-liquid extraction circuits based on metallic solvents. The incorporation of reduction and reduction/diffusion processes into the process 'scheme is discussed and a detailed description of ,several liquid-liquid extraction schemes are developed. A synopsis of experimental results obtained using this: method to separate rare earth and other metal based materials will be given.

Jan 1, 1996

By Patrick R. Taylor

Ilmenite concentrate and methane are fed to a non-transferred arc thermal plasma reactor to produce a powder that is primarily TiC and Fe. This material has promising characteristics for powder metallurgy applications. Free energy minimization plots were used to predict the feasibility of the reaction. An estimate of the optimum molar ratio between the ilmenite concentrate and methane was made based on the mineral composition. Argon-helium mixtures were used as plasma gases. The effects of power input level, carrier gas flow rate, powder feeding rate, and methane-ilmenite molar ratio were studied and the behavior of the system characterized. Two different powder injection angles were tried. A mathematical model to describe the temperature profiles in the reactor was formulated and solved. The product has been characterized by x-ray diffraction and atomic absorption. A conversion of 97 % of Ti to TiC was achieved. It was found that minor amounts of titanium oxides, iron carbide and free carbon are also present. TEM and SEM were used to study the morphology.

Jan 1, 1996

By Joon H. Jang

At a selected pH, hydrothermal oxidation of chalcopyrite was carried out under controlled F+,, at elevated pressures and temperatures (172-200°C) by balancing the rate of oxygen injection against the rate of consumption. Chalcopyrite was converted to covellite (CuS) and digenite (CU1.8S) with rejection of iron and sulfur to the solution. Covellite forms in the first stage, followed by nucleation and growth of digenite in the second stage. The effects of rapid and slow injection of stoichiometric quantities of oxygen are compared. Both the covellite and digenite form a porous layer occupying the same volume as the original chalcopyrite grain. An electrochemical kinetic model is presented to correlate the observed results.

Jan 1, 1993

By H. Y. Sohn

The ignition and combustion of chalcopyrite particles under suspension-smelting conditions, in which the particle-particle interaction is neglected, has been analyzed by considering the intrinsic kinetics of oxidation and heat and mass transfer between the particle and its surroundings. Reasonable agreement has been obtained between the calculated results and experimental results from a laminar-flow furnace reported in the literature. This computation- al procedure has further been applied to flash-smelting conditions. Under suspension-smelting conditions (Sh = Nu = 2), chalcopyrite particles ignite at around 960 K. The effects of various parameters, such as oxygen concentration, particle size, and gas temperature, have also been evaluated. Comparison between calculated results in this work and experimental observations indicates that SO is the important gaseous product that forms at the surface of the particle.

Jan 1, 1993

By S. E. Khalafalla

A method for preparing ferrochromium alloys containing less than 2 pct carbon has been devised in a single vacuum furnace reactor. This method can conserve chromium and should reduce the capital and energy requirements relative to chromite electrothermal reduction. Reduced products containing less than 2 and as low as 0.01 wt pct carbon were obtained by reacting pellets of chromite and carbonaceous reductant mixtures at pressures of 0.1 to 1 ton and temperatures of 1,230° to 1,320° C. The extent of reduction increased with increased temperature and decreased pressure; however, operating conditions were limited due to the onset of significant chromium vaporization at higher temperatures and lower pressures. Foundry coke, anthracite, and carbon black were found to be superior to graphite as reductants. The reduction of chromite to metallics was found to proceed via the carbide intermediates Fe3C or Cr3C2. Lime accelerates the. rate of solid state reduction of chromite and can shorten the furnacin1r time at 1,3000 C under vacuum from 13 hours to less than three hours. Additional lime and silica are added to the hot reduced chromite after releasing the vacuum and raising the furnace. temperature to 1, 700° C. Soaking the charge for about 20 minutes gave a button of low carbon ferrochromium alloy beneath a well-defined slag layer.

Jan 1, 1985

By B. R. Baldock

The converting of high-grade nickel matte for production of low-sulphur matte or nickel metal is a process which has eluded metallurgists in the past because of the limitations of conventional converting furnaces. The high temperatures required and the refractory nature of nickel oxide has prevented practical success in a process which has been known to be theoretically feasible for a long time. The Ausmelt top submerged lancing system is capable of operating under close control of the smelting conditions. High temperatures and both rapid oxidation and rapid reduction can be achieved. These features have provided the basis for successful pilot plant trials of the desulphurisation of high-grade matte from the Kalgoorlie Nickel Smelter. Sulphur level in product was lowered from 20 to 25% to as low as 0.2%, with iron levels in matte in the range of 1.0 to 3.5%. The theoretical background of matte desulphurisation is surveyed and the pilot plant operations described. The implications of the results in relation to commercial plants and possible refinery operations are summarised.

Jan 1, 1993

By Michael Zinigrad

The quality of metallic materials depends on their composition and structure and these are determined by various physico-chemical and technological factors. To effectively prepare materials with required composition, structure and properties it is necessary to carry out a research in two parallel directions: Comprehensive analysis of thennodynamics, kineties and mechanisms of the processes taking place at the solid-liquid-gaseous phase interface during welding processes and development of mathematical models of the specific welding technologies. We have developed unique method of mathematical modeling of phase interaction at high temperatures. This method allows us to build models taking into account the thennodynamic characteristics of the processes, the influence of the initial composition and temperature on the equilibrium state of the reactions, the kinetics of heterogeneous processes, the influence of the temperature, composition, hydrodynamic and thennal factors on the velocity of the chemical and diffusion processes. The model can be implemented in the optimization of various technological processes in welding, surfacing, casting as well as in manufacturing of steels and non-ferrous alloys, materials refining, alloying with special additives, removing of non-metallic inclusions.

Jan 1, 2003

By J. V. Atwood

The U.S. Bureau of Mines has developed a novel Double Membrane Electrolytic Cell (DMEC) that exhibits unique features for recycling contaminated metals and metal alloys. The DMEC incorporates two anionic ion exchange membranes, separating anodic and cathodic regions of the cell. The ion exchange membranes prevent significant transport of unwanted cationic impurities to the catholyte from the impure anolyte while the anion/cation balance in cell compartments is maintained through the free movement of anions between compartments. The membrane barrier makes it possible to electro refine highly contaminated materials or to electrowin from solution while utilizing alternate anode reactions. Sinceanolyte and catholyte cross contamination has been eliminated, premium cathode products are produced. The DMEC has been tested at bench, pilot, and commercial scales. Configuration of the DMEC, cell operation, scale, up efforts, and significant design factors are discussed. Two separate recycling investigations utilizing DMEC technology are presented. The first investigation examines recovery of high purity cobalt and nickel from severely contaminated super aIloy scrap. The second involves? upgrading contaminated cobalt in the U.S. Government's National Defense Stockpile. Capital and operating costs for both potential applications are presented.

Jan 1, 1995

By C. P. Manning

This paper reports recent progress in the development of a unique metal extraction technology utilizing zirconia-based inert anodes for the electrolytic reduction of metals from their oxides. In this process, the target metal oxide is dissolved in an ionically conducting liquid solvent phase. An extended anode consisting of an oxygen-ion-conducting stabilized zirconia membrane in intimate contact with a catalytically active electronic phase and an inert electronically conducting cathode are inserted into the molten flux containing the oxide. When the appropriate electric potential is applied between the electrodes the target metal is reduced at the cathode and oxygen ions are selectively transported across the stabilized zirconia membrane and oxidized at the anode. When the process is conducted at temperatures between 1200-1400°C, the ohmic resistance drop across the stabilized zirconia membrane is low, and high current densities on the order of I A/cm2 or greater can be obtained. In addition, the process efficiency can be increased further by directly reforming hydrocarbon fuel over the anode. Laboratory experiments at Boston University have demonstrated the technical viability of employing zirconia-based inert anodes for environmentally sound production of metals such as magnesium, tantalum, aluminum, etc., directly from their oxides. Significant progress has been made in the application of this concept to the electrolytic reduction of magnesium at 1300°C. The research topics covered include stability of the zirconia membrane in the selected molten solvent (flux), volatility of the flux, electrochemical characterization of the electrolytic cell, and analysis of the metals produced.

Jan 1, 2003

By O. Durand

The Cerro Verde Hydrometallurgical Plant, located at Arequipa in the southern part of Peru, started its operation in 1977 with a design capacity of 33,000 MT/year of copper cathodes. The plant has treated 61,055,000 MT of ore mainly oxides with a content of 1.01% total copper and 0.67% of soluble copper. The leaching plant has three pads that produce 4.0 gpl copper solution. The solvent extraction plant has four trains with three extraction stages, two stripping stages with a single mixer in all stages. The mixer-settlers are 316 stainless steel and the pumps are vertical turbines. The flowrates of 1,300 gal/mil of aqueous and 1,300 gal/min of organic at a 1/1 ratio. The electrowinning plant contains 208 commercial cells and 18 starting sheet cells. Each cell has 47 anodes and 46 cathodes. In addition to describing the hydrometallurgical plant, this paper also mentions efforts directed at reducing costs and improving operations. The initial results from leaching secondary sulfides, which started October 1985, are also discussed.

Jan 1, 1987

By Rodney L. Williamson

Optimal estimation theory has been applied to the problem of estimating process variables during vacuum arc remelting (V AR), a process widely used in the specialty metals industry to cast large ingots of segregation sensitive and/or reactive metal alloys. Four state variables were used to develop a simple state-space model of the V AR process: electrode gap (G), electrode mass (M), electrode position (X) and electrode melting rate (R). The optimal estimator consists of a Kalman filter that incorporates the model and uses electrode feed rate and measurement based estimates of G, M and X to produce optimal estimates of all four state variables. Simulations show that the filter provides estimates that have error variances between one and three orders-of-magnitude less than estimates based solely on measurements. Examples are presented that verify this for electrode gap, an extremely important control parameter for the process.

Jan 1, 2001

By A. V. Reddy, C. Beckermann

"The DC continuous casting of a grain refined AI-4.5%Cu round ingot with realistic boundary conditions is numerically simulated. Of particular interest are the effects of the transport of free solid in the form of equiaxed grains on the macro segregation patterns and the final grain size distribution. The study uses a previously developed two-phase model that incorporates descriptions of heat transfer, solute redistribution, melt convection, and solid transport on the system scale with microscopic models of solutal undercooling, microsegregation and grain impingement. The numerical results indicate that grain transport inhibits the formation of inverse segregation in the ingot shell and promotes negative centerline segregation. This is explained by the reduction in the solid coherency next to the mold and the advection of solute-lean grains towards the centerline. Comparisons with the experiments of Finn et al. [5] illustrate the need for considerable improvements in the model. IntroductionMacrosegregation continues to be one of the concerns in DC continuous casting of aluminum ingots. The variation in composition over the ingot cross section results in the need to adjust alloy composition in order to meet mechanical property specifications in finished products. The extent of macrosegregation is greatly affected by the casting conditions, such as casting speed, superheat, cooling rate, mold size, alloy composition, and grain refining practices. Thus, it is of great interest to develop a comprehensive mathematical model to simulate the casting process, enabling the selection of conditions that minimize macrosegregation while maintaining a high productivity."

Jan 1, 1994

By J. B. W. Bailey

The Noranda Horne smelter in Quebec, Canada has change considerably during the last two decades to accommodate varying custom concentrate receipts, closure of the Horne mine, better working conditions, environmental programmes, new technology and increased energy and labour costs. This paper highlights the reasons for changing the smelter from two calcine charged and one wet charge reverberatory furnaces fired by coal to a smelter using. tonnage oxygen oil, natural gas and coal in a single wet charged reverberatory furnace and a Noranda Process continuous Reactor. The current operation 1 described, including three major topics; the use of oxygen/fuel burners on the charge banks of the reverberatory furnace which has increase the smelting rate from 680 to 1100 tonnes of concentrate per day; the oxygen enrichment of the Noranda Process converting air to achieve smelting rates of over 1800 tonnes of concentrate per day; the converting of the mixture of 73 percent copper matte produced from the Noranda Process and the 33 percent copper matte produced from the reverberatory furnace.

Jan 1, 1983

By Mark Tsirlin

Kinetics of the initial oxidation stages of diffusive silicide coatings on 8 molybdenum and niobium at 1100 - 1700 and under the pressure of 400 and 1330 Pa has been studied using methods of gravimetry and gas phase analysis of oxygen, as well as by SEK, XRD and EDMA methods. The first oxidation stage described by asymptotic equation in case of NbSi coating changed over to the stage described by parabolic equation. The asymptotic law was shown to depend on non - stationary conditions on the oxide layer boundaries. Interconnection between silicides and quartz structures, on the one hand, and peculiarities of oxidation kinetics, on the other, is [discussed. The possibility of estimation oxygen atom jump frequency in quartz and fractions of oxygen reacting with metal and with silicon proceeding from the analysis of the kinetic data was ascertained. Conditions of oxidation kine- tics transfer from asymptotic (or parabolic) stage to a non - protective "linear" stage, associated with volatile ~roduct formation, are also discussed.

Jan 1, 1995

By Barry Welch, Kai Grjotheim

"The capital intensive nature of the present process for aluminium smelting, the low productivity per unit reactor, and pressure to reduce the electdcal energy demand have motivated the search for an alternative process. Optional routes include carbo-thennal reduction of alumina (using an alloy phase immediate), chlorination followed by electrolysis of aluminium chloride, and electrolytic decomposition of alumina using inert electrodes. Materials performance and reactor design constraints have been a major limitation for alternatives. However parallel research has led to considerable advances in the process efficiencies and scale of both the Bayer process and the Hall-Heroult cells.Future development of alternatives is dependent on breakthroughs in Materials Science such as the development of stable conducting anodes and stable wettable cathode materials. However if successful it is probable that some spin-offs will be retrofitted to existing cells. Therefore the basic Hall-Heroult technology will continue as the dominant process for at least the next half century.IntroductionThe present Bayer/Hall-Heroult process for production of aluminium is just over 100 years old. Frequently, during the century of its technological development questions have been raised as to whether it is the ideal route for metal production. The questioning was particularly intense in the period between the mid-1950s and the mid-1060s when the limitations of the Hall-Heroult electrolytic stage were evident. Then the cells were only 30 to 35 % efficient with respect to the utilisation of the hydro-electricity (requiring 16 18 kWh/kg, thus making it strongly dependent on cheap electrical energy), while the size of cells being installed were 80 to 130 kA. Hence the process was capital intensive, the productivity per reactor volume low, and the process was labour intensive (requiring about 15 man hours per tonne of aluminium). In addition, the use of pitches for Soderberg anodes and the fluoride electrolyte were creating problems through emission. At that time material science had paid little attention to the manufacture and use of carbonaceous materials or the development of alternatives that were corrosion resistant to cryolite or liquid aluminium. Hence cell lives were short - typically 600 to 1000 days - thus adding to operating costs. Thus the grass over the fence, as foreseen in 1960s vintage crystal balls appeared much greener for alternative processes."

Jan 1, 1988

By A. Kar

A mathematical model is presented for pure titaqium deposition from titanium tetrabromide on a stainless-steel (SS 304) substrate. Five three-dimensional, transient, and nonlinear partial differential equations are used to account for the diffusion of various species inside the deposition chamber and the thermal decomposition of titanium tetrabromide, titanium dibromide, and titanium monobromide at the surface of the substrate in order to determine the thickness of the titanium film deposited on the substrate. The effects of various process parameters on the deposition and shape of titanium films are examined, and under certain conditions, the deposited titanium films are found to have volcanic profiles.

Jan 1, 1992