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By Y. Iguchi, T. Narushima, T. Shiozawa, M. Maruyama, R. Arashi

"In situ observation system for thermal oxidation using Raman spectroscopy' was constructed, and oxide films formed on liquid pure Al and Al-Mg alloys (Mg contents = 1 and 4 mass%) were analyzed at room temperature to 1273 K in dry oxygen. In situ Raman spectra of the surface of a liquid Al-:-4mass%Mg indicated the formation of MgO • AlP3 (spinel) as oxidation products, while a -AlP3 and MgO • Alz03 (spinel) were observed on a liquid Al-1mass%Mg alloy. It was suggested that the formation of MgO film affected oxidation behavior of these alloys.IntroductionLiquid aluminum alloys are cast to ingots mainly by the continuous casting process. It is well-.known that surface cracks could be caused by oxide films formed on the surface of melt during continuous casting and defects due to the film. With regard to oxidation behavior of liquid aluminum alloys, many investigations l -s have been carried out from the view point of formation of ceramic metal composites(CMC) which are expected as cutting tools and structural materials 1.2. It is very important for reasonable continuous casting and CMC formation processes to elucidate oxidation behavior of melts.Oxidation behavior of materials generally depends on compositions and properties of oxide films formed on the surface. If in situ observations of oxide films are available during oxidation, evaluation of oxide films and interpretation of oxidation mechanism could be expected. Laser Raman spectroscopy is one of the most appropriate techniques for in situ observation of oxide films under various atmosphere at high temperatures. The authors have discussed the effects of atmospheres and sample compositions on oxide film formation mechanism on Fe-Si alloy6 and SiC-B4C composite7 on basis of an in situ observation by Raman spectroscopy. In spite of many previous studies, systematic and clear explanations have never been gotten on oxidation behavior of liquid aluminum alloys. And no in situ observation has been made except for transmission electron microscopy(TEM) and X-ray diffraction(XRD)."

Jan 1, 1996

By A. K. Kyllo

A study has been carried out on the dusts from Hudson Bay Mining and Smelting's Flin Flon copper smelter. The aim of the work was to determine the mechanisms of dust formation and the deportment of the various constituents. The work concentrated on the copper converters, but the electrostatic precipitators and baghouse also clean the reverberatory furnace off gas, so some mixing will have occurred. The dust composition was found to vary with distance from the furnace, and to be made up of three major components: solidified droplets, unreacted flux, and condensed particles. The solidified droplets were formed from material ejected from the converter during blowing, while the flux was blown out of the converters immediately after charging. The condensed particles contained the majority of the lead and zinc, as well as the volatile impurities. There was also a significant soluble content of the dusts, increasing with distance from the furnace. The condensed material may be separated from the remainder by a simple washing and sizing technique.

Jan 1, 1996

By Rashmi Kumar, Amit Chatterjee, Sanjay Chandra

The practice of adding alloying materials to a molten bath is an integral feature of many pyrometallurgical operations. However, very little is known about the dissolution rate and solution mechanisms of solid additives in liquid melts. In foundries where large tonnages of liquid metals are handled, there is considerable interest in achieving optimum metal quality at minimum cost. This objective is influenced by several factors and the solution is often plant specific. Though the amount, sequence and mode of ferroalloy addition vary from plant to plant, various fundamental factors determine how quickly these additions dissolve in the bath. At the Ingot Mould Foundry (IMF) in TATA STEEL blast furnace hot metal is used to cast ingot moulds. The composition of hot metal desired for making ingot moulds demands addition of 20 kg each of Ferromanganese and Ferrosilicon in the 12 T transfer ladles into which the blast furnace metal is poured at the IMF. Owing to low temperature of hot metal at the IMF, casting commences immediately and complete dissolution of the ferroalloys is often not possible. To study this aspect in detail and to evolve suitable corrective measures, a mathematical model for the melting of a solid particle in a liquid metal bath was developed at TATA STEEL. The model was validated using the data available in literature. In keeping with published work, two separate dissolution periods were identified - a "shell period" and a "free dissolution period". The maximum thickness of the crust formed around a spherical particle shortly after immersion, can be obtained by using the mathematical model which has been developed. The model can also be used to investigate the effect of various parameters such as superheat of the bath, size of the particle, etc., on the maximum crust thickness and the particle melting time. On the basis of this study, the addition of ferromanganese and ferrosilicon was optimized at the IMF in Tata Steel.

Jan 1, 1996

By B. I. Hop

The f10wfield set up by the standard Hydro gas purging unit has been predicted by a numerical model. In addition turbulent trajectories of gas bubbles released from the rotor are predicted. Here the deposition rate of inclusions on the bubble surface is allowed to depend on local conditions. Bubbles passing regions with strong pressure gradients, such as close to the rotor, will experience large slip velocities and large deposition rates. This model can deal with any distribution of bubble sizes and inclusions. The results found from the multidimensional flow predictions are discussed in relation to what can be obtained from a much simpler metallurgical engineering approach. The differences between these two approaches to predict the same process will be discussed. The model predictions are compared to experimental results for removal of SiC-particles from aluminium.

Jan 1, 1996

By Patrick R. Taylor

This investigation studied the inflight calcination kinetics of nuclear waste simulant using a thermal plasma reactor. A series of experiments were performed to determine the conversion of insoluble aluminum compounds to the soluble compounds and the decomposition of complex organic and nitrite compounds present in the simulant waste. Thermodynamic calculations based on free energy minimization were performed to establish a theoretical basis for this investigation. A kinetic model to describe the conversion of gibsite to sodium aluminate has been proposed. The products of the calcination were characterized using XRD, Gas Chromatography, and chemical analysis by ICP. The results of this investigation indicated 85% gibsite conversion to sodium aluminate, 90% of nitrate decomposition, 52% TOC decomposition and 90% conversion of chromium to soluble compounds. A process is identified for inflight calcination of wastes. Key words: Plasma, waste, simulant, calcination

Jan 1, 1996

By C. Ramasamy

The tariff reductions on imports, as a part of on-going liberalisation process in India, has fueled competition within and outside India and has, in turn provided an opportunity to reach global markets. This change calls for quality upgrades and cost-competitiveness without impairing the environment. In this context, gas based processes, contributing to improvement in quality and environment as well as processes where controls are applied when gases inimical to environment are involved, are discussed in a remelt/cast-house scenario. The impact of such processes on fabrication cost of sheet ingot is seen alongwith consumption and cost of materials and compared with a world class standard plant in North America.

Jan 1, 1996

By N. A. Warner

Fundamental studies on the reaction of limestone or dolomite at high temperature with S02 are extended to the realm of large scale primary copper smelting. Whereas flue gas desulfurisation in the electric power utility industry is concerned with S02 concentrations normally less than 0.5 percent, high temperature smelting gases can have S02 levels approaching 100 percent. The reaction involved is very exothermic so proposals are made in this paper for returning the heat generated in sulfur fixation directly back to the copper smelting process. This integration leads to metal production with lower energy requirements than current technology. The anhydrite reaction product can either be disposed of locally with minimum adverse environmental impact or upgraded to a value-added product. It is assumed, of course, that no viable market exists to support sulfuric acid production.

Jan 1, 1996

By Jan Yaozhong

The composition and the possible utilization of Ti bearing blast furnace from a titanomagnetite blast furnace smelter were studied. The slag contained about 20% Ti02 and trace Sc. The mineralogical analysis indicated that Ti in the slag is mainly as perovskite. By means of magnetite separation, the Ti containing phase could not be enriched. An effective hydrometallurgical approach was proposed with sulphuric acid leaching. The method proposed for processing the studied slag renders product Ti02 and SC203. Besides the recovery ofTiO2 and SC2O3' the leaching process yields fine grained residues which can used as additives for making cement.

Jan 1, 1996

By Richard S. Dennis

Acid recovery employs ion exchange (I-X) resin as separation media for inorganic acids from dissolved metallic salts by physical adsorption and without the use of chemicals. This technology has been used for years on spent etching and plating liquors to recover acid for reuse in the bath and to reduce waste acid neutralization costs. It is also used for electrolyte treatment to facilitate valuable metal recovery via acidity reduction. TETRA's ccrxr'" I-X contactor has been used successfully for acid separation from its metallic salt counterpart in a simple, continuous operating mode using strong base anion resins. Efficient separation is enhanced by acid reconcentration to nearly its original strength or as high as 14-20%. Continuous treatment also recovers heat to the tankhouse or bath and improves metal quality due to consistent acid quality. Conventional fixed bed ion exchange (I-X) systems are impractical for acid recovery because of complex control design and large resin inventories needed to process very low liquid-to-resin treatment ratios associated with strong acid concentrations.

Jan 1, 1996

By Roma T. Dec

Many industrial wastes may require preliminary processing to change their particle size, density, surface properties or flowability to become more suitable for treatment and recycle. This can be achieved by pressure agglomeration using roll presses. In the following paper an overview of various roll press processing methods like briquetting, compacting, compacting-granulating or densification is presented together with basics of process and equipment design. The emphasis is focused on major factors influencing compaction process and responsible for pressure build up and final product quality. Finally, two examples of roll press application for briquetting of steel plant wastes and compaction of alumina base catalyst tailings are introduced.

Jan 1, 1996

By T. K. Mukherjee, C. K. Gupta

"The importance of the processing of secondary resources such as solid industrial wastes and liquid effluents as well as byroducts for the recovery of the associated metal values hardly needs any elaboration. Such processing contributes in no small measure towards the augmentation of the availability and the supply position of resources. As an added benefit, it leads to a reduction in environmental pollution caused by the undesirable waste materials. As some typical examples of secondary resources in the Indian scenario, mention can be made of spent catalysts, metal/alloy scrap, ash, consumed batteries, flue dust, slag, sludge and slime, pickling solutions, spent acids, plating rinse solutions, spent etchants, waste water from synthetic fibre manufacture and from tanneries etc .. These wastes constitute a source of a variety of non ferrous metals. In the processing of secondary resources like these, the techniques of hydrometallurgy such as solvent extraction playa pivotal role.This paper outlines the efforts made to use solvent extraction to recover (1) base metals such as copper, zinc, nickel and cobalt from a number of secondary resources like cake, and sludge (2) refractory metals like molybdenum and vanadium from sulphidic byproducts and spent catalyst and (3) nuclear metal like uranium from phosphoric acid. In the case of base metals, process flowsheet involving the use of acidic extractants such as DEHPA and PC88A have been optimised. The problem of iron removal from the leach liquor, which influences the metal recovery process significantly, has drawn a special emphasis. In the case of refractory metals, basic extractants like Alarnine 336 has been pressed into service to produce kilogramme quantities of pure salts of molybdenum and vanadium. Finally, the paper gives a brief account of plant experience in recovering uranium from phosphoric acid, using a solvent system comosed of DEHPA and TOPO."

Jan 1, 1996

By Ray Y. Lin, Randall A. Blue

"Joining of silicon carbide with infrared using a mixture of Si-30wt.%C as the brazing material has been investigated. Joining was performed at a temperature of 1500 °C in a flowing argon atmosphere for processing times ranging from 5 to 60 seconds. The joining filler materials include thin film silicon obtained by thinning down silicon wafers to about 70 /!m and graphite powder of a 15 /!m average particle size. Joint strengths were determined with a specially designed shear-in-compression jig for testing shear strengths of brittle materials. Cross section examinations of the joined specimens with optical microscopy, scanning electron microscopy and transmission electron microscopy have shown that all joints are essentially void free with excellent wetting between the base SiC and the brazing material. Silicon carbide in the B form has been identified as the reaction product in the joining zone with a transmission electron microscope (TEM) and selected area diffiaction (SAD) analysis. At 1500 °C with a joining time of 60 seconds, the joint has consisted of primarily SiC. With such a high SiC content in the joint, the joint strength is comparable to those by other joining techniques, such as diffusion bonding, as reported in the literature. A kinetic model for the formation of SiC from liquid silicon and carbon is proposed to explain the observed joint microstructural evolution.IntroductionSilicon carbide is of great interest for high temperature structural applications because of its excellent high temperature strength, wear resistance and anticorrosive characteristics [1]. Even though the interest in SiC is high, the use of the material has been limited by the high cost and difficulties involved in forming components of complicated shapes [2]. It is these limitations that necessitate the development of effective joining techniques that are cost effective and able to provide strong joints."

Jan 1, 1996

By Brian Balmforth

Solvent extraction has been applied successfully to the recovery of a range of metals from a variety of process streams. Particular benefits are derived from the use of new highly selective extractants. These will be exemplified by case studies including the recovery of zinc from sulfate and chloride media using ZENECA's new extractants which show a very high selectivity over iron and the recovery of antimony and bismuth from copper refinery electrolytes using ZENECA's strong and selective extractant DS5834. The conclusions are drawn that solvent extraction is a cost effective technology for metal recovery and recycling, even when used to treat relatively small volume/low concentration process streams, and that it can provide the essential enabling components of a larger system for waste minimisation programmes.

Jan 1, 1996

By Keith M. Axler

This report addresses issues specific to the generation of hydrogen fluoride via reaction of calcium fluoride with sulfuric acid. This process has been established on a commercial scale and is under consideration for treatment of calcium fluoride residues from uranium processing. Magnesium fluoride slags are also available as a product of uranium processing. The technique of using sulfuric acid for the production of hydrogen fluoride from magnesium fluoride is also under consideration as a residue processing scheme. In the current study, thermodynamic modeling was used to investigate these chemical processing systems. The results presented herein reveal information relevant to the selection of processing temperatures and conditions. Details include predicted effects in system composition based on operating temperatures for both the calcium fluoride and the magnesium fluoride systems.

Jan 1, 1996

By Guo Xian Jian

In this paper, the gas composition calculations on the FeS-H20 system at elevated temperature were performed. The results show that the gas constituents are H20, S02, H2S, Sj, H2, and O2 and the order of the compositions partial pressure is PH2o> PH2 >PSO2 >PSj >PH2S >PO2 when FeS is oxidized into Fe304 and FeO by steam in the temperature of 700°C -960°C, the Claus process occurs with the decrease of gas temperature in the off-gas and the S02 and H2S in the gas are transformed into Sj , the critical temperature for the transformation is 600°C, and conversion percent of Sj is 97% at 330°C,

Jan 1, 1996

By S. P. Song

A computational methodology based on the coupled finite element and boundary methods is developed to predict the free surface shapes of electrically conducting liquids supported by the electromagnetic field. The work is an extension of our previous FEIBE model for induction calculations. The free surface algorithm is developed using the Weighted Residual Method, the very same used for nonlinear finite element formulation. This allows the treatment of field computation and free surface prediction in the same manner, thus making easier the formulation of the magnetically-supported free surface problems. Like other nonlinear algorithms, the boundary/finite element free surface scheme is also iterative owing to the fact that free surface shapes are unknown a priori. But the numerical scheme is robust and efficient and is capable of handling rather complex free surface deformations. Computational algorithms will be given and are tested by comparing with other solutions whenever available. Computed results of magnetically-supported free surface shapes are presented for magnetic levitation under microgravity and floating zone refining processes under normal gravity.

Jan 1, 1996

By KNona Liddell

Many metal recovery processes Involve heterogeneous reactions In porous media accompanied by fluid flow and mass transfer. Modeling such systems Is difficult because of the number of rate processes Involved and is complicated even further by effects due to the structure of the porous medium. Data on even bulk properties of the medium are often severely limited or unavailable. For many such systems, a cell model may provide, an attractive alternative to models based on transport ,mechanisms in a differential volume. A cell model requires less input data and is computationally efficient. Identical residence time distributions can be obtained with models of both types, and both allow conversion and concentration profiles and histories to be calculated. The formulation and properties of cell models for metals recovery are described in detail.

Jan 1, 1996

By Issa S. AI-Kharusy

Oxidation/reduction (REDOX) alloy media, as used in wastewater treatment, is founded on the exchange of electrons. Because of this electron exchange, many contaminants are converted to harmless components which require no further treatment. Other types of contaminants are removed from the waste stream by electrochemically bonding to the alloy medium. This paper discusses the REDOX reactions, the role of the alloy medium in various treatment processes, and describes specific applications of REDOX alloy media for the removal and minimization of waste. The characteristics and handling of spent treatment media is also reviewed as a further consideration in waste minimization.

Jan 1, 1996

By F. J. J. van Loo, A. A. Kodentsov, J. A. van Beek, M. R. Rijnders

"A periodic layered morphology of the reaction zone has been observed in several annealed solid/solid diffusion couples, including metal/metal and metal/ceramic couples. This morphology is characterized by a regular array of alternating layers, which are either single-phase layers or bands of particles embedded in an intermetallic matrix phase. A description of several systems showing periodic layer formation is given. It is shown that the periodic layered structure with the single phase layers and the one with the bands of particles have a different mechanism of formation.IntroductionSolid state reactions in ternary systems can produce a variety of reaction zone morphologies if there are two or more reaction products. Three types of morphology have been described in detail: 1) simple layered; 2) isolated precipitates in a singlephase layer; 3) interpenetrating columnar (lamellar) or interwoven structure. Understanding the factors that govern the formation of different morphologies is of importance in many fields of engineering. For solid state displacement reactions the conditions governing the formation of these morphologies are well understood [1-4]. For example, the development of a layered or aggregate reaction zone depends on the relative diffusivities of the components through the reaction products.This paper is concerned with the periodic layered morphology which has been observed in various solid state systems. We consider this to be a fourth type of reaction layer morphology. Two manifestations of periodic layered morphology may be distinguished. One form consists of regularly spaced layers of particles of one reaction product embedded in a matrix phase (another reaction product). The other form consists of single-phase layers embedded in a matrix phase. It will be shown that each manifestation has its own mechanism of formation. In section A we consider a system (Ag/Ti-foil/Si) in which periodic layer formation will be explained as a special case of the Liesegang phenomenon. In section B we consider systems where the periodic layered structure has a different origin."

Jan 1, 1996

By Satu Jyrkönen

A single-particle laminar-flow technique was used to study oxidation of four synthetic nickel mattes, which were screened into three size fractions, Experimental conditions were: reaction gas from N2 - 21 to 75 vol-% O2; gas preheating temperatures ranging from 500 to I 100'C. The four mattes were synthesized so that Ni/Cu ratios of I and 10 were obtained with high and low iron contents. Chemical analysis of the particles was used to determine the oxidation degree of the materials, and optical and scanning electron microscopy were used to detect their morphology, internal composition and structure. The best sulfur removal from the synthetic nickel mattes was achieved under the most oxidizing conditions with the finest size fraction. The matte with Ni/Cu = 1 and high iron content was found to be most reactive. The least reactive matte was with Ni/Cu = 10 and low iron content; the coarse fraction particles did not react at all under the conditions studied.

Jan 1, 1996