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By James B. Pfeiffer

TETRA Technologies, Inc., has applied its HDS? metals precipitation system to control a mine drainage problem. The effluent from the mine contains primarily zinc, manganese and iron, plus varying small amounts of cadmium, copper and lead. The flow from the mine averages 350 gpm, and varies considerably depending on season and weather conditions. The plant was designed to treat 1000 gpm of the water and generate a dense sludge suitable for recycling. The HDS? system contains a number of reactors, followed by post filtration and meets stringent metals discharge criteria as specified by New Source Performance Standards.

Jan 1, 1994

By Howard K. Worner

Several features of smelting and refining operations make them appropriate technology to adapt to the processing of "wastes" not only from the minerals Industry itself, but for wastes in general. These features include significantly higher temperatures than are achieved in conventional Incinerators and also good thermal stability derived from the mass of molten metal and slag in the furnace. This paper expands on Information contributed to the Mervyn Willis Symposium in July 1992 and includes knowledge generated in the last two years of waste processing R&D in a sealed 100kg capacity DC arc furnace specially constructed for the "Environment" process being developed in Wollongong. As one product of-the process is a foundry-type iron, the feed always contained ferruginous dusts or heavily contaminated scrap. For the dusts, sewage sludge has been used as a binder and also as a proportion of the fuel-reductant. To achieve the necessary bath carburisation, It is beneficial to add other lower reactivity carbons such as "kish' graphite, carbon from electrode butts, dusts from coke ovens, carbon from aluminium pot line residues, dry cell batteries etc. Metallurgical factors involved In process control, Including metal and slag, compositions, are discussed.

Jan 1, 1994

By Alan J. Hurd

"New insights into the development of microstructure in sol-gel films have recently been revealed by several diagnostic techniques, including imaging ellipsometry, ""chemical imaging"" by fluorescent tracers, light scattering from capillary waves, and finite-element modeling. The evolution of porosity during the continuous transition from dilute sol to porous solid in restricted geometries such as films and fibers is becoming clearer through fundamental understanding of evaporation dynamics and capillarity.IntroductionWith sol-gel processing, the full flexibility of solution chemistry can be exploited to make ceramic films and fibers with well controlled compositional characteristics. No less important is the ability to tune porosity and connectivity for specific applications such as optical and electrical coatings and membranes. Since the chemical and physical factors that determine the microstructure are not entirely understood, new diagnostics applied to sol-gel processing are welcome.Sol-gel films and fibers are distinguished by processing that takes a sol through continuous stages of increasing concentration and connectivity of a solid precursor. The liquid carrier is usually volatile or, at least, volatilizable through heat treatment. During deposition through states of increasing solids concentration, this sol might gel, as in bulk sol-gel processing, however, the gel state may be a fleeting transient that quickly empties of liquid. Nevertheless, the structures formed in solution during this stage influence the structure of the final solid. In particular, porosity is likely to be a remnant of networks formed in the sol-to-gel transition. Here we report on experiments whose goal is to discover the factors involved with porosity development."

Jan 1, 1994

By Saskia Duyvesteyn

Ion flotation is a technique applicable to the removal of metal ions from dilute solutions, using ionic surfactants.- While there are a number of physical and chemical parameters that influence the ion flotation process, this paper focuses on two of the important chemical ones, namely frother concentration and ionic strength. The effect of several frothers, including ethanol, iso-propanol and MIBC at concentrations ranging from 0% to 0.4%, was studied for the model Cd-dodecylsulfate and Cu-dodecylsulfate systems. The ionic strength, as well as the effect of monovalent and multivalent counter ions, was also studied in the range of 1@3 - 1 M, at constant pH. The results are discussed in terms of applicability to a range of effluents from minerals and materials processing operations.

Jan 1, 1994

By Satian Niltawach

Iron sulphate jarosite through which iron in zinc sulphide concentrate feed is removed from the production circuit of conventional roast-leach-electrowin process, is chemically unstable and environmentally hazardous even if it is mixed with lime. If zinc silicate ore is used at similar chemical conditions in place of calcine in the jarosite precipitation, the resultant silico-jarosite residue having been mixed with lime is chemically stable and environmentally friendly. The recovery of zinc from silicate ore is also higher than that from calcine.

Jan 1, 1994

The effect of change in slag composition upon metal losses to the slag and the relationship between slag composition and slag matte separation was investigated at 1400°C. The synthetic slags containing CaO, MgO, SiO2,, A1,0, and FeO were similar to those employed in the electric furnace smelting of sulphide Cu-Ni concentrates containing PGM (Precious Group Metals) from the Merensky Reef of South Africa. The matte with a grade of 9.3% Cu and 16.0% Ni was a typical electric furnace product. The results indicated that the Cu and Ni solubility in the slag increases with the increase of the basicity ratio and CaO and MgO contents of the slag. At constant CaO/MgO ratios the rise in basicity decreases the metal losses. When FeO and SiO2 contents of the slag are kept constant, the substitution of MgO with CaO decreases the metal losses. The relationship between slag composition and matte-slag separation was found to depend primarily on the basicity ratio and the FeO content of the slag. The net effect comes from a strong interaction of the two in such a way that increasing basicity and decreasing FeO contents deteriorate the clean separation of the two phases.

Jan 1, 1994

By D. D. L. Chung

"In-situ network composites are composites in which the filler network is formed during composite fabrication, in contrast to ex-situ networks which are formed prior to composite fabrication. A homogeneous in-situ network composite has the entire network at the same composition; a heterogeneous in-situ network composite has different parts of the network at different compositions. The homogeneous network composite is made either by the Method of Molten Filler Flow or the Method of Dissolution and Deposition; a heterogeneous network composite is made by the Method of Liquid-Phase Networking. Examples include polymermatrix and metal-matrix composites.IntroductionNetwork composites refer to composites containing a continuous three-dimensional network as the filler. These composites are attractive in their lack of delamination failure, which is usually characterised by two-dimensional composites. The filler and matrix in a network composite can be considered two interpenetrating networks. The mechanical interlocking of the networks adds to the cohesion of the composite. In cases where the filer is much better than the matrix in a certain property, the network nature of the filler makes the filler highly effective in improving that property in the composite in all directions. The property desired in the composite may be high strength, high modulus, low coefficient of thermal expansion, high thermal conductivity, or low electrical resistivity."

Jan 1, 1994

By Aïda Espinola

This work is part of a research program concerning the study of heavy metal removal and selective recovery from electroplating waste waters in the Guanabara Bay ecosystem, preventing the potential noxious retarded effect of landfill, specially in a country of heavy rainfall. A flow-throw cell was employed to adapt to the limits established by the local legislation for disposal in rivers and seas. The cell design is presented and preliminary results show that this cell may be applicable for the decontamination from copper.

Jan 1, 1994

By B. Q. Li, S. P. Song

"This paper describes an on-going research on developing coupled boundary element and finite element algorithms for the solution of thermal and electrodynamic problems relating to materials processing. The coupled methods are uniquely suitable for field problems involving composite regions, in which detailed information on field distributions within one particular region is of more interest and yet the solution can be obtained only if the effects of other regions are all considered. Problems of this type include heat transfer in multiple regions and also magnetic induction involving an infinite boundary. The hybrid boundary and finite element formulation, algorithm development and the applications are discussed. Two examples are given to demonstrate the capability and accuracy of the coupled algorithm for heat transfer problems. Various treatments of corner discontinuity are discussed. It is found that the double flux treatment is an ideal choice amongst those tested as it is easy to implement and also gives the most accurate solution. 1. INTRODUCTIONElectrodynamic and transport problems occur frequently in materials processing systems. Accurate solution of these problems is of great importance not only for our fundamental understanding of physical principles governing these phenomena in the processing systems but also for optimization of the existing processes as well as development of new processes. For this purpose, many numerical algorithms have been developed. These computational schemes in general can be classified into three categories, that is, the finite element and finite difference schemes and the boundary element scheme. The former two are domain based numerical algorithms while the latter the boundary-based algorithm.The finite element method, which is based on the variational calculus, is a very useful and yet popular engineering numerical method for boundary value problems defined over irregular boundaries. The use of the method requires the discretization of the entire domain. It can be applied to solve both linear and nonlinear problems, but is particularly powerful for nonlinear problems that involve the field variables defined within the computational domain. On the other hand, the boundary element method, with its root in the Green's function method, is very efficient for linear boundary value problems or nonlinear problems that involve field variables only along the boundaries. The primary advantage of the boundary element method lies in the fact that only the boundaries of the computational domain need to be discretized, and hence the dimension of the problem is reduced by one, compared with the finite element method."

Jan 1, 1994

By B. Mishra

Several reactive metal purification processes using molten salts generate effluent from which significant quantities of metal can be recovered prior to discardinglrecycling the salt. A Salt-scrub [SS] process has been applied where the reactive metals are recovered as a metal-gallium alloy by calciothermic reduction of the metal compounds. The SS alloy compositions were produced by mixing, pressing and sintering the metal-powders. Measurement of metal recovery has been studied for cerium, silver, tin and lead. The process has been optimized for variables such as the metal quantity per kg of effluent salt, amount of excess calcium over stoichiometry, stirring rate and time and holding time at reduction temperature. Over ninety-seven percent metal recovery has been obtained under optimized conditions. The development of an alloy for efficient Salt Scrub processing reduces a major contaminated waste disposal problem as well as recovering the valuable reactive metal. Surrogate metals have been used in this work to study the behavior of plutonium.

Jan 1, 1994

By V. Ramachandran

Under the Resource Conservation and Recovery ACT (RCRA), generators of listed or characteristic hazardous wastes must find satisfactory means for disposal. of wastes. Initially, for many this meant landfills and deep-well injection. Until recently, mining and metallurgical by-products have largely been exempt from RCRA, but now are coming under its jurisdiction. With the increasing closures of landfills, companies in the U.S. such as electroplaters, miners, metallurgical plants and others are turning to recycling as an alternative to treat their wastes. While the cost of recycling has been challenging, the long-term economics prove attractive because recycling interrupts the cradle- to-grave responsibility for the waste generator. The present paper describes the recycling of hazardous wastes at ENCYCLE/TEXAS. Encycle extracts marketable metals from metal-bearing sludges and wastewater using hydrometallurgical processes borrowed from the mining and metallurgical industry.

Jan 1, 1994

By G. Johnston, J. Greenly, R. G. Buchheit, D. C. McIntyre, R. Muenchausen, D. J. Rej, R W. Stinnett

"Rapid thermal treatment of materials using high energy, high flux, pulsed ion beams can produce modified surface layers with unique microstrutures and properties. High energy ions loose their energy during the slowing down process in the workpiece and thus deposit their energy continuously over a depth of a few microns. The deposition of energy can lead to melting and in some causes ablation of the heated layer. Because the pulse duration of the ion beams is typically only 50-200 ns, steep thermal gradients generated during heating facilitate rapid cooling (107K/sec-108K/sec) of the treated layer by thermal diffusion into the underlying material. Rapid heating and cooling of materials can generate surface layers with non-equilibrium amorphous or nano-crystalline microstructures that exhibit increased hardness, wear resistance, and corrosion resistance. Pulsed ion beam treatment can also lead to surface smoothening or can be used to mix thin « 1 11m thick) coatings into underlying substrates. Pulsed ion beams can be generated using existing ""flashover"" ion source technology which is capable of producing single shot, mixed C, H, and O ion beams with beam cross sections of approximately 100 cm2 and energy fluxes up to 100 J/ cm2. Recent advances in repetitive high energy pulsed power technology and development of magnetically confined anode plasma ion sources have facilitated the development of ion beam systems that generate single species beams that pulse continuously at 120 shots/second. These capabilities will allow rapid treatment of large surface area workpieces at low cost.IntroductionThe rapid solidification of liquid materials can create unique materials and material microstructures that often have properties that can lead to enhanced performance. Rapid solidification processing of the surfaces of materials using continuous and pulsed laser beams (laser glazing) has been explored for over 20 years (1-5). Advances in high energy, pulsed electron and ion beam technologies over the past decade have provided rapid thermal treatment techniques that may be less expensive to impliment than laser surface treatment for many surface modification applications (6). High energy pulsed ion beams have recently been used to harden aluminum(7), copper(8) and tool steel surfaces (6,9), increase corrosion resistance of Al alloys (6), mix coatings into underlying substrates (10), and create amorphous films (11,12)."

Jan 1, 1994

By George Nekoksa

The biofilm activity monitoring probes measure applied current during intermittent short-term polarization of the probe electrodes and current or potential between the electrodes after removal of the polarization. The probe polarization mimics conditions at crevices, welds and inclusions where the biofilm activity and microbially influenced corrosion usually concentrate. Monitoring of AC resistance between the probe electrodes can provide infornation about the thickness of deposits.

Jan 1, 1994

By Lloyd R. Nelson

Selective carbothermic reduction is the preferred method of treatment of electric arc furnace (EAF) dust (listed hazardous waste, K061). The process maximizes the recovery of recyclable constituents by concurrent production of saleable zinc metal (directly condensed from the furnace off-gases), an innocuous, disposable iron oxide-rich slag, and some metallic iron. Results of a mineralogical investigation of a foaming slag produced during selective carbothermic reduction treatment of EAF dusts are presented. Wiistite and tricalcium silicate were identified by reflected light microscopy as the primary crystalline phases contained in a glassy matrix, but this technique failed to reveal any solid phases that could have significantly contributed to foam stability. It was concluded therefore, that the foam had been unstable, and had been primarily generated by copious gas evolution associated with the sudden reduction of the slag by an inadvertent addition of carbonaceous reductant. This is consistent with the susceptibility to foaming, when subjected to sudden excesses of carbon, of the slags produced by selective carbothermic reduction, because they still contain unreduced components such as iron oxide.

Jan 1, 1994

By Michael J. McGuire

Rostoker, Inc. has developed a process to smelt solid hazardous/non-hazardous inorganic wastes. Near seven hundred experiments were performed. Actual industrial wastes as well as reagent grade chemicals were used. By mixing a multiplicity of these wastes to proper formulations, then furnacing them, it was determined that saleable end products could be reclaimed; metal, fume and slag. The slag, due to its siliceous structure was tested to be leach resistant (40 CFR). This formed the essence of our patent, #5,180,421 "Method and Apparatus for Recovering Useful Products from Waste Streams". What is unique is that a HTMR (High Temperature Metal Recovery) process has been developed that can treat a multiplicity of wastes within the same furnace. The discussion will include a list of waste streams we have treated, details of proper waste formulation and experimental results.

Jan 1, 1994

By K. E. Gonsalves, G. M. Chow

"Nanostructured powders (particle diameter of 1 - 100 nm) have uses in electronic, magnetic, structural, thermal applications as well as advanced processing of materials. Among many methods of making nanostructured powders, chemical routes offer many attractive features such as feasibility of cost-effective bulk quantity production, design of chemistry at the molecular scale, and chemical homogeneity of the powders. In this talk, two systems of chemically synthesized nanocomposite powders are presented, namely, granular magnetic materials of Fe-Cu and Co-Cu, and thermal-structural materials of AIN-BN. Synthesis and processing, characterization and properties of these materials are discussed.IntroductionNanostructured powders (particle diameter of 1 - 100 nm) are attractive materials because of many useful properties (e.g. catalytic, optical, magnetic etc.) and processing advantages (e.g. lower sintering temperature) [1]. There are many methods of making nanostructured powders, for example, physical and chemical vapor deposition, mechanical attrition, and solution chemistry [1, 2]. A common method of making composite powders involves the grinding, mixing and blending of constituents powders, but it has the limitation of inhomogeneous mixing. Chemical routes have many useful features. Using solution chemistry, precursors can be molecularly tailored and homogeneously mixed at the molecular level. The chemical approach may result in better properties of the final product. Compared to vapor-phase fabrication techniques, chemical routes are more cost-effective in producing large quantity of material. In addition, control of particle size, size distribution and stabilization of the nanoscale particles against agglomeration can be more effectively manipulated via solution chemistry.In this paper, we present an overview of some of our work in nanocomposite powders prepared by solution chemistry. Metallic systems of FeCu and Co-Cu, and ceramic system of AIN-BN are discussed. The powders were characterized using x-ray diffraction (XRD) , scanning electron microscopy (SEM), conventional and high resolution transmission electron microscopy (TEM, HRTEM), vibrating sample magnetometry (VSM), inductively coupled plasmaatomic emission spectroscopy (ICP-AES)."

Jan 1, 1994

By Derek J. Fray

Electric arc furnace dusts, especially those containing zinc ferrite, are notoriously difficult to process to give valuable products and non-toxic residues. The ideal process would remove and recover the toxic non-ferrous metals as pure metals, of commercial value, and non-toxic residue which can be used as a raw material in the steel industry. From an examination of the thermodynamics of the oxides and chlorides of the various elements in the dust, it is apparent that the chlorides of the toxic non-ferrous elements are more stable than the oxides while the reverse applies to the ferrous elements. This offers the opportunity for a complete separation of the zinc, lead and cadmium from the iron oxide. Results are presented for the chlorination of electric arc furnace dusts under oxidising conditions and the subsequent treatment of the chlorides to recover the pure metals and chlorine which can be recycled back to the reactor.

Jan 1, 1994

By T. T. Natarajan, Nagy EI-Kaddah

"Numerical simulation of electromagnetic confinement systems generally requires large CPU time due to the strong coupling between the electromagnetic and the free boundary problems. The present paper examines the accuracy and the computational efficiency of the most common numerical schemes used in modeling such systems. Levitation melting was taken as a test case. In this study, a comparison was made between the finite element and surface integral methods for electromagnetic field calculations. The computational efficiency of Lagrange and the modified Hestenes methods for solving the free boundary problem were investigated. The convergence of the Lagrange method was found to be much faster than the modified Hestenes method. It was also found that finite element method not only gives accurate solutions, but faster convergence to the final equilibrium shape than the surface integral method. The applications and the limitations of these techniques in modeling electromagnetic confinement systems will be discussed.IntroductionIn recent years there has been a growing interest in the use of electromagnetic forces for confinement of molten metals as a means to eliminate molten metal contamination during melting and to improve surface quality of cast products. Continuous casting of metal without contact of a mold is now a reality, and is being commercially applied for casting of aluminum slabs /1/, and copper rods /2/. New applications of electromagnetic confinement in melting and casting include containerless melting (Magnetic Suspension Melting) /3/, edge containment in twin roll casting, and meniscus shape control in continuous casting of steel /4/.Modeling of confinement systems involves the determination of the electromagnetic field and the equilibrium shape. These two problems are strongly coupled due to the dependence of the field on the shape of the melt. While significant advances have been made in computational electromagnetics /5/, the application of developed computational techniques to electromagnetic confinement problems is not a simple task. The principal difficulty in using these methods is that the solution domain is not known a priori. due to coupling between the electromagnetic field and the free boundary problems. These two problems have to be solved simultaneously, leading to an iterative solution procedure. As a result, numerical simulation of electromagnetic confinement systems are computationally intensive with computational time at least an order of magnitude larger than the fixed domain problems."

Jan 1, 1994

By D. T. Smith, L. M. Hsiung, J. J. Schmitt, J. W. Golz, R. L. Lankey, H. N. G. Wadley, J. Z. Zhang, B. L. Halpern

"The microstructure and mechanical properties of Al/AI2O 3 metal-oxide nanolaminates fabricated by' a novel Jet Vapor Deposition (JVD) process at substrate temperatures of ~25° and -250°C have been investigated using transmission electron microscopy (TEM) and nanoindentation methods. The thickness of the oxide layer was held constant between 2 and 5 nm, whilst the Al layer thickness was systematically varied from -3 to -50 nm. Continuity of the Al layers was significantly improved when the nanolaminates were deposited at an elevated substrate temperature (-250°C). The yield strength of the nanolamintes with Al layers greater than -25 nm follows a Hall-Petch type relationship, whereas that of the nanolaminates with Al layers less than -25 nm is better predicted by a Koehler-Lehoczky strengthening model. IntroductionAluminum-aluminum oxide (presumably A12O3) nanolaminates have been recently fabricated using a novel Jet Vapor Deposition (ND) process developed and patented by Jet Process Corporation [1-4]. ND uses sonic, high purity helium (He) gas jets to entrain atomically dispersed vapor and deposit films. It is of interest here because it can deposit multilayered structures (laminates) inexpensively at high rates. Materials with a thin, multilayer structure are of interest because they potentially offer novel mechanical and physical properties [5]. Koehler in 1970 used an image force model to investigate the strength of laminated materials and proposed the use of alternating layers of high and low shear modulus metals to produce high strength composite materials [6]. He predicted that dislocations would have to overcome a large repulsive image force in order to move from metal layer B of lower shear modulus (uB) into metal layer A of higher shear modulus (uA)' The image force (F) is given by the relation:"

Jan 1, 1994

By Thomas M. Harris

Cation exchange is not sufficiently selective to be used for the removal of heavy metal ions from a general industrial wastewater. However, if the metals can be converted to polyvalent anions through complexation, they may be removed both selectively and efficiently by anion exchange. This approach, referred to as chelation-assisted anion exchange (CAAE), has been examined using industrial wastewater samples contaminated with Ni2+ and Cr3+. For this particular application, the Ni2+ is complexed with 8-hydroxyquinoline-5-sulfonic acid, and the Cr3+ with sulfosalicylic acid. Removal efficiencies and adsorption isotherms for both the complexants and the complexes were determined in batch-mode tests.

Jan 1, 1994