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By John B. Cocanour

The U.S. Bureau of Mines (USBM) has developed a laboratory-scale on-line analysis and process control system for a decopperization electrolytic circuit. This system is software driven, running on a 486DX-33 personal computer (PC) utilizing a portable energy- dispersive x-ray fluorescence (XRF) spectrometer as the sample analyzer. The XRF copper reading obtained was used as the control variable through an RS-232 serial interface to the PC for software-based control of feed flowrates. When the copper concentration in the electrolytic cell (as measured by the XRF) deviated from the set point, the feed flowrate to the cell was automatically altered using software-based proportional-integral-differential (PID) computer control to yield the desired copper concentration at the electrolytic cell outlet.

Jan 1, 1994

By Frank M. Kimmerle

Spent Potlining (SPL) contains recoverable chemical elements (C, F, Na and Al) which are lost in stabilization or immobilization processes primarily aimed at eliminating cyanides and reducing leach rates of soluble fluorides prior to landfiling. They can be recovered in a variety of mineral forms for recycling in the aluminum industry and elsewhere. Alcan has developed a cost-effective hydrometallurgical route, combining a number of proven unit processes to destroy cyanides, recycle the chemical values and provide a zero-discharge process. Pilot plant studies of this Low Caustic Leach and Liming (LCL&L) Process prove that the fluoride scan be converted to acid grade fluorspar, while the sodium and aluminum are recovered as a sodium aluminate and caustic feed to the Bayer Plant operations. The remaining brick and carbon fraction constitutes a high ash solid fuel which meets TCLP leach criteria and whose reduced sodium content enhances its value as a chemical reducing agent.

Jan 1, 1994

By Baozhong Zhao

In-situ vitrification (ISV) is a new technology used for treating radioactive, organic and inorganic contaminated soils. In this process, electricity is applied through electrodes buried in the contaminated soil to melt it and form an environmentally stable glass-like solid. The organic contaminants and volatile metals are vaporized during heating up, the non-volatile inorganic elements are dissolved and incorporated into the melt. In present full-scale operation, the ISV process can treat 4 to 6 tons of soil per hour at consumption of about 1000 kwh per ton of soil. In this study, various configurations of electrodes were examined in a mathematical model. The results may be used to optimize the ISV process.

Jan 1, 1994

By Claire A. Chanenchuk

Catalytic Extraction Processing (CEP), a technology commercialized by Molten Metal Technology, Inc., a US.-based company, can convert industrial, household, and government wastes into commercial resources. CEP is an innovative elemental recycling technology that uses a molten metal bath to completely dissociate hazardous or toxic components of a feed and convert them to valuable products. The catalytic action of the molten metal bath converts the feed to its elemental constituents and the reducing atmosphere prevents the formation of any dangerous byproducts (NOx, SOx, dioxins, furans, etc.). Selective reactant addition allows engineering of valuable products from otherwise unexploited resources. Synthesis gas is generated from hydrocarbon feeds, ferro-alloys from metallic wastes, and ceramics from select inorganic species. Commercial-scale processing of multiple wastes and waste surrogates has been carried out at a destruction and removal efficiency exceeding 99.9999 wt.%, validating theoretical predictions. Unlike conventional hazardous waste treatment technologies, CEP offers resource recovery, minimal byproduct generation, and the potential for closed-loop recycling.

Jan 1, 1994

By S. G. Kumar

Experimental studies on high carbon steelmaking through LD Converter - Vacuum Arc Degassing - Bottom Pouring route to produce low oxygen steels were carried out. The results indicated that it is possible to produce steel with a total oxygen content of less than 15 ppm. Thermodynamic and mass balance calculations are made on low-carbon steels that are treated by a complex deoxidation practice based on primary deoxidation of aluminum, manganese and silicon additions; followed by secondary deoxidation of vacuum degassing with simultaneous additions of aluminum. The results showed that primary deoxidation is mainly due to aluminum and the effect of carbon under reduced pressures on deoxidation of molten steel that is already killed by aluminum is negligible. The effect of process parameters on total oxygen content of steel, like carbon content, slag composition and inert gas purging, are discussed.

Jan 1, 1994

Four slag types covering the range of Fe-Ca-Si-O compositions and two iron blast furnace slags were melted at 1300 °C and doped with 1% of arsenic, antimony, cadmium, zinc and chromium. The melts were either slow cooled or quenched and the solidified slags were leached according to TCLP procedures. The morphology of the solidified slags was characterised using XRD, optical and electron microprobe techniques. Theoretical considerations showed that the capacity of the molten slag to hold the above toxic elements depended upon slag basicity and this was confirmed in practice. The experiments showed that the leaching of the toxic elements was a function of surface area and the phases present, both of which were affected by the mode of cooling. Iron silicate slags produced in nonferrous smelting operations and blast furnace slag from ferrous smelting operations both show promise of being suitable media for immobilising low levels of toxic elements and complying with current regulatory requirements.

Jan 1, 1994

By B. J. Jody

Each year, about 11 million tons of metals (ferrous and nonferrous) are recovered in the U.S. from about 10 million discarded automobiles. The recovered metals account for about 75% of the total weight of the discarded vehicles. The balance of the material or shredder residue, which amounts to about 3 million tons annually, is currently landfilled. The residue contains a diversity of potentially recyclable materials, including polyurethane foams, iron oxides, and certain thermoplastics. This paper discusses a process under development at Argonne National Laboratory to separate and recover the recyclable materials from this waste stream. The process consists essentially of two- stages. First, a physical separation is used to recover the foams and the metal oxides, followed by a chemical process to extract certain thermoplastics. The status of the technology is discussed, and the process economics are reviewed.

Jan 1, 1994

By Murali Thirukkonda, Rahul Shah, Srinivas Tangrila, Shankar Rachakonda, Jan Kajuch, Arthur Gurson

"High-temperature superconductors have potential for a variety of applications such as power generators, superconducting magnets for mine sweepers or ship propulsion motors, and magnetic levitation transportation systems. Interest in the use of superconducting wires and tapes increased dramatically after the discovery of high-critical-temperature (high-Tc) oxide superconducting compounds, which offer operating temperatures above that of liquid nitrogen. Several techniques have been proposed to produce commercially viable high-Tc oxide based superconducting wires. One of the promising methods involves multi-pass powder-in-tube (PIT) wire drawing followed by rolling and heat treatment. This work focuses on the development of a numerical model to simulate the PIT drawing process for fabrication of long lengths of silver sheathed Bi-2212 superconducting wires. The finite element based model was used to predict densification of the oxide powder, wire drawing forces, and silver sheath thickness during drawing. A cap-type pressure dependent constitutive equation was implemented in the model to simulate the powder behavior. The model incorporated experimentally obtained material data for the silver and powder. Results indicate that powder densification is increased by decreasing the initial silver thickness and increasing the silver strength. Data from wire drawing experiments were used to verify model predictions. IntroductionSuperconducting wires and tapes can be used to carry large dc currents with no measurable loss due to resistivity. When used in superconducting magnets for power generators, motors, levitation devices, magnetic detectors, or energy storage devices, they could potentially result in significantly reduced energy losses. In the past, most prototypes were tested in liquid helium at 4.2K [1]. However, the necessity to provide liquid-helium cooling systems proved to be a serious limitation in commercialization. In 1986 high-critical-temperature (high-Tc) oxide superconductors were discovered [2], which could allow for higher operating temperatures above liquid nitrogen (77 K). Since then, both academia and industry have concentrated their efforts on the development of high-Tc oxide superconducting wires, tapes and coils. As yet, large scale fabrication of long lengths of these wires with the required current carrying capacity and mechanical properties remains an enormous challenge."

Jan 1, 1994

Bath smelting options for recovering valuable metals from jarositic residues containing 22-28% lead and 16-30% sulphur obtained from pressure leaching zinc-lead-copper bulk concentrates were investigated using thermochemical computations and crucible-scale experiments. Direct fuming of lead and zinc from a slaglmatte bath at 1250-300°C was demonstrated successfully. Up to 93% of the lead was recovered in the fume and steady-state recoveries of zinc were predicted in the range 82-95% under these conditions. The energy required for the fuming reactions was supplied by partial combustion of the fuel, added as char, with air. An important feature of the process is that the recoveries to the fume are not significantly affected by changing: the fuel:air ratio over a wide range. Thermodynamic computations, confirmed by experimental results also showed that the presence of a matte phase is not essential for high recovery of lead and zinc to the fume. Operating conditions which produced a matte ensured that about 70% of the silver and 80-90% of the copper were recovered into that phase. Approximately 98% of the arsenic in the residue was fumed. In the absence of matte the slags contained high arsenic levels (260-330 ppm) but low arsenic (20-60 ppm) levels were achieved when matte was produced.

Jan 1, 1994

By M. L. Sorokin

The thermodynamic of nickel production from laterite ore and from sulfide concentrate can be analyzed using PO2 - PS2 diagram of the Ni-Fe-S-0-SiO2 system. The procedure of the diagram computation is suggested and the diagrams for various temperature and Fe/Ni ratio are calculated. Three-suffix Margules equations are used for the calculation of the thermodynamic properties of three solutions: liquid matte, liquid slag and solid Fe-Ni alloy. The diagrams are used for the considerations about direct one-stage metallic nickel production.

Jan 1, 1994

By M. T. Ernett

Significant amounts of arsenic are often present in effluents arising from the mining of sulfide ores for the extraction of metals such as copper, gold, lead and zinc. The arsenic is usually removed from the process effluent by co-precipitation with iron because of its common occurence in the mined ore bodies and the excellent adsorptive property of the precipitated hydrous ferric oxide compound. There has been controversy, however, over the long-term stability of the arsenic-bearing ferrihydrite which is produced. This paper presents the results of laboratory studies which indicate that the cations of calcium, magnesium, zinc, cadmium and lead, increase the pH range of effective arsenic adsorption in the Fe-As precipitate from 4-7 to 4-9. The increase in the pH range is similar for all of the added cations investigated. Sulphate ions are shown to have a minimal effect on the residual dissolved arsenate concentration. Silicate ions reduce the adsorptive capacity of ferrihydrite if they are present before the arsenic is adsorbed.

Jan 1, 1994

By Ch. -A. Gandin, M. Rappaz

"The grain selection mechanism which occurs during the growth of columnar dendritic structures is routinely used in the investment casting industry to produce directionally solidified (DS) and single crystal turbine blades. However, the evolution of the grain density with increasing distance from the chill has rarely been correlated with the evolution of the grain texture. This contribution presents a three-dimensional (3-D) stochastic modeling approach which permits the computation of grain maps, pole figures and grain density evolutions in DS superalloys. These predictions are compared with measurements resulting from an automatic indexing technique of Electron Back-Scattered diffraction Patterns. This 3-D stochastic model, which applies to uniform temperature situations, has to be extended to the dendritic growth in a thermal gradient. As a preliminary step, a 2-D Cellular Automaton (CA) has been coupled recently to Finite Element (FE) heat flow computations in order to predict the grain structures in complex shape investment cast part. The application of this CAFE model to the investment casting of a turbine blade is presented. Considering these results, the extension of the CAFE algorithm to three dimensions is discussed.INTRODUCTIONThe selection of columnar grains during the directional solidification of alloys plays a key role during the investment casting of directionally solidified (DS) and single crystal (SC) components for aerospace applications [I]. This selection mechanism, leading to a competition of the dendritic network propagation at grain boundaries, has been the subject of many investigations. In particular, the study of Walton and Chalmers [2] is remarkable since it provides a link between the evolutions of the density and of the texture of columnar grains with increasing distance from the mold wall. Since this original work of Walton and Chalmers, two new tools have become available, which enable one to revisit the problem of grain selection in much greater depth. The first one is a fully automatic indexing technique of Electron Back-Scattered diffraction Patterns (EBSPs) [3-6] which directly gives the crystallographic orientation of the solid at any location of the specimen. Pole figures, orientation distributions, misorientations between grains can be visualized very easily with this technique. This information can be directly compared with the results of a second tool: a three-dimensional (3-D) stochastic model (SM) describing the nucleation and growth of grains in a uniform temperature field [6-9]. In order to extend this model to non-uniform temperature situations, a preliminary 2-D model has been developed [10]. It is based on a Cellular Automaton (CA) algorithm coupled with Finite Element (FE) heat flow computations. Since the details of both the automatic indexing technique of EBSPs and the simulation tools have already been published [3-10], only a brief summary is given here."

Jan 1, 1994

By F. Ajersch, P: Tsantrizos, K: Shanker

"TiN films have been deposited on various substrates by a novel reactive plasma technology. In this process, a nitrogen source (NH3 or N2) and TiCl4 are reacted in the jet of a plasma torch, and are deposited onto a substrate forming TiN films at a high growth rate ( > 2µm/min). It was found that the process parameters strongly affect the microstructure, thickness, density, and growth rate of the TiN films. These parameters include source of nitrogen (NH3 or N2, N/Ti ratio, temperature of substrate, and spray distance. In general, it was found that thick and dense coatings were deposited when the N:Ti ratio was kept low, and the substrate temperature was high. Also, for the series of conditions investigated, NH3 was found to give much better results than N2•. The limitations and advantages of this technique are also discussed in this paper.IntroductionTiN is an extremely hard material and is used in many wear applications, particularly as a protective coating on cutting tools to extend their Iife(1.2). Owing to its excellent chemical stability, TiN is also frequently used as a diffusion barrier in the electronics industry for sub-micron Al/TiN/Si ohmic contact systems (3) or as a coating on high-temperature resistant alloys in gas turbine applications (4), based on its good resistance to oxidation. Other applications include decorative coatings in the jewelry industry, and specialized applications such as solar energy absorbers and transparent heat mirrors(5).TiN films can be deposited/formed using various techniques. The main techniques of deposition are CVD (Chemical Vapour Deposition) and PVD (Physical Vapour Deposition). Each of these techniques can have many variations in equipment characteristics, reactants as well as a range of process parameters (pressure and temperature). In the CVD process, TiN is generally deposited onto a heated substrate where a chemical reaction takes place. The reaction can be one of reduction(6) (e.g.: TiCI4 + 0.5N2 + 2H2 --> TiN + 4HCI), of thermal decomposition(7) (e.g. decomposition of titanium dialkylamide), or of displacement (e.g. TiCI4 + NH3 --> TiN + 3HCI + 0.5CI2)' The displacement and reduction reactions are the most common."

Jan 1, 1994

By H. J. Garcia

Biodegradation of cyanide by microorganisms isolated from solids previously exposed to cyanide has been investigated. Initial sodium cyanide concentration was 300 ppm at pH 10.5. The kinetics of biodegradation were found to be first order with respect to cyanide concentration, and the overall reaction rate constant is k = 0.102 day-1. The activation energy and the frequency factor were determined to be { A }Ea = 5.45 Kcal/mol and A = 1.28 x 10-2 sec-1, respectively. Based on these values, thermodynamic properties of an intermediate activated complex were assessed. All tests resulted in cyanide concentrations less than 0.1 ppm in about 35 days at 250C, whereas at 350C the time of biodegradation to reach this cyanide level was 30 days. Kinetic data were also established to relate biodegradation to amount of inoculum. The maximum theoretically-attainable rate, Vm , and the optimum amount of inoculum, K , were determined to be 4.8 x 10-4 M NaCN/day and 7.5 % of amount of inoculum. With respect to the mechanism of biodegradation, cyanide was shown to decompose to carbonate, bicarbonate and ammonia. Titrimetric analyses revealed concentrations of 5.6 x 10-3, 4.8 x 10-3 M, and 70.2 ppm for carbonate, bicarbonate and ammonia, respectively. The average cell population was determined to be 3.75 x 108 cells/mL.

Jan 1, 1994

By D. J. Senor

Closed chamber incineration (CCI) is a novel technique by which irradiated nuclear graphite may be destroyed without the risk of radioactive cation release into the environment. The process utilizes an enclosed combustion chamber coupled with molten carbonate fuel cells (MCFCs). The transport of cations is intrinsically suppressed by the MCFCs, such that only the combustion gases are conducted through for release to the environment. An example CCI design was developed which had as its goal the destruction of graphite fuel elements from the Fort St. Vrain reactor (FSVR). By employing CCI, the volume of high level waste from the FSVR will be reduced by approximately 87 percent. Additionally, the incineration process will convert the Sic coating on the FSVR fuel particles to SiO2, thus creating a form potentially suitable for direct incorporation in a vitrification process stream. The design is compact, efficient, and makes use of currently available technology.

Jan 1, 1994

By David G. Dixon

A mathematical model is derived in dimensionless form which simulates the effluent concentration response of reagents from spent heaps under both fresh and recycled water rinsing. The model is based on dispersion from isochoric pathways distributed in length and cross-section, oriented normal to convection channels in ideal plug flow. The effects of heap height, rinsate flow, and initial reagent concentration are examined. It is shown that the rinsing cycle undergoes a distinct shift between fast and slow rinsing at a certain time depending on the amount of stagnant solution in the heap, and the distribution of dispersion pathways. Results of preliminary column rinsing tests on both agglomerated and unagglomerated ores are presented which partially validate the model.

Jan 1, 1994

By Leonard A. Duval

This concept employs a viable energy saving method that uses a solvent to separate oil from particle matter; it can be used in metal forming industries to deoil sludges, oxides, and particle matter that is presently committed to landfill. If oily particles are used in their oily state, severe consequences to environmental control systems such as explosions or filter blinding, occur in the air handling equipment. This is due to the presence of hydrocarbons in the stack gases resulting from the oily particles. After deoiling, the particles can be recycled and the separated oil can be used as a fuel. The process does not produce a waste of it's own and does not harm air or water. It demonstrates the dual benefits of being commercially viable and in the national interest of conserving resources.

Jan 1, 1994

By S. N. Ojha, Gouthama, R. K. Mandal

"Spray deposition processing of liquid immiscible alloys, based on AI-Pb and Cu-Pb systems have been investigated. Process variables have been optimized to generate uniform dispersion of ultrafine second phase particles in· the matrix of the primary phase. Mechanisms governing the microstructural evolution in this synthesis methodology are discussed. Results of the present investigation are used to demonstrate that rapid solidification of atomized droplets initially provides a high nucleation rate of the second phase during the liquid phase separation. The solid matrix phase nucleates at a later stage and grows with a high velocity enabling trapping of the dispersed phase. Subsequent alteration in the size and size distribution of the second phase is suggested to arise further during deposition of high velocity droplets. Possible reasons for this effect are brought out. Microstructural features of atomized powders and spray-deposits of these alloys are presented to support the present approach of synthesizing composites. IntroductionIn recent years, synthesis of advanced materials with metastable microstructures and ultra fine dispersion of second phase particles has led to the development of novel techniques of materials processing. The other requirement of such a processing methodology is to achieve near-net shape geometries in less number of processing steps. The solidification processing method via spray deposition route qualifies these criteria. This process primarily involves atomization of a melt by high energy gas jets into spray of droplets which are subsequently propelled by the kinetic energy of the gas towards a deposition substrate to build-up a thick high density preform. Although the concept of spray deposition was pioneered by Singer [1] in the early seventies, the fundamentals of the deposition process has been understood only recently [2-4]. Several benefits of spray deposition processing are by now well established [5,6]. Rapid solidification effects are inherent in spray deposition processing due to high heat exchange rate at the droplet-gas interface and also on the deposition surface by force convection. Since considerable heat extraction occurs from the atomized spray prior to droplet consolidation, a relatively low processing temperature is ensured in this process. As a result deleterious coarsening phenomenon can be minimized. In addition, controlled maneuvering of the substrate provides the capability of the process in producing disc, sheet or tube shape preforms of difficult to work materials in a single operation. A significant improvement in properties, resulting from microstructural homogeneity and refinement in grain size induced by spray deposition has been reported for several alloy systems [7,8]."

Jan 1, 1994

By Ilie Butnariu

Steel manufacture in VOD procedure needs a very attentive correlation and pursuit of the technological stages ,on the background of keeping the influence factors within best performances zones. For a better co-ordination of the main stages specific to this process ,this work presents a detailed study of the optimization possibilities for each stages ,beginning with the furnace charging ,going on with the pre-aftinage and aftinage stages in the electrical furnace and then with the refinement stages in the VOD installation. One has intended the effective emphasis of the main influence factors with global implications on the process and especially on the purity and quality of the stainless steel ,Among the main novelties proposed by this work , we can emphasize the following: - a computer assisted charging method ,with the possibility of using a large scale of wastage, also respecting the density proportions of the components of the charges; - the advanced recuperation of the elements of the charge by reducing the combustion of the valuable elements ; - the optimization of the oxygen blast conditions and of the aftinage stage ,by establishing some calculations concerning critical carbon content , that requires the oxidation to be continued very carefully; - the simulation of the thermic and chemical parameters by modeling the alloying process of the stainless steel in the case of some large amounts of additions.

Jan 1, 1994

By Bo Björkman

Four different arsenic containing dusts from the Boliden plant, Boliden mineral AB, Sweden have been examined. A kinetic study of the As elimination was performed in a laboratory scale roasting furnace for roasting furnace ESP dust and smelting furnace ESP dust. Characterisation and thermodynamic calculations were carried out to determine the mineralogy, and the stability of compounds in the dusts studied. The characterisation methods used were chemical analysis, X-ray diffraction analysis and microprobe analysis. It was found in the experiments that a high degree of As elimination was obtained for roasting fumace ESP dust and a low degree for smelting fumace ESP dust. Derived kinetic models are given. A prediction of the As-elimation for settling furnace dust and converter ventilation dust is presented.

Jan 1, 1994