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By B. Mishra, W. A. Averill

"The application of various hydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, ego metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been investigated and suggested for dealing with some of these wastes and scrap material.The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EM] and decontamination and decommissioning [D&D].IntroductionThe high temperature carbothermic or metallothermic smelting reduction methods for metal production are associated with the generation of significant quantity of waste as slags, flue dusts, sludges, residues, effluent salts etc. Certain hydrometallurgical processes also generate lots of aqueous waste due to the inherent nature of the technique. Also, the gas-based reduction processes are not applicable to many stable metal compounds, such as alumina, titania, beryllia, lanthanide and actinide oxides, etc. due to thermodynamic considerations. All these methods cause substantial environmental hazard. There is a need to develop alternative processes which have low waste or ideally a ""zero-waste"" generation.Pyrochemical processes using molten salts provide a unique opportunity for the extraction and refining of many reactive and valuable metals either directly from the beneficiated ore (aluminum, beryllium, neodymium, plutonium, uranium, etc.) or from other process effluent that contain reactive metal compounds. The processes reduce metal compounds electrolytically (A12O 3 and BeCI2) on a carbon anode or by calciothermic reduction (Po, Nd). The by-product, in the latter case, is a calcium oxide saturated halide salt. The waste-treatment to recycle the halide has to be done as a separate step or stored as a contaminated waste. A successful separation technology can provide a new insight to the waste minimization strategy for the nuclear industry."

Jan 1, 1996

By Veena Sahajwalla

The cupola furnace is a coke-fueled shaft furnace used as a primary melting unit in iron foundries. Control of chemical composition of the iron tapped from the cupola is a key factor in productivity and quality control. In an effort to develop a control model for the cupola, a fundamental approach based on physical and chemical principles has been taken to describe the melting process. The behavior of oxidation of the solid charge in the stack of the cupola has been studied. Sulfidation of the charge materials by sulfur-bearing components released to the furnace gases from the coke has been described. Carburization of metal droplets of iron and of steel in separate molten streams has been characterized. Finally, reactions with alloying elements in the hearth (well) of the furnace have been defined. These reactions have been described in a computer-implemented model developed to predict the composition of the iron tapped from the cupola. The model has utilized the thermodynamics and kinetics of the oxidation, sulfidation, and carburization reactions, including temperature and physical aspects, in the various zones of the melting unit. The model predictions have been compared favorably with operating results.

Jan 1, 1992

By David S. Holmes

An overview of existing biological technologies for the recovery of copper and uranium is presented. Engineering and biological challenges and opportunities in these areas. are discussed. New opportunities for the biooxidation of refractory gold ore are described. Techniques for the development of new strains of microorganisms. for commercial metal recovery applications are discussed with special reference to the genetic manipulation for bacterial strain improvement.

Jan 1, 1991

By Edgar Peek

Lixiviant regeneration is by definition a precondition for any hydrometallurgical process. In chloride hydrometallurgy either HCl or Cl2 has to be regenerated in order to establish an economically viable metallurgical process. One such regeneration process is widely used with steel pickling where HC1 is regenerated through the thermal decomposition of ferrous chloride in either spray roasters or fluid bed pyrohydrolyzers. This standard HC1 regeneration process deserves to be considered as a potential separation process, since thermodynamic calculations show that a fluid bed pyrohydrolyzer can function as a ferrous-nonferrous separator. Several nonferrous,metals such as zinc, lead and cadmium can be volatilized as a chloride under ferrous chloride pyrohydrolysis conditions. If such a nonferrous metal volatilization could be achieved in the case of slurry feeding of "contaminated" iron oxides, then this would increase the Fe/H2O ratio of the (process) feed and thus save on fuel per ton of iron, while yielding a marketable iron oxide product. Previous test work on synthetic materials revealed that the near-complete separation of zinc, lead and cadmium from iron oxide was possible in a pyrohydrolytic atmosphere, even if zinc was present as zinc ferrite (more than 99.5%). This investigation, which was carried out in a tube furnace at 1100 K has now been extended to treat synthetic zinc minerals and also franklinite ore. For the latter, it was found that 85% zinc volatilization could be achieved in 4 hours at 1300 K. It is postulated that complete zinc volatilization could not be attained due to the formation and/or presence of gahnite and hardystonite, which might be stable in HCl/H2O atmospheres at 1100 K. The effect of adding small amounts of calcium chloride to react with gahnite and hardystonite to give zinc chloride and both calcium aluminates and silicates is being discussed. Test work on slurry feeding of this complex ore in a recently constructed 4-inch diameter fluid bed pilot unit has been planned for the near future.

Jan 1, 1995

By B. C. Blakey

Unlike most hydrometallurgical slurries, those containing significant concentrations of goethite are typically highly viscous and shear-thinning, even at solid volume fractions below 5%. The viscosity may also depend upon time. These characteristics must be taken into consideration in slurry transport and heating. The technical literature is replete with apparent contradictions regarding the viscous behavior of these slurries, which may be due, in part, to variations in viscosity-measuring techniques. We present techniques that yield consistent results suitable for use in process design. A striking degree of time-dependent behavior is demonstrated for a laterite slurry. Reliable methods to design and analyze tubular transport and heating systems for time-independent slurries are summarized. Rules of thumb are then offered to account for the effects of time-dependency.

Jan 1, 2000

By O. Barbosa F.

The thermochemistry of the systems SCN-H2O, Au-SCN-H2O and Ag-SCN-H2O is discussed. Potential-pH diagrams at 25°C are drawn for each system considering several sets of concentrations of the species involved. The information provided by the potential-pH diagrams is.complemented by distribution curves for each series of gold and silver complexes with thiocyanate. The analysis includes comparisons between the thiocyanate systems and the analogous cyanide systems, pointing out analogies and differences between the leaching of gold and silver with thiocyanate and with cyanide. The possibility of using soluble oxidizing agents such as ferric ions, hydrogen peroxide and Caro's acid is evaluated. The thermodynamic data used in the calculations and the chemical reactions represented in the Pourbaix diagrams are all reported in three Appendices. The overall results indicate the thermodynamic conditions for gold and silver leaching by thiocyanate.

Jan 1, 1989

By S. K. Wu, Ray Y. Lin, Sunil Annaji

Infrared joining of TiAI using aluminum foils as the filler material was investigated at temperatures between 1050 °C and 1350 °C in a flowing argon environment for times varying between 15 and 60 seconds. Using aluminum foils, the attempt was to form the Al3Ti phase in the joint as a result of reaction between Al and TiAI at temperatures above the melting point of Al. It has been found based on X-ray diffraction and TEM analysis that, Al3Ti, indeed is the product of infrared joining of TiAI using Al as the joining alloy. Al3 Ti was detected even in the joint processed at 1050 °C for only 15 seconds. Since the aluminum foil used in this study contains 27 at% Si, the t 2 phase in the Ti-Al-Si ternary system is believed to have also formed at the joint/base TiAI interface. Cross sectional studies on the joined specimens have shown different degrees of reaction depending on the temperature and time of joining. Micro hardness evaluations across the joint show that the hardness near the center of the joint is typically smaller than that near the joint edge next to the base material. However, as the joining temperature and time increase, the increment of the hardness at the center of the joint is faster than that around the periphery of the joint.

Jan 1, 1996

By lchiro Aoi, Hideo Nakae, Makoto Yoshida, Makoto Ishino

"The influence 6f gravity on the microstructure of unidirectionally solidified Cu-Pb monotectic, Ag-Si and Fe-C eutectic alloys is studied. In order to examine the influence of gravity in a lg environment, both the upward (opposite to direction of gravity) and downward (direction of gravity) unidirectional solidifications are carried out. The results are as follows: (1) For the upward solidified Ag-Si eutectic alloy, the eutectic Si continuously grows. On the other hand, in the downward solidified Ag-Si alloy, the Si grows discontinuously and disperses into the ex-Ag matrix. (2) No morphological difference in the eutectic growth is observed between the upward and downward solidified Fe-C eutectic alloys. (3) In the case of the upward solidified Cu-Pb monotectic alloy, a banded structure, which consists of Pb-rich layers and Cu-rich layers, is observed. However, such a banded structure -is not observed in the downward specimen. (4) The banded structure is not found in the upward solidified Cu-Pb-0.05 mass % Al and Cu-Pb-0.1 mass % Al alloys. In the Cu-Pb-0.05 mass% Al alloy, a fibrous -L 2 phase grows continuously parallel to the growth direction at low growth rate. Only 500 mass ppm addition of aluminum induces the morphological change of the monotectic L2 phase.IntroductionThe influence of gravity on the solidification of eutectic and monotectic alloys has been investigated in microgravity environments [l-9]. The purpose of these studies was to obtain a homogeneous microstructure of eutectic or monotectic alloys, most of which alloys tend to solidify with macro-segregation under gravity. However, in most of the previous experiments, e.g., in free fall systems, in aircraft or in space laboratories, the growth rate was too high to realize a planar solid/liquid interface. This would be due to the limited time for solidification. Thus, it was difficult to examine the influence of gravity on the planar coupled growth of the eutectic or monotectic alloy. In this study, both the downward U.D.S. (unidirectional solidification by gravity) and upward U.D.S. (opposite direction to gravity) are carried out in order to examine the influence of gravity on the coupled growth in a lg environment [l0, 11]. In the case of the downward U.D.S. using the current Bridgman method, the molten alloy must be confined between the crucible and the solid."

Jan 1, 2000

By N. Tsuchida

Sumitomo Metal Mining Co. Ltd. (SMMC) is currently developing the flowsheet to treat stockpiled limonite, a type of laterite ore, at Rio Tuba on southern Palawan Island, Philippines. The new plant will be commissioned at the end of 2004. Rio Tuba Nickel Mining Corporation (RTNMC) has been mining saprolite since 1977, and the limonite ore located above the saprolite ore body has been stockpiled separately according to nickel and magnesium content. Ore from these stockpiles will be blended and used for the operation. The annual production of nickel will be 10,000 metric tons for the next twenty years. The proposed process consists of ore preparation, high pressure acid leach (HPAL), counter- current decantation wash, impurity removal and sulfide precipitation. Precipitated mixed sulfide will be processed to electrolytic nickel by the Matte Chlorine Leach Electrowinning (MCLE) process at Niihama, Japan. SMMC has established new technologies during the process development, such as zinc removal and sulfide precipitation. Applying this technology, preferential removal of zinc can be achieved by hydrogen sulfide gas with negligible loss of nickel. Precipitation of nickel by hydrogen sulfide gas is carried out at low temperature. Slow kinetics is selected for control of the particle size of the precipitated mixed sulfide. Keywords: HPAL, Zinc Removal, MS Production

Jan 1, 2004

By Tetsuro Ohashi, Tooru Matsumiya, Yoshio Abe

"The three-dimensional deformation of a continuously cast slab was modeled into two-dimensional deformation by developing the solidified shell of the slab. The developed solidified shell was divided into rectangular elements. The thermal strain produced as the slab is wi thdrawn over one roll spacing in the casting direction was calculated from the temperature change during that time and the increment of the geometrical unbending strain during the time was calculated from the change in the radius of curvature of the slab by assuming that the neutral axis of bending is located at the mid-thickness of the slab and that the transverse section of the slab is kept in a plane during unbending. These strains were imparted to each element as initial strains. The interaction between the elements and the overall deformation of the solidified shell were analyzed by the finite element method.The analysis was performed on a slab being cast on a machine of the circular arc type with progressive unbending. The following findings were obtained as a result. The effect of unbending is spread in the upstream and downstream directions of the slab by the shear deformation of the narrow and wide faces. As the shear deformation increases, the strain in the unbending zone decreases and the strain outside of the unbending zone increases. The effects of secondary cooling conditions, slab size, radius of caster circular arc section, compression casting, etc., were also analyzed. IntroductionTo develop a method for preventing the internal cracking of continuously cast slabs, it is important to acurately analyze the deformation of the slab and this subject has been extensively investigated. Many researchers, including the present authors, have analyzed slab bulging. (1)- (11) Analysis has also been made of thermal deformation that assumes importance in continuous casting of small-section blooms.(12)-(18) However, unbending deformation, an extremely important subject for continuous casters of the circular arc type, has not been fully analyzed."

Jan 1, 1986

By J. Fraser Forbes

"The meaning of the term ""process control"" has evolved significantly since its widespread use began in the manufacturing industries in the 1940s. Further, the scope of process control applications has drastically increased both in terms of the breadth of industries using process automation technologies and the vertical integration of these technologies within a single industry. This evolution and integration of process control technologies within the manufacturing industries has proceeded to such an extent that process automation is an integral part of modern business practices.This paper will examine the current status of process control technology from simple process regulation through process performance optimization to business planning. Each layer of the operations automation hierarchy will be discussed both in. terms of the current state-of-the-art and the directions in which these technologies are evolving. The key tools and tasks necessary for success at every level of the automation hierarchy will be introduced. Finally, the critical challenges that must be faced in accomplishing the goal of complete Computer Integrated Manufacturing (CIM) will be described.Finally, although this paper addresses issues of practical importance to any manufacturing company, the discussions will be framed in terms of the particular challenges facing and the opportunities available within the materials manufacturing industries."

Jan 1, 2000

By F. J. J. van Loo, J. K. Kivilahti, M. Paulasto

"Activation mechanism and interfacial reactions in brazing of ShN4 with different AgCuTi filler alloys has been investigated thermodynamically and experimentally. During brazing the AgCuTi filler alloy is divided into two liquids Ll and L2, where the (Cu,Ti)-rich liquid L2 gathers at the ShN4 interface and reacts with it. The concentration of Ti in L2 is high, but due to the strong attractive interaction between Cu and Ti, the activity of Ti in L2 is considerably low. In reaction between ShN4 and Cu-containing brazes a Ti-Cu-Si-N compound is typically formed at the interface. In absence of Cu, in joints brazed with AgTi based filler alloys, extremely Ti-rich solution reacts with ShN4 and as reaction products TiN and TisSh[N] are formed. IntroductionAdvanced ceramics like silicon nitride are increasingly used as structural components in demanding applications as well as in electronics industry. Complex, multicomponent structures for engineering applications generally require interconnections and therefore joinability of ceramics largely determines the possibilities of metal-ceramic structures to enable demanding functions. Brazing with active filler metals, most of which are based on the Ag-Cu-Ti system, has been commonly employed for joining of ShN4 to other ceramics and metals. The interfacial microstructures formed when ShN4 is brazed with Ag-Cu-Ti braze alloys have been discussed in several recent studies [1-7]. However, some inconsistencies exist in the reported results. The formation of layers of TiN and titanium silicides, possibly TisSh, next to the ShN4 has been reported in several studies [1-5], while in another investigation, a layer of an orthorhombic TiSi- Cu-N phase was found beyond the TiN layer [6]. In few investigations the thermodynamics of the ShN4-Ti system has been considered, but no detailed thermodynamic analysis of the chemical interactions between the braze and ShN4 has been provided. In order to resolve which chemical reactions are possible under various joining conditions and thereby to be able to control the brazing of ShN4 the reactions in brazing has to be studied using both microstructural and thermodynamic analysis."

Jan 1, 1996

By Rolf R. von Oppenfeld

Onsite hazardous waste processors often find obtaining a Treatment Storage and Disposal (TSD) permit one of their first major challenges. Some processors may spend the time and money required by the permitting process, only to find out later that a permit was not necessary. This paper will present and analyze four strategies that processors may use to avoid obtaining a TSD permit. Some facilities will be able to remove their waste streams from RCRA's oversight by ensuring the material is not "hazardous" waste. Parties that treat waste while it is in process may be able to avoid generating "waste" altogether. Certain treatment facilities have been specifically exempted by EPA. Finally, treatment of waste while it is in generator storage tanks may be allowed without a RCRA TSD permit. Hazardous waste point of generation, an important determination relating to these strategies, will also be discussed. Generators and processors will find this paper useful when evaluating their permit exemption potential

Jan 1, 1996

By F. F. Aplan, G. Simkovich

"A review is given of the effects of solid state point imperfections upon a number of mineral benefication processes and a metal extraction process. It has been found in numerous flotation studies that small amounts of aliovalent impurities (dopants) in binary compounds may show major effects upon flotation behavior. Both semiconducting and ionic conducting compounds are affected. These effects are also seen in hydrometallurgical studies as well as in electrostatic operations. Additionally, de-copperization of lead melts appears to be strongly influenced by similar defects. It is hypothesized that the effects observed in these studies are present in actual operations and should be considered in designing processes. A few speculations concerning future efforts are advanced. IntroductionImperfections [point (e.g., vacancies, interstials, quasi-free electrons, electron holes, impurity ions), line (e.g., dislocations), two dimensional (e.g., grain boundaries) and three dimensional (e.g., 2nd phases) defects] are generally present in solid materials and these imperfections may, and often do, have important effects upon a variety of properties and processes. In general, one may, in most cases, attain elimination of three dimensional defects by a separation process of one type or another (e.g., gravity, electrostatic, magnetic, flotation, hydrometallurgical etc.,). Thus, this type of defect has rarely been investigated in a systematic fashion. Two dimensional defects are always present in non-single crystal materials but have also escaped systematic studies in processes primarily because the control of such defects is not easily attained. Line defects are non-equilibrium entities which are present in ill-defined quantities so that they present a variable that cannot be easily controlled although through careful systematic experiments one can attain some reproducible relations pertaining to this type of defect.Contrary to the lack of studies concerned with the effects of 1, 2 and 3 dimensional types of defects there has been some activity concerned with point defects and their effects upon a number of mineral/metallurgical processes, especially flotation processes. Thus, this article will present a review primarily of point defects in relation to their effects upon flotation although other processes and defects will also be mentioned."

Jan 1, 1988

By Denise Corrêa de Oliveira

Common dry batteries use zinc as the negative electrode. Producers commonly use additives such as mercury to prevent corrosion and to increase the mechanical resistance of the zinc anode. Alkaline batteries also contain it, as an anti-corrosive agent. When mixed with the common municipal solid waste, heavy metals as zinc and mercury pollute soil and ground water supplies, moving to the food-chain and affecting human health. Due to these possible damages, this kind of waste must be properly disposed, or recycled. Thus, even in low amounts (ppm) in batteries, mercury has to be eliminated or, at least, its content should be reduced. This work presents the use of pyromettalurgical processes, to reduce mercury content and recover zinc. The tests involved batteries treatment at temperatures from 300° to 1000°C. Mercury is eliminated up to 650°C, and zinc is evaporated at higher temperature treatment. C

Jan 1, 2001

By W. Petruk

The behaviour of galena, chalcopyrite and tetrahedrite during floration of a fine-grained base metal ore from New Brunswick was investigated by image analysis study of the mill concentrates and tailings. The minerals were analyzed to determine the grades and recoveries as related to free and unliberated mineral grains and their size distributions. The results show that only 37 wt % of the galena was liberated but 88 wt % of the free galena was recovered, indicating good mill performance for the lead. The lead recovery was 65 wt %, with the main loss due to unliberated galena. Most of the unliberated galena lost to mill tailings is so fine-grained that galena liberation and Pb recovery would not improve significantly by re-grinding. Chalcopyrite liberation was 56 wt % but only 75 wt % of the free chalcopyrite was recovered. Copper recovery was 45 wt %, with the chalco-pyrite loss in the mill tailings being both as large free grains, and as small and large unliberated grains. It was calculated that copper recoveries could be improved about 8 to 10 wt % by changing the concentrator operations and by regrinding. Concentrator operations hive already been modified and copper recoveries have improved about 5 wt %. About 29 wt % of the silver was lost to tailings mainly as both free and unliberated, large and very small, Silver-bearing tetrahedrite grains. It was calculated that about 25 wt % of the silver in the tailings might be recovered by improved milling conditions and by regrinding.

Jan 1, 1981

By Filiz Sahin

This paper presents a synthesis of TiB2 via carbothermal reduction method using a mixture of TiO2, B4C and C prepared in molar ratio of 2:1:3. Reduction experiments were carried out in a high temperature graphite furnace in a graphite crucible under argon atmosphere at different time (0, 15, 30 and 60 min.) and temperatures (1400, 1500 and 1600 °C). The products obtained were investigated using XRD technique.

Jan 1, 2008

By J. T. I. Poijärvi

Outokumpu Harjavalta Metals Oy operates copper and nickel smelters, three sulphuric acid plants and nickel refinery at Harjavalta and copper refinery and precious metal plant at Pori. The by-products of these plants are presented in this paper. The by-products of the smelters include products from slag cleaning of flash smelting furnaces and converters, flue dusts and smelter off-gases. Weak acid and sludges from cleaning of smelter off-gases and acids are the by-products of the acid plants. The by-products out of the copper refinery are crystallized metal sulphates and sludges from electrolyte purification, on which a co-production process of the copper tankhouse is based. The main by-products of the precious metals plant are products from anode slime treatment and platinum metal group concentrates in the recovery of precious metals. Sludges from nickel matte leaching and precipitates from solution purification are the by-products of the nickel refinery. The formation, treatment and processing as well as the research work done for the utilization instead of dumping of the by-products in the production of copper and nickel will also be discussed in this paper.

Jan 1, 1995

By Richard D. Hagni

The techniques of reflected light microscopy and cathodoluminescence microscopy are uniquely suited to the study of the products from many important industrial problems. Ref1 ected 1 ight microscopy provides the means to rapidly identify the mineralogy of an industrial sample, determine the abundance of each phase, and examine the mineral intergrowths or textures. Cathodoluminescence microscopy is a relatively new instrument that provides the means to cause many minerals to cathodoluminescence under the microscopy. The cathodoluminescence of a mineral allows it to be readily distinguished from other phases that differ in cathodoluminescence but are similar in optical properties. Cathodoluminescence microscopy is especially useful to detect cathodoluminescence minerals that are present in only small quantities. Reflected 1ight microscopy and cathodoluminescence microscopy have been successfully applied in studies of beneficiation products, prediction of beneficiation and leaching problems, phosphatic iron ores and mill products, pyrometallurgical products, roasted refractory gold-bearing sulfides, ceramic build-ups, electric arc furnace and smelter dusts, and other industrial products.

Jan 1, 1993

By Ajay K. Singh

The surface quality demands for galvanized and galvannealed steel sheets by the automotive and appliance industries have been getting increasingly stringent over the past few years. Intensive efforts by Hot-Dip-Galvanizers to meet these demands have resulted in substantial improvement to the hot dip coating process. However, elimination of zinc bath contaminants which directly affect the coated strip surface quality continues to remain a tough challenge. As part of our effort to improve the zinc bath cleanliness, Inland Steel Company has developed a test method to quantitatively measure the contaminants in incoming zinc spelters and establish a specification for incoming zinc quality. The test is currently being used for auditing the incoming zinc quality. The zinc suppliers are also using this test for quality control purposes. The purpose of this paper is to describe the test method and how it has improved the galvanizing operation at Inland.

Jan 1, 1992