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By W. K. Connor, O&apos

The U.S. Bureau of Mines, in cooperation with the Idaho National Engineering Laboratory (INEL), conducted over 30 hours of melting tests to vitrify simulated low-level radioactive wastes from the INEL Radioactive Waste Management Complex (RWMC). Five separate waste compositions were investigated, each consisting of noncontarninated soil from the RWMC and surrogate materials used to simulate the actual buried wastes. The RWMC soil and five waste compositions were melted in a 50-lb, single-phase electric arc furnace with a water-cooled shell. These tests were conducted to determine melting parameters in preparation for a large-scale melting campaign to be conducted in the Bureau's 1-metric ton (mt), water-cooled-wall, 3-phase electric arc fumace. Bulk chemical composition was determined for each of the feed materials and for the slag, metal, fume solids, and offgas furnace products, and distributions were calculated for the key elements. The material balance for the furnace operation indicates that from 63 to 84 pct of the feed reported to the slag. Cerium, used as the surrogate for the radionuclides in the wastes, demonstrated an extremely strong affinity for the slag product. Although slag temperatures as low as 1250° C were recorded when melting the RWMC soil, temperatures in excess of 1600° C were necessary to achieve the fluidity required for a successful slag tap.

Jan 1, 1994

By E. A. van Dijk

Dusts from steel-making processes contain substantial amounts of zinc. Such dusts are also a hazardous waste and dumping them becomes unacceptable from environmental point of view. Therefore processes that can recover zinc and possibly other metals from steel-making dusts are being investigated. The aim of this paper is a contribution to the more fundamental kinetic aspects of zinc reduction from silica free calcium ferrite slags. The effects of alumina, lime and magnesium oxide contents of the slag, the COICO, ratio and the effect of initial Fe2O3/CaO ratio were studied experimentally at 1400°C The results indicated that the reduction of zinc from molten slag was possibly a first order reaction. As expected higher COICO, ratios increased both the extent and the rate of reduction. It was also observed that a higher iron content of slag improved the reduction of zinc from calcium ferrite slags. This fact seems to support the proposed mechanism that zinc is partly reduced by ferrous iron to zinc vapour and that ferric iron is reduced by carbon monoxide. The reduction rate of zinc in these slags was decreased by increasing alumina content of the slag. Alumina decreased the calculated optical basicity of the slag showing the fact that reduction of zinc oxide was more favorable in more basic slags. Probably the formation of complex ions by alumina and zinc oxide such as ZnAl2O32+ lowers the activity of Zn2+ ions in the slag and hence render them more difficult to reduce.

Jan 1, 1999

By G. B. Harris

Much has been written over the past decade concerning the disposal of arsenic from metallurgical processes. In Canada, there are proposed regulations which would classify arsenic in the Primary Group of twenty one persistent, toxic pollutants to be banned or phased out. Since many nickel and cobalt ores, not to mention those of copper, gold and uranium, contain significant amounts of arsenic, it is pertinent to assess the current state-of-the-art of its disposal. The literature is reviewed, and it is demonstrated that from a purely chemical point of view, the family of ferric arsenates largely immobilize arsenic. There is clear evidence from laboratory studies that both crystalline ferric arsenate (scorodite) and amorphous ferric arsenates in which the molar Fe/As ratio is at least three (Fe/As = 3) have very low arsenic solubility; plant data are given to support this. The debate over the long term stability of these compounds continues however; the evidence presented for long term stability and for compound breakdown is critically reviewed in the light? of the recent structural studies, and the role of base metals in these compounds evaluated. Finally, conclusions are drawn as to the viability of a purely chemical process for the long term disposal of arsenic from metallurgical processes.

Jan 1, 1993

By David Seymour

Newmont Gold Company (NGC) located in Northeastern Nevada has been processing carbonaceous and sulfide refractory gold ores through a chlorination circuit prior to cyanidation. A "Flash Chlorination" pilot plant was installed in 1987 in an effort to obtain higher chlorine utilization efficiency and increase gold extraction. The Flash Chlorination process oxidizes organic carbon and sulfide sulfur. It also deactivates preg-robbing carbon, making the ore amenable to cyanidation. Significant recovery improvements were observed using this new process. This scheme has also been instrumental in the processing of higher than normal grade ores at economic chlorine levels. The Flash Chlorination pilot plant has been successfully treating carbonaceous ore on a production scale since April 1988. This paper summarizes laboratory and pilot plant optimization test work, using conventional and statistical methods.

Jan 1, 1989

By C. J. Malek

The CONTOP® smelting cyclone technology is a large-scale and time-proven method which in combination with other technologies (grinding, drying, pyrolysis, etc.) provides for a cost- efficient and ecological disposal of a wide range of waste materials from industry and households. In this report the basic principle of smelting cyclone technology will be explained first. Subsequently, the paper will discuss substantial concepts for the recovery of various remainders.

Jan 1, 1996

By Alan James Parker

Chalcopyrite can be converted to pure copper by the following five steps. An exothermic sulfation roast of chalcopyrite; leaching of cupric sulfate from the calcine with dilute acid; precipitation of Chevreul's salt and or other copper sulfites with ammonium sulfite or precipitation of crude copper by autoclaving ammonium sulfite and cupric sulfate at 150°C; dissolution of Chevreul's salt, or the crude copper, as cuprous sulfate, using acidic cupric sulfate in an acetonitrile-water solution as oxidant; precipitation of pure copper by thermal disproportionation of the cuprous sulfate solution. Acetonitrile and acidic cupric sulfate solution recycle. Advantages over conventional processes include lower cost, lower energy consumption as waste heat, sulfur removal as ammonium sulfate or gypsum, rather than as sulfur dioxide and rapid throughput. The net reaction is: 2 CuFeS2 + 4H20 + 15/2 02 + 8 NH3?2Cu + 4 (NR4)2 SO4 + Fe2O3

Jan 1, 1976

By Donald Voit

"The reaction between zirconia/zircon, coke, and chlorine involves a slow reaction between the coke and the zirconia/zircon and a fast reaction with chlorine. Because of the fast chlorine reaction, the reaction rate for zirconia/zircon is nearly independent of chlorine concentration for most conditions. The reaction between zirconia/zircon and coke is particle size controlled and related to the degree of physical contact between the zirconia/zircon and the coke. Since particle-particle contact is critical, compaction of finely ground coke and zirconia/zircon produces the highest reaction rates. Uncompacted, coarse coke and zirconia/zircon has the slowest reaction behavior with static bed tests.SummaryZirconia reacts with chlorine in the presence of carbon to form zirconium tetrachloride, carbon monoxide, and carbon dioxide. A similar reaction occurs with zirconium silicate with the additional formation of silicon tetrachloride. The reaction rate depends primarily on temperature and the intimacy of contact between the zirconia and the coke. The reaction is multi-stepped with a slow reaction between coke and zirconia to form an intermediate that reacts rapidly with chlorine, causing the order of the reaction for chlorine to be near zero. Chlorination rates in the range of 1 µmole/hr/cm2 are seen for fluid bed reactors. Plug flow, and static bed reactors have reaction rates of the order of 1 mmole/hr/cm2, where the area is based on the zircon surface area in plug flow and fluid bed reactors and the boat cross sectional area in a static bed. Chlorination rates measured in zirconia/coke briquettes are higher with rates as high as 400 mmole/hr/cm2 reported. High chlorine diffusion resistance, not accounted for in the analysis of experimental results, has led to a lot of confusion in the literature interpretation of chlorination data.In general coke and zirconia/zircon particle size, coke and zirconia/zircon intimacy, coke to zirconia/zircon ratio, chlorine concentration, and temperature are important variables for chlorination. Decreasing the coke and zirconia/zircon particle size generally increase the reaction rate. The coke to zirconia/zircon ratio affects the reaction in a more complex way. Increasing the chlorine concentration generally increases the reaction rate, but the effect appears to be more related to the concentration dependency of diffusion than to its role in the kinetics. The reaction rate increases with temperature but the exact behavior is complicated by temperature effects on diffusion."

Jan 1, 2011

By Yukio Ishikawa

Sumitomo Metal Mining Co,. Ltd. (SMM) has been producing 22,000 t/y of electrolytic nickel at Niihama by nickel matte electrorefining process since 1970. Although the matte electrorefining is an established process and the productivity has been greatly improved in the last 20 years, SMM has intensively developed the chloride process for the nickel production since 1970's. The nickel and cobalt refining process involving solvent extraction and electrowinning from the chloride solution has been successfully developed for the treatment of the mixed sulphide in 1975. The first application of chlorine leach to the anode slime has been succeeded since 1986. Based on those technology, the matte chlorine leach electrowinning process (MCLE) has been developed as an alternation to the relatively old technology of matte electrorefining. The new process offers significant cost down and excellent quality of the product. In 1986, the feasibility of MCLE was confirmed by the test work using the integlated pilot plant. The innovation of the chlorine leach process has been undertaken by this work. The new refining process can be divided into three stages including chlorine leach stage, purification stage and electrowinning stage. More than 99 % of nickel was extracted in atmospheric chlorine leach. Although copper ion was used for electron carrier in the chlorine leach, the excess copper from the feed matte is bled off from the leach circuit by de copperizing electrolysis. The copper ion of the pregnant solution is fixed on nickel matte by the cementation reaction. The nickel matte containing copper is processed in the chlorine leach. In the purification circuit, cobalt, iron and other impurities were removed from the nickel chloride solution. The nickel chloride solution is then fed into the electrowinning cell. Based on the process established, the new plant with a capacity of 330 t/M electrolytic nickel was commissioned in order to obtain the engineering data for design of the full scale plant in 1989. The performance of the plant was fully satisfied and the new process demonstrated the potential application of modern process control.

Jan 1, 1992

By S. G. Kumar

The performance of nickel based high temperature materials is directly related to their microstructure, which is controlled by the various processing steps. Nickel base alloys are melted and refined by a variety of processes that include Vacuum Induction Melting (VIM), Vacuum Arc Remelting (VAR) and Electroslag Remelting (ESR). The limitation of VIM is that the metallrefractory reactions lead to the disintegration of the crucible and hence contamination of the product due to macrosegregation. This macrosegregation is alleviated to some extent by controlling the solidification in VAR. The main attraction of ESR is its ability to produce a clean product by controlling the deleterious inclusions. In recent years Electron Beam Melting (EBM) is emerging as an alternative to the VIM, VAR and ESR. This paper reviews the current status of these processes and outlines the scope for further improvements in the processing technology.

Jan 1, 1993

By Miroslav Raudensky, Kallol Bera, Jaroslav Horsky, Jee G. Chang, Ampere A. Tseng

"A combined experimental and finite element approach to study the local heat transfer coefficient is presented in this paper. The heat transfer coefficients at different cooling regimes in a roll are quantified by an inverse heat conduction technique; the heat transfer phenomena involved are then discussed. A discussion of the application of the heat transfer information found in the present study for better design of a roll cooling system is also included. Finally, an identification of areas where further work is needed is presented.IntroductionIn metal rolling processes, the roll is used as a tool to deform the workpiece at very high speeds. As shown in Fig. 1, the heat transfer phenomena involved in the process are complicated by the interaction between the roll and the strip, mainly including 1) the heat transferred from the workpiece to rolls in the contact regions, 2) the heat created in the interface due to the deformation of the workpiece and the friction between the workpiece and roll, and 3) the heat removed by watercooling as well as the ambient air. All of these transport phenomena occur at extremely high pressure, high speed, and high heat flux; these make the control of the roll temperatures an extremely challenging problem.In hot rolling, proper cooling of rolls can lead not only to improve the roll shape quality by controlling the thermal crown of the roll, but also to extend the roll life by minimizing the thermally induced stresses [1,2]. Also, knowledge of roll temperatures can contribute to insights about the roll/workpiece interfacellubricant behavior, and lead to the desired surface condition of the workpiece. Therefore, adequate roll cooling or control of roll temperatures is of critical concern to mill designers and process engineers. In order to have proper operation of the process, a good understanding of the influence of cooling practices on the roll is essential [3]."

Jan 1, 1994

By R. Hurman Eric

The dew-point technique of activity measurements take advantage of the volatility of a component in solution. The pressure of the volatile component over a sample is determined from observations of the temperature at which condensation of the vapor occurs. The method is applicable best when the vapor pressure of the components would differ by about two to three orders of magnitude. Experimentally, this is a closed system involving the use of evacuated and sealed transparent quartz sample probes. Furthermore reliable vapor pressure data of the volatile component is essential along with a specialized high temperature furnace capable of giving reproducible results. In this context, the vertical Dew-Point Furnace (DPF) was designed and built after elaborate trails until enough proficiency was gained for reproducible results. Over the years the DPF was modified and improved. The DPF developed was versatile and could easily be used for activity measurements in the isopiestic mode (another method of measuring activities of a volatile component in a solution). The necessary ancillary systems; namely evacuation-flushing-evacuation followed by sealing of quartz sample probes under vacuum were also perfected over the years. As and when necessary the dew-point technique was supplemented by classical equilibration-quenching method employed on the sealed quartz sample probes to reveal necessary phase equilibrium information. The following were studied utilizing the above technique: (i) Activities in CU2S-PbS and FeS-PbS binaries and CU2S-FeS- PbS ternary at 1200°C; (ii) Activities in Cu2S-SnS and FeS-SnS binaries and Cu2S-FeS-SnS ternary at I200°C; (iii) Phase equilibria and thermodynamic in Cu-Pb-S, Fe-Pb-S, Fe-Sn-S, Cu-Sn-S and Ag-Sn-S systems. Most recently the following systems have been tackled: (i) Phase equilibria and thermodynamics in the Ag-Pb-S and Sn-Pb-S systems; and (ii) Activities in Ag2S-FeS-CuzS-PbS quaternary at 1200°C.

Jan 1, 2003

By B. L. Chulu

In the carbothermic reduction of lead sulfate to produce lead, the inclusion of soda ash (Na,CO,) in the charge provides for the control of sulfur dioxide in the effluent gas. An important mechanism in the process appears to be the carbothermic reduction of the sodium carbonate whereby sodium gas and carbon monoxide are produced. These intermediates then participate in the reduction of the lead sulfate to produce lead metal and stable sulfur species in the molten slag phase. In addition, there is some evidence that the presence of lead metal in the charge may also serve to increase the lead recovery in the process. These aspects were investigated by conducting laboratory-scale smelting tests with small charges (;3g), at 1173°K(9000C). Recovery did not exceed 74w% and the role of incipient lead metal in the charge could not be clearly assessed.

Jan 1, 1993

By Kazuhiro Nisizono, Takashi Kuroki, Nobuyuki Mori, Keisaku Ogi

"The improvement of critical current density and mechanical property is essential to the practical application of the superconductive oxides. A solidification technique is developed in this study for the growth of columnar or single Y123 crystal with finely dispersed Y211 and Ag particles through a monotecto-peritectic reaction of Li.(Ba-Cu-Ag-0 rich liquid)+ Y211-+ Y123+Lz(Ag rich liquid). The large solidification rate and temperature gradient can refine the Ag and Y211 particles. But Ag-free region is widely formed along the crystal growth direction in the central part of the Y123 cell. Since this phenomenon occurs because of the cellular growth, it is necessary to narrow Y123 cell width or to grow Y123 crystal with flat freezing interface. By controlling crystal growth direction using a seed crystal, Y123 columnar or single crystal with uniformly dispersed fine Ag particles are obtained. The· behavior of Ag and Y211 particles during the solidification of Y123 crystal is simulated by the peritectic growth model of faceted Y123 crystals.IntroductionY-Ba-Cu-0 superconducting oxide (YBCO) with high critical temperature also has excellent superconducting characteristic under the high magnetic field. The critical current density (Jc) has been enhanced by ·using unidirectional-solidification technique, which can overcome the weak-link problem at grain boundaries and control the crystal orientation and the distribution of Y211 particles which give effective magnetic flux pinning centers in the Yl23 matrix [1-4].In addition to improving superconducting properties, it is necessary to improve mechanical property for the practical application. The silver addition to the melt-textured YBCO superconducting oxide has been reported as the effective method to improve mechanical properties without degrading superconducting properties. Since the material properties are considered to be largely affected by silver particle size, form, dispersion state etc. in the Y123 phase, it is important to control Ag distribution in YBCO/Ag composites. Besides, it is also reported that the silver addition improve the corrosion resistance to the water and CO2 [5,6]. Nishizono et al. [7-9] have reported that the silver distribution in the YBCO/Ag composites is largely affected by the solidification condition, but yet some unclear points are also remained. YBCO has been also fabricated by the zone melting method [10-12], and Furuya et al. [5] and Hirano et al. [13] have reported the fabrication of silver added YBCO composites, but the distribution and behavior of Ag are not investigated in detail"

Jan 1, 2000

By P. R. Khangaonkar

The variety of intermediates, middlings, complex materials and wastes produced in the conventional processing of tin ores as experienced in the tin industry in South East Asia is reviewed. The problems associated with the treatment of these materials so as to produce useful products by hydrometallurgical or pyro-cum-bydrometallurgical approaches are discussed. Results of treatment of amang middlings consisting of cassiterite, struverite, ilmenite, zircon, monazite etc by chlorination with carbon tetra chloride are presented. The efforts to leach tin without letting iron coming in, by alkali leaching of certain wastes of tin processing are also briefly indicated. It is felt that pyro-cum-hydrometallurgical approach can help a viable treatment of these materials so as to obtain usable or value added products.

Jan 1, 1994

By Donald R. Sadoway

Molten salt electrolysis is a proven technology for the extraction of metals -- all the world's primary aluminum is produced in this manner. The unique properties of molten salts, also make them excellent media in which to treat a variety of forms of waste. Of special .note in this regard is electrolysis in molten oxides, a .concept put forward by. the author, initially as a ."clean technology" for producing primary metal. However, in the context of waste treatment, electroly-sis in molten oxides is a process offering the prospect of changing the. valence of dissolved heavy metals while making pure oxygen gas as the main by-product .Laboratory tests conducted at a temperature of 1550°C on chromate sludge dissolved in an melt composed of Al2O3 and MgO have confirmed electrochemical production of oxygen on a carbon-free anode.

Jan 1, 1996

By Carl C. Nesbitt

A study was conducted to examine the treatment of metal-bearing effluents by precipitating the metals as sulfides and simultaneously collecting the particles by flotation. The precipitant was hydrogen sulfide gas which was introduced into a bench-scale column cell with air. The study included experiments of various flotation reagents and column configurations in treating solutions containing dissolved copper, lead, mercury, iron, zinc and cadmium. An acidic laboratory waste from a local copper operation was used to test the column with a solution containing several metals and arsenic. Precipitates were observed to form at the gas/liquid interface when the gas mixtures were rich in H2S. Copper, mercury, lead, and cadmium were precipitated from solution as sulfides to concentrations near detection limits. The flotation of these precipitates was enhanced with small amounts of S-7151 promoter from American Cyanamide Company and Dowfroth 1263 mixed with the feed. The recovery of the precipitates in this manner produced a smaller volume slurry which was easier to dewatering than a slurry produced by conventional precipitation techniques. The low pH and high oxidation-reduction potential in the cell from H2S addition was not conducive to form precipitates of iron, zinc or arsenic. However, these ions were precipitated as sulfides by raising the pH of the column discharge.

Jan 1, 1994

By D. Zhao

High temperature deformation characteristics of austenitic 304L, and martensitic 410 and 416 stainless steels were investigated by conducting compression tests over a wide range of temperatures and strain rates (950-1250 C and 0.001-20 s-1). Flow behaviors of the three alloys were characterized. Optical metallography was performed to determine the as-deformed microstructures. The flow behaviors were related to microstructural phenomena during high temperature deformation. Dynamic recrystallization was responsible for the flow softening. Both dynamic and static recrystallization were operating, and the recrystallized grain size increased with increasing temperature and decreasing strain rate. Strain rate sensitivity was found to increased with increasing temperature and decreasing strain rate. No defects such as cracking and shear bands were observed at those test conditions. Preferred processing conditions can be selected by considering as-deformed microstructure and strain rate sensitivity.

Jan 1, 1994

By G. Upadhya

Of late, solidification modeling has progressed considerably to emerge as a viable simulation tool for the foundry engineer. A wide variety of tools exist in the commercial market to cater to the various needs of the design/ foundry engineer. In fact, recent developments in the area of solidification modeling have been so rapid that a comprehensive review of the state-of-the-art is very much needed. In this paper, an attempt is made to summarize the various issues of solidification modeling, at the same time addressing the historical evolution of the subject. The various phenomenological issues covered in this paper include: heat transfer, fluid flow during mold-filling, solidification kinetics and microstructural evolution, quick-analysis schemes for approximations, porosity prediction models, and the phenomena of fluid flow in the mushy zone. Modeling issues related to the development of solidification stresses which lead to defects such as hot tears and the development of artificial intelligence concepts in the area of rigging design are also discussed. Due emphasis is given to the various phenomena which add to the complexity of the whole subject, and the various alternatives available for solving a particular problem. For example, the heat transfer problem can be approached by the use of simple modulus schemes or by solving the conduction equation to obtain a more accurate temperature distribution. Similarly the microstructural evolution can be handled in a deterministic way by use of nucleation and growth models, or in a probabilistic way by use of empirical models. The main goal of this paper is to put the multi-faceted problem of solidification modeling in proper perspective so that it can serve as a guide for future developments in this area.

Jan 1, 1994

By M. A. Barron, D. Y. Medina, R. T. Hernandez, I. Hilerio

"Chromium Nitride (CrN) thin fihns were deposited on steel AISI 316 substrates with reactive magnetron sputtering method. CrN films were produced under two different conditions. In the first one, the substrate was heated by a d.c. source. At the second coating was applied a negative substrate bias voltage. X ray diffraction, quantitative energy dispersive and scanning electron microscope, were employed to characterize their phases, chemical composition and microstructure. Additionally microhardness was evaluated using a microhardness tester. The results show that the phase formation of CrN thin films in the first case (with temperature) is better. Both coatings presented homogeneous surface. Their compositions shows differences though that gases flow are same. In attention to their hardness, presents an increment if it's compared with hardness substrate.Nomenclature.P Ar =Argon gas pressure during coating.PN2 = Nitrogen gas pressure during coating.Ts = Substrate temperature during coating.T f = Coating melting temperature. (CrN = 1050°C).E=Potential difference.t =Coating time.P=Target power (Cr) in magnetron sputtering de.HV = Vickers hardness.F = Applied charge.d= Average length of longitude of the two diagonals (mm)Introduction.Wear causes losses in materials surface, generating that components of mechanical systems suffer irreversible changes in their properties, causing a faulty operation of the system. It is important to control their effects, measuring and interpreting their causes clearly."

Jan 1, 2013

By Janusz Majta

The aim of this work is to investigate the control of microstructure evolution through variation of particular deformation parameters in the two-phase (intercritical) region. Niobium-microalloyed and low-carbon steels were investigated. A detailed examination of the factors affecting the ferrite microstructures of tested steels indicated that there were distinct advantages of finishing at temperatures in the austenite-ferrite region. The various results of deformation in the two-phase region are presented. Consequently, the influence of the most important process parameters on the microstructure evolution and mechanical response of the material is determined. The prime objective of the realized research work is the determination of relationship between the history of deformation and final product quality i.e. texture and mechanical properties. To reach the objective, the constitutive equations are proposed for modeling the effects of the hot-deformation process occurring in the austenite and austenite-ferrite region of low carbon and microalloyed steels on the mechanical properties of the resulting product. These models link advanced, finite element approaches simulating metal flow and heat transfer during hot-plastic deformation with constitutive equations describing microstructural processes and mechanical properties.

Jan 1, 2003