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By L. H. Gevantman

A program for the compilation of evaluated physical and chemical numerical properties data is being pursued at the National Bureau of Standards within the Office of Standard Reference Data. This program is being sponsored by the Department of Energy and managed by the Battelle Office of Nuclear Waste Isolation in Columbus, Ohio. The intent is to assemble a reliable body of numerical properties data concerning candidate mineralogical materials in which high-level radioactive wastes are to be buried. The ready accessibility of the data to site designers and the credibility achieved through the evaluative process are designed to help assess and compare the feasibility of each candidate material for use as a disposal site. Both generic and site-specific data are to be assembled. To date, generic rock salt properties have been assembled and published by the NBS as NBS Monograph 167. Details of the effort to produce this book are discussed.

Jan 1, 1982

By Chikabumi Yamauchi, Mitsuru Tanahashi, Toshiharu Fujisawa

"Thermodynamic properties of impurities in molten silicon are of prime importance in developing economical production methods of solar grade silicon. In the present research work, thermodynamic properties of boron, the most difficult element to remove from molten silicon, were measured by chemical equilibration techniques at 1723 and 1773 K. Activity coefficients and self-interaction parameters of boron in molten silicon were determined by equilibrating the melt with solid BN under controlled nitrogen partial pressures. Interaction parameters between boron and nitrogen in molten silicon were also determined by equilibrating the molten Si-B alloys with solid Si3N4• Based on the data obtained, the stability diagram of the Si-B-N system was established.IntroductionPhotovoltaic power generation using a silicon solar cell is expected to be the most promising energy source, because it is inexhaustible, cleaner and more safety than conventional energy sources, such as thermal or atomic power generation. At present, expensive off-grade silicon for semiconductor (SEG-Si) is used for a solar cell production. However, if a large-scale photovoltaic energy conversion using silicon solar cell comes into wide use in the near future, silicon will be sure to be in short supply for the cell. Therefore, a development of a new large scale process for solar grade silicon (SOG-Si) production is definitely necessary, which can remove contained impurities from silicon.Among the impurities contained in silicon, boron is one of the most difficult ones to remove by a zone melting or an unidirectional solidification, because its segregation coefficient in silicon is close to unity (0.8). In addition, boron behaves as a p-type silicon semiconductor dopant and, therefore, its content in SOG-Si must be severely controlled. Although some attempts to remove boron by various metallurgical methods have been carried out [I -4], quantitative analysis has not been made due to lack in the information on the thermodynamic properties of boron in molten silicon. From this view point, the activity of boron in molten silicon was determined in the present study by chemical equilibration techniques at 1723 and 1773 K."

Jan 1, 1998

By Ann M. Hagni

"Ceramic matrix composites are inorganic materials that are particularly resistant to heat and abrasion. A magnesia (MgO) and aluminum nitride (AlN) based composite is formed by exposing a magnesia preform to a metallic alloy block in a nitrogen atmosphere at 950°C. The metallic alloy, which is composed primarily of aluminum, is wicked into the preform. Aluminum nitride matrix is grown between MgO particles as the wicked metallic aluminum reacts with nitrogen. Unused metallic alloy, remnant metallic alloy (carcass), and composite produced after 8 hours, 50 hours, and 225 hours of processing are characterized mineralogically. Reflected light microscopy, transmitted light microscopy, scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction techniques reveal that in addition to anhedral to euhedral AhNi, AbSbSr, and Al crystallizing in the metallic alloy carcass, AIN and (Al,Si)N have formed as well. Nitride rings and nodules in the carcass may hinder AIN growth in the composite. Fine-grained residual AhNi and AhShSr are dispersed throughout the composite matrix. The nitride matrix is composed of AIN and (Al,Si)N. Rim replacement of MgO by spine! occurs in the composite. Aluminum nitrides in the metallic carcass cathodoluminesce deep violet-blue, unlike non-luminescent AIN in the composite matrix. This distinction in cathodoluminescence suggests a different mode of formation for composite AIN than for carcass AIN. Phase interpretations and textural characterizations deduced from the implementation of sophisticated mineralogical techniques have contributed to the understanding, and will aid in the improvement, of MgO/ AlN-based ceramic matrix compositeprocessing."

Jan 1, 1999

By Sutham Niyomwas

Biomorphic Cellular TiCIC ceramics were produced by vacuum-infiltrating carbon preforms with Ti02 sol and subsequent synthesis by the carbothermal reduction process. The carbon preforms used in the study were obtained by pyrolysis of parawood and neem wood. The effect of infiltration time on the composition and microstructure of the biomorphic TiCIC ceramic was analyzed by X-ray diffractometry and scanning electron microscopy. The biomorphic structure of the TiCIC ceramic is consistent with that of the biotemplate natural parawood and neem wood.

Jan 1, 2008

By A. Mezei

A process has been developed to recover cobalt, gold and bismuth from the NICO deposit in Canada. The process consists of a bulk rougher flotation followed by an optional separation by flotation to produce a bismuth concentrate and a cobalt concentrate, grading on average 12.8 % Bi and 1.8% Co, respectively. Cobalt is leached by pressure oxidation at 97% efficiency, producing a pregnant solution suitable for further processing. Before optimization, about 38% of the bismuth is recovered in the selective concentrate, wherefrom it is recovered by ferric chloride leaching followed by cementation, at overall efficiencies exceeding 98%. The gold is recovered from the cobalt and bismuth leach residues by cyanidation, at 95% efficiency. Previous work described the results of the leaching of the concentrates, recovery of gold (Part I) and the recovery of bismuth (Part 11). This work describes the results of the cobalt recovery testwork and the resulting conceptual flowsheet. The sulfur dioxide-oxygen system was the most efficient for the oxidationlprecipitation of iron and arsenic from cobalt bearing pregnant leach solutions, producing purified solutions assaying <1 mg/L As and <8 mg/L Fe. The efficiency of cobalt solvent extraction (from the resulting purified PLS containing about 1 g/L Co) ranged from 9 1 to 98%; the co-extractions ranged from 88 to 100% for copper, from 28 to 33% for magnesium, from 6 to 7% for calcium and from 96 to 98% for zinc. Sulphide precipitation processes (using either sulfur dioxidelelemental sulfur or sodium sulfide) produced residual copper concentrations in the cobalt strip solution ranging from 0.1 to 2 mg/L Cu. About 90% of the calcium and magnesium were separated by scrubbing the organic with cobalt sulfate, producing residual concentrations of 12 mg/L Ca and from 180 to 330 mg/L Mg in typical feed solutions directed to cobalt carbonate precipitation tests. Cobalt carbonate precipitation efficiencies ranged from 75 to 78% when calcium and magnesium co- precipitations were restricted from 8 to 17% and 0.3 to 0.4%, respectively. The limits required by most stringent specifications on commercial grade cobalt carbonate products were met or exceeded.

Jan 1, 2002

By G. L. Fredrickson, T. A. Johnson, B. R. Westphal, J. C. Wass, S. X. Li, D. Vaden

"Recovery of uranium from the Mk-IV and Mk-V electrorefiner vessels containing a LiCl/KCl eutectic salt has been on-going during the pyrometallurgical processing of used nuclear fuel for 14 and 12 years, respectively. Although austenitic stainless steels are typically utilized for LiCl/KCl salt systems, the presence of cadmium in the Mk-IV electrorefiner dictates an alternate material. A 2.25Cr-1Mo alloy (ASME SA-387) was chosen due to the absence of nickel in the alloy which has a considerable solubility in cadmium. Using the transition metal impurities (iron, chromium, nickel, molybdenum, and manganese) in the electrorefined uranium products, an algorithm was developed to derive values for the contribution of the transition metals from the various input sources. Weight loss and corrosion rate data for the Mk-V electrorefiner vessel were then generated based on the transition metal impurities in the uranium products. To date, the corrosion rate of the 2.25Cr-1Mo alloy in LiCl/KCl eutectic is ""outstanding"" assuming uniform (i.e. non-localized) conditions.IntroductionLow-enriched uranium products are being recovered from the Experimental Breeder Reactor-II (EBR-II) and Fast Flux Test Facility (FFTF) used nuclear fuels by a pyrometallurgical treatment process at the Idaho National Laboratory (INL). The treatment process comprises a set of operations designed to neutralize bond sodium, recover uranium from radioactive fission products, and place the fission products into acceptable waste forms [1-2]. Reactive sodium metal, essential for heat transfer purposes during reactor operations, is readily converted to chloride during the process. Electrorefined uranium products are currently being stored pending a final disposition decision. Treatment of the EBR-II used driver fuel was initiated in June 1996 while blanket fuel processing started in September 1998. These treatment processes continue on the balance of the used fuels."

Jan 1, 2011

By Larry M. Southwick

There is much ongoing work in research and development of new processes for the recovery and recycling of met.a.ls and other materials from various waste and scrap streams. Commercialization of such new technologies requires the bringing together and successful execution of a considerable effort involving a variety of activities. These include process conceptualization, research and development, detailed design and construction, and then plant startup and operation. Processes evolve through all of these steps by engineering due diligence, making objective and critical analyses of results, and troubleshooting processing steps to, hopefully, arrive at a sequence that has the best chance to succeed operationally and economically. After a summary review of the above steps, several processes will be described in more detail that provide mostly successful examples of the above procedures. Finally, some observations will be made on areas that will become critical in the near future to the success of new processes for wastes and residues.

Jan 1, 2000

By Pesic. Batric

A novel chitosan-pyridoxal-epichlorohydrin was synthesized and evaluated in our laboratories. The evaluation was achieved by performing kinetic and equilibrium studies of copper sorption. The parameters examined were pH, temperature, concentration of copper, particle size and selectivity of copper sorption against iron, zinc, cadmium and cobalt. It was found that pH was the most important parameter, and sorption of copper increased with pH increase in the range pH 2.5-6.0. The low activation energy of the sorption reaction, 1 1.13 kJ/mole (2.66 Kcal/mole), showed that temperature was not an important parameter. The synthesized chitosan was selective against iron, zinc, cadmium and cobalt. The selectivity with respect to last three metals was achieved by the kinetic difference of sorption, as sorption of copper was much faster than for other metals. Iron (Fe2+) does not adsorb on chitosan. The mechanism governing the sorption of copper is intraparticle diffusion. This finding was supported by the dependance of copper sorption on the square root of time, the low activation energy, and the fit of experimental data in the diffusion through the product layer equation.

Jan 1, 1994

By N. A. Warner

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

Jan 1, 1996

By Irshad A. Rana

In a modern copper smelter, the capital cost of a sulfuric acid plant constitutes the largest single cost item of the total investment. It is thus essential to properly size the acid plant in order to reduce its capital cost and enhance the economic viability of a new smelter project. Whereas the off-gas from a smelting furnace is continuous and generally uniform, the gas flow from the Peirce-Smith converters is intermittent with significant fluctuations. The converters off-gas volume is dependent upon a number of interrelating factors. The most significant factors are the matte feed grade, the system air infiltration, the converter&apos;s size and blowing rate, the maximum number of converters simultaneously blowing and the gas cooling system employed. The acid plant size, therefore, is heavily influenced by the converter off-gases. Several of these factors are discussed, and their impact in determining the acid plant size is explored.

Jan 1, 1993

By Peter K. Everett

One of the major driving forces behind the development of the Intec Copper Process has been the increasingly stringent regulations governing SO2 emissions and, in some parts of the world, a declining H2SO4 market. Other incentives include operating cost (9.2 US c/lb Cu), capital cost (US $1400/annual tonne Cu compared with smelter cost of US$3-4000/annual tonne Cu) and the ability to treat low grade and contaminated concentrates. With such advantageous features, widespread use of the process is expected over time, leading to the production of large amounts of residues containing around 25% elemental sulfur, together with approximately 50-60 % akaganeite (FeOOH) and the ganggue minerals originally present in the concentrate feed. This paper briefly describes the Intec process chemistry involved in the formation of elemental sulfur, thereby avoiding atmospheric sulfur dioxide pollution, and the investigations to be carried out either to extract it or to turn the residue into a valuable by-product while minimising any adverse environmental effects, The process is being developed jointly by a group of fifteen major international mining companies.

Jan 1, 1996

By Jr. Foot

The Bureau of Mines, U.S. Department of the Interior, investigated flotation methods for recovering fluorite and byproduct beryllium from the Fish Creek deposit of Nevada. The preferred method includes (l) fluorite rougher and cleaner flotation, (2) de sliming at 20 micrometers, (3) muscovite flotation, (4) silicate flotation, (5) hypochlorite wash of silicate concentrate, and (6) beryllium rougher and cleaner flotation from the silicate concentrate, Laboratory results showed that over 94 pct of. the fluorite was recovered in a concentrate containing 96 pct CaFz. Beryllium flotation produced .concentrates .containing in excess of 5 pct BeO with recoveries over 70 pct. A 1.00-lb/h continuous flotation unit was constructed to demonstrate this procedure,

Jan 1, 1985

By Emil B. Milosavljevic, Ljiljana Solujic

Cyanide is exceptionally reactive, and in typical gold/silver processing liquors, cyanide may be transformed into various species and forms depending on the mineralogy of the ore and chemical make-up of the process water. The exact speciation and relative concentrations depend on the Eh and pH values, as well as the free CN concentration in the system. Very good cyanide balances can be achieved by the judicious selection of the analytical techniques used. The choices an analyst has to make (which analytical methods to use and which ones to avoid) in order to gain better understanding of cyanide speciation and balances in a particular system under investigation will be discussed. Examples of cyanide balances obtained for the laboratory scale tests (agitated leach and column tests) will be presented and discussed.

Jan 1, 1999

By Sven Eck, Andreas Ludwig, Menghuai Wu

"Phase separation is a frequently occurring phenomenon during solidification accompanied by melt convection, sedimentation or, in the case of two unmixable liquids, a Marangoni driven motion. In order to describe these phase separation phenomena a two-phase volume-averaging model was employed for globular equiaxed solidification of binary alloys and decomposition and solidification of hypermonotectic alloys. The model considers nucleation and growth of equiaxed grains or second phase droplets, motion and sedimentation of grains or droplets, feeding flow and solute transport by diffusion and convection. It allows the prediction of macro segregations and the distributions of grain size or droplet size. Evaluations were made by comparing the numerical predictions with experimental results. For example it is shown that the numerically predicted grain size distribution in a plate casting (Al-4wt%Cu) agrees reasonably well with the experimental analyses.IntroductionModeling of metallurgical processes is a rapidly expanding field and the research activities in the last decades cover a wide range of areas including melt pre-treatment, solidification and subsequent manufacturing routes. Among those activities solidification stands in the central position, because the primary structure of the materials, and even many defects such as porosity, (macro or micro) segregation and inclusions form during solidification. Those primarily formed structures or defects once existing are difficult to be removed or modified by the subsequent material processing.Solidification is a multi-disciplinary field involving thermodynamics, fluid dynamics and solid mechanics, heat and mass transfer, and other disciplinesr1 -31• One of the most challenging problems in solidification modeling is the complex interactions between physical phenomena occurring on different length scales ranging from atomic rearrangement over single crystal-melt interactions to heat extraction, momentum and species transport at the system level. Modeling an industry process on atomic scale is umealistic, even on grain scale (e.g. phase field method) it would need another 40 years to be able to model the exact grain morphology in a casting space envelope of 10x10x10 cm3 [ 4]. Therefore, the realistic models for industry process are based on the solution of the macro transport equations (mass, momentum, enthalpy and species) on system scale. The microscopic phenomena such as thermodynamics, nucleation law, crystal growth kinetics and interactions at the liquid-solid interface are considered with simplified models, which are coupled with the macroscopic transport equations."

Jan 1, 2004

By Milorad Cirkovic

Kinetics of copper concentrate oxidation in roasting processes in a fluidized bed reactor has been studied at temperatures between 600°C and 720°C using particles of 0.038 to 2.5 mm in average size. The analysis of composition of samples has been done by chemical methods. Phase composition has been determined by Siemens X-ray equipment with Cu anticathode and Ni filters at a voltage of 40 kV and a current of 18 mA. The content of sulphur has decreased from 33.23 to 19.02 mass percent with the increase of temperature, but the content of Fe304 has increased from 0.15 to 17.14 mass percent. The new mechanism of copper concentrate oxidation in a fluidized bed reactor is proposed in this study. It has been shown from the mathematical model that the velocity of oxidation of copper concentrate between 600°C and 720°C is virtually controlled by the rate of diffusion of 02 through the layer of reaction product.

Jan 1, 1999

An EAF dust generated in a Swedish steel mill has been leached in hydrochloric acid at The solution obtained has been subjected to purification by cementation followed by precipitation of zinc with sodium carbonate. The thermal decomposition of the precipitate was studied using thermal analysis and X-ray diffraction. The results show that during the calcination of the precipitate three different reactions occur. The decomposition of the solid phases Zn5(CO3) (OH)6, CaZn(CO3)2 and CaCO3 occur completely at 370°C, 560°C and 940°C respectively, yielding a final product containing 61.9% ZnO and 38.1% CaO. Methods to minimize calcium and manganese in the final product are discussed.

Jan 1, 2003

By S. Z. El-Tawil, K. A. El-Barawy, M. B. Morsi, M. M. Nasr, Z. I. Zaki

"Tue sulphatization of zinc concentrate produced from heated zinc concentrate of Um Ghieg area, eastern desert by ammonium sulphate as sulphatizing agent is carried out at different conditions to achieve the appreciable formation of soluble sulphates. The maximum zinc recovery as soluble sulphate equfils to 95% upon using 1.5 stoichiometry ammonium sulphate at 600 °C for one hour. Tue obtained leached zinc sulphate solution is subjected· to purification process to prepare high pure zinc metal and zmc compounds such as pure zinc sulphate, zinc caibonate and zinc oxide. The products obtained are analyzed chemically and identified by X-ray analysisTue mechanism and kinetics of the sulphatization process of zinc concentrate are considered where the activation energy is calculated and equals to 33.3 K.J.mol""1 A process flowsheet for the overall sulphatization process of zinc concentrate by ammonium sulphate is proposed.IntroductionConsiderable reserves of zinc ores are present in Um Ghieg area eastern desert, Egypt. The possibility of extraction zinc from these ores and preparing its valuable compounds by choosing a more feasible technology become of vital importance. An attention is focused on the sulphatizing roasting processes (1-9) to achieve the appreciable formation of soluble sulphates. Previous publications are reported in our division by El. Tawil and others (10-16) using ammonium sulphate as sulphatizing agent for the successful treatment of nonferrous bearing materials.Therefore, the present work aims to study the different factors affecting the sulphatizing roasting process of local zinc coocentrate by anunonium sulphate to extract completely zinc and preparing its main compounds. Tue mechanism and kinetics of the different chemical reactloos that 1ake place in the process are considered."

Jan 1, 2000

By G. G. Richards

The zinc slag fuming process is used to recover zinc from molten iron-calcium silicate slags by treatment with pulverized coal and air. The rate of zinc fuming is controlled by the complex interaction of several kinetic factors including the rate of entrainment of coal in the slag, the extent of the coal-slag reaction and the rate of ferrous oxide oxidation to ferric oxide. This paper briefly outlines the mechanism of fuming and, on this basis, optimization of process parameters is discussed. Modelling analysis and recent industrial trials at Cominco show that coal entrainment in the slag, bath temperature, and bath depth are critical variables affecting process rate and efficiency. The first step in process optimization is to assess coal bypass of the bath. In general, changes which promote operation at a higher temperature, greater coal entrainment in the slag and extended residence time of the coal in the bath increase fuming performance. Coal entrainment is controlled by injection conditions whereas bath temperature is a function of coal combustion and ferrous oxide oxidation. Residence time of the coal is largely a function of bath depth. The implication of model predictions for continuous fuming is shown.

Jan 1, 1994

By Helfried Nafe

"For about a century thermodynamically absurd facts have been propagated in conjunction with the iron-carbon phase diagram. These facts concern fundamental relationships of chemical thermodynamics. Attention is turned here to the discussion of only one of the relevant aspects of the subject, i.e. the definition of the thermodynamic activity of the solute and its implications for the iron-carbon solution.IntroductionThe view on the iron-carbon solution is characterized by the assumption that the solute may appear in two different forms, i.e. graphite and cementite. Accordingly, two carbon solubilities are differentiated, on the one hand for graphite and, on the other hand, for cementite. As a consequence, two versions of the phase diagram exist simultaneously, the application of which depends on the prevailing conditions, (i) the so-called stable phase diagram with graphite as solute and (ii) the metastable one that is based on the cementite-in-iron solution. These diagrams are joined together in the double phase diagram that originates from Heyn [l ], with the first ideas mainly going back to Stansfield [2] and Charpy [3].Thermodynamically, the most inadequate implication of the Fe-C double phase diagram is that the carbon activity may take values larger than unity. With the standard state of the activity being that of the pure substance, i.e. the Raoultian one, such a value implies the nonsensical existence ofa state purer than pure. The explanation of this physical state, ifthere is any, vaguely refers to supersaturation and, in the wider sense, to the physico-chemical phenomenon of metastability. Other aspects of chemical thermodynamics are likewise involved. Therefore, the comprehensive investigation into the present subject requires more topics to be considered than only one separate issue. Not only should the criticism of the present view be in the focus but also the discussion of new ideas capable of reconciling the experimental facts, known about the F e-C system, with the fundaments of chemical thermodynamics. All this, however, cannot be provided here because of the limited space available. As a consequence, in what follows only a part of the whole problem is under scrutiny, i.e. the definition of the thermodynamic activity and its role for the interpretation ofrelevant experimental facts."

Jan 1, 2014

By Geoffrey A. Brooks, M Akbar Rhamdhani, Md Saiful Islam

A novel electrically-enhanced metal purification using slag has been developed. This was achieved by applying DC potential between liquid metal and slag phases. The concept was demonstrated through small-scale experiments at temperatures of 1500-1600oC for the removal of boron from Si-B melt using CaO-SiO2-16wt%Al2O3. Silicon (containing B) and slag were reacted in an alumina crucible in a resistance tube furnace. A circuit was produced by immersing graphite rods into the silicon bath and the slag layer. Electrical potential differences of up to 3.5 V were applied during the reactions. The reaction rates, the opencircuit voltages and short-circuit currents (in the case when the potential was applied) were then measured and determined for various slag to silicon ratio. It has been shown from this study that both the apparent rate and the boron partition ratio were increased by a factor of approximately 1.6.

Jan 1, 2014