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By Grigore Matei

The thermodynamic properties of CuzS-FeS system are important not only in the ease of copper smelting but also in the case of general pyro-metallurgy. However there arc not many reported activity data In this study, activities of FeS and CU2S in the Cu2S-FeS system were calculated using the Darken's method from the activity data of the Cu2S-FeS-Sb2S3 systems measured by the transportation method at 1050°C. The activities of Cu2S and FeS in the Cu2S-FeS system showed negative deviation from the ideal behaviour and satisfied the relation of the Gibbs-Duhem equation.

Jan 1, 2003

By Makoto Ohlsuka

The ternary Ni2MnGa intermetallic compound is an intelligent material which has both a ferromagnetic property and a shape memory effect (SME). The use of the shape memory alloy films for an actuator of micro-machines is very attractive because of its large recovery force. The purpose of the present study is to investigate the effects of fabrication conditions and to clarify the relationships between these properties and fabrication conditions of the Ni-Mn-Ga films. The Ni-Mn-Ga films with a thickness of nearly 5 um were deposited with a radio-frequency magnetron sputtering apparatus using a Ni50Mn25Ga25 or Ni52Mn24Ga24 target. They were heat-treated at various temperatures between 873 and 1273 K for homogenization and ordering and then cooled in a furnace. The composition of the films depended on the sputtering power. The as-deposited films were crystalline and had columnar grains. After the heat treatment the grains widened and the grain boundary became indistinct with the increasing heat treatment temperature. The martensitic transformation temperature of the heat-treated films increased with increasing nickel content. Furthermore the effect of plastic deformation and constraint aging on SME is also investigated. After plastic deformation, the two-way SME was shown through the martensitie transformation and its reversion, The intensity of X-ray diffraction peaks from stress-induced martensitie phase was found. The constraint-aged films also showed the two-way 3ME by thermal cycling.

Jan 1, 2003

By Ali Nadir Khan

Depleting copper resources and advancing technologies have challenged industries to develop more viable, adaptable and cost efficient processes using also secondary raw materials in copper production. This study is targeting to that goal by dynamic modelling of flow and heat transfer coupled with chemical kinetics in an industrial scale flash smelting furnace settler using commercial CFD software ANSYS Fluent. First, different physical phenomena occurring inside the settler, for example, settling and separation of the matte/slag phases, and heat transfer between slag/matte phases and settler walls are studied. Secondly, reaction kinetics between matte and slag, and between slag/matte and settler walls, and impurity element distribution will be studied. This would also include phase changes phenomena due to these reactions and the flow of the reaction gases inside the settler. Settling of polydispersed droplets, their coagulation, breakage, and WEEE particle behavior are further targets of the modelling work.

By S. Ajima

The Naoshima Smelter and Refinery is the most important copper operation of Mitsubishi Materials Corporation. There are a Mitsubishi Continuous smelter and a conventional type of copper tankhouse. The continuous smelter with 240,000 mtpy of anode production was commissioned in May 19914 replacing two existing smelters, i.e an original Mitsubishi Process line and a conventional reverberatory furnace line. In July 1992, the copper tankhouae was expanded for the purpose to close the gap of production capacity between the smelter and the tankhouse. The cathode production capacity was increased from 13,800 to 15,800 mtpm. By these plant modifications, the distribution of minor elements was significantly changed and the impurities load is getting on increase reflecting recent shortage of clean copper concentrates supply. The paper discusses the distribution of minor elements and the impurity control strategy at the smelter end the refinery.

Jan 1, 1995

By L. W. Beckstead

In a conventional zinc refinery plant, zinc concentrates were roasted at 950°C. The calcine was ground and leached in a series of leaching vessels using sulfuric acid. The pH in the first leaching vessel was maintained at 2.5, while the pH of the solution exiting the last vessel was about 5.4. The leached residue typically contained (in percent) 0.1 Ag, 0.2 As, 0.7 Cd, 2 Cu, 15 Fe, 10 Pb, and 15 Zn, and it was classified as hazardous material according to the EP-toxicity test. In order to make the residue non-hazardous, and to recover most of the metal values from the residue, a brine leach process was developed. The process consisted of leaching the zinc leach residue in CaCI, brine solution at pH 2 for 1 hour at 90°C. Silver extraction was about 95 percent, while lead, copper, cadmium, zinc, and iron extractions were about 80, 50, 50, 30, and less than 0.5 percent, respectively. More extreme conditions of acidity could have been used in the leaching stage to increase zinc dissolution, but iron dissolution would have significantly increased which would have complicated subsequent recovery steps. The leached and washed residue passed the EP-toxicity leach test and could be disposed as non-hazardous. Silver, copper, and lead in the leach solution were recovered by zinc cementation, while zinc and cadmium were recovered by sulfide precipitation. The resulting solution can be recycled in the process after magnesium precipitation.

Jan 1, 1993

By Hu Long

In this, the first systematic study of the oxidation of orpiment (As2S3) in sulfuric acid solution under oxygen pressure at temperatures above 170°C, the effects of retention time, temperature, particle size, oxygen partial pressure, the concentration of sulfuric acid and pulp density were evaluated. The effects of cupric and ferric ions on the oxidation rate of As(III) to As(V) were also examined. The products of oxidation are As(III), As(V), SO42- and elemental sulfur. At temperatures ranging from 170 to 230°C, most of the arsenic was found to be in the trivalent state, and oxidation to As(V) with oxygen was very slow. This was confirmed by attempting to oxidize a synthetic arsenious solution. However, the rate of oxidation of As(III) to As(V) is rapid in the presence of ferric ion. Elemental sulfur was found at all temperatures investigated, which can be further oxidized to sulfate at high temperature.

Jan 1, 1999

By J. L. Jambor, H. W. Nesbitt

Oxidative dissolution of pyrrhotite and pyrite is largely responsible for the sulfate-rich waters of the vadose zone in the Waite Amulet tailings. Although the shallowest of the sulfate-rich waters are of the Fe-SO4 type, they change to Mg-SO4-type, near-neutral waters within 1-2 m of the tailings surface. Phyllosilicates and amphiboles are the only minerals present in sufficient quantity to ameliorate the amount of acidity produced. X-ray diffraction and microscopic studies of bulk sample indicate that quartz, chlorite, talc, amphiboles, magnetite, albite, and micas are the major and minor non-sulfide minerals, but their variations with depth do not give clear indications of depletion in the vadose zone. Mineralogical and bulk chemical compositions of the tailings confirm that Fe2O 3 has accumulated in large quantity in the vadose zone, with the Fe having been derived from Fe sulfides. When the effect of Fe2O3 is accounted for, the bulk compositions suggest that SiO2 is slightly more abundant in the vadose zone than in the saturated zone. This may be the result of residual enrichment of siliceous minerals such as quartz and albite in the vadose zone. Weathering of the tailings since the cessation of deposition in 1962 has resulted in a well-defined zone of sulfide depletion and secondary sulfate-mineral development. Although some silicate dissolution is indicated by pore-water compositions, the role of silicates in providing neutralization seems to have been minimal. The contribution by silicate minerals in laboratory tests of neutralization potential may be excessive relative to that in natural settings.

Jan 1, 1999

By Grégory Miette

The paper deals with a process that allows the recycling in a cupola of EAF dusts with 18 % Zn. It produces dusts with zinc grade higher than 50 - 55 % and commercial cast iron with less than 200 ppm Zn, 50 ppm Pb, 0.15 % S. The paper focuses mainly on lab tests made with the aim to develop an effective formulation of self reducing - melting pellets. With such a formulation, agglomerates develop a breaking load higher than 125 - 150 kg without any thermal treatment. Zinc and lead are volatilized in the cupola with yields higher than 95 % at 1200 OC, before any melting. Sulphur is transfemed into gas and slag. All these conditions allow to lower zinc, lead and sulphur grades below the cast iron specifications. Results of first bench scale tests performed at Fonderie Piret to validate the process will be presented.

Jan 1, 2002

By Takeshi Nagano

Copper pyrometallurgy in Japan has experienced quite fundamental changes in last fifteen years. The severe environmental restriction coupled with increase of energy costs accelerated the development work of the new continuous process in Mitsubishi Metal Corporation. After several years of pilot plant test work the commercial plant was put into operation at Naoshima Smelter in 1974, the design capacity of which was 4,000 tonnes of copper per month. Many modifications and improvements have been incorporated into the process and 7,200 tonnes per month of copper production was achieved in 1983, proving that continuous process was much more economical than conventional process. It is now possible to design and operate the continuous process in wide range of capacity. This paper will review the process and describe the progress of the process in these 10 years. 311

Jan 1, 1985

By Arthur E. Morris

Process modeling software is used extensively in process engineering, but there is a notable lack of affordable software for educational uses. This paper describes two educationally oriented software programs for thermochemical modeling of processes involving metals, minerals, and ceramic materials. Both programs run as Excel@ spreadsheet files. The first is FREED, a thermodynamic database program containing datafiles for 2500 species. It contains the entire U. S. Bureau of Mines and most of the U. S. Geological Survey database, plus data for scores of other species drawn from various sources. Several modules are available for manipulating and viewing the data. The second program is THERBAL, for making thermodynamic calculations using FREED data. Equilibrium calculations can be made for systems with non-ideal solutions, for a specified set of pressure, temperature, and input amounts of reactants. An optional heat balance is also calculated. The results are displayed as tables or charts in Excel worksheets. Examples of the use of THERBAL will be given for the reforming of natural gas for DRI production, DRI production, and EAF steelmaking. Some observations will be made on its use in the classroom. The development of FREED and THERBAL was initially carried out at the Department of Metallurgical Engineering, University of Missouri - Rolla as part of a project to preserve and enhance the Bureau of Mines database. The current versions were developed privately by the authors.

Jan 1, 2002

By A. M. T. S. Bandara

The solubility of rare earth (RE) salts in aqueous solutions depends on many factors including the type of cations and anions in solution, their concentrations, temperature and the type of solid precipitated. Experiments were conducted using anhydrous La2(SO4)3 and Ce2(SO4)3⋅8H2O as solids and lanthanum(III) perchlorate prepared by dissolving La2O3 in HClO4 solutions as RE-sources. Solutions of H2SO4, H3PO4 and their mixtures in the presence or absence of Na+, Ca2+, Fe(III) or Al(III) as perchlorates served as test solutions. Saturated solutions and precipitated solids were assayed and characterized using standard techniques to show that the La(III) and Ce(III) ions precipitate as hydrated sulphates, phosphates or double salts with sodium, depending upon the solution composition. The change in solubility of RE-salts with solution composition and temperature is the result of the composite effect of changes in solubility products (pKSP) of salts, pKa of acids and other equilibrium constants for ion-association.

By Hee Dong Jang

Crystalline metal oxide nanoparticles such as lithium cobalt oxide (LiCoO2) and indium tin oxide (ITO) were synthesized from sprayed droplets of aqueous precursor solution by flame spray pyrolysis. Complete thermal decomposition of the aerosol precursors was obtained at high flame temperature. Molar concentrations of the precursor solution, and the flow rate of combustion gas such as hydrogen, oxygen and air were varied to control particle size, size distribution and crystal structure. The crystalline nanoparticles synthesized were nearly spherical, and their average primary particle diameters ranged from 11 to 35 nm for LiCoO2 and from 8 to 15 nm for ITO.

Jan 1, 2006

By Jaeheon Lee

Gold-copper alloys are shown to form during the cementation of gold on copper in a solution containing 0.25M [S2O32-] at 25oC. The alloy composition is strongly dependent on the initial Cu:Au ratio in solution and ranges from Au3Cu to AuCu3. XPS results for Au, Cu, S, and O are reported as a function of depth through an entire deposited film with an initial solution containing 20 ppm [Au] and 30 ppm [Cu]. The deposit contained about 20 atomic % gold and was predominantly Cu3Au. Underpotential deposition (UPD) theory is discussed as a mechanism for explaining the formation of these alloys. Several other systems that produce alloys during contact reduction/cementation are also discussed.

Jan 1, 2003

By W. G. Davenport

A survey of world copper refining tankhouse .practices has been carried out. This paper compiles the results and examines changes in operating practices .since the similar 1987, 1991 and 1995 surveys. Continuing trends are the installation of ISA Process and Kidd Process stainless steel cathode technology, polymer concrete cells, anode preparation machines and automatic cranes. Instrumentation and automatic control are increasing, particularly for addition agent optimization; solvent extraction .and ion exchange techniques are being increasingly applied for electrolyte purification. The overall consequences of these changes have been 'improved cathode purities and enhanced tankhouse productivities.

Jan 1, 1999

By M. Potesser

In the primary and secondary copper industry the anode furnace is the most important process step in the refining procedure to reach an enhancement in value and quality of the copper by a selective oxidation and reduction. By combining the advantages of the conventional tilting hearth anode furnace and the benefits of the drum type anode furnace a new aggregate was developed and patented. The cross-section of the furnace is elliptical and the whole unit is tiltable. During the melting period, the contact surface between the burners and the bath or the scarp is enlarged - an increased energy input is the consequence. For the refining period the furnace is rotated, whereby a high bath level is guaranteed. Due to the longer residence time of the gas in the copper melt, not only the gas consumption is reduced but also the efficiency/quality of the refining process is improved. This investigation shows a metallurgical comparison between the new anode furnace concept with the elliptical profile/cross section and the conventional, tiltable hearth anode furnace as well as the drum type anode furnace. The CFD modeling of the currents in these different furnaces delivered helpful data to compare the geometry of the different furnaces. The investigation covered the refining of blister copper from primary metallurgy, from secondary metallurgy as well as from a mixture of both copper melts. The paper underlines the possibilities for a reduction of the tap-to-tap time and for an increase in production capacity, which can be achieved by applying the new furnace concept in comparison to the conventional furnaces.

Jan 1, 2006

By B. R. Adams

This paper discusses the use of a reacting CFD model to determine chalcopyrite kinetics in a drop tube furnace and to predict the reaction of a chalcopyrite concentrate in the reaction shaft of an industrial smelter. Reacting CFD codes can be applied to determine the consequences of the interaction of gas with particles and therefore improve the ability to derive kinetic parameters that take into account the temperature and oxidation histories that different particles will see. This paper describes the application of such a model to derive improved kinetic parameters for the pyrolysis and oxidation of chalcopyrite. The reaction shaft model includes the effects of turbulent fluid mechanics, entrained flow mixing, turbulent particle dispersion, heterogeneous particle reactions, radiative and convective heat transfer, and' surface and bath deposition rates. Particle reaction and composition characteristics are predicted as a function of particle trajectory and deposition and are used to aid in evaluating shaft performance.

Jan 1, 1999

By Jan Petter Maehlen

Solid H-absorbing materials are in focus of ongoing R&D to offer viable solutions for the hydrogen storage and supply systems aimed on use of hydrogen as energy carrier for automotive transportation. Low operating pressures, combined with high gravimetric and volumetric efficiencies, together with fast kinetics of hydrogen release at ambient temperatures (providing conditions for a low energy loss due to decomposition), are the most important features of the ?ideal? H storage material. Hydrides of the light elements are the only possible candidates to build systems with an overall efficiency similar to those accommodating liquid or compressed (700 bar) hydrogen. One promising material from this point of view is aluminium trihydride, alane AlH3 with a gravimetric storage capacity of 10 wt.% H. This work was focused on studies of the crystal structure and thermal decomposition of alane by application of powder synchrotron X-Ray diffraction.

Jan 1, 2006

By Shunsuke Yagi

A surface alloying technique was investigated using alternating pulsed electrolysis in an aqueous solution containing a single metal component for the formation of an Fe-Cr layer on an iron substrate. In the process, the iron substrate was dissolved during each anodic polarization of the pulsed electrolysis, providing iron ions in the vicinity of the substrate, while the Fe-Cr alloy was electrodeposited during subsequent cathodic polarizations. A bright, flat, and crack-free Fe-Cr layer with a composition gradient was obtained using a solution containing a trivalent chromium component and a complex forming agent together with some supporting or buffering salts.

Jan 1, 2006

By Darryl Lovato, Ramiro Pereyra, Daniel S. Schwartz

"During an annual inventory of nuclear material, a plated steel container which contained plutonium oxide failed. The container had been packaged for temporary storage but had been overlooked and remained in storage for more than 23 years. Although it was determined that the failure occurred through the slip-top rim, a metallurgical evaluation was requested to help to determine the integrity of the container.Optical metallography and scanning electron microscopy were used to analyze the character and degree of corrosion in the container. The depth of corrosion, measured at approximately 10 µm, did not pose a threat to the integrity of the container. However, the corrosion morphology and chemistry did suggest that a galvanic cell had developed between the tin and steel from the condensation of water. The morphology also suggests that the attack of the steel took place over a series of cycles due to changes of the environment.IntroductionMetallographic analysis was requested as part of the investigation into the mechanism of the failure of a slip-top container (#38621) containing plutonium oxide (PuO2) powder. The container had leaked during a special nuclear material (SNM) annual inventory causing contamination and closure of the vault. A photograph of the container and interior container is shown on the right in Figure 1. An initial investigation established that the source of contamination was the consequence of the failure of multiple layers of containment. Initially by the deterioration of the interior plastic bottle and polyvinyl chloride (PVC) bagout bag, and finally through the lid and steel container interface at a location where tape had not adhered properly [1]. Although the source of the breach was established, it was determined that metallographic analysis was important to establish the extent of deterioration of the steel container."

Jan 1, 2008

By Alan M. Russell

In recent years, several rare earth intermetallic compounds with the B2-type structure have been reported to exhibit high tensile ductility and high KIC fracture toughness at room temperature. These materials retain considerable ductility even at 77K. These are noteworthy findings because most intermetallics possess poor room temperature ductility and low fracture toughness unless one or more special contrivances are applied (e.g., doping with small additions of interstitial elements, offstoichiometric compositions, testing in ultra-dry atmospheres, etc.). This paper summarizes recent findings on rare earth B2 intermetallics. These include the determination of the active slip systems; the strain rate sensitivities; yield strength maxima at elevated temperatures; the search for possible twinning and stress-induced phase transformations; ab initio calculations of their defect energies and the anisotropy of dislocation line tension. Potential applications of these materials and the possibilities that this study may suggest strategies for increasing ductility in other intermetallic compounds are discussed.

Jan 1, 2008