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Cuspidine (3CaO?2SiO2?CaF2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel. The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiOrCaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been determined by an electromotive force method using CaF2 as solid electrolyte and a transpiration method as follows: The chemical potential diagram and constituent activities for the CaO-Si02-CaF2 system have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

By Sharif Jahanshahi

Calcium ferrite slags are often associated with Professor Yazawa due to his pioneering work on the thermodynamics of this type of melts. Over the past years CSIRO has invested some effort in studying physico-chemical properties of such melts to fill in some gaps in our knowledge and explore opportunities for application of the understanding developed. These investigations cover thermodynamics, transport properties of calcium ferrite based slags, as well as the kinetics of reactions of such slags with refractories. The present paper provides an overview of some of these studies and highlights some of the interesting behavior of such melts, The oxidation state of copper and arsenic in calcium ferrite based slags are predominantly Cu+ and As3+, respectively, at oxygen potentials below 10-7 atm. The concentration of CU2+ in such slags becomes significant at oxygen potentials of greater than 10-7 atm at 1300 °C. The activities of CuO0.5 and AsO1.5 in calcium ferrite slags show strong deviations from the Raoultian Law, while that of CoO is very close to ideal behaviour with respect to pure solid CoO. Addition of SiO2 to calcium ferrite slags can have significant effects on the activities of FeO and Fe2O3 and hence the stability of magnetite phase. Transfer of oxygen in calcium ferrite slags is fast with diffusivity of 2x 103 cm2/s at 1350 °C and activation energy of 16 kcal/mol. Presence of solid phases, such as magnetite, has pronounced effect on the viscosity of calcium ferrite slags. The observed dependence on solid loading and shear rate indicates deviation from Newtonian behaviour. The interfacial tension between copper mattes and calcium ferrite slags is strongly dependent on the matte grade, with the determined values being much lower than the corresponding ones for interfacial tension between similar mattes and iron silicate slags. MgO, Cr2O3 and MgCr2O4 have low solubility in calcium ferrite slags and their solubility increases with increasing copper oxide content of the slag at 1300°C. The oxidation state of the slag has strong effects on phase transformation, dissolution rate and disintegration of refractories in calcium ferrite slags. Other key factors with major impact on slag-refractory interactions include viscosity and surface tension of slags as well as the contact angle between slag and refractory material,

Jan 1, 2003

By A. S. Usrnani

Due to both turbulence and the highly variable geometry of castings, a realistic numerical simulation of the metal flow is prohibitvely expensive with current technology. However, when the chief purpose is to achieve realistic thermal fields a precise How simulation is not necessarily required. In this paper we assume a laminar flow regime and obtain the flow field by solving the incompressible Navier-Stokes Equations using a velocity-pressure segregated semi-implicit finite element method. The free metal surface is predicted by advecting a pseudo-concentration function via the computed How field. This involves an explicit finite element solution of a pure advection equation. The thermal field is calculated by solving the convective-diffusive energy equation by an explicit finite element method using the computed flow field and the location of the free surface. All the advection terms are discretized using a Taylor-Galerkin method. The interface between the metal and mould is modelled using special interface elements. The model is demonstrated by solving practical example problems. The results show that a sharp thermal front is maintained during the course of filling without excessive diffusion. The heat diffusion in the mould can be controlled by varying the metal mould heat transfer coefficient.

Jan 1, 1994

By R. Burkhard

Recovery of metals from complex mixed wastes is a challenging task of modem material and waste management strategies. Thermal methods are an important tool in this respect. Plasma turned out to be particularly useful for treatment of complex or toxic wastes and residuals. In order to study plasma processes at reasonable costs, a pilot plasma plant has been used and wastes like ~pent Raney-Nickel catalysts, copper and ah.:lminum drosses, and. other metal containing wastes were investigated. The paper summarizes the most significant findings

Jan 1, 1995

By Pengfu Tan

A thermodynamic model and computer program, CuModel, has been developed to model the distribution behaviors of Cu, Fe, S, O, Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag, copper loss in the slag, and heat balance in copper smelting process, matte converting process and copper con-tinuous smelting process. It can be predicted for any set of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxy-gen-enriched air. This model accounts for physical entrainment between matte and slag phases. It can be used in Isasmelt process, copper flash smelting process, Mitsubishi process, P-S con-verting process and Noranda process. The predictions by the present computer model are com-pared with the known commercial data from Guixi Smelter in China, PASAR Corporation in Philippines, Horne Smelter in Canada, MIM Limited in Australia and Naoshima Smelter in Ja-pan. The agreements between the computer predictions and the commercial data are excellent. In this paper, the applications of CuModel in the copper metallurgical industries have been pre-sented. CuModel has been used by Daye Smelter and Guixi Smelter in China, and by PASAR in Philippines as well.

Jan 1, 2004

By Ali Hasham

Reduction rates of FeO in CaO-SiO2-Al2O3 slags by Fe-C melts have been investigated experimentally at 1723 K. The rates were estimated using experimentally determined CO(g) evolution rates. Flash X-ray images were employed to visualize the behavior of the melt-slag interface during the reactions. The influence of melt interface was examined by conducting two types of experiments - (i) dropping one (or several) Fe-C droplet(s) weighing 2 g into the molten slag bath, and (ii) dropping a small amount (10-30 g) of slag onto a Fe-C melt weighing 400 g. The rates from both types of experiments were compared and analyzed to determine the rate limiting steps. It was established that neither the carbon transport in the Fe-C melt, nor the transport of gas species in the gas film adjacent to Fe-C melt was responsible in limiting the reaction rate. It is possible that the slag phase mass transport may be controlling the initial reduction rate in the droplet experiments. However, a, different mechanism was responsible in limiting the reduction reaction when the overall %C in the droplets fell to about 2-3.

Jan 1, 1992

By A. González

Arsenic is one of the main contaminants present in Chilean copper concentrates and its abatement represents a challenge for the process metallurgy, particularly under the strong environmental requirements in the global community. The possibility to form ferric arsenate directly from a gas phase by means of a heterogeneous reaction between an arsenic gas bearing and iron oxide was studied at laboratory scale. A thermodynamical analysis for the system Fe-As-O-S has been initially made, in order to obtain the stability conditions for the ferric arsenate or other FexAs2O2 type compounds. Experiments were made using an hematite sample suspended in a thermogravimetric device. AS4O6 gas generated from solid AS203 that was passed through the iron oxide sample and its instantaneous weight change was recorded directly. A kinetic study for the AS4O6 volatilization was made to control the gas composition. A chemical control between 300 and 600°C with an apparent activation energy of around 14 Kcal/mol As2O3 was determined. The samples after the reactions were chemically and XRD analysed. Arsenates detected corresponds to complex compounds. Results shows a dependence on temperature and oxygen content in the gas phase. The kinetics for iron arsenates formation is slow, reaching an arsenic capture of 6% after 80 minutes of reaction when an oxygen content of 50% is fed continuously at 800°C and 3,56% As in the gas. Experiences made at the same temperature but under higher oxygen content in a closed reactor, allowed arsenic capture close to 60%. For higher temperatures the capture is considerably lower.

Jan 1, 2003

By Taiping Lou

The effects of slag composition, additive agents, and heat treatment conditions on the perovskite (CaO ? TiO2) crystal morphology, the precipitation behavior, the crystal growth and the volume fraction (VF) in the Ti-bearing blast furnace slags were investigated. The morphology of perovskite is dispersed dendriform in molten slags. The crystal growth mechanism of the remelting of fine dendrites and the coarsening of larger grains exists throughout the solidification of molten slags. With the temperature decrease, the VF was increased and Perovskite transformed from fine dendrites to coarsening ones or equiaxed grains. The lower cooling rate can increase the VF and coarsen the grain obviously, while higher cooling rate will decrease the VF and reduce the average equivalent diameter (AED) of Perovskite. When .increasing the content of CaO and Fe20}, the VF can increase obviosly. However, high basicity will give rise to the increasing of viscosity of slag, which result in the reducing of the AED. The experimental results showed that additive CaF2 and MnO can efficiently decreased the viscosity of the slags, and obviously improved the morphology of perovskite and promote growth.

Jan 1, 2000

By Seetharama C. Deevi, Mohammad R. Hajaligol, Sarojini Deevi

"Carbides and nitrides of iron are being considered as magnetic materials for high-density recording due to their chemical stability and high-saturation magnetization values (> 100 emu/g). Iron carbides and iron nitrides with magnetic properties suitable for magnetic media were synthesized by employing a novel synthesis procedure based on fluidization of powders in reactive atmospheres. Fluidized-bed reactors of laboratory, bench, and pilot scale were employed for the synthesis of iron carbide, FeSC2, by reducing and carburizing U-Fe203 in the temperature range of 300 to 550 ºC. A temperature of 400· ºC and a reaction time of 2 to 3 h are found to be optimal for the synthesis of iron carbide. When the carburization was carried out in a reducing and carburizing atmosphere such as carbon monoxide, nucleation and growth of FeSC2 occurred directly from Fe304 with no intermediate phases such as FeO or Fe. Longer carburization times resulted in the deposition of carbon on the surfaces of FeSC2 particles due to Boudouard reaction, and higher temperatures favored the formation of a mixture of carbides such as FesC2 and Fe3C. Iron nitrides were synthesized by reducing u-Fe203 in the temperature range of 350 to 550 ºC, followed by nitriding in the temperature range of 350 to 550·ºC. The powders were characterized using X-ray diffraction, scanning electron microscopy, thermogravimetric analyzer, and a vibrating sample magnetometer.IntroductionRecent demand for high-quality recording of optical, electrical, and audio signals generated interest in magnetic tapes with high-recording densities as compared to the conventional magnetic tapes based on U-Fe203. At present, commercially available magnetic tapes contain maghematite, U-Fe203, as a magnetic material with a saturation magnetization of90 emu/g and a coercive force of 400 Oe. Recording of signals at a higher density per unit volume of magnetic material demands magnetic materials with high-saturation magnetization and a reasonable coercive force. Although metallic iron particles possess a saturation magnetization of 130 to 150 emu/g and a high coercive force of 1000 Oe, the gradual oxidation of iron-to-iron oxides (of lower saturation magnetization) prevents the use of iron particles for high-density recording. In contrast, iron carbides such as FesC2, Fe7C3 and iron nitrides such as Fe4N and Fe3N possess excellent magnetic properties coupled with good electrical conductivities and high hardness. The carbides and nitrides of iron have generated significant interest as magnetic materials for the next generation of magnetic tapes due to their unique magnetic properties and relatively greater oxidation resistance as compared to metallic iron particles [1-4]."

Jan 1, 1994

By Fiseha Tesfaye, Pekka Taskinen

"Thermodynamics of the equilibrium phase assemblage Ago_9Cul.lS-Cu2-xS-CuS have been studied by an EMF -method. The ternary phase was synthesized from the pure Cu2S and Ag2S in vacuum furnace at high-temperature and mixed with appropriate compositions of Cu2S and CuS to form the cathode electrode. The EMF-measurements were made on the solid-state galvanic cell Pt(-) I Ag I RbAg,ils I Ago9Cu1.1S-Cu2-xS-CuS I Pt(+), in a temperature range from 316 K to 498K.Based on the measured EMF vs. T relations, thermodynamic functions (?fG° , ?fS and ?fH°) of stromeyerite (Ag0.9Cu1.1S) in equilibrium with Cu2-xS and CuS have been determined. The obtained experimental values have been compared with the available literature values. New experimentally determined thermodynamic properties of the solid solution (Ag,Cu)2Sss were determined.IntroductionDue to intense mining of high grade sulfide ore minerals in the past, recently, the available sulfide ores are poor in metals and becoming increasingly complex; such that, the production of high grade metals by the conventional pyrometallurgical processes is compromised. Consequently, smelters are in need to modify their operating flow sheets and strategies for processing more complex feed materials economically, while meeting the strict environmental regulations. To make the appropriate modifications, accurate thermochemical data of phases and phase assemblages which exist in these complex ore minerals are essential.Silver-bearing sulfosalts are encountered in ore minerals for the production of base metals and are common sources of silver. Among the silver-based sulfosalts, stromeyerite (Ag0_9Cu1.1S) is relatively common ore mineral in most hydrothermal vein and replacement deposits [1]. Recently, the ternary chalcogenide compound Ago0.93Cu1,07S has been studied, intensively, due to its high ionic conductivity and gradual disorder in the sequential phase transitions [2]. Therefore, accurate knowledge of the thermodynamic properties of stromeyerite has considerable fundamental and practical interest in many aspects of extractive, chemical and physical metallurgy."

Jan 1, 2014

The cleaning of copper containing fayalite slag using a CuFe alloy was studied under an oxygen pressure ranging from 10-7 to 5 X 10-11 atm at 1200º c. The reduction of copper from fayalite slags by Cu-Fe alloys was found to be very effective. For example, at a P 02 of 10-7 atm, the copper content in the slag was reduced from 4.1 to 0.402 wt. percent after 90 min. of reaction time using a Cu- 5.27 wt. percent Fe alloy. The copper reduction rates were found to be independent of P02 in the gas phase when using Cu-Fe alloys which exhibit an iron activity of greater than 0.4. A mechanism for slag c1eaning is proposed based on the concept that the Cu-Fe alloy lowers the oxygen potential of the slag according to Eq.1 1, fol1owed by the reduction of cuprous oxide by wustite as shown in Eq.2. Here X represents element X in the alloy phase while (X) represents the element in the slag phase. The copper and iron transfer behaviour obtained in this study are explained by a ?Stepwise equilibrium model.

Jan 1, 1985

By Zbigniew Zurecki

The selection of atmosphere composition is critical for controlling surface quality of reactive aluminum alloys during solution treatments. An improper selection of annealing atmosphere can result in surface blistering in AI-Mg and sub-surface depletion of lithium in AI-U ingots. To determine optimum atmosphere compositions for homogenizing A1-Mg and Al-Li alloys, Ii number of exploratory experiments were carried out in air, nitrogen, and carbon dioxide based atmospheres including reactive impurities or additive such as moisture and sulfur hexafluoride. This paper describes the influence of these atmospheres on high-temperature oxidation and sub-surface defects. The results are discussed in terms of the change in Pilling-Bedworth ratio.

Jan 1, 1996

By Kimio Itagaki, Torn Matsumoto, Makoto Ohtsuka, Kentarou Harada

"The structure and hydrogen-absorption properties of LaNis thin films were investigated in the present study. LaNis thin films were prepared by a sputtering method with a radio-frequency power, Ws, of 50 -400 Wat substrate temperature, Ts, of323 -573 K. Nickel content of the films decreased with increasing Ws, however, there was no dependence on Ts. At low Ws and low Ts, amorphous films were deposited. In other conditions, the films were polycrystalline. The films prepared at high Ws and low Ts, or at low Ws and high Ts, exhibited only a (h k · 0) peak in the X-ray diffraction profiles. This indicates that the c-axis of crystalline films was oriented parallel to the substrate plane. At high Ws and high Ts, the films with columnar structure were obtained. Hydrogen-absorption capacity of the thin films increased with increasing Ws. The pressure plateau did not appear on the pressure-composition isotherms. The films deposited at high Ts represented a higher equilibrium pressure.IntroductionThin films of hydrogen storage alloys can be applied for an electrode of rechargeable battery or fuel cell, a filter for H1 purification and various kind of sensor. Some studies on the preparation of the thin films of LaNi5 intermetallic compound, which is a typical hydrogen storage material, have been done hitherto. Adachi et al. , 2) and Sakaguchi et al. 3) prepared amorphous and crystalline LaNi5 thin films using flash evaporation of alloy powders and measured the pressure-composition isotherm for the prepared film utilizing a quartz crystal mass monitoring (QC:MM) method. It was found that the prepared amorphous film absorbed hydrogen without disintegrating into the powders and the hydrogen-absorption capacity of the films increased with the degree of crystallinity. Sakai et al. 4) reported that the maximum hydrogen storage capacities of amorphous and crystalline LaNi5 thin films, fabricated by a RF sputtering method using combination targets, were about 40 mA h g-1 (LaNisHo.7) and 160 mA h g-1 (LaNi5H2.6), respectively. Uchida et al. 5, 6) prepared LaNi5 thin films using flash evaporation of alloy powders and measured volumetrically the pressure-composition isotherm for the prepared film. It was reported that the hydrogen-absorption capacity of the films changed by the annealing treatment."

Jan 1, 1998

By Mototsugu Matsuno

A new process has been developed to treat fly ash generated from municipal incinerators, which contains not only toxic metals such as lead and cadmium, but also dioxins. The process includes the following steps; fly ash is formed into green pellets with some additives and the pellets are then roasted to eliminate or stabilize the toxic metals and to decompose dioxins. A pilot plant with a capacity of approximately 100 kg/hr was used to test the process. The tests verified that heavy metals were either volatilized or stabilized and dioxins were decomposed by high-temperature roasting. The pelletized ash was found to be non-toxic, so that it can be recycled as artificial lightweight aggregate. It was also found that volatilized metals collected as secondary ash can be recycled as smelting resources.

Jan 1, 2003

By Rick Honaker

Rare earth elements (REEs) contained in coal and associated mineral matter exist in several forms including micro-dispersed minerals, ion adsorption onto clay surfaces, and chemically bound. Tests found that REEs can be effectively recovered from certain components of three coal sources by leaching under mild conditions followed by solvent extraction. A range of pH values were evaluated at solution temperatures of 25 and 75 °C. When using 1.2 M of sulfuric acid, nearly 85% recovery of the REEs was extracted from the middlings material collected from an operating plant. Acid leaching of a second middling source from another plant resulted in 60% of the total REEs being recovered under the same leaching conditions. Solvent extraction treatment of the leachate produced from six different coal sources resulted in products containing up to 50% total REEs from feedstocks starting with around 300 ppm.

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to predict the distribution behaviors of Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag in copper pyrometallurgical process. In this model, as more as 21 elements (Cu, S, Fe, Ni, Co, Sn, As, Sb, Bi, Pb, Zn, Au, Ag, 0, N, C, H, Ca, Mg, Al, and Si) and 72 compounds (in fayalite-slag-making system) or 74 compounds (in ferrite-slag-making system) are considered. Accessory-element behavior is studied for two types of slag , fayalite and ferrite, and two levels of oxidation. The allowance is also made to account for physical entrainment in the melts.-Model simulations are carried out to study the effects of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxygen enriched air. The model can be used in copper flash process, Mitsubishi process and Noranda process. The predictions by the present computer model are compared with the known industrial data from Gui Xi Smelter in China, Home Smelter in Canada and Naoshima Smelter in Japan and excellent agreement between calculations and industrial data is obtained. In this paper, the effects of oxygen enrichment, matte grade, smelting temperature, and types of slag on accessory-element behavior among matte, slag and gaseous phase have been elucidated.I . IntroductionThe presence of trace quantities of minor elements such as As, Sb and Bi in copper significantly reduces its ductility, electrical conductivity, and lowers its thermal conductivity. Embrittlement of copper also occurs due to impurity-phase precipitates at the copper grain boundary interfaces. They deteriorate not only the electrical conductivity of copper but its workability in hot working."

Jan 1, 1998

By Józef Czemecki

Polish copper concentrates are characterized by high levels of impurities, particularly Pb and As. Two technologies are being used for copper concentrate smelting at KGHM Polska Meidz S.A., namely the shaft furnace process (Legnica Copper Smelter, Glogów I Copper Smelter) and a single-stage process for direct to blister concentrate smelting in a flash furnace (Glogów II Copper Smelter). Both technologies are used at different physical and chemical conditions which results, in different impurities behavior. The paper presents flow sheets for copper production in a plant using the shaft furnace process and in another in which a single stage flash process is used. The metals distribution in particular semi-products is given as well as a method for elimination of impurities from the copper production cycle. Methods are also discussed for alloy and matte converting and copper refining to obtain low Pb and As concentrations in anode copper (0.3% Pb and 1500 ppm As maximum) that are being used in the KGHM Polska Meidz plants. Useful co-operation between the plants using different technologies, aimed at the limiting the effect of undesired impurities on the quality of blister copper produced, is also described.

Jan 1, 1998

By P. A. Rusin

Many manganiferous silver deposits remain undeveloped because standard chemical extraction methods yield poor recoveries or are ' environmentally unacceptable. Biotreatment of such ore deposits in our laboratory resulted in manganese and silver recoveries of greater than 90%. Ore and sediment samples were collected from mining sites in Colorado and Arizona. Portions of samples were incubated in a semi-solid mineral salts medium amended with 20 mM glucose mid manganese dioxide (Mn medium). The cultures were incubated at 3(fC until manganese reduction was detected by a .color change fr:om .black to clear. Bacteria from these cultures were purified on Tryptic Soy Agar and individual isolates were retested for Mn reduction by an agar overlay method. Bacteria were identified according to Bergefs Manual ?of Systematic . Bacteriology. Most of the Mn-reducing bacteria are Bacillus species. Bacterial manganese reduction kinetic experiments were performed in 52 ml mineral salts broth supplemented with manganiferous silver ore instead of manganese dioiide. These cultures were incubated with agitation for 16 d. Aliquots were removed periodically and analyzed for solubilized manganese by atoniic absorption (AA). Cyanide (1,0 M) Vias added to the remaining ore-medium mixture for a 24 h bottle roll. The supernatant was analyzed for soluble silver by AA. Similar experiments were conducted on a larger scale using 15% pulp density. After bfotreatment of the ore, standard bottle rolls were performed. The pregnant solutions and the residues were analyzed for manganese and silver?using AA or fire assay as appropriate. In sterile. controls-which received no biotreatment, manganese and silver recoveries were 0.3% and 10% respectively; During biotreatment, total manganese solubilizatiori was as high as 99.8%. The reduced manganese could . be stripped from ?the growth medium using hydrometallurgical techniques. Silver recovery vaned from 70% to 92.5%. Microbial treatment of refractory mangairlferous ores can result in high recoveries of manganese and silver. Retention time varies depending upon the relative concentrations of manganese, silver, and other metals in the ore with only two days required in some cases, The biotreatment of ore is environmentally' acceptable while the use. of chemicals such as sulfur dioxide is less so.

Jan 1, 1991

By Lenny Winkel

With the aim to develop a solar-driven process for the extraction of copper from sulfide concentrates research on the decomposition of copper sulfides under inert atmospheres has been initiated. Thermogravimetric measurements on chalcocite,(Cu2S) revealed that copper is formed already at 1823 K. Chalcopyrite (CuFeS2) also disintegrates at this temperature, although at a lower rate. Copper and iron have been identified in the solid residue. The results confirm the feasibility of copper extraction by direct decomposition of sulfides under atmospheric pressure. The decomposition under inert atmosphere prevents generation of SO2, it also alters the behavior of volatile impurities during decomposition of copper sulfide concentrates. Chemical equilibrium calculations for chalcopyrite contaminated with enargite (Cu3AsS4) have shown that the absence of an oxidic slag allows for a complete evaporation of arsenic and subsequent separation from intermediate sulfides. The need to better assess the potential of direct sulfide decomposition has prompted the development of an experimental setup for studying the decomposition reactions. The experiment has been devised such that data on the decomposition kinetics and on impurity removal can be obtained at temperatures up to 2500 K.

Jan 1, 2003

By P .. R. Ammann

A two-stage pyrometallurgical process has been developed for the recovery of copper (and other non-ferrous metals) from copper smelter slags. All types of slags, including highly oxidized, converter-type slags, are cleaned in an electric furnace which employs mechanical mixers to promote magnetite reduction and copper extraction at high rates. In a 10-ton pilot furnace, it has been demonstrated that slags can be cleaned to 0.2-0.3 per cent copper with economically acceptable usage of raw materials and energy; copper is recovered as a high-grade matte. Pilot plant data have been scaled up to a commercial furnace and engineering designs have been made for a furnace to treat 60 tons per hour of slag from a Noranda Reactor and the associated converters. Plans are being formulated for the construction of a prototype slag cleaning furnace.

Jan 1, 1976