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By Leo Brewer, Kazuyoshi Shimakage, Mamoru Mitomo, Toshiyuki Nishimura, Yoichiro Uemura, Shinji Hirai

"In the synthesis process of ß -La2S3 via the sulfurization of La2O3 powder using CS2 gas, La2O2S was formed. This occurred at an initial stage of the reaction for sulfurization temperatures below 973K, and ß -La2S3 was also formed at a shorter period for higher sulfurization temperatures. It was found that the oxygen content in ß -La2S3 powders decreased gradually with an increase in sulfurization temperature. On the other hand, the carbon content in these powders increased gradually with an increase in the sulfurization temperature. Though it has been reported that ß -La2S3 was transformed to Y -La2S3 at 1723K± 50K, the sintered compact of double-phase Y -La2S3 and ß. -La2S3 was formed at a rather higher temperature of 1973K when the synthetic powder of ß -La2S3 containing a high amount of oxygen was used. However, phase transformation of -La2S3 to Y -La2S3 progressed preferentially with a decrease in the oxygen content of synthetic ß -La2S3 powder. The Seebeck coefficient of the sintered double-phase Y -La2S3 and -La2S3 was higher than that of the single-phase Y -La2S3, reported previously.Introduction La2S3 exists in three polymorphic forms that are similar to a series of Ce2S3, Pr2S3 and Nd2S3: a, ß , and Y'. The a -La2S3, which is stable at low temperature, is irreversibly transformed to ß -La2S3 of various compositions in the solid-solution range between La2S3 and La3S4, at 923 ± 50K. The -La2S3 may also be an oxysulfide of La10S14O2. Moreover, the ß .-La2S3 phase is transformed to Y -La2S3 ,which has a Th3P4 structure, at 1573 ± 100K. The melting point of Y -La2S3 is 2398 ± 30K where this temperature is similar to those of common refractory materials such as silica and alumina. Therefore, it can be predicted that y -La2S3 which has a high melting point and a thermodynamic stability due to the strong affinity of La for S, would have &high refractory character and chemical inertness in many molten metals. The y -La2S3, colored vivid faint yellow is stable up to 623K in air, where oxidation starts. y -La2S3 is frequently used as pigments for plastics and paints3. Furthermore, Y -La2S3 which is a semiconductor, is considered to be useful as a thermoelectric conversion materials, because it has a high Seebeck coefficient."

Jan 1, 2000

By E. A. Werner, A. Pichler, A. Spalek, G. Reisner, P. Stiaszny

"Interstitial free (IF) sheet steels are used for complex shaped parts because of their excellent formability. If a deep drawn part is subjected· to a impact deformation at low temperature brittle fracture of the part may occur. This phenomenon\ is called secondary work embrittlement (SWE). One possibility to characterize this material/structural behavior is the drop-weight test. The result of .this .test is a temperature at and below which a crack can initiated in a deep drawn part under the investigated set of parameters. This paper addresses the influence of the preforming process on the sus- . . ceptibili.ty of IF steels to SWE.IntroductionInterstiiial:free (IF-) steels are frequently used in the automotive industry for complex· shaped p·arts because of their excellent deep drawability. The microstructure of the steel consists of a highly ductile ferritic matrix with embedded precipitates of nitrides and/or carbides. Brittle fracture can occur in deep drawn parts, if they are subjected to a high speed deformation at lo""w temperature. This phenomenon is called ~econdary Work gmbrittlement (SWE) [1-11]. Up to now there are no standardized testing procedures available to quantify the sensibility of IF-sheet steel to SWE. Neveitheless, a reasonable testing procedure which allows to quantify the tendency of a predeformed part to SWE is necessary for further material development. A commonly used test method is the drop-weight test performed at low temperatures. In such ·tests a cone-like drop weight expands a deep drawn cylindrical cup [l-3, 6, 8, 9, 11]. From this expansion experiment the temperature is determined at and below which a brittle crack can be initiated in the deep drawn cup under the investigated impact test parameters. The highest measured temperature at which a deep drawn cup fails by brittle fracture is called frack appearances !emperature (CAPT). The lower the value of the CAPT the lower is the sensibility of a deep drawn part of IF-sheet steel to SWE. This paper aims to clarify the role of the preforming process on the impact behavior of an IF steel. For this purpose a numerical analysis of the deep drawing process and cup expansion tests are conducted."

Jan 1, 2000

By Alex Moyano

The Codelco-Chile is considering different processing options for the projected concentrate from the Alejandro Hales mine (former Mansa Mina mine with high arsenic and antimony content of 6% and 0.6%, respectively), that will produce complex blister copper with high impurities contents, higher than the present values produced at the converting process of the Codelco Norte smelter processing only Chuquicamata concentrates. In order to know both the anodic copper quality and the metallurgical implications when a complex blister copper is processed in the refining process of the CN smelter, the Codelco and IM2 ?task force? evaluated positively the refining process for the complex blister copper by addition of alkaline fluxes at laboratory and industrial scale tests. The promising results of the tests done at laboratory scale at the Tohoku University facilities, allowed a large scale test planning to validate the lab-scale results in 3 refining furnaces of 250 t capacity at the CN smelter. The obtained results demonstrate the industrial technical feasibility to process a complex blister copper in the refining furnaces producing an anodic copper quality suitable for the electrolytic process.

Jan 1, 2006

By A. Valenzuela

During the last years, Chile has been the largest copper producer, either as concentrates or cathodes. Copper obtained via pyrometallurgy is produced by seven smelters, which have carried out modernization plans to increase smelting capacity or to achieve environmental regulations established in the Chilean legislation. Thus, the present work updates technological innovations in smelters, environmental regulations and presents solutions for SO2 handling, particulate matter and arsenic. Also, the authors emphasize the important role of CODELCO Chile, the most important state-owned copper company, in developing technologies such as EI Teniente Converter and EI Teniente Slag Cleaning Furnace,

Jan 1, 2003

By Naiyang Ma

"High oil concentration is one of the major barriers for recycling of mill scale of steel hot rolling mills. It is of vital importance to find cost-effective technologies of reducing oil concentration in mill scale in order to recycle the mill scale without causing detrimental effects on production and environment. This paper discusses in-process separation of mill scale from oil at steel hot rolling mills. Formation of mill scale and status of oily wastewater at hot rolling mills are reviewed in the first place. A mathematical model is then formulated to relate oil concentration in mill scale to physical properties of mill scale, chemical and physical properties of wastewater and interacting parameters between mill scale particles and wastewater. From this model, three approaches of in-process separation of mill scale from oil are derived: (1) avoiding contacts between mill scale particles and oily wastewater, and (2) maintaining low oil concentration in wastewater, and (3) collecting mill scale in upper streams of wastewater flows. In-process separation of mill scale from oil might have advantages of lower capital cost, lower operating cost and less additional environmental concerns, compared to other strategies of separating mill scale from oil.IntroductionHot rolling is an inevitable step in producing finished steel products. Figure 1 schematically shows a steel hot rolling process. Semi-finished steel products, slabs here, are reheated first, and then the reheated slabs are discharged from the furnaces and transported on hot rolling trains to descaling units for removing scale with pressurized water. After being descaled, the slabs are rolled by roughing mills. After treated with cropping and the second descaling, the slabs are finally rolled into finished products, coils here, by finishing mills."

Jan 1, 2012

By Victor Zavodinsky, Sergey Rogov

"Pseudo-potential fully relaxed total energy calculations are used to predict a hypothetical Si1-xCxO2 (x<0.5) compound formed from SiO2 ß -cristobalite by substitution of some SiO2 complexes by CO2 molecules. The simulation shows that the Si1-xCxO2 compound can be quasi stable if the CO2 content is less than fifty per cent. It is assumed that six-molecule Si6-nCnO12 (n=3) rings can play a role of nucleuses for formation of the Si1-xCxO2 compound from SiO2 and CO2 molecules. Thus, silicon dioxide can be considered as a possible solid store for gaseous CO2.IntroductionThe problem of increasing of CO2 in the Earth atmosphere is one of the main modern problems of mankind. One of conceivable ways to decrease the harmful value of CO2 is to convert a part of it to solid state. Iota et al. [1] reported a polymeric (quartz-like) phase of CO2 solid synthesized at high pressure (~40 GPa) and at high temperature (~1800 K). Shortly after this experimental work, Serra et al. [2] reported a total energy calculation of several possible phases of CO2 using plane wave pseudo-potential density functional theory. They concluded that there should be a transition from a molecular phase to a phase isostructural to SiO2 -quartz in the range of 35 to 60 GPa. The latest calculations by Dong et al. [3] have shown that the more favored solid CO2 phase is ß -cristobalite. Recently, Kume et al. [4] have demonstrated the polymerization of CO2 even at room temperature at high pressures up to 80 GPa. Transformations of gaseous CO2 to different solid phases were studied recently experimentally and theoretically [5-8]. The main obstacle for using synthesized CO2 solid as a solution for the CO2 problem is its pressure instability. However the SiO2 ß -cristobalite with the same structure is stable.The question is whether a silicon-oxide system in which a part of atoms of silicon is replaced by atoms of carbon will be stable? If the answer is positive, this system can be considered, in our opinion, as a possible store for CO2."

Jan 1, 2009

By M. Zamalloa

Slag foaming is an important phenomenon in many metallurgical processes. It creates large surface areas for multi-phase reactions to take place. In other applications, it protects electrodes and improves the energy efficiency by reducing radiation from hot surfaces. However, it may also be a source of serious disturbances. To control and optimize the use of slag foams, an extensive knowledge of the factors controlling the foam formation and stability is required. Slag foaming experiments were carried out using synthetic FeO-CaO-Si02 slags at temperatures ranging from 1200 to 1350 "C. A data acquisition system was used to continuously measure the foam height, gas flow rate, bubble frequency and temperature. The experimental results show that the gas injection rate has a strong effect on the behaviour of slag foams. At high flow rates and rapid bubbling, unstable foams with short decay times were created. The addition of P20, favours the foam formation and stability by lowering the surface tension of the slag. The average foam life increases with decreasing basicity (CaO/Si02). It is proposed that this is attributed to the increase of the surface viscosity due to surface adsorption of a thin film of silica, retarding the drainage of the liquid films.

Jan 1, 1992

By Carlos G. Levi

"The principles involved in the rapid solidification of supercooled metal droplets and existing numerical models are reviewed. The limitations of these models for studying alloy solidification are discussed in terms of the effects of alloying elements on the relevant heat transfer, thermodynamic and kinetic parameters. Analysis of the enthalpy-temperature diagram reveals how the extent of rapid solidification is hindered by the addition of solute. A solidification model incorporating thermodynamic and kinetic relationships into a Newtonian heat transfer formulation is used to analyze the thermal history and concurrent solute redistribution during recalescence. IntroductionIt is well acknowledged that microstructural evolution during solidification is intimately associated with the thermal history of the liquid-solid interface. Structural parameters like chemical homogeneity, morphology and size scale of the phases can be related to the interfacial temperature and velocity. These in turn change by the interaction of the interface with the thermal and solutal fields in its neighboring environment.The thermal history of powder solidification can be conveniently described on the enthalpy-temperature diagram for a pure metal shown in Figure 1 and discussed in detail elsewhere [1). A system can conceivably follow any path of decreasing enthalpy in the supercooled region of Figure 1 (~ < 1), starting at the nucleation temperature (oN < 0) on the liquid line, and ending at some point on the solid line. A vertical path represents an isothermal transformation, of which a limiting case is solidification without significant barriers to nucleation and growth, with the interface at the equilibrium temperature TM (path one in Figure 1). A horizontal path represents isenthalpic (or adiabatic) solidification whereby the system could form an amount of solid proportional to the initial supercooling of the liquid without further heat loss to the environment. A liquid that can completely transform to solid under adiabatic conditions is said to be ""hypercooled""."

Jan 1, 1986

By M. A. Barakat

Large amounts of zinc ash and flue dust containing more than 80 % zinc are accumulated during galvanization processes at the surface of molten zinc bath and in the chimney respectively. Pyrometallurgical recovery of zinc from both of the ash and dust samples has been carried out. The ash was sieved with the help of an industrial sieve shaker provided with mesh sieve having a pore size 0.9 mm. The oversize fraction cut (+ 0.9 mm) was melted at 550 °C under ambient conditions. The produced ingot (1) was analyzed whereas the coarse fraction of the produced slag (+ 0.9 mm) was treated as the coarse ash or added to it. The dust was enriched with suitable fluxing salt prior to heat treatment at 600 °C for 1 h. The produced ingot (2) was analyzed whereas the resulting slag was mixed with the fines of the ash and treated by hydrometallurgical processing to prepare valuable salts of zinc. Parameters affecting recovery processes such as time, temperature and flux percentage were studied. Results obtained revealed that the two prepared ingots (1&2) were successfully recovered with recovery efficiency amounts to =85 %. The obtained samples meet the standard specifications with relatively low price. Also in the light of the strict environmental regulations of pollution control, reuse of these wastes materials will help in keeping the environment clean.

Jan 1, 2000

By R. N. O'Brien, E. Peters

"It has been discovered that copper concentrates can be leached in strong (40-60%) sulfuric acid with nitric acid, or with oxygen if nitric acid is present as a catalyst. Chalcopyrite is rapidly decomposed at temperatures well below the boiling temperature of the lixiviant (-150 C.) and the resulting copper and ferric salts are precipitated as CuS04.H20 and FeH(S04)z.4H20. Other metal sulfides such as zinc, lead, nickel, etc. are also converted to sulfates that are nearly insoluble. Sulfur is partially converted to elemental and partially to sulfuric acid. Reduction products of nitric acid can be recovered from the distillate with good recovery. Conversion of as-received copper concentrates is largely complete in about 1 hour. Introduction9 molar sulfuric acid is an unusual hydrometallurgical lixiviant: it has a boiling point of about 150 C. and a low solubility for base metal sulfates. Below about 6 molar acid, the boiling point falls below 120 C. and yields much higher sulfate salt solubility, while above 12 or 13 molar acid and at higher temperature sulfuric acid becomes an oxidizing agent, yielding gaseous S02' Thus, sulfuric acid within this range of concentration is capable of acting well above the temperature of boiling water without requiring autoclave conditions, and if typical oxidative leaching conditions are applied to suspended mineral sulfide concentrates, it is possible to obtain a conversion of these sulfides into 'crystalline sulfates. Thereafter, the sulfates can be separated by filtration or by solid - bowl centrifuge and the solution can be recirculated to the reactor vessel. Meanwhile, the solid sulfates can be treated in a typical hydrometallurgical circuit, i.e., dissolved in a return stream that is essentially water, separated from each other by, for example, solvent extraction, and recovered as metals by electrowinning."

Jan 1, 1997

By C. Flores

The direct cementation of copper from a loaded D2EHPA 20 % vol. in kerosene using zinc, zinc-lead alloy and iron metallic powders was studied. Copper was loaded into the organic solvent from an aqueous copper sulfate solution. Results indicated that copper is reduced spontaneously with relatively fast reaction rates. The effects of several operating parameters such as water content in the organic system, initial copper concentration, reductant surface area, oxygen and nitrogen atmosphere, intensity of the agitation and temperature on the galvanic stripping of copper were studied. For a better understanding of the electrochemical reactions involved in the galvanic stripping, the dissolution of metallic copper in the organic solvent was also studied. Copper did not dissolve unless a small amount of water was present in the organic system. The results and possible reaction mechanisms are discussed.

Jan 1, 1999

By Karl A. Gschneidner

Magnetic refrigeration was first used in the mid-1920&apos;s and new developments seem to have taken place about every 20 years, and this is especially true for the mid-1990&apos;s. The active magnetic regenerator magnetic refrigerator has the promise to become the first practical machine utilizing the magnetocaloric effect for cooling (and also heating). The basic principles are briefly discussed. Since the temperature lift for the magnetocaloric effect spans about 50 K, one will need to utilize several ferromagnets with different magnetic ordering temperatures in order to reach temperatures below ~250 K. The basic properties, behaviors, limitations, and new phenomena and knowledge are discussed.

Jan 1, 1997

By Nobuaki Sato

For decontamination of SO2 containing waste gases from industries such as ferrous and non-ferrous metal companies, desulfurization with hydrogen production by the reaction of Br2 and SO2 was proposed as bromine-sulfur (BS) process. In this process, SO2 is fixed as H2SO4 in the presence of Br2 and H2O forming H2SO4 and HBr. Then hydrogen is produced by the decomposition of HBr and Br2 as byproduct is recycled. The reaction of Br2, SO2 and H2O was found not to occur in liquid phase but to occur in vapor one. The production ratios of H2SO4 and HBr showed a maximum at temperatures around 60 oC. The highest production ratio was obtained at 70 oC with a mixing ratio of Br2:SO2:H2O=1:1:10. The experimental results were discussed with thermodynamic consideration.

Jan 1, 2006

By Gustavo Díaz, Miguel A. García, Carlos Frías

"Under the auspices of the Commission of the European Union, a consortium composed of six European organi~ations has conducted a project to scale up the PLACID electrowinning cell to industrial size within the Placid process development. This paper is concerning the results and achievement of the industrial cell prototype after more than 1,000 hours operating time and about 10,000 Kg electrolytic lead production. In general, results have been very satisfactory, demonstrating the ability ofthe PLACID electrowinning cell to produce top quality electrolytic lead (> 99.99 %) with high current efficiency and low energy consumption.IntroductionThis paper is concerning the development of an industrial size PLACID electrowinning cell within the PLACID process development. This project began on January 1993 and was finished on April 1996.Lead metal production and manufacturing industries produce large amounts of dusts and also lead bearing slags. Spent lead-acid battery recycling also produces lead oxides from the battery pastes rather similar to those mentioned above. Those lead secondary materials are hazardous and difficult to handle by usual procedures.Existing processes to treat-lead oxides may inflict considerable damage on the environment, incur high operating costs and have limitations to produce top quality lead.The main aim of this project has been to develop a novel hydrometallurgical process able to deal with different lead bearing materials, mainly lead oxide secondaries: lead-acid battery pastes, lead fumes, furnace slags, oxide residues, etc., producing ""four nines"" pure lead in an efficient manner with a benign influence on the environment; it is called the PLACID process."

Jan 1, 1997

By Z. Zhang, Zongshu Zou, Nan Wang

"Thermodynamic calculation is applied to make an investigation on the equilibrium phase relations and liquids of CaO-SiO2-Al2O3-FeOx system for different temperatures. The calculated results with FactSage6.1 show that the effect of temperature on the the equilibrium phase relations and liquidus of CaO-SiO2-Al2O3-FeOx system and its sub-systems is appreciable. The liquid phase regions enlarge with increasing temperature from 1573K to 1873K, while the primary phase fields reduce distinctly.IntroductionThe main oxide components of vitrified bottom ash slag are CaO, Al2O3, SiO2, Fe2O3, MgO, and Na2O, accounting for more than 90% of the bottom ash by weight[1]. During slag processing, the knowledge of thermodynamic properties and liquidus temperature in the related slag systems is highly required [2, 3], which is not yet available. Through literature survey [4-6], it is clear that the systematic information on the concerned complex slag system is scarce. So far the engineers in the field have to make assumptions of the thermodynamic properties of the simplified oxide system, without taking into consideration the interactions of the different oxide components, which hinders the development of the slag valorization and utilization. In order to provide thermodynamic properties for the application of the vitrified bottom ash, the six-component oxide system (CaO-MgO-Al2O3-SiO2-FeOx-Na2O) is highly required. A preliminary phase diagram of the CaO-MgO-Al2O3-SiO2-FeOx-Na2O system can be obtained from extrapolation of the thermodynamic functions of constituent subsystems such as CaO-SiO2-FeOx-MgO, CaO-SiO2-FeOx-Al2O3, CaO-SiO2-Na2O-MgO and CaO-SiO2-Na2O-Al2O3. In this work, the equilibrium phase relation and liquidus of CaO-SiO2-FeOx-Al2O3 system, one subsystem of the concerned complex slag system, are calculated and the effect of temperature is also discussed."

Jan 1, 2012

By B. C. Blakey

The economic feasibility of the sulphuric acid pressure leaching route for the extraction of nickel and cobalt values from limonitic ores is highly dependent upon the behavior of aqueous aluminium. This is primarily due to its precipitation as hydronium alunite ((H30)A13(S04)2(OH)6), which is one of the major scale-forming compounds found in autoclaves used for pressure leaching. As a result of renewed interest in the pressure leaching process, an investigation of the aqueous-solid eqilibria in the aluminium-sulphate-water system under acidic (< pH l), high temperature (230 to 270°C) conditions has been conducted. Pure hydronium alunite was synthesized in an autoclave by leaching boehmite (A100H) at elevated temperatures in sulphuric acid solutions initially 0.25 to 0.75 m H2S04 in concentration. Spontaneous, in situ precipitation of hydronium alunite followed. A high temperature solution speciation model was used for the analysis of the resulting solubility data in order to calculate equilibrium constants for the precipitation reaction.

Jan 1, 1994

By Mark Cross, Diane McBride, Nick Croft

Extractive metallurgical processes rate amongst the most complex from the perspective of computational modeling. They typically involve multi-phase and multi-component fluid flow in very complex geometries, heat transfer driven by a number of interacting phenomena, solidliquid- gaseous phase change and mass transfer together with complex thermodynamics and associated chemical reactions. Beyond the model building itself, key challenges have always involved being able to identify the phenomena present together with interactions to characterize processes and experimental laboratory and plant data to parameterize the arising models – it is in this milieu, which require considerable process understanding and subtlety of thought, that David Robertson has made his contributions. We will review the achievements, over the last couple of decades, in computational modeling of extractive metallurgical processes and address some of the remaining challenges to enable simulation based process design, as we move through the 21st century.

Jan 1, 2014

By D. G. C. Robertson

The thermodynamics and kinetics of the reactions involved in fuming zinc from oxide slags using coal or coke were first studied in 1955 and have been the subject of many investigations since that time. The key reaction is ZnO(in slag) + CO = Zn(g) + CO2 This paper will review the some of the recent work, and will add new insights obtained in experiments carried out by the authors. In the first series of experiments it was shown that the reaction does not occur at an appreciable rate, as is expected from thennodynamic considerations. In the second series of experiments it was shown that zinc does not fume from the slag at a significant rate unless a reductant has been added. This again is in accord with thermodynamic considerations, but is in contradiction to some of the experimental results reported in the literature. A third series of experiments was carried out with excess coke being present, so that the rate of supply of reductant was not in any way controlling the rate. The kinetics of zinc oxide reaction were then found to be independent of the zinc oxide concentration, but increased with increasing basicity, and temperature. The presence of high concentrations of FeO in the slag also improves the kinetics. At low zinc oxide coneentrations iron oxide reduction occurred in parallel with zinc oxide reduction. We propose that (under the conditions of this work) the kinetics were controlled by a chemical step, namely the rate of desorption of an adsorbed CO2 species. This is the same mechanism as reported by Belton and co-workers for the kinetics of the reduction of FeO. This explains why the reduction of metal oxides in slags by hydrogen is often faster than by CO.

Jan 1, 2003

By KNona Liddell

Many metal recovery processes Involve heterogeneous reactions In porous media accompanied by fluid flow and mass transfer. Modeling such systems Is difficult because of the number of rate processes Involved and is complicated even further by effects due to the structure of the porous medium. Data on even bulk properties of the medium are often severely limited or unavailable. For many such systems, a cell model may provide, an attractive alternative to models based on transport ,mechanisms in a differential volume. A cell model requires less input data and is computationally efficient. Identical residence time distributions can be obtained with models of both types, and both allow conversion and concentration profiles and histories to be calculated. The formulation and properties of cell models for metals recovery are described in detail.

Jan 1, 1996

By Rajesh S. Ransing

An intelligent tool has been developed to analyse the quality of diecast components. The influence of both design and process parameters has been studied in great detail. The tool, based on expert systems related technologies, can identify the causes for the defective castings manufactured. Design related causes such as gate position; gate area, runner design etc. as well as process related causes such as cycle time, cavity filling time and melt temperature are suggested by analysing the data on defective castings for a manufacturing campaign. This intelligent analysis is useful for both design as well as production engineers in the decision making process. All the causes for the occurrence of defects are classified into two categories. The firs category is the &apos;rootcauses&apos; i.e. the causes which are related to the actual process, material and design parameters and which can be directly monitored. The second category is more abstract in nature and is classified as `metacauses&apos;. These capture the scientific rationale implicit in the cause and defect relationships. This knowledge on causes and defects is represented in the form of a structured graph rather than by a set of rules, which, coupled with forward reasoning and heuristic search techniques results in an elegant and efficient approach. Uncertainties and the degree of relationship among causes and defects are represented by a fuzzy probabilistic model.

Jan 1, 1994