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By Takeo Fujino, Nobuaki Sato, Yarong Wang, Kohta Yamada

"Ternary mixed sulfides of some transition metals MTS3 (M=Ba, ·Pb, T=Ti, Zr) were synthesized by a relatively low temperature process using sulfur melt. The mixture of starting materials, such as, metals and/or binary sulfides and a large excess of sulfur was reacted in a vacuum-sealed Pyrex or quartz ampoule at 350- 600 °C for one to three weeks. After the reaction, the remaining sulfur was completely removed by a process composed of filtration of sulfur melt and followed dissolution in CS2• The binary sulfides impurities coexisted in the products were removed by rinsing the products in water and acetone. By using the above method, BaTiS3, PbTiS3 and BaZrS3 'Were obtained in pure form. The effect of addition of halides on the yields of these ternary sulfides were also discussed.IntroductionThere have been a vast number of studies on the preparation and physical and /or chemical properties of mixed metal oxides. As is well known, some of such compounds exhibit excellent materials properties, causing them for use in mechanical, electronic, magnetic and chemical devices. Not a few mixed metal sulfides show similar physico-chemical properties to those of the corresponding mixed metal oxides. However, the study of the mixed sulfide crystals is rather sparse mainly due to difficulties in preparing these compounds. In various methods which have been adopted for preparing mixed sulfides, the simplest method would be the solid-solid reaction of the component binary sulfides or elements. However, there are always diffusional constraints with regard to the reactions in solid phases causing it necessary to heat the reactants at sufficiently high temperatures, viz. 800-1200°C. On the other hand, some mixed sulfides are unstable at high temperatures or to change their materials properties due to sulfur nonstoichiometry and structural modification depending on temperature, i.e., synthesis of such compounds needs to be made at lower temperatures. Processing in alkali halide melts is hopeful to overcome the above problems but to obtain the halide melts the temperatures above ~ 600 °C is needed. Low temperature reaction has been carried out for the preparation of Hg1.24TiS4, which was formed by the ·combination of TiS2 and molten Hg metal at 320°C[l]. Reaction of WS2 with LiBH4 melt at 350°C yielded LixWS2[2]. These sophisticated methods, however, can be applied only to the vary special cases."

Jan 1, 2000

By William Petruk, J. H. Gilles Laflamme, Jean Robitaille, Louis J. Cabri

"A quantitative mineralogical study using ore microscopy, electron microscopy, proton-microprobe, image analysis, and material balances was done on samples from the circuit of a concentrator in Quebec, with particular emphasis on the Cu concentrate. The ore contains many different minerals, of which the principal ones, in decreasing order of abundance, are pyrite, sphalerite, chalcopyrite, bornite, galena, tennantite, and pyrrhotite. Minor to trace amounts of covellite, chalcocite, stannoidite, mawsonite, colusite, wittichenite, miharaite, hessite, petzite, electrum, and an unidentified Cu-Pb-Bi-sulfide also occur.Liberation of pyrite is very high in all size fractions for all samples (ranging from 80-91 %). Liberation of chalcopyrite, bomite, sphalerite, and tennantite is relatively high, on average, in the head .sample and Cu concentrate (55-78% and 66-88%, respectively). Most of the chalcopyrite in the flotation tails is not liberated, whereas about one half of the tennantite and sphalerite are liberated in both the flotation and :final tails. Recoveries calculated for the Cu concentrate (on the basis of assays, mineralogy, and image analysis) are chalcopyrite 72. 5%, bornite 73. 7%, sphalerite 41.0%, tennantite 70.9 %, and galena (together with some trace minerals) 34.2%. It was also calculated that the Cu concentrate contains 10.0 % of the pyrrhotite and i.4 % of the pyrite.Materials balance calculations were done on the five major sulfide minerals to determine the mineralogical distribution of 13 major, minor, and trace elements (as determined by protonmicroprobe analyses). It was determined that tennantite is the principal carrier of Bi (67%), As (90%), and Te (86%) in the Cu concentrate. Therefore, removal oftennantite, which is mostly liberated in the Cu concentrate would significantly reduce these three contaminant elements, but at a loss of9% of the Cu, 2.0% of the Zn, and 0.7% of the Ag. The precious metals (Au, Ag) occur as discrete minerals (electrum, petzite, hessite). Some of the Ag also occurs in solid solution in bornite (23.1% of Ag in Cu concentrate), tennantite, and sphalerite. Four of the major sulfides (chalcopyrite, bomite, sphalerite, tennantite) in the ore also contain measurable concentrations of the following trace elements: Se, Cd, In, Sn, and Sb, occurring mostly as solid solutions. Some of these elements are also concentrated (up to about 18%) in minor and trace minerals such as colusite, stannoidite, and mawsonite."

Jan 1, 1999

By Shengli Wu, Fengjie Zhang, Feng Chang, Hua Lu, Kaiping Du

In order to make a complete understanding of steel plant metallurgical dusts and to realize the goal of zero-waste, a study of their properties was undertaken. For these purposes, samples of two sintering dusts (SD), two blast furnace dusts (BFD), and one electric arc furnace dust (EAFD) taken from the regular production process were subjected to a series of tests. The tests were carried out by using granulometry analysis, chemical analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy via SEM (EDS), and Fourier transform infrared spectroscopy (FTIR). The dominant elements having an advantage of reuse are Fe, K, Cl, Zn, C. The dominant mineralogical phases identified in sintering dust are KCl, Fe2O3, CaCO3, CaMg(CO3)2, NaCl, SiO2. Mineralogical phases exist in blast furnace dust are Fe2O3, Fe3O4, with small amount of KCl and kaolinite coexist. While in electric arc furnace dust, Fe3O4, ZnFe2O4, CaCO3, CaO, Ca(OH)2 are detected.

Jan 1, 2015

By M. Tamura, K. Fujita, K Shinozuka, H. Daimon, H. Esaka

"In-situ observation of unidirectional solidification using transparent substance has been performed to investigate the growth direction of solid phase. Cell or dendrite of which preferred growth direction is not parallel to the heat flow direction was observed with various solidification conditions. Dimensionless growth direction (p) changes from 0 to 1 with increasing growth velocity at a constant temperature gradient. Introducing the dimensionless growth velocity, the relation between p and growth condition could be correlated.IntroductionTransition in macroscopic solidified structure from chill to columnar zone which is found in normal castings takes place via grain selection1). Cast products such as turbine blades are unidirectionally solidified, grain selection plays an important role to choose suitable crystals which have reasonable orientation in the region called ""starter"", which is a very initial part of casting2). Therefore, grain selection is a very important process in the formation of casting structure. The present authors have been studying on the process of grain selection using succinonitrile, which is a transparent organic substance and have found that the growth distance necessary for grain selection depends upon the solidification condition3-5). When the solid/liquid interface is dendritic, the grain selection occurs quickly. On the other hand, when the solid/liquid interface is cellular, it occurs slowly. We supposed that the growth direction of dendrite is different from that of cell when the substance is unidirectionally solidified. Indeed, Kurz and Fisher wrote in their text book that dendrite grows along its preferred growth direction, <100>, regardless of heat flow direction and that cell grows along heat flow direction regardless of its preferred growth direction1). However, there is no quantitative description about the growth direction when the solid/liquid interfacial morphology is cellular. Furthermore, there have been little works6) to study the growth direction of cell and dendrite."

Jan 1, 2000

By J. Grogan

Leaching of galvanized steel coatings allows the steel substrate to be used as a zinc-free scrap source to steel and iron furnaces. In this study the behaviors of sulfuric acid leaching solutions are investigated. The ranked significance of the variables are shown to be acid concentration > temperature > zinc concentration. Examination of the leaching mechanism finds the rate-limiting step to be the cathodic hydrogen reduction reaction. This rate is not only influenced by acid concentration, but also by the hydrogen reduction exchange current density. Dezincing leaching rates are improved by taking advantage of the higher exchange current density of the iron substrate versus the zinc coating. This is accomplished in practice by increasing the exposed interfacial zinc:iron surface area through shredding. Also, a leach control mechanism is proposed through online monitoring of the zinc-iron couple mixed potential.

By Michael A. Eamon

Magma Copper Company has operated its San Manuel SX-EW Plant facilities since 1986. The original plant facilities have a design capacity of 25,000 tons per year of electrowon copper cathode produced by processing pregnant leach solutions from an open pit/heap leach operation. In 1988, the plant was expanded to 50,000 tons per year to incorporate processing leach solutions from an insitu leaching operation. This paper presents a general overview of plant practices with particular emphasis on process innovations developed and implemented by Magma during construction and operation.

Jan 1, 1991

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 Tom W. Gonzales

Magma Metals Company commissioned a 3000 tpd Outokumpu flash smelting furnace in July 1988. Through September 1992 the PSP has smelted a first campaign record 4.1 million tons of concentrate. This paper discusses modifications made to the original process equipment to overcome design flaws as well as future design changes currently under consideration.

Jan 1, 1993

Thallium is a very minor element found in lead ores. It&apos;s behaviour during lead smelting has recently become of much greater interest due to the effects it had on the health of waste heat boiler maintenance contractors at a Canadian smelter. In this paper the behaviour of thallium in both traditional and direct lead smelting processes will be examined using computational thermodynamics techniques. Yazawa and his coworkers have made extensive use of computational thermodynamics to examine and illustrate pyrometallurgical processes. It has been shown that thallium behaviour during smelting is strongly influenced by the extent of oxidation of the lead concentrate and by the presence or absence of chlorine in the charge. The condensation behaviour of thallium species in the waste gas handling system was also modelled and it has been confirmed thallium-rich deposits can form at the high temperatures prevailing in waste heat boilers.

Jan 1, 2003

By P. H. Chang, J. E. Gould

"Solidification structures and austenite decomposition in some spot welded O.05%C - O.3%Mn steels have been studied with the aid of a numerical thermal model. The model is a one dimensional finite difference formulation, and accounts for melting, temperature dependent thermal properties, effective heat transfer in the liquid, and contact resistances. The model was used to predict solidification conditions during resolidification of the nugget. These solidification conditions were correlated with the primary dendrite spacing using available primary dendrite spacings modelling. The model was also used to predict cooling rates in the temperature regime for austenite decomposition. These cooling rates were used to interpret the underlying microstructure.INTRODUCTIONThe metallurgical transformations which occur during the spot welding of low carbon steels have traditionally been characterized only in the most general of fashions. This is most probably due to the similarity of spot welded microstructures to other welded microstructures, and that the mechanical integrity of spot welds has not been a concern. In addition, little information about the particular thermal cycles experienced during spot welding has been available. The introduction of HSLA (microalloyed) sheet steels has, however, raised new concerns about the integrity of spot welds. These steels have on occasion shown irregular weldability, as well as brittleness in the weld nugget on destructive testing l - 4 .In response to these concerns, considerable work has been done attempting to characterize thermal cycles in spot welds 5-12. This has largely taken the form of thermal modelling, with the end purpose generally to estimate the size of the nugget formed. This work uses the thermal model developed at Inland Steel 13 ,14 to try and understand, in a more fundamental way, microstructural evolution in spot welds. Two facets of this microstructural evolution are examined in detail:"

Jan 1, 1986

By Kafui Nyavor

The indirect, and the direct contact mechanisms of bacteria oxidation of sulfides were studied using Thiobacillus ferrooxidans and pyrite. The aim was to determine which of the two generally aeeepted mechanisms played a dominant role, if any, during acid mine drainage (AMD) formation from the oxidation of sulfide minerals. The results show that at a pH of 4.5 where T. ferrooxidans are quite active, but where initial chemical oxidation of pyrite to Fe2+ is limited, the bacteria were unable to directly oxidize pyrite to any significant extent. Whereas, in the presence of Fe2+, T. ferrooxidallS assisted oxidation of pyrite by the indirect mechanism was observed and sustained over the pH and Eb range where the bacteria is active. The results lead to the conclusion that the direct contactmechanism of pyrite oxidition by T. ferrooxidans is insignificant. The predominant, and possibly the only, pathway involves the indirect bacteria oxidation of available Fe2+ to Fe3+, which in turn oxidizes FeS2 to generate additional Fe2+ and acidity in a cyclic process.

Jan 1, 1996

By M. M. Monte

A method for removing metallic mercury from contaminated tailing, using the flotation process, is described. In order to define some relevant parameters for the mercury flotation system, microflotation and electrophoretic mobility tests were carried out on (pure) metallic mercury in the presence of several surfactants. Based on the results obtained from fundamental studies a series of bench scale flotation experiments with mercury containing tailings from two wetland sites in Brasil were done. The results of microflotation tests with mercury showed that by using cetyl trimethyl ammonium bromide, an increase in mercury flotability is observed in the acid pH range, whereas in the presence of potassium oleate the highest mercury flotability was found in the alkaline pH region. The mercury flotability using potassium amyl xanthate was improved by the addition at sodium dithionate as an activator. The bench scale flotation tests with contaminated tailings from Poconé (brazilian wetland site) showed a recovery of 70% when sodium dithionate was used as activator and potassium amyl xanthate as collector. The resulting coefficient of separation is around 60%. However, the results of the flotation experiments with fine fractions from amalgamation tailings from Peixoto de Azevedo (brazilian wetland site) showed a low mercury recovery (32%).The results from this work suggest that since in the Poconé site tailings, the metallic mercury is not completely associated to the finer particles, the flotation process to recover the metallic mercury seems very promisor.

Jan 1, 1996

By Sang-Beom Lee

For thermodynamic prediction, the deoxidation equilibrium of aluminum in Fe-36%Ni alloy was studied with a cold crucible under Ar gas atmosphere at 1773K. For the deoxidation reaction in liquid Fe-36%Ni base, i.e.: A12O3(s) = 2A1 + 3O The interaction parameters and the equilibrium constant between aluminum and oxygen in liquid Fe-36%Ni alloy are given in the following: eo Al = -3.8, roA1=0.9, eAl° = -6.4, rAl° = 700, rAIAIo = 3.1, roA1o = 833 within the composition range of [Al] < 1 mass%. The temperature dependence of the equilibrium constant was obtained in the range of 1773K < T < 1973K by using reported data and present results as follows: log KAo= 0.58-24463.7 / T The deoxidation equilibrium with aluminum in Fe-36%Ni could be thermodynamically well described in the range up [Al] < 1 mass% with first and second order interaction parameters as well as the equilibrium constant determined in this study.

Jan 1, 2002

By N. Kanari

Kinetics of the carbochlorination of Cr2O3 has been studied with C12+CO gas mixtures between 500 °C to 900 °C using thermogravimetric analysis. The apparent activation energy is about 100 kJ/mol. Mathematical fitting of the experimental data suggests that the shrinking sphere model is the most adequate to describe the carbochlorination mechanism of chromium oxide and that is controlled by the chemical reaction. In the temperature range of 550 "C to 800 OC, the reaction order is about 1.34 and is independent of temperature. Changing the C12+CO content from 15 pct to 100 pct increases the reaction rate and does not affect the reaction mechanism. Similarly, changing the ratio of C12/(Cl2+CO) from 0.125 to 0.857 do not modify the carbochlorination mechanism of Cr203. In these conditions, the reaction rate passes through a maximum when using a chlorinating gas mixture having a Cl2/(C12+CO) ratio of about 0.5.

Jan 1, 1998

By C. Mattich, A. L. Beyzavi

The Waelz Plant at Taiwan Steel Union Co. Ltd. (TSU) was erected within nine months from September 1, 1998 to May 15, 1999. The nominal capacity of the plant is 50,000 tonnes per year of electric are furnace dust (EAFD). The plant, consisting of material handling, a waelz kiln, a waste gas cleaning system, waelz oxide leaching and waste water treatment, was commissioned within three months from July 1, 1999 until October 12, 1999. The specific problem of the plant is the high chlorine content in the EAFD pellets which is up to 6 %. Lurgi Metallurgie GmbH, Frankfurt, Germany was responsible for the engineering erection and commissioning of the plant.

Jan 1, 2000

By Yilin Fang, Alain Bonneville, Timothy. D. Scheibe, Zhijie Xu

"We present a hydro-mechanical model for geological sequestration of carbon dioxide. The model considers the poroelastic effects by taking into account the coupling between the geomechanical response and the fluid flow in greater detail. The simplified hydro-mechanical model includes the geomechanical part that relies on the linear elasticity, while the fluid flow is based on the Darcy's law. Two parts were coupled using the standard linear poroelasticity. Analytical solutions for pressure field were obtained for a typical geological sequestration scenario. The model predicts the temporal and spatial variation of pressure field and effects of permeability and elastic modulus of formation on the fluid pressure distribution.IntroductionIn order to achieve a substantial reduction of CO2 emissions and alleviate the atmospheric carbon problem, massive scale carbon sequestration is required involving millions of tons of carbon dioxide injection over several decades. The geomechanical response is important upon the injection of substantial supercritical carbon dioxide into deep geological formations. Supercritical CO2 is less dense than brine waters and the buoyancy driven flow of CO2 requires the aquifer to be capped by low permeability rock (""caprock"") to prevent the upward migration of C02 (as shown in Fig.1 ). Massive scale injection of C02 changes the overall stress state in the caprock and formation. This change leads to large deformation that can damage the caprock, create fractures, and open new flow paths for supercritical C02. Therefore, a coupled hydromechanical model becomes essential for the caprock integrity analysis."

Jan 1, 2012

"Injection technology has been an important subject from the early days of ladle metallurgy until the present. During the last decade, there have not been many publications in the area of injection technology. It is the author's opinion that with the challenge to find new solutions especially to environmental and energy related problems as well as better understanding of phenomenas from computer modelling, a new era of inventive injection technology developments is at hand. This is illustrated in the article with examples from six different areas where MEFOS is or have recently carried out R&D work related to issues from the injection technology field. IntroductionThe boom in injection technologies came with the introduction of ladle metallurgy treatment during the '70s and '80s. Since then, the theories and principles have been thoroughly laid down by a number of scientists and also published at several early SCANINJECT conferences.Not many new technologies/applications have been presented during the last ten years. This might lead one to believe that everything is known and done. Those, like MEFOS, who are challenged to find technological solutions to a number of environmental problems and energy saving issues in the pyrometallurgical field are, however, continuously faced with the task of developing new injection technologies.Especially, the call for sustainable technologies to solve environmental problems is a challenge for metallurgists all over the world and it will surely induce a revival of injection technologies. So, in order to encourage all injection experts, let us share some new experiences and let us encourage each other's creativity to solve some of the demands of the future society.The following show some examples of technologies under development, or recently tested."

Jan 1, 1996

By C. P. Snyman

Three independent methods of coal classification can be distinguished, namely on the basis of grade, type and rank. The latter two can be determined accurately and unambiguously only by means of microscopical techniques. These three independent variables affect all the coal properties and therefore also the technological behaviour of a particular coal. The influence of the inorganic constituents of coal on the fusibility of the ash and on the length of the slag, and also on fouling and slagging, is discussed. The fractionation of the ash-forming constituents during combustion and gasification of pulverised coal shows that fouling and slagging are not related directly to the fusibility and composition of ash of the coal as a whole. The results of combustion experiments using a drop furnace technique indicate that the ignition temperatures of the light volatiles in the coal, and of the formed char, as well as the burn-out time of the char are more dependent on the rank than on the type or grade of the original coal. High-ash coals, however, apparently ignite at lower temperatures and are more reactive than low-ash coals of similar type and rank. The surface properties of coal, which are important in froth flotation and oil agglomeration, correlate well with the inherent moisture content (and by inference with the heat of wetting and the calorific value) and therefore with the type and rank of the coal. In coal exploration, variations of rank offer the possibility of predicting the presence of an intrusion near the seam, thus contributing to more effective exploration and mine planning.

Jan 1, 1991

By E. A. van Dijk

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

Jan 1, 1999

By R. E. Sundell, S. M. Correa

"A mathematical model is developed for the fluid flow in tungsten-inert gas weld pools. The fluid is taken to be incompressible, viscous, electrically conducting, and confined within a pool of specified shape. The flow is driven by surface-tension gradient (thermocapillary), electromagnetic, and buoyancy forces generally in this order of importance. Analysis indicates that the electromagnetic field may be calculated a priori and so decoupled from the nonlinear fluid mechanics and heat-transfer problem. The resulting set of equations is solved numerically by a line relaxation process. Computational errors caused by truncation in finite-difference schemes and by inadequate grid distributions are considered. The model is used to study several cases of differing heat and current input to the pool with and without surfactant-induced thermocapillary forces. The principal conclusions are that the thermocapillary flow, when present, is dominant with surface velocities on the order of 1 m/s. The heat transfer, as deduced from isotherms within the pool, is crucially dependent on the flow. Also, flow velocities and weld-pool surface temperatures were measuredand agree well with the model.2. IntroductionThe requirements of improved control and of automation in the TIG (tungsten-inert gas) welding process have led to the development of mathematical models for the heat transfer to the workpiece. It is now widely recognized that the fluid flow in weld pools sufficiently distorts the conduction heat transfer pattern to warrant inclusion in a process model. The experiments of Woods and Milner (1), among others, demonstrated that TIG weld pools could be driven by the electromagnetic J x B body forces present, J being the current distribution and B the induced magnetic field. Atthey (2) calculated that in typical pools the buoyancy force was about an order of magnitude less important - despite the large temperature gradients present - and neglected it in a computational study of the magnetohydrodynamic (MHD) flow. This work also reviewed many earlier studies of MHD flow caused by a source of current at a fluid surface, including analytical studies by Shercliffe (3), Sozou (4), and Sozou and Pickering (5), and a numerical study by Andrews and Craine (6). These works establish the importance of the electromagnetic force in the weld-pool flow."

Jan 1, 1986