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By H. Y. Sohn, S. PalDey

"A new chemical synthesis process for the preparation of intermetallic compounds has been developed. It involves the vapor-phase reduction of mixtures of constituent metal chlorides by magnesium vapor to produce intermetallic compounds in the form of fine powder. The advantages of the process include (a) the use of inexpensive raw materials, (b) low reaction temperatures, and (c) products in the form of fine particles. Titanium and nickel aluminides were prepared by this method. The effect of AlCl/TiCl3 partial pressure ratio on the formation of different titanium aluminides was studied. A two-phase mixture containing 80 mol % of TiAl and 20 mol % of TiA13 formed at an AlC13/TiC13 ratio of 10. The amount of TiA13 was maximized to 72 mol% at an AlC13/TiC13 ratio of 16. The maximum conversion of the limiting chloride TiCl3 was 94 % . In the case of nickel aluminides, NiAI, NiAl3, and Ni2Al3 were formed by reducing mixtures of NiC12 and A1Cl3 vapors. The effect of the partial pressure ratios AlCl3/NiC12 and Mg/NiC12 on the formation of nickel aluminides was studied. The maximum content of NiAl obtained was 98 mol % . At the AlC13/NiC12 ratio of 19, a two-phase mixture of 17 mol% of NiAl and 83 mol% of NiA13 was produced. The product particles were very fine in the size range of 0.05 to 0.2 µm.A. IntroductionIntermetallic compounds are attracting much attention [1]. Titanium and nickel aluminides have attracted a great deal of attention from the aerospace as well as automobile industries because of their potential for high-temperature application (e.g., low density, good oxidation resistance, and high-temperature strength retention [2, 3]). Gamma TiAl and two-phase (TiAl and Ti3Al) alloys [4] are used for gas turbine engine rotational components as well as automobile exhaust valves. TiAl3 is one of the most extensively investigated aluminum-rich intermetallics. Nickel aluminides are attractive because of their low densities, relatively high melting point and good high-temperature strength properties. For example, Ni3Al shows increasing rather than decreasing yield strength with increasing temperature [5]."

Jan 1, 1998

By Songsong Wang

Recently, replacing Pierce-Smith converting process with the oxygen bottom-blowing continuous converting technology has become a new research focus. Based on the principle of Gibbs free energy minimization, the thermodynamic model of oxygen bottom-blowing continuous converting multiphase equilibrium system has been established. The elements distribution behavior is calculated at the same burden composition and operation parameters as the industrial production. The results show that the absolute errors of the mass fraction (wt%) of Cu, Fe, S, Pb, Zn, As, Sb, Bi in crude copper are 0.06, 0.0030, 0.070, 0.38, 0.39, 0.020, 0.017, 0.034, 0.010, respectively, and the absolute errors of the mass fraction (wt%) of Cu, Fe, S, Pb, Zn, As, Sb, Bi in slag are 0.53, 0.81, 0.020, 0.23, 2.5, 0.0048, 0.0010, 0.0030, 1.49, respectively. The calculated results agree well with the actual industrial production data, indicating that the model can be well applied in the oxygen bottom-blowing continuous converting practice.

By S. Ozbilen

"Al-Li binary alloys with nominal Li contents of0.15, 1.1and2.8 (in wt%) were aged naturally at room temperature for two months, aged at low temperatures ( 65 and 1 OOEC) for up to 2 months and aged artificially at 190EC for 4 days after water quenching to 25EC following solutionizing at 530EC for 20 minutes. Ageing behavior of these binary alloys were studied by Vicker's Hardness measurements and DSC thermal analysis. Thermal analysis results indicate the formation of GP zones of Al-Li system in Al-2.8wt%Li binary alloy. In the same alloy, rapid quenching from one phase region (a) gives rise to precipitation of small o' particles in a matrix (a) with still high supersaturation. During ageing of this alloy below lOOEC an additional transformation, i.e., GP zone formation occurs proceeding at a very high rate which is described on the basis of the theoretical analysis for the quenched Al-Li system proposed by Khachaturyan et al [6]. Ageing at temperatures below 11 OEC takes place slowly by the formation of small d' particles of lower thermal stability than the quenched-in d precipitates in addition to GP zones resulting in an increase in hardness compared to water quenched samples. During artificial ageing, GP zones transform by dissolution to d' precipitates while d' particles already in the microstructure coarsen during under aged condition at which hardness increases with time till peak aged condition.IntroductionIn binary Al-Li alloys the d' (Al3Li) fully coherent internally ordered inetastable phase of Li2 structure with a=0.4038d [1-5] forms homogeneously between 120 and 190EC before the formation of stable d' (A!Li) phase and cause the superior mechanical properties. This is due to an appreciable age hardening effect resulting because of the d' precipitation during ageing [1]. The response of d' to decomposition and its formation kinetics have been studied previously and it is believed that the decomposition of the a-supersaturated solid solution occurs in a two stage process; i.e., a 6 d' (Al3Li) 6 d(A!Li). Khachturyan et al [6] theoretically investigated precipitation of the d' phase and gave an interpretation of the transformation paths of the quenched Al-Li alloys. They predict that the disordered supersaturated solid solution congruently orders, and then the uniformly ordered solution decomposes into ordered regions that differ in Li-content. Finally, ordered d' phase forms in the disordered matrix."

Jan 1, 1998

By Salustio s. Guzman

The standard .free energies of formation of tin chlorides were estimated with reviewed and estimated basic thermodynamic data, and measured reversible potentials for the disproportionation of tin dichloride into metallic tin and tin tetrachloride. Values for cºp, Sº, Hº?-Hº 298, -(Gº - Hº298) /T,.Hºf, Gºf, and log Kp are given in tabular form, these estimations are compared with estimations reported in the literature.

Jan 1, 1985

By Thomas P. Battle

Titanium is the ninth most common element in the Earth's crust, yet only in this century has titanium come into use as an engineering material, particularly in aircraft structures, as the metal, and in pigments, as the dioxide. In this presentation, the metallurgical aspects of processing titanium-containing raw materials will be reviewed. Particular emphasis will be given to the ores and beneficiation techniques which lead to the production of titanium dioxide pigment, which accounts for over 90% of world titanium production.

Jan 1, 1993

By George Oprea, Tom Troczynski, Joe A. Rigby, Waiman Lo

The refractory lining of the tuyere line in Peirce Smith converters have usually much shorter life in service than the rest of the lining, above or below it. There are already recognized chemical, thermal and mechanical factors which contribute to the wear of the lining. Our study presents the experimental results on microstructural changes occurring on these tuyere line bricks in a nickelcopper converter. The experimental bricks, after use at the tuyere line, were investigated using SEM/EDS and XRD techniques, to identify the mineralogical changes due to interactions with the nickel-copper matte or fayalite type slag at the process temperatures. The microstructural changes were correlated with physical and mechanical properties of the brick before and after use and a wear mechanism was suggested. Although the matte does not theoretically react with the mineralogical components of the brick, a partial oxidation of the Ni-Cu sulphides was identified using a line analysis by SEM/EDS in the densified layer at the hot face, which allows for mineralogical changes at the matte-refractory interfaces, with a high probability of microcrack formation due to the thermal cycling during use. These microcracks were also identified to open through inter-granular fractures parallel to the hot face, which appeared to be the main cause of lost lining during use. The reactions between the fayalite slag and refractory brick could eventually play a role in chemical dissolution of the brick only in the superficial layer at the hot face, as no slag components were identified deep into the brick.

Jan 1, 2009

By Guy L. Fredrickson

A modified transpiration reactor was used to measure the composition of the equilibrium gas phase formed above compounds in the Hg-O-S system at high temperatures (600 to 900K). A thermodynamic database {(AGo°f AH°t. AS°t)} for-HgO, HgS, HgSO4, Hg2SO4, HgSO4?HgO, and HgSO4?2HgO was developed based on the experimental results. Prior to this study, only estimated data were available in the literature for the sulfates and oxysulfates at temperatures above 298K. A series of vapor pressure' stability diagrams were constructed from 473 to 973K with isobars of Hg(g), HgO(g), S2(g), and SO3(g). These diagrams were found to be significantly different than those available previously and do provide insight to the phase relations of importance during the thermal processing of Hg-containing wastes. The thermodynamic results were used to conduct a series of Gibbs energy minimization calculations for a thermal processor' afterburner system for the treatment of HgS-containing wastes. The retention of Hg in the discharge calcine was examined as a function of temperature and excess air. Hg was found to report to the calcine as HgSO4, Hg2SO4, or HgSO4 HgO depending on the process conditions, and Hg retention occurs at temperatures as high as 930K. The precipitation of Hg-containing phases from cooled afterburner discharge gas starts at approximately 900K and the cooling of the gas an additional 30K (to 870K) results in over 50% of the Hg being preCipitated as HgS04?HgO. It was also determined that for small amounts of Hg present in sulfide concentrates during roasting, the Hg will be retained as HgSO4 or HgSO4?HgO at temperatures as high as 870K.

Jan 1, 1996

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 I. Mc Dougall

"The matte/slag tidal zone in a platinum smelting furnace is subject to severe process conditions which can often lead to premature failure of the lining. The MgO-FeO-Si02 slag is aggressive to refractory bricks, whilst the Ni-Cu-Fe-S matte is aggressive to water-cooled copper cooling elements, and can penetrate and sulphidize refractory bricks, particularly at the high matte temperatures often experienced in the PGM industry. A novel approach to the lining design was taken at Lonmin's new 10MW Furnace 2. An indirectly-cooled graphite ring was applied in the matte/slag tidal zone, with refractory bricks on the hot face. Thermal Finite Element modeling was conducted to determine the optimal lining design in this region of the furnace. The resistance of two graphite grades to damage by slag and matte was evaluated experimentally. The graphite lining is not wet by the matte, and is resistant to slag attack at operating temperatures. In comparison to water-cooled copper in various configurations, cooled graphite shows promise as an indirect refractory cooling system in the tidal zone area of furnaces.IntroductionIn South African Platinum Group Metals (PGM) smelting operations, the PGMs are associated with nickel-copper sulphides in magmatic rocks. After ore is mined, it is concentrated by means of a flotation process prior to smelting. Both rectangular 6-in-line and circular 3 electrode AC submerged arc furnaces are used for this purpose. A new 10 MW round furnace is currently under construction by Tenova Pyromet at Lonmin's Marikana Smelter Division. An overview of Lonmin's smelting operations and Lonmin's approach to smelting high chromite containing PGM concentrates is given by Eksteen et al. [1]"

Jan 1, 2012

By Roy J. M. van Lier

In industrial aqueous solutions, germanium generally occurs in trace amounts amid high concentrations of other metals, such as zinc, copper and iron. Separation of germanium from these metals as well as its isolation from gallium and indium pose a real challenge to the hydrometallurgist. After a brief discussion of the aqueous chemistry of germanium, this paper reviews the flowsheet of the Apex Mine in Utah. The Apex property was the only mine in the world to be operated primarily for production of gallium and germanium, but apparently closed due to great operating difficulties. Several process variants proposed for the treatment of the Apex ore, including bioleaching methods, are addressed. Following a more general description of the behavior of germanium in hydrometallurgical zinc processing streams, available technology for its recovery from aqueous solutions is summarized. Precipitation, solvent extraction, ion exchange, electrowinning, ion flotation and liquid-membrane separation are all outlined in terms of the aqueous chemistry of germanium. Finally, the production of high purity germanium dioxide and metal is briefly discussed

Jan 1, 1995

By Y. A. Chang

The objective of the present study is to evaluate and compile the relevant phase equilibria and thermodynamic data reported in the literature for the ternary system Cu-Fe-S. It is hoped that the results presented here will be useful to practising engineers and scientists in industry who are attempting to improve continually the existing processes of copper extraction and refining. At the same time, the present work will undoubtedly reveal the lack of some basic data which are important for the improvement of our existing extractive processes. Lastly, this work will also show that the development of theoretical models for the alloy phases in the Cu-Fe-S system is essential before complete consistency between the phase equilibria and the thermodynamic data can be achieved.

Jan 1, 1976

By Guy Deschênes

Thiourea solutions can be used as leach liquors to treat gold ores or slimes. It is also efficient to elute resins or strip solvents that were loaded in cyanides solutions. The hydrogen pressure reduction is a practical step to recover gold and silver from leach solutions, and strips and eluates without any destruction of thiourea. It is a critical point because these processes have to consider the recycling of the liquors to be irore economical. The effect of temperature, pressure, acidity, compotation of the solution and the nature of catalysts on pressure reduction by hydrogen were investigated. An electranetallurgical study was? carried out to investigate the mechanism. The composition of the products was studied by different analytical methods. The process shows a good selectivity to precipitate gold and silver in a thiourea solution containing iron and copper. Gold and silver concentrations can be decreased to 0.2 ppm and 0.1 ppm at respectively 70 KPa H2 and 28°C. No decomposition of thiourea was evident during the tests. Metals such as nickel powder or platinum activate the reaction and improve the reduction.

Jan 1, 1989

By T. Wang, R. G. Reddy, D. Mantha

"A new eutectic LiN03-NaN03-KN03-KN02 quaternary molten salt system was calculated using thermodynamic modeling. The eutectic temperature was predicted to be 100°C. The melting point and heat capacity of the salt eutectic composition were determined using DSC. The experimentally determined melting point is in excellent agreement with the predicted value. The melting point is more than 124°C lower than that of the KN03-NaN03 solar salt. The density of the molten salt was experimentally determined as function of temperature. Using the density, heat capacity and the melting point, thermal energy storage density and gravimetric storage density of the quaternary molten salt were calculated and compared with that of solar salt. The larger storage density value of this molten salt indicates that this salt has a better energy storage capacity for solar power generation systems.IntroductionMolten salts have been used as thermal energy storage media for solar energy applications. Nitrates are being used in the solar energy applications for their low melting point, low unit cost, high heat capacity, high thermal stability, negligible vapor pressure and high energy storage density [l]. Solar salt (NaN03/KN03: 60/40) is the most popular thermal energy storage medium which is currently being used with the freezing point of 221 ·c [2]; another ternary system HITEC® which contains NaN03, KN03 and NaN02 has freezing point of 141°C [3]. Newer nitrate salt mixtures are being studied and projected as potential candidates for thermal energy storage (TES) and heat transfer (HT) applications. Based on these favorable features, molten salt can work directly as the energy storage medium below 500°C [l]. Development and synthesis of newer molten salt mixtures with freezing point lower than those currently used for thermal energy storage applications is necessary for sustained utilization of solar energy. The approach to develop lower freezing point molten salt mixtures is by the prediction of new eutectic mixtures and also by the development of new nitrate compounds."

Jan 1, 2012

By Musa Karakus

In an attempt to explain the phenomena of lead entrainment during Cu drossing of lead bullion, two different synthetic lead bullions were heated to 1050°C, cooled slowly to various temperatures, and then quenched. The morphology and composition of dross particles that form when Mn is used to desulphurize bullion also were examined. Polished sections of these pyrometallurgical products were examined by process mineralogical techniques to identify the impurity phases, determine their chemical compositions, examine the morphology of the impurity phases and evaluate the potential for lead entrainment in such crystals, and characterize pre-quench and quench-generated phases. The phases crystallized were metallic lead, metallic copper, galena, chalcocite, albandite, Cu14.4Pb2S9. and 5.5Pb2S3.5. Metallic copper formed isometric skeletal crystals, chalcocite formed platy and skeletal crystals, and 1formed crystals and eutectic intergrowth with chalcocite and Cu14.4Pb2S9 or Cu5.5Ph2S3.5. The pre-quench crystals are larger and usually exhibit skeletal forms; the quench-generated phases are only a few micrometers across and disseminated throughout the lead matrix. Skeletal crystals of metallic copper and chalcocite form three dimensional networks that entrain large amounts of metallic lead.

Jan 1, 1989

By U. Lauwers

The influence of different waste materials in sinter blends on the quality and mineralogical composition of a sinter is described. As a result of partial preservation of the original textures of waste materials in the final product the degree of assimilation of the original material in the sinter product can be ascertained. Recycling of waste materials such as dolo char , arc-furnace slag, scrap fmes, mill scale and BOF-mud via the sintering process a saving on costs of raw materials such as flux and fuels, and a reduction on pollution can be achieved. A comparison of a typical sinter with a sinter produced through the utilization of waste materials showed a distinct correlation between certain types of waste material and some metallurgical properties. Dolochar in a sinter blend acts as part of the fuel and flux that are normally added to a sinter mix. Generally dolochar improves the quality of the sinter and decreases the consumption of coke. Other waste materials adversely influence the quality of the sinter. The glass and calcium ferrite content of a sinter when dolochar is used in the blend is similar to that of a sinter produced with only coke as a fuel in the sinter mix. The glass content is lower and the calcium ferrite content is higher, in a sinter produced from dolo char in the blend compared to a sinter produced with additions of other waste materials. Changes in the mineralogical composition are related directly to the metallurgical properties of the sinter product.

Jan 1, 1991

By Mark H. Hashiguchi

Examination of tensile bar surfaces shortly after destructive testing was conducted to search for clues that would aid in optimization of mechanical properties, especially tensile strength, yield strength and elongation to fracture. Cu-Ni-Si-Cr alloy bars in the as-cast, forged, rolled and extruded conditions were examined. Low ductility bars (<4% Elongation) showed dramatically different features than the fracture surfaces of high strength - high ductility bars (7 to 10% Elongation). Analysis of the fracture surfaces at 15X to 2000X and use of Energy-Dispersive X-Ray Spectroscopy (EDS) identified Ni-Si and Ni-Si-Cr precipitates of varying sizes and morphologies. Thermo-mechanical processing techniques to control the size and distribution of these precipitates show promise in improving the properties and performance of this alloy system and appear to correlate with improvements in the fracture surface morphology.

Jan 1, 2008

By H. Bai, B. G. Thomas

"A three-dimensional finite difference model has been developed to study the liquid steel-argon bubble two-phase turbulent flow in continuous casting tundish nozzles. Experiments have been performed on a 0.4-scale water model to verify the computational model by comparing its prediction with velocity measurements using PIV (Particle Image Velocimetry) technology. The computational model was developed using CFX and then employed to investigate the effects of various casting process variables. A fast, simple inverse model to quantify relationships between those process variables was developed, based on interpolation of the numerical model results, using Bernoulli's Equation and advanced multivariable curve fitting methods. Predictions using this model compare well with plant measurements. The model has been applied to present trends and observations on the relationship between casting speed, tundish depth, slide gate opening, and argon gas injection rate. The results can also be used to predict .the theoretical steel flow rate through the nozzle, so that clogging conditions can be identified in the plant.IntroductionTundish nozzle geometry is one of the few variables that are both very influential on the casting process and relatively inexpensive to change. Designing an effective nozzle requires quantitative knowledge of the relationship between nozzle geometry and other process variables on the influential characteristics of the flow exiting the nozzle. This relationship depends on the flow pattern within the nozzle components. Most previous modeling studies of flow in the nozzle have focused on single-phase flow [1-4]. Argon injection into nozzle is an efficient and widely employed method to reduce nozzle clogging, even though the real working mechanism(s) are still not fully understood [5]. Argon injection may greatly affect the flow pattern in the nozzle, and subsequently in the mold. Therefore, two-phase flow modeling is needed to improve understanding of fluid flow in the nozzle."

Jan 1, 2000

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60&apos;s, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, PSo, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of O2 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By Michael L. Sorokin

The behaviour of cobalt during processing of nickel raw material is analysed within the Ni-Co-Fe-S-O-SiO2 system using the computer model. For this purpose the thermodynamic parameters for "three-suffix" Margules&apos;s equations in Co-Fe-S and Co-Fe¬Ni-O-S1O2 systems were computed! Phase and iso-activity diagrams for Co-Fe-S system, and phase diagrams for the systems Co-O, Co-Fe-O, Co-Ni-O, C-oO=SiO2 and Co-Fe-O¬SiO2 are calculated using the developed computer programs and identified parameters. The diagrams are used to analyze cobalt behaviour at smelting and converting.

Jan 1, 1995

By J. L. Jambor

Sulfide-rich tailings accumulated in a 4l-hectare impoundment at the Waite Amulet minesite near Noranda, Quebec, have undergone partial oxidation and destruction of the principal sulfides (pyrite and pyrrhotite) in the vadose zone. Mineralogical studies and whole-rock chemical analyses of 18 samples from 3 boreholes along a cross-section of the tailings pile indicate that the principal chemical manifestations of the alteration are a pronounced depletion in sulfide-sulfur, and an enrichment in total Fe as Fe203&apos; Other elements such as Al, Mn, Mg, Ca, Na, and K in the solids show erratic or inconsistent variations, but a trend to Si enrichment in the oxidation zone is clear. The trend is interpreted to be a relative enrichment whereby the proportion of the stable silicate minerals has increased as a consequence of the consumption of pyrite and pyrrhotite in the oxide zone.

Jan 1, 1989