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By Matthew John M. Krane

"The macrosegregation patterns and convective behavior of a Pb-5wt%Sb-35wt%Sn alloy are studied using new numerical treatments of solid particle motion and of transport phenomena occurring during the solidification of ternary metal systems. At this composition, the solidification which occurs while the local liquid composition is in the (Pb)-(SbSn) binary eutectic trough has a significant effect on these phenomena. The effects of this solidification path on fluid flow and macrosegregation are compared to the more familiar binary alloy patterns and the effect of solid particle transport is evaluated. The final predictions of macrosegregation are compared to measured composition profiles. IntroductionThe macroscopic maldistribution of alloy constituents during solidification, commonly called macrosegregation, is a defect which occurs in real metal processing systems. This nonuniformity of species distribution, especially when it forms a high composition gradient or a poor distribution of secondary phases, can lead to areas of high stress concentration, which contribute to cracking during extrusion or forging of wrought alloys or when an as-cast piece is severely loaded in service [1, 2]. Macrosegregation studies in binary systems have become quite common since the introduction of single-domain numerical models which feature one set of conservation equations and boundary conditions for an entire, fixed computational domain containing solid, liquid and multiphase regions. A complete review up to 1995 has been presented by Prescott and Incropera [3]. However, most commercial alloys generally have more than two species in amounts significant enough to affect the convective flows which lead to macrosegregation and other defects. The formation of secondary solid phases, including eutectic and peritectic reactions, also may occur in commercial metal alloys and should be treated using appropriate thermodynamic models."

Jan 1, 1999

By Shengqi Chen

The reduction smelting of nickel laterites produces slag, consisting principally of the chemical components MgO, "FeO", SiO2, and A12O3, and ferro-nickel alloy. Despite the fact that the phase equilibria for the ternary MgO-"FeO"-SiO2 up to 1500°C is well established limited experimental data are available in the MgO-"FeO"-SiO2-Al2O3 system, which is relevant to commercial operation of the process. A methodology has been developed for the experimental investigation of the liquidus temperatures for the multi-component system MgO-"FeO"-SiO2-Al2O3-Cr2O3 in equilibrium with metallic iron. Experiments have been carried out using high temperature equilibration, quenching, followed by electron probe X-ray microanalysis (EPMA). Liquidus temperatures have been determined in the silica primary phase field in the composition ranges directly relevant to the Cerro Matoso S.A. ferro-nickel smelting slag. Liquidus isotherms have been determined for temperatures between 1450 to 1600°C. The study enables the liquidus to be described for a range of MgO/FeO ratios. It was found that liquidus temperatures in the silica primary phase field decrease significantly with the addition of AI2O3. Keywords: Liquidus temperature, ferro-nickel, pyrometallurgy, smelting

Jan 1, 2004

By Makoto Ohlsuka

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

Jan 1, 2003

By Bogdan Petkovic, Boban Todorovic

In the early 90's a completely unknown problem was encountered at the converter Department: it was a chronic shortage of the cold copper charge needed for the second operating period. A high temperature operating regime was caused which further provoked a chain of consequences such as a drastic drop of the number of operations in campaigns. The consumption of repair bricks reached the quantity of 8.3955 kg / tonne of anode Cu. In 1994, we won the process of cold material smelting during the "copper" blowing [2]. The number of operations per campaign reached 180-200 again. Also in 1994 we won the process of smelting cold materials to obtain "tin" blowing with the purpose of completing their processing cycle [2]. During the period 1994 – 2007 a total of 107,845 tonnes of cold material were remelted to make copper and 56,794 tonnes were re-smelted to obtain "tin". Upon synthesizing these two processes, a completely new model was achieved in 2005, by Bogdan Petkovic, which entirely utilized all available energy of the Peirce-Smith (PS) converters of the Bor Copper Smelter and now represents the basis of the time cycle. The cold material now enters the converter plant, copper recovery is increased and the method itself is environmentally friendly. 167

Jan 1, 2009

By P. Lussiez

Precipitates consisting of amorphous ferrihydrite and crystalline goethite have been prepared by aging hydrolyzed Fe (III) solutions at room temperature. The precipitates have been characterized by x-ray diffraction and differential thermal analysis. The amorphous ferrihydrite transforms to goethite with time. The ferrihydrite to goethite transformation is affected by the presence of small amounts of copper or nickel coprecipitated with the iron. .The addition of copper decreases the amount of goethite at a given aging time and increases the amount of coprecipitate which is initially dissolved in sulfuric acid, but it does not seem to affect the dissolution of the crystalline part'. It is proposed that adsorption of copper hydroxo species on goethite nuclei delays the ferrihydrite to goethite transformation. The effect of nickel is less dramatic than that of copper. Apparently a portion of the added nickel is adsorbed on the goethite crystallite surface rather than incorporated into the goethite lattice.

Jan 1, 1981

By P. N. Anyalebechi

"The as-cast microstructure of two commercial-size ingots of aluminum alloy 3004 produced by the electromagnetic casting process was quantitatively characterized. This involved the quantitative determination of through-thickness and across-width variations in dendrite cell size, grain size, macrosegregation of alloying elements, interparticle spacing, and the types, volume fractions, and sizes of the constituent or second phase particles. More than ninety-five percent of the constituent phases in the ingots consisted of the A16(Mn,Fe) phase; the desirable a-Al 12(Fe,Mn)3Si phase was not detected in any of the ingots by Guinier X-ray diffraction analyses or electron probe X-ray microanalyses. A significant microstructural heterogeneity through the thickness and across the width of both ingots was observed. For example, macrosegregation, and the sizes of the constituent phase particles, dendrite cells, and grains increased concomitantly from edge to mid-width and from surface to center of the ingots. There was a -20% depletion (negative macrosegregation) of Mg and a +54-87% enrichment (positive macrosegregation) of Ti in the center of the ingots. With the exception of grain size, there was no significant microstructural difference between the two ingots examined. The causes and practical implications of the observed microstructural heterogeneity in the ingots are discussed.IntroductionThe first step in the fabrication of majority of wrought products of aluminum and its alloys is the casting of large ingots or billets of simple shapes (round or rectangular). The sizes of the ingots vary from 10 mm to 450 mm diameter or 25 mm to 780 mm thick. The quality of the finished products is established at the ingot casting stage. This is because the microstructural characteristics, such as secondary dendrite cell size or arm spacing, amount of alloying elements retained in solid solution, macrosegregation, and the characteristics of second phases, produced during casting cannot be reversed by subsequent processing. Up until twenty-five years ago, the effect of as-cast microstructure of large ingots on the structure and behavior of thin sheets (0.34 mm thick) during drawing and ironing processes was incorrectly assumed to be minimal or nonexistent. This was based on the erroneous notion that the thermal treatments and large reduction (>99.94%) and strain that the ingot undergoes during production of the sheets completely destroys the original ingot structure and its inherent heterogeneity. However, the effects of ingot structure can, a priori, be deduced from the observed effects of constituent phase particle size, type and volume fraction on recrystallization, development of texture during annealing and deformation, and earing. In fact, careful examination of the behavior of products produced from different size ingots or castings have shown that the original microstructure of the ingot has a direct impact on the properties and performance of the end products."

Jan 1, 2011

By Muammer Kaya, Sait Kursunoglu

"The aim of this study was to investigate the effectiveness of ascorbic (C6H8O6) / oxalic (C2H2O4) acid as a reductant for the simultaneous recovery of zinc and manganese from a spent and mixed zinc-carbon and alkaline battery powder in sulphuric acid leaching. The effects of sulfuric acid concentration, ascorbic/oxalic acid dosages, reaction temperature and leaching time on the zinc and manganese dissolutions were investigated according to 2k full factorial experimental design; then, a simple optimization study was carried out for the best reductant. The optimum reductive acid leaching conditions were determined at 3 hours leaching time, 70°C leaching temperature, 0.5M sulfuric acid concentration, 13 g/L ascorbic acid dosage, 1/20 g/mL solid/liquid ratio and 200 rpm stirring speed. Under these conditions, the dissolution efficiencies were 99.9% for Zn and 99.3% for Mn. When our results were compared with the previous results, our findings were better than previous studies.In addition, the manganese dissolution kinetics was undertaken, and the activation energy was found to be 7.04 kJ/mol. Selective precipitations of Zn and Mn from acid solutions were carried out using NaOH and KOH. Using 3M NaOH as precipitating agent at room temperature and at pH 8; 95.4% of Zn and at pH 10; 93.7% of Mn were precipitated from the leaching solution. Under the same conditions, using 3 M KOH at pH 8; 91.6% of Zn and at pH 10, 96.4% of Mn were precipitated. Based on the experimental results obtained, an appropriate flow sheet was proposed to recover zinc and manganese."

Jan 1, 2012

By Xiping Chen, Wangxing Li

"Spent potlining is unavoidable solid waste from aluminum smelters. About thirty kilograms spent potlining is discharged in China to produce per ton primary aluminum. Spent potlining has high level soluble fluorides and cyanides so that it brings heavy pollution to environment. It is prohibited to keep a large amount of spent potlining in open air because it will lead concentrated pollution to local soil and water source due to hydrated reactions between spent potlining and rain water/moisture in air. Landfill may solve pollution of spent potlining provisionally, but it is difficult to be accepted by aluminum smelters because of its high investment, troublesome monitoring and perennial maintenance. Detoxifying of spent potlining not only can remove deleterious fluorides and cyanides in SPL, but also can make fluorides in SPL recycle and return to aluminum electrolysis cells, at the same time benign SPL solid residue can be recycled and ready for cement production.IntroductionChina became the largest primary aluminum manufacturer in 2001. In the past few years, its aluminum output increased by twentyfive percent every year and reached 12.56 million metric tons in 2007. The whole world was very surprised and focused attention upon Chinese aluminum industry. It is more and more important to keep sustainable and steady development with the rapid development of Chinese economy. Aluminum industry is an important base industry and does a great contribution to Chinese economy. But aluminum industry is high energy-consumption and heavy-pollution industry. The government has paid more attention to aluminum industry in recent years. Nowadays the bothersome problem which counterworks Chinese aluminum industry is pollution from solid wastes. Main Solid wastes from aluminum industry are red mud from alumina refineries and spent potlining (short as SPL) from aluminum smelters. Spent potlining are waste lining materials from aluminum electrolysis cells. During production of aluminum, due to reactions between melted electrolyzer and pot lining as well as penetrating of fluorides into pot lining, newly-formed compounds inlayed in pot lining, destroyed the lining structure and brought pot lining cracking. Melt rushed out of lining cracks, cells have to be stopped running and ready for heavy repair. Cell life generally varies from 1500 to 2000 days. Spent potling is an unavoidable solid waste from aluminum industry."

Jan 1, 2008

By Michael Zinigrad

The quality of metallic materials depends on their composition and structure and these are determined by various physico-chemical and technological factors. To effectively prepare materials with required composition, structure and properties it is necessary to carry out a research in two parallel directions: Comprehensive analysis of thermodynamics, kinetics and mechanisms of the processes taking place at the solid-liquid-gaseous phase interface during welding processes and development of mathematical models of the specific welding technologies. We have developed unique method of mathematical modeling of phase interaction at high temperatures. This method allows us to build models taking into account the thermodynamic characteristics of the processes, the influence of the initial composition and temperature on the equilibrium state of the reactions, the kinetics of heterogeneous processes, the influence of the temperature, composition, hydrodynamic and thermal factors on the velocity of the chemical and diffusion processes. The model can be implemented in the optimization of various technological processes in welding, surfacing, casting as well as in manufacturing of steels and non-ferrous alloys, materials refining, alloying with special additives, removing of non-metallic inclusions.

Jan 1, 2003

By Wenjun Duan, Qingbo Yu, Qin Qin, Junxiang Liu

In the study, the coke-oven gas (COG)-steam reforming process using hot blast furnace slag (BFS) as the heat carrier is explored for producing hydrogen and recovering high-grade waste heat of hot BFS. The method of the Gibbs energy minimization approach through Lagrange multiplier is adopted in the thermodynamic analysis of reforming process. The simulation is carried out to study the operation pressure, temperature and steam to carbon ratio (S/C) based on the chemical equilibrium calculations. The optimal operation conditions are determined to improve the yield and fraction of hydrogen in the COG-steam reforming process. The results suggest that the preferential operation conditions for COG-steam reforming process to produce hydrogen are achieved at 600ºC, 1.5MPa and S/C (5.0). Due to the CaO and other melts in BFS, CH4, CO and CO2 in COG are converted and removed efficiently, especially CO2. The hydrogen fraction reaches to 86.7% and its production is about 1.22mol with 1mol of the COG.

Jan 1, 2016

By G. Van Weert

The pellet reactor was developed approximately 20 years ago in the Netherlands for softening drinking water. Since then, some 35 plants have been built, ranging in capacity up to 8500 m3/h. Applications now also include removal of phosphates and fluorides and the production of metal carbonates and sulphides from waste streams. The pellet reactor consists of a fluidized bed, wherein the process solution is thoroughly mixed with the precipitation reagent at special inlet nozzles to give over-saturation of the compound to be precipitated. In water softening applications, the compound is CaCO,. In the case of nickel or other metal waste streams, Na2CO3 solution is added in sufficient amounts to precipitate metal (hydroxy) carbonate on the fluid bed particles. These grow typically to dense spheroids, which are removed when they reach 0.8 to 1.0 mm diameter. These spheroids are easily dewatered, free flowing and low dusting. The latter property is becoming an attractive advantage in connection with new plant hygiene regulations. The operation of a 60 cm diameter pellet reactor on nickel containing plating waste is described and the properties of the produced nickel carbonate spheroids are discussed.

Jan 1, 1993

By M. K. Mohan

Lead recovery from process solutions contributes not only to the conservation of resources but also clean environment. Zeolites are natural aluminosilicates, which finds applications as catalysts and in wastewater treatment. In the present investigation, studies were taken up on the processing of Pb from process solutions by zeolites. Effects of pH of the solution, time and type of zeolite viz. chabazite, mordenite, erionite and clinoptilolite on the removal of Pb from solutions was investigated. Rate of sorption was found to depend on the pH of the solution and about 99 pct. recovery was observed at pH 6. Optimal conditions were established for the maximum recovery of lead from process solutions. Possible sorption mechanisms were proposed. The calculated adsorption constants calculated from Langmuir and Freundlich equations showed that the adsorption of lead on chabazite was strong.

Jan 1, 1999

By Rodney Clary

Building on work completed in earlier papers, the current paper presents a techno-economic evaluation of two recently demonstrated technologies for treatment of arsenic containing refractory gold concentrates. Using defined project parameters and inputs, the authors compare capital and operating cost estimates for pressure oxidation (POx), and the Albion Process™. The paper incorporates data now publicly available from the Albion Process™ plant, which has operated at the GeoProMining Gold (GPM Gold) project in Armenia since 2014, as well as recent POx circuits.

By Faustino G. Prado

In the, quest for an economical and environmentally friendly reclamation of metallurgical dusts generated during pyrometallurgical operations, our goal has been the separation and recovery of most of the components, as well as the complete recycle of all the reagents. Effluents have been avoided, within acceptable economic parameters. This presentation, which can be applied to a large spectrum of dusts and other residual-materials-, has focused on the dusts generated by the operation of Secondary Copper Smelters. Those dusts show a wide range of components, including zinc, lead-, copper, cadmium, tin, chlorine and-alkalies. Our present work deals with the use of ammonium salts in the separation and recovery of-the above mentioned elements in a marketable form. Most of the chemistry and techniques involved have teen already confirmed in commercial scale operations. Others have gone through pilot scale tests or bench scale tests. The recycle of reagents has also been- confirmed at the same operating levels. A preliminary evaluation indicates that the chosen route, in addition to a viable economy, offers a complete and safe reclamation within the most strict environmental regulations.

Jan 1, 1995

By P. Henry

A novel electrochemical cell has been developed for the recovery of MnO2 from residue of pyrolusite ore leading loaded with Fe, Al Ni, Co and Si impurities, This new process can be considered as an alternative to the traditional methods : S02, H2O2 or bioleaching. It has been observed to proceed fairly rapidly and could prove to be a more economically viable process, as well as being more environmentally acceptable. Electrochemical characterization and kinetic studies have shown that MnO2 is effectively leached by electrogenerated ferrous ions at high current density from a pulp containing less than 5 g8 Fe. The chemical reactions are : Cathode (inox) : 2F23+ + 2e ? 2 Fe2+ Bulk: MnO2 + 2 fe2+ 4H+ ? Mn2+ + 2 Fe3+ + 2 H2O Anode (Pb-Ag) : H2O ? ½ O2 + 2H+ + 2e Global: MnO2 +2H+ Fe2+ = Mn2+ + H2O + 1/2 O2 The catholyte (MnO2 pulp) circulates upward in the expanded mesh cathode separated from the sulfuric acid solution anolyte by a separator which shows high mechanical resistance, low porosity, low potential drop, and reasonable cost. Laboratory and mini-pilot tests have led to the construction of an OT crating pilot plant (100 kg/hr) able to leach more than 95% of Mn, Ni, Co at 1000-1200 A/m2, 50°C with high faradic yield (> 95 %) and low power consumption (3.2 kWh/kg kWh/kg &4D). New applications like the treatment of spent Zn-Mn batteries, polluted soils, spent catalysts and oxide ore (cobalt, nickel) with electrogenerated redox species are now investigated at a laboratory and mini-pilot scale.

Jan 1, 2000

By M. H. Staia

A Venezuelan ilmenite concentrate has been chlorinated at a temperature of 700" C by carbon tetrachloride. In the experimental rig, built at laboratory level, the direct chlorination process yielded a TiCI, recovery of approximately 85% after 280 minutes processing. The partial pressure of carbon tetrachloride was nearly atmospheric (0.94 atm). Product vapors from the reactor were fractionally condensed in a condenser which was maintained at a temperature of 250°C meanwhile TiCl, vapors were condensed in refrigerated coils at a temperature of -20°C. The concentrate used in this investigation was obtained by applying gravitational and magnetic concentration methods to the black sands. The experimental results have shown the need to asses the influence of the weight ratio of ilmenite to carbon tetrachloride on the resultant products. The equilibrium of the heterogeneous system has been calculated taking into account the initial experimental conditions.

Jan 1, 1995

By J. M. Zhuang

Lignosulfonates, by-products of the sulfite pulping process, have been utilized in a process [1, 2] to treat acidic rock drainage (ARD). This process is referred to as the LignorTM process. In the present study, lignosulfonates were found to protect lime from developing an external surface coating, and hence to favor its dissociation. Further, the addition of lignosulfonates to ARD solutions increased the clotting and settling rate of the formed sludge. The capability of lignosulfonates to form stable metal-lignin complexes makes them very useful in retaining metal ions and thus improving the long term stability of the sludge against leaching. The LignorTM process involves metal chelation with lignosulfonates, ARD neutralization by lime to about pH 7, pH adjustment with caustic soda to 9.4 ? 9.6, air oxidation to lower the pH to a desired level, and addition of a minimum amount of FeCl3 for further removal of dissolved metals. The LignorTM process removes all concerned metals (especially Al and Mn) from the ARD of the Britannia Mine (located at Britannia Beach, British Columbia, Canada) to a level lower than the limits of the BC Regulations. Compared with the high density sludge (HDS) process, the LignorTM process has many advantages, such as considerable savings in lime consumption, greatly reduced sludge volume, and improved sludge stability.

Jan 1, 2003

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 T. Shibaraki

A new larger, more efficient and economical Mitsubishi furnace line at Naoshima was put into operation in May 1991. Naoshima Smelter had produced previously about 230,000 mtpy anode copper with two smelter lines, i.e., a conventional reverberatory furnace line and Mitsubishi furnace line, which had been shutdown at the same time of the start up of the new smelter. At the beginning of the operation, there were several initial problems at the area of off gas trains and feeding system. By overcoming them now the process has been continuing satisfactory operation at the design rate. The paper describes about the design concepts and the actual operation of the new smelter.

Jan 1, 1993

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly. subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fumeless fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003