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By Marie-Aline Van Ende, In-ho Jung

A thermodynamic database for the oxyfluoride system CaO-MgO-Al2O3-SiO2-Na2O-K2O-Li2OMnO- FeO-F has been developed based on the critical evaluation and optimization of all available experimental thermodynamic and phase diagram data. The developed database can be used for phase diagram and equilibrium solidification calculations for multicomponent systems and for understanding the solidification behavior of mold fluxes. Based on this thermodynamic database, a simple kinetic model was developed to simulate the interactions between the mold flux and molten steel using effective equilibrium reaction volumes combined with the thermodynamic database.

Jan 1, 2014

By G. Kyle Green

Zirconium chlorinator residues contain an array of rare earths, scandium, unreacted coke, and radioactive thorium and radium. Because of the radioactivity, the residues must be disposed in special waste containment facilities. As these sites become more congested, and with stricter environmental regulations, disposal of large volumes of wastes may become more difficult. To reduce the mass of disposed material, the U.S. Bureau of Mines (USBM) developed technology to recover rare earths, thorium and radium, and unreacted coke from these residues. This technology employs an HCl leach to solubilize over 99% of the scandium and thorium, and over 90% of the rare earths. The leach liquor is processed through several solvent extraction stages to selectively recover scandium, thorium, and rare earths. The leach residue is further leached with an organic acid to solubilize radium, thus allowing unreacted coke to be recycled to the chlorinator. The thorium and radium waste products, which comprise only 2.1% of the original residue mass, can then be sent to the radioactive waste facility.

Jan 1, 1995

By C. E. M. Meskers, U. Boin

"The increasing use of coated magnesium in consumer products results in creation of coated Mg scrap during product manufacture and after End-of-Life product treatment. Currently this material is generally not recycled, leaving a material resource unused. Closure of the magnesium cycle in a sustainable manner is necessary. In order to do so, the effect of coatings on the recycling process has to be quantified, predicted and minimized. For this purpose metrics have been developed, based on first principles supported by detailed understanding of the recycling process. The developed 3D metric enables quantitative assessment of the recyclability and links coating design, product design and recycling to each other in a visual manner. The parameters that form the metric can be measured and predicted, hence an engineering basis for Design for Sustainability of coated magnesium is provided.IntroductionEvery product progresses through the four phases of the product life cycle depicted by figure 1. In each phase residues are created. Their amount and composition is largely determined by the complex material combinations created/invented during product design in the manufacture phase. Compared to the ideal cycle the magnesium cycle is far from closed (fig. 2). Most noticeable is absence of the link between the EoL phase and raw materials production. A closed cycle only exists for class 1 scrap, which goes from the product manufacture phase directly to production from industrial material and returns to the manufacture phase as magnesium alloys. The four problematic streams are marked by ???. Coated semi-products are present in two of the four residues, namely in rejects and collected scrap. When these semi-products are recycled the amount and composition of the dross and salt slag residue is affected as well.During product design selection of the coating takes place, fixing the coating character¬istics and properties from this moment on for the rest of its life cycle. The choices made in the manufacturing phase are therefore critically linked to the recyclability of coated semi-products as well as the sustainability of the magnesium cycle as a whole. Sustainable closed life cycles, in which the quality of materials is preserved and residue creation and resource depletion are minimized, can be attained by selecting the appropriate alternative during product design. To realize this the effect of design choices on the life cycle and more specific the recycling process has to be known and quantified."

Jan 1, 2008

By Gerardo H. Achurra

During the last years, the Caletones Smelter, like others copper smelters in the world, has evolved from the conventional, inefficient, pollutant and expensive technologies, to modern, environmental1y friendly and efficient ones. For this reason as wel1 as to improve its competitive position this Smelter shut down the reverberatory furnace, started up two big acid plants and has developed some pyrometal1urgical technologies. The main facilities of the Caletones Smelting and Converting Process, in the present and the future, are the Teniente Converters, the reactors with a high operational availability that have reached concentrate top process capacities near to 2,400 tpd. These reactors operate in most of Chilean smelters as well as in other smelters in the world such as in Zambia, Peru and Mexico. Since 2000, the Caletones Smelting and Converting Process, has been adapted in two Teniente Converters, four Slag Cleaning Furnaces and four Pierce Smith Converters. These facilities, together with the operation of two Fluidized Bed Dryers and two Oxygen Plants have allowed to reach concentrate smelting capacities and copper productions of 1,250 ktpy and 380 kftpy, respectively. Associated to El Teniente Division Expansion Plan, Caletones Smelter, in the first stage, will increase its capacity to 1,440 ktpy in 2004. In the long term, Caletones has different options, such as the processing of 1,600 to 2,000 ktpy of concentrate, producing anodes, white metal or a mixture of them. These options are connected with CODELCO's Smelters & Refineries Strategic Plan, including Mejillones Project. The main challenges of Caletones Smelter are associated to the development and the consolidation of the Continuous and Environmental Friendly Processes, automation and control of different processes and to the improvement of its leadership between other Copper Smelters in the world.

Jan 1, 2003

By Bruce W. Wessels

"Metal-organic chemical vapor deposition has been shown to be a highly versatile technique for the synthesis of complex oxides. High dielectric constant oxide thin films of SrTiO3, BaTiO3, Ba1-xSrxTiO3 and SrxBa1-xNb2O6 can be be be deposited at 800 ºC with this technique. The fluorine substituted B-diketonate precursors have been shown to be well-suited for the deposition of high quality, epitaxial thin films of these materials.IntroductionThere has been a resurgence of interest in thin film ferroelectric oxides as a result of the development of techniques to deposit high quality material. Both physical and chemical vapor deposition techniques have been realized. Of the chemical vapor deposition techniques, metal-organic chemical vapor deposition (MOCVD) has received the most interest for the deposition of ferroelectric oxide thin films. This results, in part, from the availability of a number of volatile metal-organic precursors.(l) Moreover, MOCVD offers the advantages of high growth rates, uniform coverage over large areas, conformability, abrupt interfaces and excellent epitaxial crystallinity. Of the metalorganic precursors, the B-diketonate complexes have played an important role especially in the deposition of ferroelectric oxides containing alkaline-earth metals such as BaTi03 and Ba1•XSrxTi03. For example, barium tetramethylheptanedionate Ba(thd)2 has been used in the preparation of BaTi03 by MOCVD.(2) These compounds, however, are not without their problems. Ba(dpm)2 has a relatively low volatility; and as a consequence, temperatures in excess of 180·C are required for volatilization. This leads to the necessity of a complex precursor delivery system to insure that the precursor does not condense before the reaction zone. Moreover, the Ba precursor tends to oligomerize leading to a decrease in vapor pressure as well as a problem with reproducibility. To counter these problems, novel liquid source and solid source precursor delivery systems have been developed. (3)(4)"

Jan 1, 1994

By Evgueni Jak

Recent advances in analytical, experimental techniques, and computer-based theoretical modelling of fundamental properties and elemental processes, provide new opportunities to develop the next level of whole-of-reactor pyrometallurgical furnace models. These models have the potential to significantly improve the prediction of, and adding value to, industrial operations. In non-ferrous smelting, the starting point of these models is the development of multicomponent thermodynamic databases for gas-slag-matte-speiss-metal-solids phases supported by systematic experimental research. The whole-of-reactor-models additionally should take into account kinetic processes taking place at micro- and macro- scales, and other key factors. Examples of applications of the latest research tools and modelling approaches to analysis of industrial flash and top submerged lance (TSL) sulphide smelting processes are presented. Different levels of industrial modelling are discussed from elemental local reactions, through general and more detailed whole-of-reactor-models, to plant sections and further to whole plant operation models. Some principles for development of pyrometallurgical reactor models are discussed.

By Qian Li, Haiyan Leng, Kuo-Chih Chou, Haoyuan Xiao, Zhigang Yu

Magnesium borohydride and Magnesium alanate were synthesized by mechanochemical metathesis reaction. The thermal decomposition behaviors of Mg(BH4)2-nMg(AlH4)2(n=0.5,1) systems were investigated as potential hydrogen storage materials. The results showed that the systems started to desorb H2 at 120 ℃ and desorbed 3.9 wt. and 4.9 wt.% H2 below 300 ℃ when n equals 0.5 and 1, respectively, while individual Mg(BH4)2 started to desorb H2 at 250 ℃ and desorbed only 0.82 wt.% H2. Because of the exist of the Mg(AlH4)2, the isothermal desorption kinetics of Mg(BH4)2 in the Mg(BH4)2-0.5Mg(AlH4)2 systems was 50% faster than that of pristine Mg(BH4)2. In addition, the re-hydrogenation rates also increased 49.4% and 37.9%.

Jan 1, 2015

By Young-Geun Park

A new decarburization model for the RH system was constructed for calculating the decarburization reaction using a three-dimensional fluid dynamics program. The entire fluid flow in the RH process was calculated by evaluating the shape and volume of the plume zone, formed by Ar gas blown through multiple nozzles on the wall of the snorkel. On the basis of this fluid flow, the decarburizaiton reaction was calculated through establishing the decarburization reaction model, which considers the thermodynamics, reaction kinetics, and the decarburization sites (Ar bubble surface, bath surface, and the CO bubble fomtation at inner sites). The results from this model were compared with a real RH operation results with good agreement. Because it is possible to predict the carbon concentration at various conditions using this model, it may be useful in increasing the decarburizaiton rate. Key words : RH process, plume zone, decarburization, Ar bubble surface, bath surface, inner site, circulation flow rate.

Jan 1, 2001

By Rashmi Kumar, Amit Chatterjee, Sanjay Chandra

The practice of adding alloying materials to a molten bath is an integral feature of many pyrometallurgical operations. However, very little is known about the dissolution rate and solution mechanisms of solid additives in liquid melts. In foundries where large tonnages of liquid metals are handled, there is considerable interest in achieving optimum metal quality at minimum cost. This objective is influenced by several factors and the solution is often plant specific. Though the amount, sequence and mode of ferroalloy addition vary from plant to plant, various fundamental factors determine how quickly these additions dissolve in the bath. At the Ingot Mould Foundry (IMF) in TATA STEEL blast furnace hot metal is used to cast ingot moulds. The composition of hot metal desired for making ingot moulds demands addition of 20 kg each of Ferromanganese and Ferrosilicon in the 12 T transfer ladles into which the blast furnace metal is poured at the IMF. Owing to low temperature of hot metal at the IMF, casting commences immediately and complete dissolution of the ferroalloys is often not possible. To study this aspect in detail and to evolve suitable corrective measures, a mathematical model for the melting of a solid particle in a liquid metal bath was developed at TATA STEEL. The model was validated using the data available in literature. In keeping with published work, two separate dissolution periods were identified - a "shell period" and a "free dissolution period". The maximum thickness of the crust formed around a spherical particle shortly after immersion, can be obtained by using the mathematical model which has been developed. The model can also be used to investigate the effect of various parameters such as superheat of the bath, size of the particle, etc., on the maximum crust thickness and the particle melting time. On the basis of this study, the addition of ferromanganese and ferrosilicon was optimized at the IMF in Tata Steel.

Jan 1, 1996

By M. A. Neri

A lead-free solder alloy Sn-57.5Bi-0.5Ag has been developed by mechanical alloying and foundry processes, and has great potential as a lead-free solder system, to low temperature applications. The mechanical alloying powders show a microstructure different to the microstructure obtained by the foundry process for the same alloy. Its melting point of 142°C is slightly higher than that of eutectic tin- bismuth solder. Examination of the microstructure revealed that eutectic microstructure is refined by the mechanical alloying process Ag additions. The lamellar structure of tin-bismuth gradually disappeared with the process of mechanical alloying, while intermetallic compounds AgaSn phase was formed. The Cu-Sn intermetallic compound layer formed at solder-copper interface is the Cu6Sn5 phase. Keywords: Lead-free solder, Microstructure. Mechanical alloying

Jan 1, 2003

By Li Yuhai

Kinetics of non-isothermal precipitate process and crystal growth of perovskite (CaO ? Ti02) phase in CaO-TiOz-Si02-AlP3-MgO system were studied. The experimental results show that the relative volume fraction can be described by the equation given by K. Matusita et at. and the experiential expression of average crystal radius was obtained. The particle coarsening in non-isothermal process has important effects on the crystal growth of perovskite phase.

Jan 1, 2000

By Xuerong Wen

The oxidation behavior of TiAl3 intermetallics was investigated as a hnction of time at 1273K in pure dry oxygen. The oxidation experiments were carried out using TGA method. The oxidation scales were analyzed using SEM, EDS and X-ray diffraction methods. The structures of oxides formed at the different oxidation times were analyzed. The mechanism of oxidation of TiAl3 intermetallics was discussed.

Jan 1, 1998

By R. T. Seaman

Pressure oxidative treatment of whole ores and/or mineral concentrates is used to leach or liberate metals of value for downstream recovery. Silver, when present, is often lost in processing, precipitating as a cyanide-insoluble jarosite in the residue. Depending on pressure oxidation conditions, the degree of silver loss to jarosite can vary dramatically. Batch bench-scale testwork is often performed to define that loss, and then assess the implications in continuous operations. This paper focusses specifically on the impact of CESL pressure oxidation conditions on silver recovery, and discusses limitations of batch bench-scale testing as well as means of overcoming these limitations to better predict silver recovery in the scale up from bench-scale to continuous operations. Since silver is only partially soluble in both sulphate and chloride media, it will gradually leach and deport to a jarosite as oxidation progresses. When a silver-insoluble anion, for example iodide, is dosed prior to oxidation, there is a marked improvement in silver recovery from batchgenerated residue; however, that benefit is not consistently seen in continuous operations. The difference has been attributed to the dynamic solution conditions in the batch test, specifically the first few moments of oxidation. Using these principles, a predictive correlation has been established between initial leach concentrations of iron and acid and ultimate silver recovery with iodide addition.

By Jose F. Hevia

This study is part of a broader project on the hydrothermal conversion of copper concentrates to metallic copper by solid state reactions in which the copper remains localized in the solid phases. The kinetics of the solid/solid hydrothermal hydrogen reduction of tenorite (CuO) and cuprite (Cu,O) to metallic copper are presented. After an induction period, the process is governed initially by a nucleation step followed by rapid solid state reduction. Nucleation promoter agents decrease the induction period and control the particle morphology. Separate nucleation and reduction rate processes have been identified. Following nucleation, reduction follows a shrinking core process.

Jan 1, 1994

By Qinmeng Wang

The oxygen bottom blown copper smelting process is a new technology which has been widely applied to the copper production in China. In this work, a computational thermodynamics model for this technology has been established, based on smelting mechanism and theory of Gibbs free energy minimization. The calculated results from the model agree well with the actual industrial data, indicating that the model can be used for the predictions under different operating conditions. The tendencies of the key parameters (such as Cu losses and Fe3O4 content in slag) and the distribution ratios of the minor elements (such as Pb, Zn, As, Sb and Bi) can be predicted by adjusting the oxygen/ore ratio charged into the bottom blown copper smelting furnace. The model can be used to monitor and optimize the industrial operations of the oxygen bottom blown copper smelting process.

By C. H. Tsau

The intermetallic compounds of Ni-25Al-xFe, x is 20-40 at.%, were prepared by arc melting and drop casting into ingots, and were rapidly solidified into ribbons by melt spinning. The microstructure evolution of these alloys with varied Fe content were examined by the x-ray diffraction, optical microscope, scanning electron microscopy and transmission electron microscopy. The results reveal that two phases, {y'} and {B} phases, are existing in the alloys with low Fe content, and the microstructure changes from the mixture of y' and {B} phases to a single 0' phase when the Fe-content reaches to 40 at.%. Also, the formation of y' phase will be suppressed by rapidly solidified process. For annealing both of the melt-spun and the cast specimens, a disorder 0 phase was revealed in both of the ribbon and the cast ingot of Ni-Al-Fe alloys with higher Fe content. In addition, increasing the increment of iron which substituting nickel in this alloys results in increasing the lattice parameter of both {y'} and{B} phases.

Jan 1, 1992

By Carl C. Nesbitt

A study was conducted to examine the treatment of metal-bearing effluents by precipitating the metals as sulfides and simultaneously collecting the particles by flotation. The precipitant was hydrogen sulfide gas which was introduced into a bench-scale column cell with air. The study included experiments of various flotation reagents and column configurations in treating solutions containing dissolved copper, lead, mercury, iron, zinc and cadmium. An acidic laboratory waste from a local copper operation was used to test the column with a solution containing several metals and arsenic. Precipitates were observed to form at the gas/liquid interface when the gas mixtures were rich in H2S. Copper, mercury, lead, and cadmium were precipitated from solution as sulfides to concentrations near detection limits. The flotation of these precipitates was enhanced with small amounts of S-7151 promoter from American Cyanamide Company and Dowfroth 1263 mixed with the feed. The recovery of the precipitates in this manner produced a smaller volume slurry which was easier to dewatering than a slurry produced by conventional precipitation techniques. The low pH and high oxidation-reduction potential in the cell from H2S addition was not conducive to form precipitates of iron, zinc or arsenic. However, these ions were precipitated as sulfides by raising the pH of the column discharge.

Jan 1, 1994

By L. Z. Villanueva

An investigation and evaluation has been performed to determine the potential utilization of electron beam irradiation technology for sulfur oxides removal from reduced-S02-strength metallurgical gases from copper smelters. These off-gases, though too weak to be converted to usable, concentrated: sulfuric acid by conventional means, are characterized by SO2 content higher than 2,000 ppm and a complex chemical composition, including high oxygen content and its generation occurring in a cyclical, fluctuating pattern. This work was based on information supplied by principal smelter companies in Chile. A laboratory facility with flow rate of 20 Nm3/h and equipped with an electron accelerator of beam energy 8.00 keV, has been used for testing. Influence on SO2 removal efficiency of operational parameters such as gas temperature, water vapor content, ammonia feed ratio and irradiation dose was established. The main conclusion of this work, from experimental laboratory tests as well as engineering studies, is that the Electron Beam Process (EBDS) is a cost-effective, simple and appropriate chemical process means for emission abatement. EBDS can, on a site-specific basis, adequately augment SO2 removal to upgrade overall abatement as required and in an optimal manner.

Jan 1, 1999

By Gaballah I.

Elimination of arsenic, mercury and zinc from synthetic solutions containing H;\A.sD4. HgCI2 and ZnCI2 using modified barks was investigated. The pH range was varied from ?1 to 10. The initial concentrations of individual element were 10,100 and 1000 ppm. More than 99 % of mercury and 65 % of zinc cations were removed by the modified bark .. In this case, the modified bark reacts as a cation exchanger leading to the release of ' two protons for every HgII or ZnII fixed by this material. About 30 % of arsenic was eliminated from the solution. This 'low efficiency could be attributed to? the presence of arsenic ,as. anion. Decontamination of a treated industrial effluent containing 4 ppm of ion? metals was performed on a pilot plant scale by the modified bll(k. More than 70'% of these ion metals were eliminated.

Jan 1, 1995

By James J. Komadina, Robert R. Beebe

"Heap leaching of gold ores has enjoyed wide acceptance in the arid and semi-arid regions of the western U.S., Australia and South America. There are areas, however, where cold weather or excessive precipitation can limit the usefulness of heap leaching. Even in Nevada difficulties can be encountered which call for special operating procedures.The paper discusses the general climatological limitations and some of the techniques used to extend heap leaching into colder conditions. A case history of the Cripple Creek and Victor Gold Mining Company operation in Colorado examines 'valley-fill"" technology as an ideal cold-climate solution, where topographical conditions permit.AcknowledgementsThe authors gratefully acknowledge the management of Independence Mining Company for their permission to present this paper. The contributions of Golder Associates; Pikes Peak Mining Company Environmental Affairs Department staff, and the Colorado Department of Mines and Geology were all invaluable in successfully concluding this project.BackgroundWhen heap leaching of oxidized gold ores was introduced in the rnid-1970s it was aimed at large tonnages of low-grade material which could not, in general, be developed via conventional milling. Normally, the reasons for this were economic rather than technical: capital and operating costs for milling were simply too high. At first, grade was almost the only criterion, but deposits too small to justify milling were also potential targets for heap leaching.Renewed interest in gold was centered in the western United States and Australia, where exploration for milling-grade deposits had never really died. When heap leaching came along, it was in these areas that the first developments took place. Coincidentally, these same areas were favorable for heap leaching: climates were temperate for most of the year and competing land uses were limited. Even so, in the western United States in particular, winter temperatures were low enough to complicate operations. Precipitation was less a problem, although heavy snowfalls could periodically interfere as well."

Jan 1, 1997