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By R. D. Brittain

In order to analyze and control the transport of harmful trace-element impurities in various smelting processes, it is necessary to have fundamental information about the chemical thermodynamic properties of the pertinent condensed and vapor phases. This paper describes recent thermodynamic studies of the gaseous arsenic sulfides and of the activity of arsenic in a copper-iron sulfide matte phase. These studies were carried out by high temperature mass spectrometry and by effusion vaporization techniques, which permitted clear identification of the molecular species involved, a decided advantage in such complex systems. The nature of the results obtained and comparisons with previous interpretations will be described.

Jan 1, 1983

By Harsh Deep Chopra, Jason N. Armstrong, Susan Z. Hua

"Existence of anisotropic Curie temperature materials [E. R. Callen, Phys. Rev. 124, 1373 (1961); J. Appl. Phys. 32 S221 (1961)] is a longstanding prediction - materials that become paramagnetic at a lower temperature along certain crystal directions while remaining magnetically ordered in other directions up to a higher temperature. Validating Callen's theory, we show that all directions within the basal plane of monoclinic F e1Ss (pyrrhotite) single crystal remain ordered up to 603 K while the c-axis becomes paramagnetic at 225 K. Results prompt a re-evaluation of existing magnetic materials with a focus on magnetic characteristics along different crystal orientations above instead of below the ordering temperatures. Theoretical guidelines for identifying new materials with large anisotropy of Curie temperature are also given, and analysis protocol to characterize them in a self-consistent manner is discussed. Materials with such a large directional dependence of Curie temperature open the possibility for uniquely new devices and phenomena, including energy storage and spintronics devices.IntroductionThis paper is an overview of our recently published work on anisotropic Curie temperature materials [l]. As a background, ferromagnetic and ferrimagnetic materials are characterized by a critical temperature below which magnetic interactions prevail over thermal agitation, leading to the appearance of a spontaneous magnetization. Above this critical point, called the Curie temperature, thermal energy eventually overcomes magnetic interactions and the material becomes paramagnetic.It is less well known that the Curie temperature varies with the orientation of the crystal. In ordinary ferromagnets this orientation dependence of Curie temperature is negligible because of the vanishingly small ratio of anisotropy to exchange energy, i.e., the spherical or isotropic exchange term dominates. Thus Curie temperature in ordinary ferromagnets appears to be an isotropic property, and assigning it a single characteristic ordering temperature suffices. However, a 'small' difference is not equivalent to being the 'same', and under appropriate set of conditions the anisotropy of Curie temperature is predicted to become appreciable, as discussed in the following.In formulating the theory of 'anisotropic magnetization' [2, 3] E. R. Callen and H. B. Callen first discussed the ""interesting possibility"" of anisotropic Curie temperature [2] or ACT; Callen and Callen noted that it was W. J. Carr, Jr. who initially raised this question, and they discussed it in detail at the Conference on Magnetism and Magnetic Materials (NY, November 1960), see footnote on page 320 of Ref. [2]. Soon thereafter, E. R. Callen developed the theory underlying the anisotropy of Curie temperature and conditions conducive to its observation [4, 5]."

Jan 1, 2013

By Lauri Holappa

Copper converting is mostly performed in Peirce-Smith converters. The process is still very similar to the original one developed in the early 20th century. It is a batch process in a horizontal cylindrical reactor with air blowing via tuyeres along the length of the reactor side. The Peirce-Smith converter has its roots in Bessemer's inventions in the 1850's as he tested both horizontal and vertical vessels for steel converting. However, for steel making a vertical pear-shaped converter with air bottom-blowing was established. In the course of time, there was a distinct necessity for oxygen usage instead of air due to harmful effects of nitrogen to steel properties and its cooling effect. In-bath blowing of oxygen did not succeed, however, and top-blown oxygen converter with oxygen lance (LD or BOF) was first developed in he 1950's and emerged rapidly to a dominating position. Somewhat later oxygen bottom-blowing via special shrouded tuyeres was developed (OBM or Q-BOP) but has attained only fractional share. Bottom-blowing technique had, however, impact on the current combined blown converters which adopted the benefits of both top and bottom blowing. In copper converting Peirce-Smith type converters have kept their position until today although new processes have been introduced and at least few of them seem to be emerging. In one respect copper converting has a clear leading position i.e. in the progress of continuous converting processes (Mitsubishi, Ausmelt). These processes utilise top-blowing lances instead of in-bath blowing tuyeres. A different principle for continuous converting is flash converting by Kennecott Outokumpu, which makes smelting and converting independent of each others. Solid ground matte is used as a feed for flash converting in a reactor shaft similar to Outokumpu matte flash smelting. A comparable process has been presented by Inco too. The paper discusses principal physico-chemical and process technical similarities and differences in copper and steel converting. Although these processes are metallurgically quite different it seems that during the modem history of ferrous and non-ferrous metallurgy, starting from the 1850's, the exchange of knowledge between these disciplines has been quite intensive. In long-term perspective, many similarities in the development can be found but also divergences due to different ambient circumstances.

Jan 1, 2003

By Corby G. Anderson

Antimony has been utilized by mankind for thousands of years. However, due to recent environmental concerns, antimony is often considered to be an impurity element, Since antimnoy is commonly found in precious metal refractory ore bodies, extraction is essential. The Sunshine Mine in Kellogg, Idaho has recovered antimony from its precious metal tetrahedrite deposits since the 1940's. A plant was initially constructed as a primary antimony source during World War II. This facility also decreased the downstream smelting penalty for the silver copper-lead concentrate and provided an industrial commodity from a potential environmental nuisance.' This paper describes the Sunshine antimony processing- facility. Specifically, the relevant process chemistries involved in concentrate leaching, metal electrowinning, and sodium antimonate production will be discussed. In addition, ongoing areas of research to improve unit operations and treatments implemented to meet environmental' discharge requirements will be covered.

Jan 1, 1992

By F. Elgersma

A high purity electrolysis solution is essential for hydrometallurgical zinc winning processes. For this reason ferric iron containing compounds such as jarosite are precipitated as iron and impurity collector during the calcine leaching. Jarosite thus forms a chemical waste and creates environmental problems. This research contributes to the development of a wet jarosite treatment process, where less contaminated jarosite is produced which can act as an iron source. The present work studies jarosite precipitation kinetics and the uptake of zinc cations in batch and continuous experiments. The distribution coefficient for zinc in continuous experiments is constant for a wide ratio of zinc over ferric ions in the solution. Addition of NH, + ions in batch experiments accelerates the conversion rate equivalent to the driving force increment. Addition of 50,2-ions above the stoichiometric ratio increases the conversion rate less then could be expected from the increase in the estimated driving force. Zinc ions tend to retard the conversion rate. An increasing reaction temperature increases the conversion rate. Below 75 ?C the conversion rate approximates zero.

Jan 1, 1990

By C. A. Young, J. D. Miller

Adsorption isotherms previously determined by in-situ Fourier transform infrared/internal reflection spectroscopy (FT-IR/IRS) for oleate adsorption at calcite and fluorite surfaces near pH 9 and at various temperatures are compared. Results indicate that, at both mineral surfaces, chemisorption occurs at equilibrium concentrations below approximately l x l0-5 M oleate while calcium dioleate surface precipitation occurs at higher equilibrium oleate concentrations. The extent of chemisorption at the calcite surface is 3 to 5 times less than that at the fluorite surface while the extent of calcium dioleate surface precipitation on calcite is nearly a magnitude larger than that on fluorite. However, for both minerals, surface precipitation decreases with increasing chemisorption. Contact angle measurements and flotation recoveries show the hydrophobicity of fluorite to be greater than that of calcite at each of the temperatures and oleate concentrations studied. Significant differences are noted only in the chemisorption region. Unlike calcite, the hydrophobicity of fluorite was sensitive to the presence of oxygen in the system. Multichannel Laser Raman Spectroscopy (MLRS) showed this behavior was caused by the double-bond reactivity of adjacent chemisorbed oleate molecules and subsequent formation of an epoxide/polyether complex at the fluorite surface. Such a reaction product could not be detected at the calcite surface. These differences in adsorption density, hydrophobicity, and polymerization behavior are discussed in terms of the intrinsic surface properties of the minerals.

Jan 1, 1999

By G. Mark Aylmore

Various processes have been developed using a combination of elevated temperature and chemical treatment processing to recover Li from silicate minerals. To facilitate further process development, a comprehensive understanding of the deportment of Li and associated minerals in ore bodies is essential to allow the industry to predict the response of ore reserves to metallurgical treatment options. This paper describes results from the integrated use of the John de Laeter Centre’s state of the art analytical and mass spectrometry techniques to characterise a selection of Li bearing ore bodies and determine their amenability to potential processing options for the extraction of Li. The mineralogy, mineral associations, and liberation characteristics of ore-bearing and gangue minerals were characterised using a combination of the TIMA and XRPD studies. The Li content and distribution within minerals were defined using LA-ICPMS and field emission scanning electron microscopy techniques (EBSD, ToF-SIMS) and atomic probe microscopy.

By F. H. (Sam) Froes, C. Suryanarayana, K. C. Russell, C. M. Ward-Close

"Far from equilibrium synthesis allows development of novel crystal structures and microstructures, leading to achievement of enhanced physical and mechanical properties. A number of ""far from equilibrium"" techniques are reviewed with emphasis on the amount of departure from equilibrium. The ability of two such techniques, mechanical alloying (MAl, and physical vapor deposition (PVD) to develop novel structures are discussed in detail. For the MA process emphasis is placed on intermetallic compound compositions. Solubility extension, beyond rapid solidification (RS) levels, is found in terminal compositions but not for the intermetallics. Nanostructure-sized grains (< 100nm) form which can be retained after ""low temperature"" compaction. On continued milling in many cases the nanometer-sized grains transform to an amorphous structure. Ordering is destroyed by MA, except in those intermetallics with large negative enthalpies of formation. For the PVD process, a review of application to terminal light alloy compositions is presented. This includes a new high-temperature aluminum alloy, layered materials with nanometer spacing, corrosion-resistant magnesium alloys and low-density titanium compositions. IntroductionTo enhance the mechanical property combinations of advanced structural materials innovations in process/synthesis are required [1-6]. In this paper the capability of various ""far from equilibrium"" synthesis techniques [7,8] to produce novel constitutional and microstructural effects, and hence potentially enhanced physical and mechanical properties, in advanced materials is presented. The application of two such methods, mechanical alloying (MA) and physical vapor deposition (PVD) is discussed in detail. For the MA process emphasis is on intermetallic compositions with consideration given to solid solubility extension, microstructural refinement, amorphization, and formation of intermetallic compounds. For the PVD process application to terminal light alloy compositions is discussed."

Jan 1, 1994

By M Philip Schwarz

"This paper reviews the status of computational modelling of a variety of common metals reduction processes, namely the blast furnace, rotary kiln and fluidised bed, and one new process not yet commercialised, namely smelting-reduction as in the HIsmelt Process. In each case, the last decade has seen the emergence of the capability to simulate the processes using multi-phase reacting computational fluid dynamics techniques. In some cases this capability is still in the process of being developed, and the next few years will see the maturing of the modelling techniques. As they become established, it will be possible to apply them to further refine the older technologies such as blast furnaces and rotary kilns, and assist in the optimisation, commercialisation and acceptance of the newer technologies such as fluidised bed and molten bath reduction. The development of a computational fluid dynamic model of bath smelting-reduction is described in some detail to illustrate how a large number of complex and interacting phenomena can be successfully simulated within a CFD framework. IntroductionPyrometallurgical reduction processes, such as the iron blast furnace, have become increasing more sophisticated through the centuries, so that today they are often highly efficient. There are continuing pressures, however, to refine existing processes and develop new ones. The imperatives are often economic, given that the long-term trend in the price of metals is always downward. In recent times, there has been the additional need to improve the environmental impact of metal production. Given that they almost inevitably require the use of carbon, metal reduction processes are large sources of greenhouse gases, and even a relatively small improvement in efficiency can be valuable in reducing CO2 production. Local environmental issues, such as the need to control of particulate emissions, are also driving incremental improvements in equipment.In addition to the economic and environmental drivers mentioned above, new process development is also being driven by the need to process new ores, and the need to produce unrefined metal in a form more compatible with alternative routes for downstream processing. An example of the latter is the production of DR! (Direct Reduced Iron) as a feed for EAF Electric Arc Furnace) in mini-mills.Further improvement of processes that have already been honed by continual plant experimentation over many years is not an easy task. To deliver further gains in efficiency, throughput, or product quality requires a highly sophisticated tool: one such tool· is computational modelling."

Jan 1, 2001

By W. K. Connor, O&apos

The U.S. Bureau of Mines, in cooperation with the Idaho National Engineering Laboratory (INEL), conducted over 30 hours of melting tests to vitrify simulated low-level radioactive wastes from the INEL Radioactive Waste Management Complex (RWMC). Five separate waste compositions were investigated, each consisting of noncontarninated soil from the RWMC and surrogate materials used to simulate the actual buried wastes. The RWMC soil and five waste compositions were melted in a 50-lb, single-phase electric arc furnace with a water-cooled shell. These tests were conducted to determine melting parameters in preparation for a large-scale melting campaign to be conducted in the Bureau&apos;s 1-metric ton (mt), water-cooled-wall, 3-phase electric arc fumace. Bulk chemical composition was determined for each of the feed materials and for the slag, metal, fume solids, and offgas furnace products, and distributions were calculated for the key elements. The material balance for the furnace operation indicates that from 63 to 84 pct of the feed reported to the slag. Cerium, used as the surrogate for the radionuclides in the wastes, demonstrated an extremely strong affinity for the slag product. Although slag temperatures as low as 1250° C were recorded when melting the RWMC soil, temperatures in excess of 1600° C were necessary to achieve the fluidity required for a successful slag tap.

Jan 1, 1994

By J. C. Yannopoulos

The quest for a continuous copper smelting and converting process, which has been going on for a long time, has not as yet reached its objective. The most recent efforts for the development of a continuous copper?making process started about two decades ago. Among the contending proposed processes, four have been piloted and three of them are currently in operation: the WORCRA process., the NORANDA process, the MITSUBISHI process, the OUTOKUMPU process. The WORCRA process, after some long pilot plant tests, failed to develop as an industrial process: The NORANDA process, as currently operating, is a smelting process and not a continuous copper?making reactor as initially conceived. The MITSUBISHI, although the only continuous process, has not been widely accepted. The OUTOKUMPU process can be applied only to a low iron concentrate feed and co?produces blister and high in copper slag. The thermodynamics of these "continuous" systems and the practical problems of their industrial application are reviewed and discussed. The achievement of efficient and inexpensive environmental control should&apos; be the primary objective of any new process development. A review of the environmental problems of the copper industry indicates that the quest for a continuous smelting and converting furnace should be intensified.

Jan 1, 1983

By Howard K. Worner

"In a rewarding career spanning nearly two thirds of a century, the author has worked at the frontier of such diverse fields as the creep of metals, structure properties and production of novel dental and surgical materials, molten salt electrolysis for titanium production, greatly improving the productivity of large iron blast furnaces and of oxygen steelmaking. While each of these has given great satisfaction, special thrills have derived from the development of new methods for the continuous production or refining of both ferrous and non ferrous metals. A rewarding segment was the evolution of various aspects of WORCRA technology. Unfortunately, several of these inventions have been ""ahead of their time"". Introduction""I am greatly honoured by the convening of this meeting to recognise my contributions to pyrometallurgy. My appreciation is the greater because this is the third Howard Worner Symposium; the first took place in the University of Newcastle in 1988, close to my 75th birthday. It was arranged by the local branch of The Australasian Institute of Mining and Metallurgy with the theme, ""Frontiers in Pyrometallurgy"". The second was organised by the University of Wollongong in conjunction with the Australian Academy of Science and the Australian Academy of Technological Sciences and Engineering; it celebrated my 80th birthday and, at my request, covered a broad range of topics under the heading of ""Recent Advances in Science and Technology"". Now, this very international meeting on ""Injection in Pyrometallurgy"" has been convened by the G K Williams Co-operative Research Centre for Extractive Metallurgy in my alma mater. I am both delighted and honoured that the cosponsors are the TMS (USA) and ISIJ (Japan).Dr Madhu Nilmani consulted me about the field to be covered and I readily concurred because ""injection"" has been of keen interest to me since the beginning of the 1960s when I began my pioneering work on sequential oxygen (or air) injection into flowing streams for both refining of blast furnace hot metal to steel and for the continuous smelting-converting of copper and nickel."

Jan 1, 1996

By Richard D. Hagni

Microscopic examination of selected, representative, unweathered samples of Birmingham, Alabama, Silurian, sedimentary iron ores has fully revealed the nature of the phosphorous-bearing mineral grains. The grains are composed of carbonate-fluorapatite (collophane), range in size from 1 um to 2.25 mm, and exhibit varied types of intergrowth with hematite. Modal analyses conducted under cathodolumi-nescence have provided quantitative data on the a3undance of each of 15 types of phosphorous-bearing mineral grains and made it possible to assess the potential phosphorous liberation from four types of iron ore. The results indicate that 27% of the total phosphorous contained in the iron ores in the western part of the Birmingham district can be expected to be liberated by fine grinding; 60% for ores in the eastern part of the district.

Jan 1, 1982

By Albert Wraith, Thomas Price, Wayne Boyd, Skip (I. E. ) Hills, Cameron Harris

Most Peirce-Smith converters inject air through tuyeres, with nitrogen representing the majority of gas passing through the process. The nitrogen controls the temperature of the vessel by carrying away heat from the reactions, both globally and locally at the tuyere tip. However, nitrogen adds energy to the bath and contributes to splashing and limits the blowing rate. High oxygen smelting has made streams of gas containing high concentrations of sulphur dioxide commonplace, which can be used to substitute SO2 for nitrogen and drastically changes Peirce- Smith converting (and all other smelting/converting processes as well). Less SO2 is required to carry away the same quantity of heat, which allows higher concentrations of oxygen and leads to the possibility of increased production. The paper investigates this substitution, its impact on converter productivity, and on the remainder of the plant. 181

Jan 1, 2009

By Vaughan R. Voller

"The wide range of length and time scales found in solidification processes are outlined and discussed. Methods for Direct Microstructure Simulation (DMS) are introduced. Key features in sharp interface and phase field models are presented. Concepts in micro-macro solidification modeling are covered. Basic details of microstructure and segregation models are provided. A description of a recent segregation micro-macro model is presented in detail.IntroductionA solidification process involves the containment of a liquid region, which, due to cooling, transforms over time to form a fully solid product. The development of the solid microstructure and the segregation of solute components during this transformation are controlled by phenomena that occur across a wide range of length and time scales. A ""successful"" model of a given solidification process needs to account for these phenomena. Standard models of solidification employ a discrete grid of node points and associated volume elements in the special domain, with a discrete time step to track the transient changes of nodal values, describing the composition and microstructure. Through the use of such models significant progress has been made towards a complete understanding of solidification process and phenomena (see the conference proceedings in Refs [1-9]). As solidification models become more sophisticated, however, they all run into the problem of resolving the full range of disparate space and time scales.Two approaches can deal with this problem1. Direct Microstructure Simulation (DMS) where the grid size and time step are chosen to scale with the smallest length and time scales of the given problem.2. Micro-macro modeling where the grid size and time step scale with the macroscopic process scale and phenomena at smaller scales are accounted for via sub-grid modeling and volume averaging.Currently full DMS of solidification is beyond the reach of available computer power and the application and development of micro-macro models is an important and critical research area."

Jan 1, 2001

By S. W. Marcuson

Smelting of nickel-copper sulfide ores at Vale Inco’s Sudbury operations commenced in 1888 and the first converting plant went into operation in 1892. As the demand for nickel grew, the smelting operations expanded and by the 1960’s the Copper Cliff Smelter featured the longest converter aisle in the world with space for nineteen Peirce-Smith converters. During this long period, different converting techniques and vessels were employed. The evolution of converting is reviewed with special emphasis on the modifications made to the Peirce-Smith vessel to accommodate the metallurgical and process needs of the changing times.

Jan 1, 2009

By James Douglas

A century ago the AIME meeting of 1899 was held at the Palace Hotel in San Francisco California in September. For his presidential address, James Douglas presented this paper which is reprinted in full with the kind permission of the AIME. It presents an interesting comparison relating to events and circumstances in the metallurgical industries at the close of last century. Being on the eve of a new century ourselves, the Editors of this volume of the COPPER 99-COBRE 99 Proceedings considered this paper would be of general interest, hence it is included here. Douglas believed in effective interchange of technical experiences and ideas. He considered the extreme secrecy surrounding the copper works at Swansea, Wales, the world center of copper only years before the time his paper was delivered, as one key reason for its decline, (and eventual closure of all copper plants there). In his paper, the pace of developments in various sectors such as transportation (railroads, the dominant means of I transportation at the time), the iron and steel and copper industries were examined, in much the same way as one might do but on the high technology of today. James Douglas was born in Quebec City, Quebec, Canada and spent his early life there. Forced to move to the United States for family and financial reasons, he went on to become a pioneer in the new Arizona copper industry, and with luck and good judgement with his interest in the new mining properties he also became very wealthy. Douglas was an accomplished mining and metallurgical engineer. He was the first President of Phelps Dodge and helped transform the small trading company of Anson Phelps and William Dodge into a mining giant.

Jan 1, 1999

By John W. Graydon

Incineration is an attractive alternative to the disposal of MSW in landfill sites. However, the process of incineration generates fly ash which contains significant levels of leachable heavy metals - particularly cadmium, lead, and zinc - and it is essential to manage this fly ash in an environmentally sound manner. The compositions, phases, textures, morphologies and size of fly ash particles have been studied by light microscopy, scanning electron microscopy, X-ray microanalysis, and X-ray diffraction. The detailed spatial relationships and speciation of the environmentally significant constituents have received particular emphasis. The information obtained is useful in understanding how fly ash is formed during incineration, in understanding the leaching behavior of untreated fly ash if it is disposed of in a landfill and, most importantly, in guiding the development of the best treatment strategies for fly asti to mitigate its environmental impact.

Jan 1, 1992

By J. Wong

We report a successful use of x-ray absorption spectroscopy to probe the chemical and structural environment of trace elements in coal. When applied to vanadium in coal, it was found that vanadium exists in at least two environments: a trivalent site 6-fold coordinated by oxygens at ca. 2.0~ and a tetravalent site 5-or 6-fold coordinated also by oxygens, one of which forms a short V=O bond at ca. 1.6a. No evidence of nitrogen (porphyrin)1&apos;or sulfide environment was found. It was also found that the vanadium environ-ments in the raw coal did not survive unchanged in a liquefaction process. These findings have implications for coal cleaning processes and for trace element release into liquefaction process streams.

Jan 1, 1982

By Jae-Ho. Lee

Mercury is a toxic contaminant encountered in the extraction of gold from mercury-containing ores. It is found in the leach solution of CIP circuits and in the cathodes of the electrolyte cells used to electrodeposit the gold. The research conducted has examined the potential for selective removal of mercury from synthetic Au-Hg-CN electrolytes containing only gold, only mercury, and both gold and mercury. Cyclic voltammograms were obtained for mercury- coated copper electrodes with these cyanide electrolytes. Exchange current densities were determined from the voltammograms in the low overpotential region. Laboratory scale batch- electrolysis at constant current was also conducted for the electrolytes containing only mercury and both mercury and gold, at 20 and 50°C and from which the kinetic behavior associated with the process was analyzed. The surface of cathode before and after electrolysis was also characterized and a copper mercury intermetallic (CyHg,) was identified. Gold codeposited with mercury during the later stages of electrolysis. The results of this work corroborate that the mercury-amalgam copper electrode offers a viable electrochemical technique for the selective removal of mercury, however a high-surface-area cathode-cell would have to be utilized to provide for the desired selectivity.

Jan 1, 1994