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By R. Boom, Y. V. Meteleva-Fischer, B. Kraaijveld, H. Kuntzel

"Segregation of impurities during refining of metallurgical grade silicon (MG-Si) is an option to produce solar grade silicon (SG-Si). Directional solidification is a last step in production of SG-Si effective for removal of metallic impurities. The possibility is investigated to use metallic impurities originally present in MG-Si for removing boron and phosphorus. MG-Si has been treated using two methods: 1) alloying with calcium and 2) refining with Na2O-CaO-SiO2 slag, both by controlled cooling. The microstructure of silicon and the impurities distribution have been studied before and after the treatments. Using EPMA phosphorus and boron have been detected in 1-2 wt% concentration range in several intermetallic compounds in grain boundaries after both treatments. This observation points to a different possible mechanism of silicon refining from boron and phosphorus. Controlled cooling improves migration of phosphorus and boron to the silicide phases in grain boundaries, which can be removed by acid leaching treatment.2. IntroductionStandards for silicon solar cells and growing demand on “green” energy require economical and efficient route to the production of solar grade silicon. Refining of cheap metallurgical grade silicon is one of the promising options, where application of existing metallurgical approaches can result in cost-efficient production on industrial scale. Focus in refining is on impurities, which are most difficult to remove: B, P, Al, Ti, due to their large segregation coefficient in silicon and low vapour pressure [1]. Moreover, more environmentally friendly technology in comparison to the traditional Siemens process [2] will be in accordance with societal needs. Based on properties of common impurities in metallurgical grade silicon, alloying refining and slag refining are suggested as competitive techniques having potential effect on removal of impurities harmful for conversion of solar energy [3, 4]. Alloying with Ca followed by acid leaching was found to be effective for removal of Fe and Ti from silicon [5] and to enhance also removal of boron [6] and phosphorus [7, 8]. In the work of Inoue et al. [8] drastically increasing removal of phosphorus from silicon has been observed with an increase of Ca content and a thermodynamics-based explanation was provided. Since phosphorus has been found to condense in the secondary precipitate mainly composed of CaSi2, it can be removed together with iron and titanium by consecutive acid leaching treatment. Slag refining is one of the metallurgical methods proposed to be effective for refining of metallurgical grade silicon from boron [9, 10]. Slags with additions of the following oxides to silica have shown positive effect on removal of boron: CaO [11-13], Na2O [11,14]. Mechanism of slag refining from boron is based on oxidation of boron followed by its incorporation in the slag network [9,11]; the same mechanism is suggested for refining from phosphorus taking into account that oxides of boron and phosphorus are known as network-formers [15]."

Jan 1, 2012

By B. C. Blakey

Unlike most hydrometallurgical slurries, those containing significant concentrations of goethite are typically highly viscous and shear-thinning, even at solid volume fractions below 5%. The viscosity may also depend upon time. These characteristics must be taken into consideration in slurry transport and heating. The technical literature is replete with apparent contradictions regarding the viscous behavior of these slurries, which may be due, in part, to variations in viscosity-measuring techniques. We present techniques that yield consistent results suitable for use in process design. A striking degree of time-dependent behavior is demonstrated for a laterite slurry. Reliable methods to design and analyze tubular transport and heating systems for time-independent slurries are summarized. Rules of thumb are then offered to account for the effects of time-dependency.

Jan 1, 2000

By Atul Kurnar

In the present research a two-cell polymer electrolyte membrane fuel cell stack (PEMFCS) with SS-316 bipolar plates has been tested. Different flow field designs were studied and a modified multi-parallel channel design is proposed. The stack is stable within ±3 mV even after 1000 hours of continuous operation, indicating efficient water management and effective removal of any metal ions from the stack. Also no iron is detected in membrane electrode assembly (MEA) by EDAX analysis after 1000 hours of cell operation. Results indicate that high operating pressures beyond 138 kPa didn't significantly increase the performance of cell, however added much to the pressurization cost of the system. Tests at different temperatures showed that at temperatures below 80°C, external humidification could be completely removed. The prototype stack is also tested under variable load conditions simulating highway-driving schedule. The experimental efficiency of PEMFCS is 48%, which is in good agreement with the model predicted efficiency of 53.8 %. Results show that 59% of the total losses are due to ohmic polarization in the cell. Further analysis on applications of the stack in automotive transportation system is in progress.

Jan 1, 2002

By K. Kalgraf

The motion and stability of the metal/electrolyte interface is determined by Navier-Stokes equation. The equation may be decomposed into two independent equations by taking the divergence and curl of Navier-Stokes equation. The divergence determines the motion and stability of magneto-gravitational waves. The curl of Navier-Stokes equation gives an equation containing only velocity and magnetic field, and states that the magnetic field is driving a circulation pattern in the cell, and this magneto-flow has its own stability conditions. The waves are called Alfven waves, and their stability properties are related only to magnetic field and geometry.

Jan 1, 2001

By Hector M. Henao

The FeOX-CaO-SiO2 base slag at intermediate oxygen partial pressures is very often used in non-ferrous smelting processes. This slag would also contain Al2O3 and MgO because these compounds are normal components in the ore and the refractory of a furnace. The objective of the present work is to determine the effect of Al2O3 or MgO addition on the liquidus temperatures of the plain FeOX-CaO-SiO2 slags in the atmosphere between intermediate pO2 of 10-6 and that of iron saturation at 1250 and 1300 °C. The experiments were carried out at given mass%CaO/(mass%CaO+mass%SiO2) ratios ranging from 0 to 1 and at spinel-tridimite double saturation. The experimental results show that the effect of Al2O3 or MgO addition on the plain FeOX-SiO2-CaO slag is not uniform and depends on the content of Al2O3 or MgO, the oxygen partial pressure and the mass% CaO/mass% SiO2 ratio. It is apparent that Al2O3 or MgO addition enlarges the spinel or wustite saturation area at almost all the oxygen partial pressures and temperatures of this research. The obtained phase diagrams will be useful in the metallurgical industry to assist in the selection of slag chemistry, operation condition and development of new processes.

Jan 1, 2006

By Paula Ana Paiva

The high economic value and unique technological properties of the platinum-group metals (PGMs), plus their growing scarcity in the Earth’s crust, justify the crucial importance of developing recycling practices for PGMs end-of-life materials. Examples of top devices relying on the use of PGMs are automotive and industrial catalysts, and electrical and electronics equipment. This article critically describes the most recent research on the use of solvent extraction to recover one PGM, palladium, from spent catalysts. Some groups focus on the development of schemes involving commercial extractants, while others prefer to design specific molecules to efficiently and selectively recover palladium from these particular complex leaching solutions. Examples of commercial extractants proposed for the former schemes are Alamine® 308, TBP and LIX® 84I; while on the other hand, sulfur-containing diamides, thioamides, thiocarbamates, and dithioethers have recently been developed. Ionic liquids have to be mentioned too.

By E. O. Ávila-Davila, F. R. Barrientos-Hernández, I. A. Lira -Hernández, Miguel Pérez-Labra, M. Reyes-Pérez, J. Antonio Romero-Serrano

Slag from smelting reduction processes were characterized by chemical analysis, XRD, SEM-EDS and XRF. The results revealed Ag concentrations of 362 g/t of slag, the slag mineralogical characterization by XRD and SEM-EDS showed mineralogical species oxidized complex containing Pb, Zn, Ca, Si, Fe, As, S in its structure, silver was found in globules associated lead in the slag and the furutobeite specie. The leaching study was conducted to evaluate process variables such as NaCN concentration: from 7.8x10-3M - 1.26x10-1M, temperature: 25-50°C, particle size: +140 mesh to -400 mesh, stirring speed of 750 rpm - 900 rpm. All studies were performed with a NaOH concentration of 0.2 M. The optimal values of silver recovery encountered in conditions of 7.8x10-3M NaCN, agitation rate of 750 rpm, temperature of 35°C and with a treatment time of 240 min. We also observed that a particle size -400 mesh will have optimum recoveries compared to +140 mesh, +200, +270 and +325.

Jan 1, 2015

By Niels Verbaan

NioCorp is developing the niobium/scandium/titanium Elk Creek carbonatite deposit. The probable reserve announced by the company in 2017 indicated significant niobium (0.79% Nb2O5), titanium (2.81% TiO2), and scandium (71 g/t), and is composed predominantly of calcite, dolomite, and ankerite. Niobium is mostly (80%) contained in pyrochlore with the balance in various Fe-Nb-Ti oxides, which also host most of the titanium. Scandium is primarily deported in dolomite, with lesser quantities in pyrochlore and biotite. The process flowsheet recovers separate niobium, titanium, and scandium products. Scandium is extracted from whole ore hydrochloric acid leach solutions using solvent extraction and is further refined through a re-leach and precipitation process. Scandium leach residues are treated in a sulphuric acid sulphation process to recover separate niobium and titanium precipitates as well as to solubilize the remaining scandium. Both hydrochloric acid and sulphuric acid reagents are recycled within the flowsheet. This paper will discuss key bench and pilot test results of the niobium extraction and recovery circuits and will present a conceptual flowsheet developed by the project team for NioCorp at SGS Minerals.

By Patrick R. Taylor

A non-transferred arc thermal plasma assisted cyclone reactor has been designed, built and operated to evaluate its use in vitrification of wastes. Simulated waste (liquid, slurry or fine particulate) is injected near the plasma flame, where nearly instantaneous dehydration and calcination reactions happen. A non-transferred arc plasma torch was attached tangentially to the cyclone and is utilized as both an enthalpy source and to provide the gas velocities required to generate the cyclonic gas flow patterns. The closed top cyclone flow sends the solid particulates to the wall, where they are captured by a thin film of molten glass that is injected as a powder at a position lower in the reactor. The molten glass is then collected in a crucible. The feasibility of simulant injection directly into the flame zone and its effect on electrode lifetimes has been studied. Several candidate refractory systems have been evaluated for their suitability for extended use under the demanding conditions present in the cyclone reactor.

Jan 1, 2002

By Hsing Kuang Lin

Ferric chloride leaching w.as applied to a complex sulfide ore from Tok, Alaska to dissolve zinc, lead, silver and copper. Gold in the leaching residue, as well as in the ore, is found to be refractory to the conventional cyanidation process. Roasting, pressure oxidation and elemental sulfur removal followed by cyanidation were tested to improve gold dissolution. Also tested were thiourea leaching and high-pressure cyanidation. The readsorption of dissolved gold by carbonaceous matter in the chloride leaching residue was analyzed. Based on the experimental results, factors causing difficulty of gold dissolution from the leaching residue are discussed.

Jan 1, 1989

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 Chris Twigge-Molecey

As emission constraints for metallurgical plants become more difficult to meet; control of major, multi-vessel, flue systems become more critical. Control instabilities can result in significant loss of system capacity or emissions to the environment. This paper will discuss the use of dynamic simulation techniques to optimize both the design and control strategies for these systems. A significant ,safety hazard is associated with pressure excursions from process upsets or equipment failures. Pressure rise rates of up to 10 kPajsec can occur. These cannot-be followed by conventional controls. Fail-safe high speed venting is required to protect both the furnaces and operating personnel'. Design options, sizing techniques and practical problems are discussed.

Jan 1, 1992

By Larry Southwick

This Peirce-Smith Converting Centennial symposium is celebrating the contributions of two men, William Peirce and E.A.C. Smith, in advancing technology allowing the copper industry to realize its full potential. However, theirs is representative of a larger story: New, simpler technology releasing the stranglehold of older, more complicated technology, new developments in vessel configuration and design finding alternate routes around dead ends in operability, advances in technique and concepts removing roadblocks of cycle time and capacity, and overall innovation opening up vast new reserves around the world to those companies willing to embrace those improvements. Our story is also one of personalities, stubborn smeltermen versus the innovators, those inside the industry versus those from outside. It is a story of an initial borrowing from the steel industry, but also Peirce and Smith, from the refining end of the copper business, taking the ideas of Baggaley from Pittsburgh’s steel and airbrake industry, who built on what Hollway, Manhès and David, Douglas, and others had done in smelter tests, further to compete with the previous primacy and closely held expertise of the copper smeltermen in Wales. These advances have been well recorded in photographs taken over the last 150 years. A number were submitted especially for this symposium. Many others were published in the mining and metallurgy press of the times. Several mining schools also retained copies of photos either taken during field trips, or donated to the school by alumni and operating companies. This presentation will provide a selection and discussion from these sources of “converters in action”, describing the various designs, operations and developments depicted. The focus here will be on the first roughly 60 years of copper converter development, from Bessemer’s days at the dawn of this new idea, up to and slightly past the time of initial adoption of Peirce and Smith’s designs.

Jan 1, 2009

By Michael G. Mayer

Since its invention in 1859 various designs of lead batteries have evolved to meet commercial needs for traction applications and standby power. In recent years major developments have taken place in lead alloys and the chemistry and mechanical design of industrial lead batteries. These are reviewed in relation to their commercial application together with the new type of maintenance free gas re-combination lead-acid batteries which are opening so many new markets for lead.

Jan 1, 1990

By Takeshi Nagano

Copper pyrometallurgy in Japan has experienced quite fundamental changes in last fifteen years. The severe environmental restriction coupled with increase of energy costs accelerated the development work of the new continuous process in Mitsubishi Metal Corporation. After several years of pilot plant test work the commercial plant was put into operation at Naoshima Smelter in 1974, the design capacity of which was 4,000 tonnes of copper per month. Many modifications and improvements have been incorporated into the process and 7,200 tonnes per month of copper production was achieved in 1983, proving that continuous process was much more economical than conventional process. It is now possible to design and operate the continuous process in wide range of capacity. This paper will review the process and describe the progress of the process in these 10 years. 311

Jan 1, 1985

By Xinhua Wang, Xuefeng Liu, Die Yang, Lifeng Zhang, Wen Yang

"CSP thin slab continuous casters are well used in recent years. The control of heat transfer in the mold is very important because it is correlated with several slab defects. The mean heat flux of CSP mold was studied based on the plant production data of LCAK steel and weathering steel. The effect of various operation conditions on the heat flux was analyzed and discussed. The results showed that the heat flux was 2.1-2.6 MW/m2 on the wide face and 1.2-2.2 MW/m2 on the narrow face for the casting of LCAK steels. During the casting of weathering steel, the heat flus was mostly 2.05-2.5 MW/m2 on the wide face and was 1.1-1.8 MW/m2 on the narrow face. The heat flux depended largely on the casting speed. The heat flux on the wide face increased obviously with increasing casting speed when the casting speed was relatively low; however, at high speed, the heat flux increased slowly or kept constant. At low casting speed, the heat flux depended little on the superheat of the molten steel. The mean heat flux depended little on the level fluctuation at continuous casting mold.IntroductionCSP thin slab continuous casters are used more frequently in recent years for its low cost of construction and manufacturing. The structure of CSP mold is very different from that of conventional thick slab casting mold, inducing the difference of heat flux between them. There have been some studies about the heat flux of thick and medium slab casters [l, 2]. Heat transfer in the mold is very important for the solidification of molten steel because it is correlated with several slab defects such as slab break-out, longitudinal crack, and surface depression. Moreover, higher casting speed is desired to improve the productivity. The control of solidified shell is extremely important. The heat flux is largely influenced by several casting parameters such as the cooling intensity of the mold, the casting speed[3], the mold flux powder [3, 4] and the carbon content of steel as well [5]. The investigation on the heat flux and affecting parameters can help to understand the solidification of molten steel in the mold."

Jan 1, 2013

By Liow Jong-Leng

A survey of the interactions of large gas bubbles formed from top and bottom injection of gases into melts was carried out. Spherical cap bubbles were found not to produce much splash when they break through the bath free surface except for that formed by plunging of the-spout at its edges. In contrast, the bursting of balloons produces cavities which give rise to liquid jets being ejected from the bath free surface. The position of the balloons relative to the bath free surface is an important parameter in the formation of the liquid jet. It is found that the interactions of multiple bubbles close to the free surface is important in determining the splash behaviour of gas injected systems.

Jan 1, 1996

By Kenneth N. Ham

Hydrometallurgy covers a wide spectrum of areas and its knowledge base is enlarged and enhanced by contributions from many other fields. Dissolution of metals and alloys in aqueous media will be used to illustrate how rich the field of metal extraction can be. Comprehensive understanding of the fundamentals of metal and alloy dissolution in aqueous systems requires creative application of thermodynamic principles, solutions chemistry, ligand complexation theory, electrochemistry, transport phenomena and heterogeneous kinetics. In addition, recent developments in instrumentation in the fields of interfacial phenomena and corrosion have tremendously advanced the field of metal extraction in aqueous system. The close relationship between metal extraction in aqueous systems and various physicochemical phenomena occurring in corrosion and interfacial systems will be discussed and illustrated with examples.

Jan 1, 2002

By T. Ueno

Naoshima Smelter & Refinery of Mitsubishi Materials Crop. commissioned a new Mitsubishi continuous copper smelter in May 1991. Process offgas volume of the conventional reverberatory furnace line, one of the previous smelters having been shut down, was very large and thus two acid plants had been operated. It was expected that the offgas volume would, be reduced at the new smelter to about a half of the sum of those from previous two smelters and the sulfur dioxide strength would be increased. So various alternatives were studied to minimize the operation cost. And it was decided to utilize both of the plants with minor modifications by diluting the gas either with air or with dilute gases. The acid plants now receive off gases from the new copper smelter, a sintering machine of a lead smelter and a decomposer of waste acid. The paper discusses plant design, operation, improvements and modifications realized in relation with the retrofitting of the copper smelter.

Jan 1, 1992

By Marcelo B. Mourao

Interactions of carbonaceous materials with liquid Fe-C melts have been investigated experimentally by determining the volatile yield due to rapid devolatilization (Flash Pyrolysis) and rates of dissolution at temperatures ranging from 1623 to 1873 K. The volatile yield increased with increasing the temperature. The comparison of results of different types of carbonaceous materials was possible by expressing the volatile yield in terms of Enhancement Factor, fE. The rates of dissolution of spectroscopic graphite and an industrial coke seemed to obey the correlation for natural convection under turbulent conditions. The experimental data for the graphite suggested that the rate of dissolution was controlled by the mass-transfer in the liquid boundary layer adjacent to the solid sample. The value for the empirical parameter correlating the dissolution coefficient and the operating variables was found to be 0.19 which was close to that reported in the literature. The comparison of the results obtained for the coke samples with those for the graphite revealed that the impurities and the porosity of the samples can effect the dissolution rates.

Jan 1, 1992