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By Albert W. Spitz

Profitably recovering copper and precious metals from copper bearing scrap is a demanding and frustrating combination of art, science and economics. With fluctuating markets, varying raw materials and increasingly stringent environmental regulations requiring process revisions, practically everything is changing. The volatile copper market constantly shifts the percentage of copper in the scrap that can be economically processed. Scrap that has value one day may incur a disposal cost the following day. Also with less copper in the scrap, more residuals, slag, fume, etc. are generated which frequently present disposal problems and infrequently generate income. The ever increasing amounts of electronic scrap add value to the copper produced by virtue of the precious metals present. Printed circuit board materials create more slag and organic off gases which must be treated. Finally, the emphasis on reducing emissions of organics and other metals, especially lead, is a continuing challenge. Stack gases, fugitive emissions and ambient air quality all demand constant surveillance.

Jan 1, 1997

By Markus A. Reuter

In this paper, the kinetics of phosphorous production in submerged-arc furnaces will be discussed as a function of temperature, as well as various ore and reductant types. Interesting positive synergetic effects on the rate of reaction could be observed when mixing different types of ores. The results will be discussed with reference to a kinetic model, microprobe analyses, etc. The effects these results have on the control of the furnace will also be discussed in detail, indicating how these could be incorporated into the electrode and metallurgical control systems for submerged arc-furnaces.

Jan 1, 2000

By H. H. Kellogg

The thermochemical properties of molten solutions in the binaries Cu-Bi, Cu-Sb and Bi-Sb, as well as the ternary Cu-Bi-Sb, have been correlated and described in mathematical form by use of the associated species concept combined with the three-suffix Margules equations to account for the non-idea 1 behavior of the solution species. Agreement of the correlations with experimental data is excellent (relative deviation of less than 2.5% in the values of the activity coefficients) in most cases. The correlations are applicable over the entire composition range of each system, and in the temperature range 700°-1250°C.

Jan 1, 1985

By Seyed Ahmad Jenabali-Jahromi

In this paper a meshless method called Finite Point Method (FPM) is developed to simulate the solidification process of continuously cast bloom steel in both primary and secondary cooling region. The method is based on the use of a weighted least-square interpolation procedure. A transverse slice of bloom as it moves with casting speed is considered as computational domain. The two dimensional heat transfer equation together with temperature dependent thermophysical properties is solved in the computational domain. The present work is verified in the mold region by the comparison of the surface temperature simulated by FPM and finite volume method (FVM) and also comparison of solidified shell thickness simulated by FPM and measured on a breakout bloom. For secondary cooling region the validation is done by comparison of the surface temperature simulated by FPM, FVM and thermovision measurements.

Jan 1, 2009

By Suguru Kohno, Yoshihiro Momose, Masakazu Honma, Tokirou Kamosawa

Copper metal surfaces have been examined by an extremely sensitive surface analysis technique called temperature programmed photoelectron emission (TPPE). The surfaces were ultrasonically cleaned and subsequently abraded by a screw in organic solvents and water. The TPPE apparatus is composed of a Geiger counter with Q gas (He+ iso-C4H10). The curve of photoelectron emission (PE) intensity vs. wavelength from 300 to 170 nm, termed PE spectrum, was repeatedly measured at different temperatures in the temperature- increase process from 25 to 350°C. The number of emitted electrons in a PE spectrum (PE total count) increased, reached a maximum at-250°C, and decreased with increasing temperature. With the surfaces cleaned alone in the liquids the maximum PE total count decreased in the order C3H70H > (CH3) 2CHOH > C2HpH > CHPH > H2O. With the mechanically abraded surfaces in the liquids the maximum PE total count changed as a function of the abrasion period and the maximum tended to appear at higher temperature with increasing abrasion period; the maximum value at 10-min abrasion decreased in the order H2O > CHpH > C2HPH > (CH3) 2CHOH > n-C3HpH. It was suggested that the TPPE behavior can be related to the acid-base interaction between the alcohols and the abraded metal surfaces and the presence of a contaminant over layer on the surface. From the XPS analysis of the 01 s spectra it was suggested that the chemical change of the adsorbed oxygen to oxide oxygen with temperature plays a substantial role in the appearance of the maximum PE total count.

Jan 1, 2000

By B. L. Chulu

In the carbothermic reduction of lead sulfate to produce lead, the inclusion of soda ash (Na,CO,) in the charge provides for the control of sulfur dioxide in the effluent gas. An important mechanism in the process appears to be the carbothermic reduction of the sodium carbonate whereby sodium gas and carbon monoxide are produced. These intermediates then participate in the reduction of the lead sulfate to produce lead metal and stable sulfur species in the molten slag phase. In addition, there is some evidence that the presence of lead metal in the charge may also serve to increase the lead recovery in the process. These aspects were investigated by conducting laboratory-scale smelting tests with small charges (;3g), at 1173°K(9000C). Recovery did not exceed 74w% and the role of incipient lead metal in the charge could not be clearly assessed.

Jan 1, 1993

By Yusuke Kimura, Ken-ichi Yamaguchi

"Secondary materials have long been processed at the S-furnace of the Mitsubishi continuous copper smelting and converting process at Naoshima Smelter and Refinery. Intensive recycling in the recent years has formed concerns that impurities in the secondary materials may cause drastic changes in the chemical properties of the CL-slag, which is separated from matte in the smelting stage. Among various impurities included in secondary materials, the authors have studied the influences of sodium oxides in the CL-slag because the behavior of sodium oxide has scarcely been studied with respect to the copper smelting slag. The examinations have been applied experimentally on the distribution between slag and matte of arsenic whose acidic characteristics suggest strong affinity to sodium-oxide of basic characteristics in silicate melts. The results have been discussed by thermodynamic evaluations and the results of pyro-tests at the commercial furnace.IntroductionAt Naoshima Smelter and Refinery, the existing line of the Mitsubishi continuous copper smelting and converting process has been operated since 1991. The Mitsubishi Process consists of three furnaces namely the S-, CL- and C-furnace as shown in Figure 1. In the S-furnace, copper concentrate and powdery secondary materials (scraps, sludges, etc) are charged through the top lances with oxygen enriched air. The other secondary materials of lumpy shapes are charged through the chute installed on the furnace roof. Charged materials are smelted by the reaction heat in accordance with the oxidization of copper concentrate. The mixed melt of matte and slag overflows through the launder into the CL-furnace, where the melt is separated into slag and matte by the difference of their specific gravity. Matte is siphoned out and sent to the C-furnace and converted to blister copper continuously. The CL-slag overflows continuously through the slag outlet to be water-granulated. Granulated slag is sold as a raw material used for the cement production and so on. Various secondary materials have been processed at the S-furnace of Naoshima Smelter and Refinery. Intensive recycling in the recent years has formed concerns that the chemical properties of the CL-slag may change drastically due to impurities originating from secondary materials. Among various impurities included in secondary materials, the authors have studied the influence of sodium oxide in the CL-slag because the impact of sodium oxide has scarcely been studied with respect to the copper smelting slag. The examinations have been applied experimentally on the distribution between slag and matte of arsenic whose acidic characteristics suggest strong affinity to sodium-oxide of basic characteristics in silicate melts."

Jan 1, 2012

By Chen Song

Cobalt basic carbonate particles were precipitated from 1.0mol cobalt nitrate or cobalt sulfate solution with ammonia carbonate. By controlling the zeta-potential of the particles and the ionic strength of the solution, the uniform particles with ellipsoid or rod shapes were obtained. During the precipitation process, the interface tension was diminished to the minimum and therefore the Ostwald ripening and secondary nucleation were both inhibited. The morphology and the size control by zeta-potential seem to be the result of thermodynamics rather than classical crystalline kinetics. The particle sizes were in the range of 0.4-0.6, 0.3-0.4 micrometer. After thermolysis, the spinel-type C0304 particles were produced. The morphologies of C0304 particles were similar to that of their precursors.

Jan 1, 2003

By Ji-He Wei

The ESR of Cu-Cr-Zr alloy has been experimentally investigated. The remelting experiments have been carried out with different slag fluxes in the Cal, + Nal, CaF2 + ZrO2 and CaF2 + NaF + ZrO2 systems on an ESR furnace of 25kg capacity; using a water-cooled copper mould of 96.5 mm diameter, with the forged square bar electrodes of 50x50 mm2. The slag amount was taken to be 1.5 kg. The remelting current and voltage used were 1600-1800A and !5-25K, respectively. The influence of the slag composition on the stability of the remelting process and the losses of alloying elements (2r and Cr) has been considered and examined. The technologies of hot working and heat treatment of the ES ingot have been described and discussed. Some physical properties of the slag in a CuF2 + NaF + ZrO2 system and the remelted Cu-Cr-Zr alloy have been determined. The results indicated that with the slag flux of CaF2 + NaF + l0 mass % ZrO2 and the other operation parameters employed, a high quality ingot of Cu-Cr-Zr alloy may be obtained at the considerably high yields of Zr and Cr by means of ESR. For the remelted Cu-Cr-Zr alloy with a specified composition of 0.5 mass % Cr and 0.1 mass % Zr, the appropriate electrical conductivity, hardness and softening temperature are as high as 45-46S/m, HRB 82-84 and 550°C. respectively. The properties of the Cu-Cr-Zr alloy products are in accordance with and superior to the requirements and specifications of ISO5l82-l99l(E).

Jan 1, 2000

By Francois Barthelat, Sam Goroshin, David Frost, Alexander Cappozi, Atefeh Nabavi

"In this study, a novel chromium–chromium sulfide cermet was produced by self-propagating high-temperature synthesis (SHS). Conventional techniques for manufacturing metal sulfides are complex, environmentally harmful, and not suitable for producing complex-shape articles. To overcome these disadvantages, a new method for the preparation of the metal-sulfur precursor charge is proposed, which can be described as reactive casting. The first cermet samples produced with the SHS process were found to be very porous, brittle, and have low mechanical strength. The possible sources for the generation of porosity were identified and analyzed and the process for manufacturing the cermet was modified. By improving the manufacturing process, the porosity inside the produced cermets was reduced from 70% to 12%.IntroductionMetal sulfide composites are in high demand in the chemical, metallurgical, and electrical industries because of their valuable characteristics such as hardness, semi-conductivity, electroluminescence, infrared transparency and catalytic properties. Current manufacturing methods for metal sulfides usually involve one of two different principal methods, including a complex multistage wet chemical process involving the precipitation of the corresponding salts from an aqueous solution with hydrogen sulfide, or hot sintering of the respective elemental reactant powders in a resistive furnace in a high-pressure inert or hydrogen-sulfide atmosphere [1, 2]. These conventional methods for synthesizing ceramic metal composites are complex, extremely time and energy consuming, environmentally harmful, and rarely able to manufacture articles with complex shapes. Therefore, in order to overcome these disadvantages, self-propagating high-temperature synthesis (SHS) was considered as an alternative method that offers significant improvements over the traditional cermet manufacturing methods [3]. SHS, which is a relatively new and attractive method for producing a wide range of advanced materials, is based on the self-sustaining feature of the highly exothermic reactions of the reactants. The SHS process results in high product purity, since the high temperatures generatedin the reaction cause any impurities to volatilize [4, 5]. SHS has low energy consumption and doesn’t require an external energy source and complex equipment, and it is self-contained [1, 5]. Since combustion synthesis has low power requirements, it is one of the few methods of materials synthesis that is feasible in outer space. Also, the process has a low cost and is capable of directly synthesizing articles with the desired shape, size and structure [5, 6]. The chemical reactions associated with SHS are typically completed in a few seconds leading to the formation of the condensed product. The high reaction rates and relatively rapid cooling in SHS reactions can avoid undesirable grain growth in products which often occurs with the conventional sintering method [3, 5, 7]. The traditional method for sample preparation in the SHS technique is to compact the reactant mixture powders in a steel die by a press to a typical density of about 80% of the theoretical maximum value, before igniting the mixture [8]. This method requires a large compression force to increase the green density and to minimize any pores in the green compact. To overcome these disadvantages, a new method for the preparation of the precursor charge in metal-sulfur by SHS is proposed which can be described as melt casting of a reactive mixture, or reactive casting in short."

Jan 1, 2012

By B. Farouk, Y. G. Kim, D. Apelian

"Continuous strip casting has received considerable attention in recent years due to its economic advantages with increased energy savings and the elimination of intermediate processing steps. A promising concept in strip casting is the twin-belt (Hazelett) process which incorporates two cooled continuously moving thin metal belts wrapped around pulleys which tension and drive the belts at a predetermined speed. Molten metal is introduced at the entry end of the caster through a tundish and feeding nozzle into the mold. The twin-belt process has been successfully used with non-ferrous metals such as aluminum, copper and brass, and is a prime candidate for strip casting of ferrous materials. A numerical model has been developed which predicts the interface locations, the temperature fields in the solid and liquid regions of the cast and the velocity fields of the liquid metal at the entrance region of the twin-belt caster. The process variables considered are the velocity and cooling conditions of the belt and the nozzle shape. A body fitted coordinate system is used to track the front locations and to solve .the Navier-Stokes equations in the liquid region. Results obtained can help design efficient casters for thin strip steel castings. The development of the numerical model is presented, and sample results are discussed. I. IntroductionContinuous strip casting of steel has attracted world-wide concerns in recent years due to its economic advantages with increased energy savings and the elimination of intermediate processing steps. New methods of thin strip casting of steel are developing. One of the promising concepts is the Hazelett process, which is being used in nonferrous applications. The process incorporates two continuously moving, intensely cooled, thin metal belts. Metal blocks linked together are sandwiched between the moving belts and form moving side mold walls.In this work, the freezing front position, the temperature field and the liquid region flow field will be analyzed for the strip casting of metal using the twin belt caster (the Hazelett process). Up to now almost all theoretical analyses undertaken of the continuous casting of metal [1-3] have used a heat conduction equation, assuming slug flow in the liquid region. The effect of convection in the liquid pool during continuous casting were first investigated by Szekely and Stanek [4]. They considered potential flow between the feed metal orifice and the liquidus front, and slug flow in the mushy and solid regions of a vertical static continuous casting process for steel. Viscous effects and natural convection affects were not included Kroeger and Ostrach [5] studied the effect of natural convection flow in the liquid pool during solidification for a pure metal."

Jan 1, 1986

By Sylvain Gouttebroze, Mohammed M'Hamdi

In a previous work, a small scale Bridgman furnace has been used to study silicon bi-grain crystallization at different cooling rate. This work expands the analysis by studying the mechanical interaction between the crucible and ingot during the solidification and cooling. The thermal model is based on a 2D-axisymetric heat-transfer model. The flux histories are then transferred to the ingot-crucible 3D-model. Anisotropic Elastic and Crystal Plasticity model are used to model the silicon deformation. Four different assumptions are applied to model the mechanical contact crucible-ingot and three grain misorientations are considered. The results show the strong impact of the alumina crucible contraction on the stresses and deformations in the silicon ingot.

Jan 1, 2015

By M. M. Swan

A stratiform gold occurrence of Precambrian age located 20 miles southeast of Prescott, Arizona, within the Agua Fria Mining District, displays chemical, mineralogical, structural and lithological patterns indicative of a distal, exhalative volcanogenic environment. Metavolcanic and metasedimentary rocks of the Proterozoic Yavapai Series (1775-1820 m.y.) host the mineralization and are'characterized by greenschist grade metamorphism, steeply-plunging penetrative folds and steeply-dipping schistosity. Mineralization is confined to a 100m thick stratigraphic section that is comprised of a series of thin auriferous massive sulfide beds and intercalated schist .containing disseminated sulfides. The mineralization extends more than 4km along strike. Coincident with, and largely confined to the mineralized strata, are anomalous amounts of As, Sb, Cu, Pb, Zn and Ag and associated silicification, sericitization and carbonatization. This exhalative mineralized system is interpreted to have been deposited in a paleo topographic low on the distal flank of a submarine rhyolite dome and to represent the final episode of a Precambrian volcanic cycle.

Jan 1, 1981

By S. K. Varma, Miriam Regalado, Daniel Salas, Erica Corral, Erika Esquivel

"Age hardenable 2014 aluminum alloys and composites containing 0.10 and 0.15 volume fractions of alumina particles (VFAP) have been solutionized at 540 and 550°C for up to 20 hours. The solutionized samples, heat treated for 5 and 20 hours, have been subjected to room temperature rolling until cracking develops. The work hardening curves have been compared to determine the effect of solutionizing time on the rolling characteristics from both hardness and the microstructural evolution points of view. Solutionizing at two different temperatures results in differences in the extent to which the composites can be rolled until fracture. The microstructural characterization by TEM has been performed to understand the room temperature rolling behavior.IntroductionThe effect of solutionizing on the age hardening response of 6061 and 2014 aluminum alloys and composites reinforced with 0.10, 0.15 and 0.20 volume fractions of alumina particles (VFAP) have been reported in the literature [1-4]. A comparison of the monolith and composites indicates that particles promote the aging process through differences in the microstructures in solutionized condition. The first effect of solutionizing is to produce a grain growth process which follows a grain growth law (square of grain diameter as a function of solutionizing time). It appears that it is possible for vacancies to be emitted during grain growth period as they try to minimize the total grain boundary surface area by increasing their diameter. This may be common to both the monolith and the composites. However, the second effect must be exclusively considered for the composites. The particles generate dislocations during the solutionizing process due to the differences in the values of the coefficient of thermal expansion (CTE) between the particles and aluminum base metal. It has been determined [1] that the dislocation density increases with increase in solutionizing time in the composites of 6061 aluminum alloys reinforced with 0.10, 0.15 and 0.20 VFAP. The improved bonding between particles and matrix can give rise to additional generation of dislocations due to curvature effects [1] with the result that the dislocation density continues to increase with increase in solutionizing time even after the CTE effect is considered to have been stabilized."

Jan 1, 1998

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

By Halvor Dalaker, Alain Marc Ferber, Thor Anders Aarhaug, Pål Tetlie

Off-gas monitoring of experimental reactors give little information about intermediate reaction products and reflect chemical equilibria at reduced gas temperatures. A reactor design with optical access was designed and tested in order to be able to qualify and quantify gaseous species from their emission spectra. By use of a sequence of sapphire, UV fused silica and IR transparent sapphire and CaF2 windows and lenses optical access to a hot, maximum 1800 °C, reaction zone was gained. A cooled area behind the reaction zone was used as a background in order to avoid signal saturation from reactor walls. In addition to molecular emission spectra, atomic emission lines are used to characterize stable gas constituents and radicals. The setup has been designed for the study of methane dehydrogenation experiments in order to investigate the carbon activity of reduction of oxide with methane, but has also been used to monitor gaseous silicon suboxide.

Jan 1, 2015

By B. Mishra

The major waste product of the alkaline extraction of alumina from bauxite [Bayer Process] is known as red-mud. Approximately, a ton of red-mud is produced for every two tons of bauxite that is mined. The red-mud produced from Jamaican bauxite is rich in hematite, alumina and titanium oxide. It has been shown that over 90 wt. pct. alumina can be recovered from red-mud by soda-ash sintering and caustic leaching. Hematite can be carbothermically reduced with a degree of metallization of over 94 pct. At this stage, the product could be charged through the tuyeres in an iron blast furnace or smelted to produce pig iron. The mineralogical characteristics of the reduced product are not amenable to magnetic separation for iron recovery. The problems associated with the use of reduced red-mud as an alternative to direct-reduced iron [DRI] has also been discussed. Special attention has been paid to lower the alkali content of the reduced material. If smelted, the concentration of titanium oxide in the slag will be significantly high justifying its recovery by an acid-leach process. This paper describes the successful efforts of iron and alumina recovery.

Jan 1, 2000

By Yong Xian, Zhaohui Sun, Honggang Zhong, Qijie Zhai, Jie Sun

Vacuum refining is admitted as an effective means to remove impurities in the process of alloy smelting. In this paper, Orthogonal and single factor experiments were carried out to investigate effects of multiple factors, such as superheat degree of the melt, degassing time and vacuum degree, on the vacuum refining process. The results showed that the best removal rate of oxygen and nitrogen is up to 82.71% and 61.3%, respectively, due to high vacuum degassing efficiency. It is found that the superheat degree is minimal impact on the deoxidization rate, in addition, nitrogen removal is controlled by the degassing time. The inclusions exist in the AlV55 alloy are mainly composed of oxides and vanadium-nitrogen compounds.

Jan 1, 2015

By Bingchen Chen, Zhitong Sui, Junwei Ma

"In the blast furnace slag, titanium disseminated in various mineral phases Titanium could be concentrated mainly in perovskite, which could be selectively precipitated and grown by optimizing the operation factors like the slag composition, temperature of heat treatment and additive agents. This study aims at establishing the titanium slag mineralogy and its distribution in the treated slag and the as-received slag, as well as the methods of perovskite separation. After heat treatment, the grain size was grown from 5 - 20µm to 80 - 200µm, the distribution of Ti02 in perovskite was increased from 48% to 81 %, the morphology was changed from snow-shaped grain to coarsening dendrites or equiaxed crystals. A concentrate were produced by gravity separation analyzing 35.25% Ti02 with a recovery of 68.28% and a tailing analyzing 9.53% Ti02 , and a possibility of flotation upgrading was discussed. I INTRODUCTION CHINA is rich in mineral resources of titanium, 92.4% of which is vanadium-titanium bearing magnetite. About 53% titanium were in iron concentrate after mineral processing, by which the blast furnace slag containing about 25% TiO2 were produced[11 • The content of TiO2 in such slag is too low to separate titanium dioxide, and it is also too high to produce slag cement[21. It has been accumulated to 50 million tons so far, which is still increasing at a rate of 3 million tons per year, and results in a waste of titanium resources and pollution of environment. Due to the dispersed distribution of titanium component in various mineral phases, very fine grain(<10µm) and complex interfacial combination, it is very difficult to recovery titanium component from the slag by traditional separating technique. In this paper, a novel technique to recovery titanium from the waste slags was proposed [3H4l, on which three continuous processes were involved: selective concentrating, selective growing and selective separating. Perovskite was designed as a titanium-rich phase, in which the most titanium was concentrated promptly, then perovskite could be selectively grown and coarsened by optimizing the heat treatment and the appropriate additives [ 5l[6l. The grain size of perovskite phase was larger than 80 µm, and the crystals appeared as coarsening dendrites or equiaxial grains like lump."

Jan 1, 2000

By Guohui Zheng

The ever increasing quantities of solid wastes generated by various industries are at the source of the growing need for proper waste disposal methods. Thermal treatment of combustible wastes is a proven technology which permits the reduction of hazardous material having to be landfilled. However, this method is not universally applicable to waste disposal. For example, the transferal of heavy toxic metals into the thermal remediation products is a major issue of public concern. This paper focuses on the analysis of morphology changes from solid sludge to ash which is a product of the sludge combustion. The morphological parameters analyzed were particle size and external surface. They were determined using Jeol 840 Super Probe. The experiments were conducted in a computer-controlled high-temperature combustion system consisting of the thermogravimetric furnace coupled with Fourier transform infrared spectrometer (TGA-FTIR). Sludge particles were made of complex fibers trapped in the aluminosilicate matrix. At low temperatures, up to 680 K, the solid residue looked similar to the initial sludge. Between 680 K and 1180 K the sludge underwent intensive burning and steadily changed into powdered ash. At the temperature of 1050 K the ash was composed of separate, flat flakes with sizes ranging from 5 to 20 um. At 1470 K the flakes aggregated into large particles. The surface observed at 1670 K was a mixture of mullite crystals. Such structure could result from the solidification of the ash material after its melting. Morphological changes influenced the distribution of metals in the solid residue. For example, Cr was concentrated in small aggregates. Such distribution should allow for recovery of valuable metals from the solid waste residue.

Jan 1, 1996