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Based on experimental and computer simulation results from our group, we report a systematic, atomic level analysis of carbon dissolution from carbonaceous materials in molten iron. Experimental results on graphite / Fe-C-S system were obtained using carbon dissolution studies, XRD and FESEM investigations and were supplemented with Monte Carlo simulations. Three basic mechanisms, namely carbon atom dissociation rate, interfacial phenomena and mass transfer in the melt were found to be responsible for the overall dissolution process. While mass transfer in the melt is governed by the concentration gradients, melt composition and temperature; impurities present in ash play a significant role in the interfacial phenomena. For less ordered forms of carbonaceous materials, carbon atom dissociation rate depends strongly on the degree of long-range order and is an important rate controlling mechanism in the overall dissolution process. A systematic comparison of dissolution rates for a variety of coal-chars, natural and synthetic graphites has been carried out in an attempt to identify rate-controlling mechanisms. The structure of the carbonaceous material appears to be an important underlying factor in the carbon dissolution process.

Jan 1, 2003

By Guy L. Fredrickson

A modified transpiration reactor was used to measure the composition of the equilibrium gas phase formed above compounds in the Hg-O-S system at high temperatures (600 to 900K). A thermodynamic database {(AGo°f AH°t. AS°t)} for-HgO, HgS, HgSO4, Hg2SO4, HgSO4?HgO, and HgSO4?2HgO was developed based on the experimental results. Prior to this study, only estimated data were available in the literature for the sulfates and oxysulfates at temperatures above 298K. A series of vapor pressure' stability diagrams were constructed from 473 to 973K with isobars of Hg(g), HgO(g), S2(g), and SO3(g). These diagrams were found to be significantly different than those available previously and do provide insight to the phase relations of importance during the thermal processing of Hg-containing wastes. The thermodynamic results were used to conduct a series of Gibbs energy minimization calculations for a thermal processor' afterburner system for the treatment of HgS-containing wastes. The retention of Hg in the discharge calcine was examined as a function of temperature and excess air. Hg was found to report to the calcine as HgSO4, Hg2SO4, or HgSO4 HgO depending on the process conditions, and Hg retention occurs at temperatures as high as 930K. The precipitation of Hg-containing phases from cooled afterburner discharge gas starts at approximately 900K and the cooling of the gas an additional 30K (to 870K) results in over 50% of the Hg being preCipitated as HgS04?HgO. It was also determined that for small amounts of Hg present in sulfide concentrates during roasting, the Hg will be retained as HgSO4 or HgSO4?HgO at temperatures as high as 870K.

Jan 1, 1996

By Etsuro Shibata

The saturated solubility of chromium oxide and the valence of chromium in the slag are important matters when considering how to effectively utilize chromium-containing slags. The experimental data of various types of slags cited in the literature were arranged according to the optical basicity in order to evaluate the effects of the oxygen potential and the slag composition. The saturated solubility of chromium oxide and the Cr2+/ Cr3+ ratio tend to decrease with the increase of the optical basicity of the slag at an oxygen potential below 10.5 atm. However, at an oxygen potential of 0.21 atm, the saturated solubility and the Cr6+/Cr3+ ratio tend to increase with an increase of the optical basicity. A practical approach was suggested to reduce chromium in the stainless steel slag and simultaneously recover it as a ferroalloy by the direct smelting reduction of chromium oxide in the molten slag using some reductant in a small furnace.

Jan 1, 2003

By Carlos Antonio da Silva

Steel refining reactors based on chemical heating are being used as an alternative to ladle furnaces. They show a high degree of flexibility in respect to heating rate in addition to carrying out refining reactions such as de-S, inclusion removal, alloying etc. IR-UT and CAS-DB are examples of such reactors. Their performance is dependent upon geometrical characteristics as well as operational conditions which determine the flow field inside the vessel. A physical model of the IR-UT process of the Companhia Siderurgica de Tubarao, steel plant located in Serra, Espirito Santo, Brazil, was developed to assess the features of the flow field and its influence on the metallurgical behavior. Results of the physical model were used to optimize the process parameters in the industrial unit.

Jan 1, 2003

By Ruiqing Li

It is possible to purify some liquid metals by exploiting the difference between the vapour pressure of the bulk metal and the minor constituents or impurities. The rates of purification can be improved by carrying out the process under reduced pressure, that is, so called, vacuum. Some commercial examples of vacuum refining are the purification of molten tin to eliminate trace amounts of lead and the refining of cobalt, also to remove lead. The objective of this paper is to review the basic theory behind vacuum refining technology in order to show how the feasibility of vacuum refining can be determined simply for a particular system by evaluating Olette's Volatility Refining Criteriont.

Jan 1, 1991

By Carlos Antonio da Silva

Steel refining reactors based on chemical heating are being used as an alternative to ladle furnaces, They show a high degree of flexibility in respect to heating rate in addition to carrying out refining reactions such as de-S, inclusion removal, alloying etc. IR-UT and CAS-OB are examples of such reactors. Their performance is dependent upon geometrical characteristics as well as operational conditions which determine the flow field inside the vessel. A physical model of the IR-UT process of the Companhia Siderúrgica de Tubarão, steel plant located in Serra, Espirito Santo, Brazil, was developed to assess the features of the flow field and its influence on the metallurgical behavior. Results of the physical model were used to optimize the process parameters in the industrial unit.

Jan 1, 2003

By C. M. Diaz

The chemistry of the main unit processes in nickel extractive pyrometallurgy is reviewed. Key re1a ions between smelter feed composition and process selection are discussed, with particular reference to operating conditions, energy requirements and products. The paper a1 so includes a brief discussion of current nickel smelters, based on the results of a recent survey carried out by TMS.

Jan 1, 1988

By Mark R. Jolly, Jean-Christophe Gebelin, Aleksander Cendrowicz

"Injection of wax patterns is the first stage of the multi-stage process of investment casting. The quality of the final casting and its dimensional accuracy is highly dependent on this stage of the process. Pattern waxes used in the industry behave in a complex visco-elastic-plastic manner. The modelling of such material behaviour is therefore not simple.In this paper a number of configurations of die will be shown in which the injection of the wax has been carried out for a range of processing conditions. Some of the dies are transparent and the movements of wax front observed can be compared with those predicted by simulation. Surface defects in final components will also be shown and compared with the location predicted by simulation software. Some discussion will be presented on the limitations of the software used and the time-scales achieved for practical use as a design tool within the foundry environment. IntroductionThis paper presents the research activities carried out at the University of Birmingham on the modelling and prediction of the behaviour of industrial investment casting waxes during the injection of wax patterns. These research activities are done in the context of a more global study of the fundamental aspects of the investment casting process, the FOCAST project. Regarding the wax injection process, the aim of the project is to achieve a better understanding of the key factors that will lead to better castings. The filling of the die during the injection has been studied. Some other phenomena such as shrinkage/warpage or creep under residual stresses are also studied, but not presented here. Two commercial investment casting waxes have been characterised in order to model their behaviour and predict mould filling and subsequent defects.This paper will present the models that have been used in our work, the simulation packages used, the experiments carried out to validate the modelling and exhibit the defects due to bad filling, and finally the numerical simulation results."

Jan 1, 2001

By Rick Honaker

Rare earth elements (REEs) contained in coal and associated mineral matter exist in several forms including micro-dispersed minerals, ion adsorption onto clay surfaces, and chemically bound. Tests found that REEs can be effectively recovered from certain components of three coal sources by leaching under mild conditions followed by solvent extraction. A range of pH values were evaluated at solution temperatures of 25 and 75 °C. When using 1.2 M of sulfuric acid, nearly 85% recovery of the REEs was extracted from the middlings material collected from an operating plant. Acid leaching of a second middling source from another plant resulted in 60% of the total REEs being recovered under the same leaching conditions. Solvent extraction treatment of the leachate produced from six different coal sources resulted in products containing up to 50% total REEs from feedstocks starting with around 300 ppm.

By Shuichiro Okada

Various efforts to reduce energy consumption and smelting cost are made at Tamano Smelter. Production of anode copper has been increased by about 30 % and energy requirement has been decreased about 50 % respectively. Challenges toward more higher goal are being continued. Details about the following are described in this paper. 1 Waste heat recovery Steam recovery at up-take of FSFE Heat recovery from waste gas of anode furnaces 2 Application of tonnage oxygen 3 Application of pulverized carbonaceous fuels to the flash smelting furnace with furnace electrodes ( FSFE ) 4 Application of computer control system to copper smelting 5 Improvement of the fugitive gas collecting system 6 Improvement of the mechanical tuyere puncher for the converter furnace

Jan 1, 1983

By J. C. Huyhua

The effect or various oxidants on gold and silver dissolution in thiourea solutions (0.05 M in H2SO4) was studied using the rotating disc technique, a.t 2s c and 600 rpm. These studies were carried out at constant (4:1) initial molar ratio or thiourea to oxidant concentrations, to produce 50 % thiourea. oxidation. The initial dissolution rate of gold was approximately four times higher in the presence. of ferric sulfate (5.37 x 10-3mg cm-2 s-1) than in the presence of hydrogen peroxide (H2O2), potassium persultate (K2S2O3), or monopersulfa.te (KHS06). The dissolution rates for silver were considerably lower than gold for the same oxidants. Oxidation of thiourea in the presence of peroxygen and persulta.te compounds is a. fast reaction and it is completed in less than ten minutes. On the other hand, the oxidation or thiourea with? ferric.sulfate is slow, yielding a second-order reaction rate constant k = 6.09 I mol-1 h-1. Sulfur formation in the ferric thiourea system begins when ferric ion reduction approaches to completion. With hydrogen peroxide, sulfur is observed at lower thiourea concentration than ferric. Suifate. The presence of a large excess or free thiourea i.e., s to 20 % thiourea oxidation) retards sulfur formation and maintains favorable dissolution rates. Finally, carbon-in-leach experiments indicate that thiourea solutions a.re stable for several days, with ferric sulfate or hydrogen peroxide. The dissolution rates of gold and silver doubles in the presence or activated carbon when hydrogen peroxide is used as oxidant.

Jan 1, 1989

By Chao Li, Lim Hongxu, Yuyue Wang, Xie Yang

"A intergrated process of sulfuric acid leaching, sodium chloride leaching, lead chloride crystallization, lead hydroxide synthesis and roasting was carried out for the recovery of lead, cadmium, copper and zinc from lead smelting dust containing various metals. The results showed that the separation of cadmium, zinc and copper from dust could be obtained after sulfuric acid leaching and corresponding leaching rate were 92.12%, 90.25% and 88.26% respectively. The subsequent sodium chloride leaching carried out for lead with optimized parameters as: sodium chloride concentration 250g/L, leaching temperature 90°C, leaching time 2h, pulp density 33g/L, 0.12mol/L CaCh; The lead compounds crystallization rate reached 86.67%, and then transferred into mPbO·nH2O, the product of 98.66% ß-PbO could be obtained through roasting under 502°C. In the end, a feasible method of ß-PbO preparation from lead containing dust was put forward.IntroductionThe pyro-metallurgy flue dust from smelting lead activities are often stockpiled and pose potential environmental risks due to the heavy toxic elements, such as Pb, Cd, As, Cu, Cl, and Zn which are contained in the dust. With the rapid depletion of rich ore resources in recent years, it has become increasingly more financially attractive to recover valuable metals from previously stockpiled dust, while simultaneously reducing the potential of environmental pollution from toxic elements contained in the dust. Nowadays, pyro-metallurgical and hydrometallurgical routes or both combined methods can be developed to treat secondary materials such as lead ash, leach residues etc. By comparison the hydrometallurgical processes are often considered more eco-friendly.Some chloride leaching processes for recovering lead have been employed using either NaCl, or MgC2 and CaCl2, or FeCl3 [1] The effectiveness of the brine leaching method is based on the formation of complex metal chlorides in concentrated chloride solutions [2] Similarly, Other metals such as zinc, cadmium and copper contained in the flue dust are often treated with sulfuric acid, hydrochloric acid, ammonium solution and sodium hydroxide etc. as lixiviants [3] The metals from leach solutions thus has been obtained by precipitation, ion exchange, solvent extraction or replacement [4]"

Jan 1, 2014

By K. Morsi

Titanium-titanium boride whisker (TiBw) composites are emerging as strong candidate materials for advanced applications within the automotive, aerospace and defense industries. Although increasing TiBw volume fraction improves the specific stiffness and wear resistance of titanium, it is usually on the expense of fracture toughness and ductility especially at increased volume fractions of reinforcements where whiskers interlock. This research addresses strategies for microstructural design that may overcome these shortcomings, by generating titanium composites that are locally reinforced with TiBw through in-situ reaction in segregated regions of the microstructure and separated by ductile Ti matrix. The effect of varying composite reinforcement particle sizes (i.e. size of the reinforced regions) on the pressure-less sintering of these dual matrix composites is discussed. Electric current activation was also used to generate high density dual matrix composites and a new simultaneous imaging and modulus mapping technique was used to characterize these unique microstructures.

Jan 1, 2008

By M. Patel, A. W. Piper, R. A. Forsdick

"Lead bullion is refined in kettles to remove the contained impurities such as copper, antimony, silver and bismuth. These impurities are removed sequentially by the addition of one, or more, reagents to the bath. Impurity elements react selectively with the reagents to form a dross layer on the surface that is subsequently removed for further processing. Mixing the lead bath using specific impeller designs, which form a vortex to ensure that good contact takes place, carries out the reactions. It is important that the mixing is controlled to achieve the optimum bath conditions and hence good dross grades.This paper presents initial modelling work on the kettle refining process using both physical modelling (Water Models) and mathematical modelling (Computational Fluid Dynamics - CFD). Comparisons between measured plant data and simulation results are given.IntroductionThe refining of lead bullion takes place in hemispherical kettles of varying sizes. It is normal practice to remove the impurity elements sequentially, by the addition of reagents, which selectively react with the impurity element. The impurity element forms a dross layer on the surface, which can be removed for subsequent processing at the end of the reaction period.All the refining stages in the production of lead and lead alloys involve mixing the lead bath, although different conditions are required for each stage. At Britannia Refined Metals mixing is achieved using either 3 or 4 angled or flat blade impellers, which generate a vortex in the central region of the kettle. However, throughout the industry a wide range of mixer types are used which are all trying to achieve the same result."

Jan 1, 1999

By Phillip B. Messersmith, Emmanuel P. Giannelis

"A versatile in-situ polymerization approach is described for the synthesis of polymerceramic nanocomposites consisting of two-dimensional layers of mica-type silicate (MTS) within polymer matrices. Functionalized, organically modified mica-type silicates (OMTS) were used to promote delamination/dispersion of the host layers and initiate polymerization of organic rrionomer. Epoxy nanocomposites prepared in this manner exhibit substantial modulus reinforcement at low silicate loadings. The water vapor permeability of the poly(?-caprolactone) nanocomposite containing 4.8% silicate by volume was reduced by nearly an order of magnitude compared to pure poly (?-caprolactone).IntroductionPolymer matrix nanocomposites are a relatively new class of materials with dimensions typically in the range of 1-100 nm.1 In general, because of the ultrafine phase dimensions involved, nanocomposites exhibit new and improved properties when compared to their micro- or macrocomposite counterparts. We as well as others are currently investigating the design, synthesis and characterization of polymer-ceramic nanocomposites. Our effort, in particular, has focused on the use of mica-type silicates (MTS) with various thermoplastic and thermosetting matrices.2-5MTS's belong to the general family of 2: 1 layered silicates. Their crystal structure consists of layers of two silica tetrahedral sheets fused to an edge-shared octahedral sheet of either aluminum or magnesium hydroxide. Stacking of the layers leads to a regular van der Waals gap or interlayer.6 Isomorphic substitution within the layers generates negative charges that are counterbalanced by cations residing in the interlayers. Although the natural forms of MTS's usually contain hydrated Na+ or K+ ions, ion exchange reactions with organic cations (e.g. alkylammonium ions) can render the normally hydrophilic MTS's organophilic."

Jan 1, 1994

By Antoine Allanore, Luis A. Ortiz, Donald R. Sadoway

"The steelmaking industry has drastically reduced its energy consumption in the last fifty years, and today’s technologies are considered to operate at their optimal efficiency with respect to energy needs. To cope with new constraints related to greenhouse gas (GHG) emissions, a change of paradigm is necessary. One of the promising technologies that could be deployed to help reach CO2 mitigation targets relies on the intensive use of electricity: molten oxide electrolysis (MOE). This paper presents the key process parameters that need to be tuned to address the practical needs for both high productivity in a steelmaking reactor and for an energy efficient process. Herein we show that contrary to common perception, the electrolysis process for ironmaking requires less energy than today’s chemical reduction route. Furthermore, we prove that most of the energy that must be provided to operate the electrolytic iron production cell is thermal energy which is readily generated by joule heating during electrolysis due to large currents being passed through the electrolyte. The energy consumption of the electrolysis cell is therefore shown to be highly dependent on the cell configuration and the chemistry of the electrolyte. As a consequence, the CO2-impact of the technology strongly depends on both the power production mode and the technological choices for design of the process, including cell configuration. Surprisingly enough, even when the electricity generation is not carbon-free, MOE still appears to be viable from the perspective of reducing GHG emissions providing sound reactor design considerations are made.IntroductionIn the context of greenhouse gas (GHG) emissions mitigation, the steelmaking industry is considering several techniques that could sustain the efforts and progress achieved by this sector in the last decades [1]. A recent report [2] on potential routes for low-CO2 steelmaking highlighted for all techniques both the strong dependency of CO2 emissions on electric power production mode and the need for a decrease in energy consumption per tonne of steel. Incited to innovate with respect to this last criterion, the steel industry considers electrolysis to be a promising technological solution, and in particular the molten oxide electrolysis (MOE) process. This process conducts electrolysis in a mixture of oxides that dissolve the iron oxide feed, which by the action of electric current is decomposed into liquid iron and oxygen gas. The opportunity for reduction in energy consumption during steelmaking by MOE is commonly attributed to the “direct” pathway from iron oxide to liquid metal offered by the use of a molten oxide melt and operation at a temperature above the melting point of iron, ideally 1600°C, to provide enough superheat for tapping the molten iron product:"

Jan 1, 2011

By M. F. Hochella

Transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analysis have been used to study the mode of occurrence and mineral associations of gold in partially oxidized high grade gold ore from the Carlin sediment-hosted deposit. Rounded.gold particles have been observed that range in size from 0.03 to 0.1 p.m (300 to 1000 A) in diameter. The gold is associated with maghemite h-Fep3l and a K-Al-Si-bearing phase that is suspected to be illite. Detailed descriptions of gold and its mineral associations in 'Carlin-type' gold deposits are critical not only to understanding the mechanism of fluid transport and precipitation of gold, but also to developing improved metallurgical techniques for the recovery of gold from refractory ore. Direct observation of gold in unoxidized ore is rare due to its relatively high degree of dissemination and low average bulk concentration which averages 9 ppm according to Radtke (1). Hausen and Kerr (2) observed 1 to 5 p.m grains of gold directly in oxidized ore but these microscopically visible particles account for only a small percentage of gold present in the ore. The samples used in this study were selected from individual beds of high grade, partially oxidized ore (4.55 oz/ton or 156 ppm gold) that were collected in the Main pit of the Carlin mine. The samples were collected from several thinly laminated carbonate micrite beds within the top 50 meters of the Roberts Mountains Formation. The carbonate micrite has been altered by hydrothermal fluids to a calcite-absent, moderately silicified rock referred to as alteration zone #3 by Bakken and Einaudi (3). Based on petrographic and SEM studies, the samples contain carbonaceous matter, and both pyrite and iron oxide pseudomorphs after pyrite. The oxidation of pyrite may be a pro-duct of deep weathering, in which case limited remobilization of gold may have occurred. TEM sections of the rock were prepared by first embedding small chips in low viscosity epoxy. The epoxy blocks were cut with a Reichert Ultracut E ultramicrotome, producing thin sections less than 0.1 p.m thick. The sections were examined with a Phil-lips 400ST TEM at 120 keV in both imaging and selected area diffraction modes. Native golci*was easily detected in TEM bright field images due to the large electron density contrast between gold and all other phases that are present (Figs. 1 and 2), Gold was positively identified with high spatial resolution EDX analysis in the transmission electron microscope, although selected area diffraction of individual grains was not successful EDX analyses of the platy and massive minerals immediately surrounding the gold particles typically indicate the presence of Si, AI, K, and Fe, However, the d-spacings derived from selected area diffraction of these polycrystalline masses (as, for example, in Fig. 2) give an exact match for maghemite. As a result, there is no diffraction information to identify the K-AI-Si-bearing phase(s). The lack of a diffraction pattern could be due to either electron beam damage or to a poorly crystalline phase(s).

Jan 1, 1987

By Ma Ying

The continuous directional solidification technique of five kinds of special ZA alloys with eutectic, peritectic and eutectoid transfonnation under the condition of continuous casting by heated mold was studied. The mechanism of surface defects appearing in ZA alloy line was discussed and the structure of some defects were analyzed by SEM. The results show that only when the fitting of various technique factors, pressure head, outlet temperature, pulling speed and cooling condition are reasonable under a certain range, can the ZA alloy smooth line be continuously pulled out. Unreasonable techniques will result in hot tear, rough surface, mush outlet, leaking and other defects. The shape and location of solid-liquid zone have an important influence on the formation of the above defects. When the solid-liquid zone is located in the mould outlet or inner mould, the surface of solidification will protrude into the inner mould. If the remaining liquid cannot counteract the solidification contraction, a rough surface will appear. If the solidification surface further into the mould, the ingot in the mould will have a great friction force when pulling and will form a hot tear. When the solid-liquid zone is moved out of mould, the solidification surface will turn into a plane, which easily results in leaking. A vibration or unstable operation will cause an ingot winding during pulling.

Jan 1, 2003

By Nozomu Hasegawa

The phase diagrams and microstructures of the slags in the Mitsubishi Continuous Copper Smelting and Converting Process were studied for the prevention of the magnetite troubles such as accretion build-up on furnace hearths and launders, blockages at the melt outlet, slag viscosity increases and so on. According to the results of those studies, the silica and lime contents in the silicate slag at the smelting furnace, and the lime content in the lime-ferrite slag at the converting furnace were changed, resulting in lower and more consistent copper levels in the discard slag, with much less need for operators to clean melt outlets and launders. However, these changes may decrease the desirable amount of accretion-coating inside the furnaces and thereby reduce furnace campaign lives. Therefore, a method of estimating the magnetite level in the melts was developed, and slag compositions and temperatures have been controlled within the appropriate ranges to prolong furnace lives and also prevent magnetite troubles.

Jan 1, 2003

By Klaus-Markus Peters, Robert M. Cravens, James G. Hemrick

"Degradation of refractories in molten aluminum applications leads to energy inefficiencies, both in terms of increased energy consumption during use as well as due to frequent and premature production shutdowns. Therefore, the ability to enhance and extend the performance of refractory systems will improve the energy efficiency through out the service life. TCON_ ceramic composite materials are being produced via a collaboration between Fireline TCON, Inc. and Rex Materials Group. These materials were found to be extremely resistant to erosion and corrosion by molten aluminum alloys during an evaluation funded by the U.S. Department of Energy and it was concluded that they positively impact the performance of refractory systems. These findings were subsequently verified by field tests. Data will be presented on how TCON shapes are used to significantly improve the thermal management of molten aluminum contact applications and extend the performance of such refractory systems.IntroductionThe production of molten aluminum creates aggressive environments for processing equipment, thereby requiring refractory materials to contain the aluminum during melting, transfer, treatment, and casting operations. Degradation of these refractories not only causes issues with reduced product quality and production yields, but also increases heat losses as the insulative properties of the refractories are compromised. Furthermore, in addition to disrupting production output, refractory failures lead to further impacts upon energy efficiency as large amounts of energy are lost during the cooling and subsequent reheating of the equipment as the refractory linings are repaired or replaced.The need for improved refractory materials is recognized throughout the industry. A joint U.S. Department of Energy and industrial workshop held in 2000 on applications for advanced ceramics in aluminum production [1] noted that refractory materials used in melt processing equipment have many limitations. The workshop report noted that these issues may be addressed by using advanced ceramics, but new materials must be cost effective when compared to current refractory materials. Also, in 2005 the Canadian aluminum industry produced a technology roadmap [2] having the goal of identifying and bridging gaps between current technological resources in the industry and future requirements. One of the areas identified as being crucial to the future of the industry was the need for improved molten aluminum-resistant materials."

Jan 1, 2009