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By George P. Demopoulos

In this paper the production and stability of crystalline scorodite (FeAsO4·2H2O) is discussed both on the basis of previously published work as well as recent work performed in our laboratory. The production of scorodite, especially from arsenic-rich and iron-deficient sulphate solutions offers a number of operational advantages such as high arsenic content, stoichiometriciron demand, and excellent dewatering characteristics. In addition to hydrothermal production of scorodite the work done over the last 10 years in our laboratory has determined that it is feasible to produce scorodite by step-wise lime neutralization at 90°C. The atmospheric scorodite possesses the same structural and solubility characteristics with the hydrothermally produced scorodite. Long term equilibration tests (up to 66 weeks) in the pH range 5 to 9 and temperatures from 22 °C to 75 °C revealed scorodite to undergo slow incongruent dissolutionyielding a highly metastable nano-sized 2-line ferrihydrite phase. The equilibrium arsenic concentration with this phase was 0.35, 0.96 and 5.87 mg/L at pH 5, 6, and 7 respectively at 22°C. In the presence of gypsum slightly lower concentrations were measured, this being more pronounced at pH>7. It was tentatively deduced that a Fe-Ca-AsO4 association (in the form of a phase resembling the mineral yukonite) contributes to the lowering of As concentration. Finally thermodynamic calculations determined that scorodite is stable in the presence of ferrihydriteunder oxic conditions up to pH 6.75 at 22 °C or higher pH at lower temperature and gypsum-saturated solutions. Keywords: Scorodite, Crystallization, Arsenic, Solubility, Stability, Precipitation, Disposal, Extraction, Processing, Metals, and Environment.

Jan 1, 2005

By Yunnen Chen

This work concerns the removal of zinc(II) and COD by means of sawdust obtained as a by-product from locally used wood. The zinc(II) and COD removal study has been carried out batchwise where the influence of physico-chemical key parameters such as tree species, pH value of solution, temperature and contacting time and dosage of adsorbent have been considered. The maximum percent removal was attained at pH 9 all for Zn(II) and COD after about 60 min. The adsorbent can be effectively desorption using 0.1 M HCl. The experimental results showed that ion exchange maybe the major adsorption mechanisms for binding the divalent metal ions to the sawdust. Sawdust was a potential adsorbent for the removal of Zn(II) from the effluent of electroplating industry.

Jan 1, 2009

By Kazuteru Tozawa

Surface tension, density and viscosity coefficient of acidic copper sulfate solutions simulating electrolyte solution for electrolytic production of copper have been measured and are summarized as a function of the solution composition and temperature. Nickel sulfatc is taken to be a representative coexisting sulfate that affects the physical properties of the copper sulfate electrolyte solution. The sulfates in the solutions, including sulfuric acid, increase the physical properties under consideration. Gelatin, representing organic additives for electrolyte solution, was found to sensitively affect the surface tension of the solution at low concentration of up to 200mgIL. The surface tension was markedly lowered by the addition of gelatin and the increasing concentration of gelatin led to a more pronounced decrease in the observed values. The surface tension gradually increases with time after addition of gelatin and the increase is enhanced by higher acid concentration and higher temperature. The observed change in the surface tension is considered to reflect the preferential adsorption of gelatin to the bubble-solution interface and the decomposition of gelatin due to hydrolysis to form various molecules having smaller molecular weights.

Jan 1, 2003

By Zdzislaw Miczkowski

At KGHM Polska Miedz S.A, a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass exchange inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed, The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ?The second zone moves slower into the grain and the rate of the movement is determined by the presence of oxygen, In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined, The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

By R. Hurman Eric

Within the Ag-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were re-established at 925°C by the equilibrium-quenching technique where samples were kept in evacuated and sealed silica capsules. Activities of Pb were measured by the dew-point method along the Ag-Pb binary at 925°C, 1100° and l200°C, positive deviations were observed and the results were modeled by the Krupkowski formalism. Activities of Ag, Pb, and S, along the ternary miscibility gap were calculated at 925°C by utilizing the boundaries binary thermodynamics, phase equilibria and tie-lines. Activities of PbS within the pseudobinary Ag2S-PbS mattes were also measured by the dew-point technique and the results were again modeled by the Krupkowski formation where negative deviations were observed.

Jan 1, 2003

By Chuanfu Zhang, Liwei Liang, Yanxin Wu, Jinliang Wang

"According to the reaction shaft operation characteristics during the flash smelting process, 15 groups of slag samples containing high Fe3O4 were prepared by some chemical reagents, and then the slag viscosities were measured using a RTW-10 type synthetic test instrument for melt physical property by the rotating cylinder method. The effects of Fe/SiO2 ratio (mFe/mSiO2), Fe3O4 content (wFe3O4), Cu2o), MgO content (WMgO) and Cao content (wCaO) on the slag viscosity were also studied. Results show that slag viscosity is decreased with the increase of temperature, mFe/mSiO2, wCu2o, wMgO and wCao, and with the decrease of wFe3O4, under the range of slag contents: mFe/mSiO2 1.36~1.78, wFe3O4 17.83%~21.18%, wCu2o 3.51%~8.34%m wNgI 2.21%~6.57%m w/caI 6.22%~9.387% and temperature range if 1250 o/c~1450 oC. Only wFe3O4m and w/caO have great influence on the slag viscosity when temperatures as high as 1400 oC. Only wFe3O4 and wCaO have great influence on the slag viscosity when temperatures as high as 1400 oC or so. To form a freeze slag with higher viscosity inside the reaction shaft, wFe3O4 should be more than 20% and wCaO should be less then 6%.IntroductionSince its appearance in 1949, Outokumpu flash smelting technology has making continuous innovation and has become the most competitive intensified smelting technology [1], widely considered to be the standard clean smelting process [2]. At present, flash smelting technology is adopted to newly build or reconstruct most of the world's copper or nickel smelting enterprise [3]. Reaction shaft is the most important part of the flash smelting furnace. During the flash smelting process, reaction shaft must be able to withstand the following harsh conditions at the same time: 1) high temperature varying from 1400 °C to 1500 °C. 2) strong oxidative atmosphere containing 50% - 80% oxygen. 3) solid particles and melt with speed up to l00 m/s. 4) high acidic or basic slag with strong chemical corrosiveness. 5) smelting gas containing 50% - 80% SO2. 6) matte with strong dissolution."

Jan 1, 2012

By R. Hurman Eric

Within the Ag-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were re-established at 925°C by the equilibrium-quenching technique where samples were kept in evacuated and sealed silica capsules. Activities of Pb were measured by the dew-point method along the Ag-Pb binary at 925°C, 1100° and 1200°C. positive deviations were observed and the results were modeled by the Krupkowski formalism. Activities of Ag, Pb, and S, along the ternary miscibility gap were calculated at 925°C by utilizing the boundaries binary thermodynamics, phase equilibria and tie-lines. Activities of PbS within the pseudobinary Ag2S-PbS mattes were also measured by the dew-point technique and the results were again modeled by the Krupkowski formation Where negative deviations were observed.

Jan 1, 2003

By K. Narayan Prabhu, W. D. Griffiths

"Heat transfer during the unidirectional solidification of a cast iron alloy against cast iron chills was investigated using an inverse modelling approach. Chills of thickness 100 mm and 10 mm were used, to simulate gravity die cruiting conditions and the use of chills in sand moulds. In both cases transient heat transfer, measured by the interfacial heat flux and heat transfer coeffieient; declined from initially high values in the first few seconds of solidification, to values about an order of magnitude lower which persisted for the remainder of the experiments. In the case of the thin chill it became saturated with heat until it was no longer in a position to extract further heat from ·the casting. These results were interpreted by studying the resistance to heat transfer from the casting offered by the ·casting-chill interface and the chill itself for example, the thermal resistance of the casting-chill interface can be influenced by the deformation of their respective surfaces and their subsequent relationship.IntroductionDie casting cast iron offers several advantages such as energy savings, higher mould yield, and better surface quality over the sand casting process1 • The process is· environmentally' friendly because of the elimination of the sand. However the design and construction of metallic moulds is expensive and a faulty die design may result in a defective casting: A simulation based process design of die castings would enable die designers and solidification modellings to try better designs of dies on the computer and arrive at a cost effective solution more quickly. This has numerous benefits for the die caster, as he would be able to produce sound castings with very short lead times.The success of a solidification model to predict accurately the thermal history and the location of hot, spots inside a solidifying casting depends to a large extent on the heat transfer data prescribed at the metal/mould interface. Many measurements of the heat transfer coeffident (or the heat flux) between a solidifying aluminum alloy and a chill have shown that the heat transfer coefficient is a function of most of the variables of the casting process2 - 8. However heat transfer studies during the solidification of ferrous alloys are rather limited. The high temperatures involved suggest that the contribution due to radiation heat transfer cannot be neglected."

Jan 1, 2000

By Wu Liu

A modified falling ball technique for measuring the viscosity of liquids is described. It consists of recording the weight vs. time of a crucible holding the liquid of unknown viscosity, as a solid ball, or liquid drop, is let to fall through the liquid. This method does not require measurements at constant terminal velocity, as the conventional falling ball technique. Also, measurements do not depend on visual observation, which is not possible in opaque liquids or containers. The effect of process parameters on the utility of this method and its potential application to liquid systems of metallurgical interest were analyzed theoretically. The paper also com- pares the gravimetric method to the conventional falling ball technique for measuring viscosity.

Jan 1, 1992

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 Robert E. Brown

Magnesium recycling has been used to recover both new scrap and old scrap. It was used extensively in Germany during WWII to expand the magnesium supply. There were a large number of magnesium recyclers in the US who got their start smelting old scrap, old airplanes and old waste dumps from the WWII build up. As the world magnesium industry dwindled, only a few companies were left that did magnesium recycling as a primary business. The sand foundries tended to recycle of their production scrap in their melting furnaces. Even the original die casters tended to put scrap directly back into melting furnaces at the die casting machines. As high purity alloys were developed and the use of die castings in automotive work increased, the tendency was to let the magnesium recyclers convert the scrap back to high quality ingot. Automotive use has grown because of the low density of magnesium. This property is the one of the biggest problems to overcome in shipping scrap. Gates and runners from die casting are very irregular shapes and it is very hard to load a truck with enough material to get a low shipping cost per pound. Recent new equipment companies have developed magnesium equipment that is specifically designed to recycle, refine and cast secondary magnesium metal. These melt cells are supplied as integrated units to magnesium casting sites. The cost and effectiveness of this approach will be discussed.

Jan 1, 2000

By Masaru Imaizumi, Hiroyuki Nomura, Mitsuharu Takita

"Cast iron possesses many superior characteristics caused from precipitated graphite structure, for example, castability, wear resistance, solid lubrication, damping capacity. But the more graphite hyper-eutectic cast iron contains, the lower its mechanical strength becomes, because graphite gives a negative effect to strength of cast iron. In addition, primary graphite tends to segregate during solidification, so uniform materials are difficult to be produced.In this study, authors introduced semi-solid processing in developing new and high quality cast iron. A series of semi-solid processing experiments were carried out to clarify the effect of stirring condition; solidification temperature and etc. on microstructures and characteristics of cast iron. In particular much attention is paid to the appearance of ternary eutectic zone at the final stage of solidification. As the results advanced hyper-eutectic cast iron was obtained with high quality of both the mechanical strength and wear resistance. As for the mechanical strength, 300MPa and 0.60% are obtained as the tensile strength and the elongation values, respectively, under the controlled stirring condition. This indicates that semi-solid processed hyper-eutectic cast iron is used prospectively without spheroidization.IntroductionCast iron has various good properties such as wear resistance, solid lubrication, damping capacity and machinability. The characteristics of cast iron are mainly decided by graphite structure, namely graphite shape and its distribution in the matrix. Mechanical strength of cast iron is large in the case of small quantity of graphite particles which are precipitated uniformly, however, it becomes small in the case of large quantity of graphite precipitated flakily."

Jan 1, 2000

By J. Jakumelt

The coupled simulation of mold filling and solidification for an investment casting process presents difficult. This is due to the complexity of the carious physical process and the geometry, To achieve this task in a precise way, the CFD program FLUENT and the casting simulation tool CASTS were closely coupled. Any physical quantity, such as velocities or temperatures, can be exchanged via files after each time step of the simulation. The communication and operating sequence of the programs is controlled by PERL-scripts. This enables the expertise of FLU ENT for flow simulation and the strength of CASTS, for casting simulation to be combined. The coupled simulation was successful applied to an aerospace investment casting. Several physical models were tested for correct treatment of the casting filters, the porosity of the mold and the viscosity of the liquid metal. The results demonstrate that even complex investment casting geometries can be investigated using CASTS-FLUENT.

Jan 1, 2003

By Zhihong Liu

Monodisperse micron size nickel oxalate particles with rhombohedron morphology were prepared from condensed Ni(OH)2 suspension by a novel gel-sol process proposed by one of the authors. Firstly, condensed nickel hydroxide gel was formed by fast adding 1 mol dm-3 NaOH solution into 0.2 mol dm-3 nickel chloride solution, and then oxalic acid solution with a concentration of 0.25 mol dm-3 was dropped into the gel drop wise through a pump equiped with a pH controller under preset pH value, and in this process, Ni(OH)2 gel was converted gradually into monodisperse nickel oxalate sol. The formation of the nickel oxalate particles was found to proceed through a dissolution-recrystallization mechanism from the nickel hydroxide gel. The product particles exhibited rhombohedron like shape with micron size long axis and sub-micron size short axis. The effects of such factors, as temperature, surfactants, et al, were evaluated experimentally on the particles sizes and morphologies.

Jan 1, 2006

By Y. Pokhvisnev, S. Vandariev, A. Yatshenko-Juk, V. Valavin, V. Romenets

The technology of the liquid-phase reduction process known as Romelt was developed in the Moscow Institute of Steel and Alloys in 1979. The pilot plant was constructed at the Novolipetsky Steel Works (Russia) in 1984. Investigations into processing zinc-containing blast oxygen furnace dust and slag from the Lead and Zinc Works at the pilot Romelt plant proved the perspective of using this technology for processing zinc and lead-containing materials. In this article, the description of Romelt technology, basic technological information of trials at the Romelt plant using zinc-containing materials, compositions of charging materials, metal, slag, gas and dust are presented. The influence of flue gas composition on the composition of zinccontaining dust is shown.

Jan 1, 2000

By M. Fujikawa, S. Goto, M. Nishikawa

"The semi-pilot scale plant for injection smelting of zinc calcine was operated under the committee of Joint Research Organization of Injection Metallurgy. The capacity of the plant is 10 ton metallic zinc per day. The plant was designed by the resul ts of basic and bench scale tests of the capacity of 1 ton metallic zinc per day which was published at ""Zinc '85"". The equipments of the plants, operational conditions, results of the operation such as recovery of zinc in injection furnace and condenser, combustion rate of powdered coke and consumption of energy in this process are presented in this paper. The results of the study of the feasibility of the commercial plant of 100,000 ton zinc per year by the injection smelting are also discussed in the paper. IntroductionThe research committee of new smelting process of zinc by injection was established in 1981 under the finantial support of Mining Promoting Foundation of Japan. Six zinc producing companies joined in this organization. The price of zinc was very low at that time and the energy cost, especially, cost of electric power in Japan was extremely high. Invention of a new economical process for zinc extraction had been stronglydesired. The author proposed a injection smelting of zinc as a economical process in energy saving after a calculation of thermodynamical equilibrium and heat balance(1 )(2).The research committee has been studying the injection process since 1981. The small basic experiment by using a crucible furnace was carried out from October 1981 to March 1983 and the reaction of reduction of calcine by injection smelting was ascertained (2). Vaporizatipon of zinc and behaviours of impurities were examined. After the basic experiment, the bench scale test with the production capacity of zinc of 1 ton per day was carried on from November 1983 to October 1984.The bench scale tests were carried out to obtain the proper design of feeding devices of calcines and coke into a furnace and also to obtain fundamental data for enlargement of this smelting process(3,4). The recovery of metallic zinc in this small equipments was about 50% and main loss of zinc was formation of dross in the condenser."

Jan 1, 1988

By Y. K. Rao

Relatively pure crystalline lead sulfate (PbSO4) can be produced by chemical vapor transport from an impure source such as the lead-acid battery paste or the roast-ore-leach-residue from a hy¬drometallurgical process-route. In a closed-reactor, transport of matter is induced by a tempera¬ture-gradient and the steady-state transfer rate can be calculated using the data on the standard free energies of formation for the species present and the pertinent binary diffusion coefficients. The present work focusses on chemical vapor transport in a tubular reactor (1.4-cm inner diameter x 10-cm long) with the source- and deposition-ends held at 850°C (T,) and 750°C (Td), respectively; PbC12(g) is the 'solvent' or 'transport agent' and NiSO4(s) placed in the source-zone -serves to maintain a sufficiently high S0,-potential such that the stability of the lead sulfate species is ensured. For the purposes of analysis, the gas-phase in the reactor is assumed to consist of eight species: H2O, PbC12, SO3, SO2. O2 HO, C12, and PbC14. The reaction between C12(g) and PbSO4(s) in the high-temperature source-zone produces PbCl2, SO2, and 02; four more reaction-equilibria in the same zone yield other species. In the low-temperature deposition-zone, reaction equilibrium involving PbC12, H2O, and SO, leads to the nucleation and growth of PbSO4 crystals; three other reaction-equilibria occur in this zone. By employing the virtual equilibrium state for the end-zones and coupling it to the Stefan-Maxwell diffusion equations for each of the gas species, the respective partial pressures for these, in the source- and deposition-zones, are computed at steady-state. From these data, the molar fluxes of PbCl2. PbCl4, and so forth, are determined. Allowing for the transport-enhancing effects of thermal convection, the net transport rate of lead (or PbSO4) is duly calculated for specified initial conditions. The predicted rates show very good agreement with measured rate data reported in the literature [ V. Plies, T. Kohlmann and R. Gruehn: Z. anorg. allg. Chem, 568, 62 (1989)

Jan 1, 1995

By Zhao-feng Xie

A new process of recycling valuable metals containing in the slag of jamesonite smelting in the blast furnace was studied. In this process, the valuable metals such as Pb, Sb, Zn and In etc. were fumed and volatilized and enriched in the dust firstly and then the dust was leached by sulfuric acid. In the leaching procedure, Zn and In in the dust entered into the leaching solution and were separated from Pb and Sb which remained in the residue.The optimal operation conditions of the fuming procedure are as follows: the mass ratio of the blast furnace slag, coal powder and lime are 100:22:10 respectively and the fuming time are 1.5~2.5 h, the fuming temperature is not below 1200C and the volatilization rates of Pb, Sb, Zn and In are 95%, 92%, 86% and 75% respectively. The optimal conditions for the leaching procedure are also presented: the consumption of sulfuric acid is 1.15 times of the theoretical consumption, the ratio of liquid to solid is 4:1 and the leaching temperature, leaching -1time and stirring speed are 90, 1.5h and 300 r?min separately. The leaching rates of Zn and In are 98.5% and 95.2% respectively. The experimental results shows that the valuable metals in the dust can be recovered and separated effectively by this process and the?ir recovery efficiencies are as follows: Pb94%,Sb91%, Zn84% and In69%.

Jan 1, 2009

By Jason M. Porter, Douglas L. Porter, David L. Olson, Travis W. Koenig, Van S. Blackwood, Brajendra Mishra, Robert D. Mariani

"Traditional alloy theory models have been applied relative to the three solid phases of uranium: alpha (orthorhombic), beta (tetragonal), and mainly gamma (body centered cubic)[l]. The Darken-Gurry and Miedema models, with modifications based on concepts of Waber, Gschneidner, and Brewer have been used to predict the behavior of four types of solutes: 1) Transition associated with alloying in and containment of the uranium fuel 2) Transuranic elements in the uranium 3) Rare earth fragmentation elements (lanthanides) 4) Transition metals and other fragmentation elements. Using these solute map criteria, elemental behavior have been predicted as highly soluble, marginally soluble, or immiscible (intermetallic phase formers) and have been used to compare solute effects during uranium phase transformations. The overlapping of these solute maps are convenient first approximation tools for predicting alloy behavior.IntroductionAn investigation is in progress to determine the role of various solute elements on size and shape of the 'Y phase field range for uranium to optimize the burning and material processing of nuclear fuel is in progress. Traditional alloy theory models based on correlations to elemental electronic and crystal properties are used to predict solubility and micro structural formation. The effectiveness of this model is based on microstructure property correlations. Darken and Gurry, and Miedema models, with modifications based on concepts of Waber, Gschneidner, and Brewer, models have been used to describe solute solubility with respect to uranium based the on correlation between elemental electronic structure and uranium phases. The alpha (orthorhombic), beta (tetragonal), and gamma (body centered cubic) phases have different solubilities for specific alloy additions as a function of temperature. Using the method of Waber, ellipse diagrams classified those solutes that should have broad solubility in the allotropes of uranium[2]. The predictive diagrams are made from four different correlations:"

Jan 1, 2012

By Qiang Yu

This paper reports on a research project supported by NSF, which aims at developing a multi-scale methodology for systematic microstructure prediction in thermo-mechanical processing of metals. This methodology is based on combining mesoscopic microstructure models with macroscopic process formulations and involves the following three main steps: (I) based on the given global processing conditions, the gross deformation patternof the entire workpiece is modeled using a continuum-based algorithm, (2) the resulting parameters are then extracted from the continuum-based simulation, post-processed and passed on to the mesoscopic numerical module, and (3) the microstructural changes are finally modeled at the mesoscopic scale. This approach is expected to overcome the disadvantages of current microstructure prediction practice employing empirical relationships between microstructural features and processing parameters. Keywords: Thermo-mechanical processing, Microstructure, Grain growth; Recrystallization; Mesoscopic models; Finite Element Method

Jan 1, 2003