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By Jr. Napolitano, Jr. Sanders

"Morphological evolution of a dendritic growth front in a binary alloy is simulated using a cellular automaton approach to establish the feasibility of modeling such growth with a local rule-based scheme. The motivation for this work is derived from the need to predict the development of solidification structures within real components of complex geometry, where significant constraint of the thermal and solutal fields may exist. Such cases present complex boundaries and large domain sizes, which may preclude the effective use of more conventional methods. In this work, a model is presented which couples a two-dimensional alternate-direction-implicit finite-difference diffusion solution with a cellular automaton growth algorithm to simulate morphological evolution in alloys solidifying under directional growth conditions. Temperature, composition, and interface curvature are incorporated into a local growth potential which is used by the automaton, allowing the interface to evolve. Alloy solidification is simulated over a range of experimental conditions, producing various structures. Issues addressed include morphological instability, primary spacing selection, interface curvature, microsegregation, and tip conditions.IntroductionThe development of dendritic structure plays an essential role in alloy solidification. Virtually every microstructural feature, within a cast alloy component, is related to the interface morphology present during solidification. Conventional solidification theory, describing dendrite tip kinetics and mushy zone phenomena, provides a means for estimating overall microstructural parameters for an alloy solidified under steady-state conditions. Microstructural prediction for actual components, which are finite in size and complex in geometry, requires a description of the evolution of the interface morphology under transient conditions and geometrical constraint and an understanding of how the structure propagates through the mold. Any useful simulation tool must be equipped to handle these circumstances within the limits of computational feasibility."

Jan 1, 1998

By Kazuteru Tozcwa

The oxidation of several sulfide minerals in aqueous ammoniacal solution is discussed thermodynamically. The region in which Cu(NH3)2 4+ is stable has been estimated as a function of pH and concentration of total ammonia, {[NH3) + [NH4)}. In ammonia leaching when copper in sulfides is assumed to be extracted in the form of Cu(NH3)2 which will be rapidly converted to cupric ammine, thermodynamic data predict that such minerals are oxidized readily in the following order, CuS, Cu2S, CuFeS2, ZnS, NiS, Ag2S. This agrees with investigations on ammonia leaching of sulfide minerals, reported previously. The leaching of copper sulfide concentrate has been examined experimentally. Copper in a copper sulfide concentrate, in which the main constituents were chalcopyrite and pyrite, was effective¬ly extracted. The copper extraction was affected by factors such as (1) agitation intensity, (2) oxygen partial pressure, (3) NH3/Cu molar ratio, (4) leaching temperature and (5) addition of ammonium sulfate. From the results obtained in this work, it is concluded that mass transfer of oxygen plays the most important role in ammonia leaching of copper sulfide minerals.

Jan 1, 1976

By Gabriel Riveros

Fire refining of copper consists of two stages copper oxidation and copper reduction. Very frequently the capacity of the anode furnace is determined by the rate of copper reduction, The analysis of factors affecting the rate of the oxygen reduction from a liquid copper with solid carbon or injected hydrocarbons pointed out the role of the mass transfer in a liquid copper in final stage of the reduction. Experimental results of copper reduction with graphite and injected natural gas in laboratory-scale crucibles showed two stages of the reduction process with a sharp change of the controlling mechanism. The estimated dynamic surface area of gas bubbles based on the measured bubble frequency and the gas flowrate allowed for the determination of the reaction constant as a degree of the partial pre-combustion of the air/natural gas mix. The variation of the used reductant as a function of the oxygen concentration and temperature has been evaluated based on the determined kinetic model. The intensification of copper reduction in fire refining has been discusses on the basis of obtained kinetic data and analysis of various factors determining the time of reduction.

Jan 1, 2003

By G. A. Brooks, R. W. Matusewicz, Nazmul Huda

"A computational fluid dynamic (CFD) model of a conventional tuyere blown slag fuming furnace has been developed in Eulerian multiphase flow approach. The model was developed by coupling CFD with kinetics equations developed by Richards et al. for zinc fuming furnaces. The model integrates submerged coal combustion and chemical reactions with the heat, mass and momentum interfacial interaction between the phases in the system. The model predicts the velocity, temperature field of the molten slag bath, generated turbulence, vortex and coal utilization behavior from the slag bath. The highest coal penetration distance was found to be at l/L = 0.2, where / is the distance from the tuyere tip and L is the total length (2.44m) of the modeled furnace. The model also predicts that 10% of the injected coal bypasses the tuyere gas stream un-combusted and carried to the free surface, which contributes to ZnO reduction near the free surface.IntroductionSignificant metal values are often discarded with slag in the form of metal oxide produced by the smelting industries. These metal values can be recovered from the slag by proper treatment. Zinc slag fuming is such a process, where a reductant source (usually coal) is injected in the molten slag bath to reduce dissolved ZnO from the bath into metallic zinc vapour. The process can be carried out in either conventional tuyere blown furnace or top submerged lance (TSL) smelting furnace. Conventional slag fuming processes are carried out on batch basis in a rectangular tuyere blown furnace. Approximately 50 tonnes of charge (either molten slag or solid slag) is fed to the furnace at the beginning of each fuming cycle. Two opposing sets of submerged tuyeres are employed to inject air and pulverized coal into the molten slag bath to carry out combustion and reducing reactions."

Jan 1, 2012

By Michael Sheedy

Sulfuric acid is widely used as an electrolyte for the electrorefming and electrowinning or metals. Impurities in this electrolyte are controlled by continuously bleeding solution from the tank house. In addition to the contaminant these bleed streams contain high levels of sulfuric acid and the metal being recovered. Subsequent treatment of these bleed streams often requires neutralization which generates large volumes of solid waste. Absorption resin technology employing a novel ion exchange technique known as Recoflo® allows the separation of the mineral acid from dissolved metal salts. The recovered acid is suitable for recycle back to the electrolyte circuit. The metal salt and other contaminants leave the process free .of the sulfuric acid. In this process, known commercially as the APU®, ion exchange resin is used to sorb sulfuric acid while excluding the metal salts. The purified acid is then removed by washing the resin with water. The process has been extensively used for the recovery of waste pickling acids in the steel industry and anodizing solutions in the aluminum industry. In the mining and metallurgical industries the process has been successfully evaluated for the separation of excess sulfuric acid from copper electrolytes, the removal of magnesium and manganese contaminants from zinc electrolytes, and nickel and copper from copper electrolytes. A full scale installation on a copper refinery bleed stream at Palconbridge's Kidd Creek plant in Timmins, Ontario has now been operating successfully for more than 1 year while pilot field trials have been successfully completed on other applications.

Jan 1, 1997

By T. Kamata, S. Takemoto, H. Takeuchi, M. Takayanagi, Y. Akahori, I. Jimbo

"A cooperative research work on the silver recycling process is underway between Matsuda Sangyo Co., Ltd. and Tokai University in Japan. Silver wastes treated here are mainly from photograph industries where the concentration of minor element is steadily increasing in the recent years. The waste materials are concentrated and the impurities are removed by evaporation and slagging. In this paper, the industrial practice of wastes treatment is introduced and the result of the laboratory studies on the removal of antimony and tin from the binary and ternary alloys will be discussed. Characteristics in the behavior of antimony and tin during the process are also discussed with the observation of practical operation.1. IntroductionPrecious metals such as gold and silver primarily come from mining practice and the byproduct in copper smelting. However, the recycled amount of these precious metals have been increased 1 along with the environmental restriction and the widely accepted idea of saving resources on the earth in the recent years.· Though the recycle process of precious metals are comparatively simple from other metals refining, the process has been getting more complicated as wastes treatment has to deal with more impurity elements which are intentionally added to the products. Among these additives, antimony is used in the film materials in the photography industries to suppress its inflammability. Tin is another concern ,that is also coming from photography wastes; These minor elements have become problematic during the recycle.The removal of these minor elements has been in operation at Matsuda through a traditional oxidation refinement process using a reverberatory furnace. However, the complexity of the charge makes the recycle process more tedious and troublesome. In order to investigate the minor element behavior in the complicated materials system during the silver recycling processes, a cooperative research work is undertaken between Matsuda Sangyo Co., Ltd. and Takai University in Japan. Silver wastes treated here are mainly discharged from photograph industries where the minor element contents such as antimony, tin and bismuth in those wastes are steadily increasing in the recent years. The liquid wastes containing silver are concentrated and then treated pyrometallurgically with solid wastes from other sources, where the impurities are removed ·by evaporation and slagging. The purpose of this study is to investigate detailed behavior of impurity elements in the silver. containing systems."

Jan 1, 2000

By A. A. Hejja

"Liquidus temperature and electrical conductivity data measured on synthetic slags were modelled by the use of neural nets (NN). In this work the applied multilayer feedforward NNs were trained by a conjugate-gradient optimisation for which a three layer formulation was used. Very good fits were obtained for both the liquidus temperature and the conductivity data. The synthetic slags were prepared from pure oxides to represent a wide range of compositions likely to be encountered in ferromanganese and silicomanganese smelting. The slag constituents were in the following range: Mn0;5-30%, Ca0;20-35%, Mg0;5-15%, Si02;27-58%, Al20 3;5%. Liquidus temperatures varied from 1300° to 1380° and increased with increasing basicity ratio. The electrical resistivity of slags decreased with the increase of basicity ratio from 0.55 to 1.1 but above 1.1 basicity ratio the resistivity tended to increase depending upon the MnO content.Neural NetsVarious neural net (NN) topologies such as Hopfied nets, Hamming nets, Carpenter/Grossberg classifiers have been discussed in some detail by Lipmann (1). In this work, the applied multilayer feedforward NNs are not trained by backpropagation (BP) using the generalized delta rule (2) (GDR), but by a conjugate-gradient optimisation [3,4] - a procedure similar to that proposed by Barnard and Cole [5]. A neural net is capable ·of learning the non-linear functional relationship existing between a set of inputs and outputs [ 6]. In this capacity a neural net is used to determine the functional relationship that exists . between N dependent and independent variables, which characterize the system under consideration For a three layer neural net [1] the following function may be formulated, which relates X; inputs to the output Y 0 from node o:"

Jan 1, 1997

By Per Anders Eidem, Merete Tangstad, Jens Davidsen

"During excavations of submerged arc furnaces producing silicomanganese, silicon carbide (SiC) has been found. Contributing to the size of the inactive area of the furnace, the active area of the furnace where reactions occur will decrease, thus reducing the potential for pre-reduction in the furnace.This work studied the formation of SiC from the liquid-solid reaction between slag, metal, and metallurgical coke. Slags and metals with different levels of silica (S1O2) and silicon (Si) have been studied. The slag and metal has been heated together with coke, and the samples investigated by microprobe. The results show that SiC was formed on the coke particle through reactions with both slag and metal. For the metal, the carbon most likely diffused through the SiC to react with Si in the alloy. SiC formation with slag is likely to go through the reduction of Si02 to Si.IntroductionToday, Silicomanganese (SiMn) is produced in submerged arc furnaces (SAF) by reduction of S1O2 and manganese oxides, mainly with metallurgical cokes. Typically, the tapped metal has a silicon content of 17 - 20 wt.%. To achieve higher levels of Si, the metal can be refined by adding off-grade silicon metal, yielding low carbon SiMn. [1]. What is believed to be SiC that has been found during dig-outs of SiMn furnaces producing high silicon alloy. It is possible that excess amounts of SiC in the furnace cause operational problems, since SiC will occupy furnace volume. As SiC accumulates, the active volume of the furnace will decrease, increasing the flow of material and gas in the active areas of the furnace. Formation of SiC is inevitable, so it is desired to keep the formation as low as possible. To be able to control the formation of SiC, one has to understand the basic mechanisms."

Jan 1, 2012

By Takahiro Miki

Soldering material widely used is Sn-Pb alloy, which have low melting point and excellent electrical, strength properties and wettability. However, Pb is one of the toxic elements, which is undesirable due to environmental and safety reasons, thus Pb-free alternative alloy is preferred for new soldering materiaL Sn-Ag and Sn-Zn based alloys have been viewed as very promising candidates, among many potential substitutes. Addition of third element to these alloys will decrease melting point of the alloys. Hence, Sn-Ag-In and Sn-Zn-Mg alloys are expected to be suitable for replacing Sn-Pb solder alloy. In order to dcsign new Pb-free soldering materials, it is crucial to understand precise thermodynamic properties and phase diagrams of alloy systems. In the present work, ion current ratios of Ag to In and Mg to Zn were measured for Sn-Ag-In and Sn-Zn-Mg alloys by mass spectrometry, respectively. Also, the authors reviewed the thermodynamic properties of terminal binary alloys determined by other researchers and evaluated a thermodynamic functions to express the excess Gibbs free energy of each binary alloy. Thermodynamic functions to express the excess Gibbs free energy of liquid Sn-Ag-In and Sn-Zn-Mg ternary alloys were determined, utilizing the assessed Gibbs free energy of terminal binary alloys with the measured ion current ratios using mass speetrometer.

Jan 1, 2003

By Pertti Koukkari, Nagendra Tripathi, Karri Penttilä, Justin Salminen

A computational fluid dynamic model for a novel flash ironmaking process based on the direct gaseous reduction of iron oxide concentrates is presented. The model solves the threedimensional governing equations including both gas-phase and gas-solid reaction kinetics. The turbulence-chemistry interaction in the gas-phase is modeled by the eddy dissipation concept incorporating chemical kinetics. The particle cloud model is used to track the particle phase in a Lagrangian framework. A nucleation and growth kinetics rate expression is adopted to calculate the reduction rate of magnetite concentrate particles. Benchmark experiments reported in the literature for a nonreacting swirling gas jet and a nonpremixed hydrogen jet flame were simulated for validation. The model predictions showed good agreement with measurements in terms of gas velocity, gas temperature and species concentrations. The relevance of the computational model for the analysis of a bench reactor operation and the design of an industrialpilot plant is discussed.

Jan 1, 2014

By G. A. Brooks

Increasing interfacial area through gas injection is one of the main methods for accelerating reaction between slag, metals, and gases in modern pyrometallurgical reactors. In slag-metal reactors, the generation of a large number of metal droplets into the slag phase through high gas velocity has a much larger effect on the overall kinetics compared to the enhanced mass transfer through mixing. Top blowing technology generates large interfacial areas (>300 m2/tonne) through high impingement gas velocity at short distances between the exit of the injection lance and the metal-slag interface. Phase separation may become a limit at the case of very high interfacial areas, though there is still only limited understanding of the trajectories of metal droplets in slag-metal-gas emulsions.

Jan 1, 2003

By H. H. Law

Large amounts of waste material in the form of flue dust are generated in the operation of copper smelter furnaces. As a result of increasingly stringent disposal, it has become important to develop methods for treating such metallurgical wastes to extract metals and convert them into salable products. A two-step closed-loop hydrometallurgical process, has been developed: (1) extraction with sulfuric acid removes about 90% of zinc and decreases the dust volume by 50%; (2) extraction with hydrochloric acid dissolves the lead and further decrease the dust volume by 75%. A process scheme for generating salable products is proposed.

Jan 1, 1992

By D. Pradhan, R. G. Reddy

"Electrorefining of aluminum scrap was investigated from AlCl3 –1-Ethyl-3-methyl-imidazolium chloride (EMIC) (Molar ratio 1.65) chloroaluminate electrolyte using copper cathodes at temperature of 90±3°C and cell voltage of 1.5 V. The deposits were characterized using scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The study was focused to determine the effect of electrode surface modification as well as deposition time on dendritic depositions of aluminum. Their effect on current density was investigated also. It was shown that the surface modification of electrodes reduced the dendritic depositions of aluminum. Pure aluminum (>99%) was deposited for all experiments with the current efficiency of 94-97%. The use of ionic liquids not only reduced the energy consumption but also minimized pollutant emissions (CO, CO2 etc.) compared to the commercial high temperature aluminum production.1. IntroductionAluminum electrorefining/recycling from aluminum scrap using ionic liquid electrolyte is an attractive process today because of the unique chemical and physical properties such as wide temperature range for the liquid phase, high thermal stability, negligible vapor pressure, low melting point and wide electrochemical window. But in conventional practice, melting of aluminum scrap and high temperature molten salt electrolysis makes this process more expensive and less energy intensive (average 13 kWh/ kilogram of aluminum) [1] . Although recycling scrap aluminum requires only 5% of the energy used to make new aluminum [1-2], but the green house emissions like CO2, CO and HF have to be counted for environmental reason. Approximately, 5.31 kilogram of CO2 emitted per kilogram of aluminum production in most of the US industries."

Jan 1, 2009

A comprehensive numerical capability for the analysis of Thermal Spray (TS) systems consisting of a three-dimensional compressible, turbulent flow Navier-Stokes model and a multi-phase particle flow model in Lagrangian formulation, was developed. This capability is validated for a set of flow conditions typical for TS. The developed methodology is used for analysis of the JP-5000 TS gun gas and coating powder flow conditions. Modeling and analysis of particle/turbulent eddies interaction is performed. Details of gas flow field, particle temperature, and particle velocity histories, and particle temperature, velocity profiles in the system are presented. For the validation of numerical analysis, the computed results are compared with available experimental measurements. The flow phenomena for different flow parameters are analyzed and explained as the results of gas dynamics and heat and momentum transfer between the gas and particle phases. This methodology can be used for process control and reliability improvement, and has the potential to significantly improve TS gun performance through control of its parameters.

Jan 1, 1996

By John Demol

Monazite, a rare earth and thorium phosphate mineral, is one of the major minerals processed for extraction of rare earths. Industry practice for treating monazite concentrates is to use either a sulfuric acid bake or caustic conversion route. In the sulfuric acid bake, monazite concentrate is mixed with concentrated sulfuric acid and roasted. The rare earth phosphate mineral is converted to rare earth sulfate which dissolves in a subsequent water leach. As the bake temperature increases above 300 °C, thorium becomes less soluble. Although acid baking is practised in industry, the bake reactions are not well understood. A combination of chemical analysis, XRD and SEM-EDS was used to identify reaction processes occurring during sulfuric acid baking of a 93 wt% monazite concentrate between 200 °C and 800 °C. The effects of these reactions on the leachability of the rare earths, thorium and phosphate were also examined.

By Shabnam Sabah, Geoffrey Brooks

In oxygen steelmaking, splashing and droplet formation play a key role in the kinetics of the process. Though splashing has been studied by previous investigators, there is only limited understanding of how different cavity modes affect splashing. Therefore, a cold model study (at various lance heights and gas flow rates) has been carried out focusing on the issue of cavity modes and how it affects splashing phenomenon. Analysis using Fast Fourier Transform (FFT) was carried out on cavity oscillation that showed that frequency and amplitude of oscillation was highest in penetrating mode. Measurements of splashing over a range of conditions showed splashing greatly reduced when cavities went from splashing to penetrating mode. The results were validated and compared with plant data and previous model investigations.

Jan 1, 2014

By Leonid N. Shekhter, Corby G. Anderson, Esra Cankaya-Yalcin, Daniel G. Gribbin, Joseph D. Lessard, Larry F. McHugh

"A new process for smelting copper, Looping Sulfide Oxidation™ (LSO™) significantly and positively alters the smelting energy balance. This process uses copper oxide in conjunction with air for the desulfurization of copper and chalcopyrite concentrates. Copper oxide is regenerated in a flash type furnace and then ""looped"" back for the oxidation of the copper concentrate. Heat and material balances show that the Looping Sulfide Oxidation™ process requires significantly lower net energy than conventional technology. This process produces anode copper and higher S02 content off-gases for efficient formation of sulfuric acid. Additionally, the process yields slags with lower copper solubility as compared to the conventional technology.IntroductionBased on the positive results from LSO™ investigations [1], further lab investigations into co=on sulfides and metal oxides were performed. It was discovered that chalcopyrite (CuFeS2) is oxidized with copper (II) oxide. In this reaction over 98.5% of sulfur was removed as S02, while a significantly improved energy balance was observed. This paper intends to analyze both the conventional flash smelting process and the newly developed Looping Sulfide Oxidation™ process, comparing heat and material balance results. LSO™ yields improvements to the energy footprint for copper, opening the door to new copper processing opportunities."

Jan 1, 2013

By Damien Wagner

To reduce the emission of greenhouse gases by the steel industry, particularly for ironmaking, the production of DRI (Direct Reduced Iron) using hydrogen as the reducing gas instead of carbon monoxide is being considered. In this context, the reduction of pure hematite by hydrogen was studied at the laboratory scale, varying the experimental conditions and observing the rate and the course of the reaction. All the reduction experiments were performed in a thermobalance and supplementary characterization methods were used like scanning and transmission electron microscopy, X-ray diffraction, and Mössbauer spectrometry. The influence of rising temperature in the range 550-900°C is to accelerate the reaction; no slowing down was observed, contrary to some literature conclusions. A series of experiments consisted in interrupting the runs before complete conversion, thus enabling the characterization of partially reduced samples. Interpretation confirms the occurrence of three successive and rather separate reduction steps, through magnetite and wustite to iron, and illustrates a clear structural evolution of the samples. Finally, the influence of the sample type was revealed comparing a regular powder, a nanopowder and a sintered sample. The regular powder proved to be the most reactive despite its larger grain size, due to a more porous final structure.

Jan 1, 2006

By Zongshu Zou, Qiang Li, Mingming Li, Mingxia Feng

The impingement onto the surface of bath by top-blown jets is a significant process characteristic in BOF and EAF steelmaking process. The cavity is one of the most important outcomes of the interaction and plays an important role on reaction kinetics and reactors performance. But to date, the understanding to cavity is still so limited. In present study, a water model for a BOF converter is established and the dimension of cavity profile is investigated. The effects of lance height, gas flow rate, nozzle inclination angle and the amounts of slag are discussed. The results show that penetration depth increases with the increase of gas flow rate and the amount of slag, and the decrease of lance height and nozzle inclination angle. Furthermore, a theoretical model of cavity dimension is proposed for multiply jets impinging liquid bath on the basis of energy balance at the stagnation point of cavity.

Jan 1, 2015

By Thomas J. O'Keefe, Pu Yu, George Houlachi, Xuewen Tang

"Impedance measurements were used to investigate the electrochemical characteristics of acidic zinc sulphate electrolytes containing Sb3+, gelatin and their mixtures. The data were correlated with cyclic voltammetry curves made using synthetic as well as industrial electrolytes. The cyclic voltammetry results were similar to those obtained in previous studies in that antimony caused a depolarizing effect while gelatin gave an increase in the potential for zinc nucleation on an aluminum substrate.The electrochemical impedance spectroscopy (ElS) evaluations were conducted on electrodeposited zinc at three overpotential values. The potentials were chosen to represent various current density regions in the zinc polarization curves. The antimony and gelatin gave characteristic impedance plots which correlated with expected behavior, particularly current efficiency. Both antimony and glue appear to modify the intermediate zinc reaction sequence, but in different ways. The data strongly suggest that film formation and stability are major factors in the zinc ion reduction mechanism.IntroductionThe zinc electrodeposition process is sensitive to the presence of a variety of organic and inorganic chemical species in the electrolyte [I]. Such components can produce either beneficial or harmful effects, depending on their relative concentrations and electrochemical behavior. Extensive investigations have been made to gain a better understanding of the changes occurring during zinc deposition in the presence of such additives. Techniques employed include microscopy, x-ray diffraction, dynamic voitammetry, current imd energy efficiency studies [2-5]. Ultimately, the objectives are to identify the factors which most affect the efficiency of the process and to provide a means to effectively control them.One of the most harmful impurities is antimony, which can be detrimental when present at concentrations as low as 10 to 20 parts per billion. Dramatic changes in zinc polarization behavior, deposition structure and current efficiency have been observed with antimony in the electrolyte. Antimony appears to lower the hydrogen overpotential by hydride formation or a similar catalytic mechanism, which allows an increase in localized corrosion and zinc dissolution [6-8]."

Jan 1, 1997