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By Mieke Campforts

The usefulness of the water-cooled probe technique to experimentally study slag solidification and freeze lining formation in pyrometallurgical reactors is evaluated. With this technique a layer of solidified slag is formed on a water-cooled probe that is submerged into a liquid slag bath. The influence of the submergence time and the heat input is examined. The solidified layers are analyzed with light microscopy, electron microscopy, electron probe micro-analysis and X-ray diffraction. Thermodynamic software is used to interpret the solidification microstructure. The results demonstrate that the technique is useful to understand freeze lining formation.

Jan 1, 2006

By Darryl Lovato, Ramiro Pereyra, Daniel S. Schwartz

"During an annual inventory of nuclear material, a plated steel container which contained plutonium oxide failed. The container had been packaged for temporary storage but had been overlooked and remained in storage for more than 23 years. Although it was determined that the failure occurred through the slip-top rim, a metallurgical evaluation was requested to help to determine the integrity of the container.Optical metallography and scanning electron microscopy were used to analyze the character and degree of corrosion in the container. The depth of corrosion, measured at approximately 10 µm, did not pose a threat to the integrity of the container. However, the corrosion morphology and chemistry did suggest that a galvanic cell had developed between the tin and steel from the condensation of water. The morphology also suggests that the attack of the steel took place over a series of cycles due to changes of the environment.IntroductionMetallographic analysis was requested as part of the investigation into the mechanism of the failure of a slip-top container (#38621) containing plutonium oxide (PuO2) powder. The container had leaked during a special nuclear material (SNM) annual inventory causing contamination and closure of the vault. A photograph of the container and interior container is shown on the right in Figure 1. An initial investigation established that the source of contamination was the consequence of the failure of multiple layers of containment. Initially by the deterioration of the interior plastic bottle and polyvinyl chloride (PVC) bagout bag, and finally through the lid and steel container interface at a location where tape had not adhered properly [1]. Although the source of the breach was established, it was determined that metallographic analysis was important to establish the extent of deterioration of the steel container."

Jan 1, 2008

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 Lamar S. Todd

The direct production of metal from a sphalerite concentrate is an attractive route for primary zinc. A series of operations and conditions have been selected to efficiently cause the following overall exothermic reaction. The process uses a continuous circulation of molten copper for material and energy transfer between the unit operations. Sulfide concentrate is reduced with an excess of superheated copper to make a copper alloy and white metal. The alloy is stripped of volatile metals under vacuum and some metals can be separately condensed. The residual copper and the white metal are fed into a copper converter to be blown with oxygen for desulfurizing and the superheated copper is recycled. The paper will include a detailed material flow sheet for the process, discussion of the operating conditions of the individual units, behavior of minor elements, and zinc quality.

Jan 1, 1999

By Hideki Yarnarnoto

The simultaneous removal for NH4+ and PO43- in aqueous solution was carried out by using Ca type zeolite synthesized from coal fly ash. The effect of pH on the cation exchange capacity and adsorption properties of the obtained zeolite, the simultaneous removal of NH4' and ~04'. in various solutions and the mechanism of simultaneous removal were investigated respectivel? ,The Ca type zeolite used in this study can simultaneously remove NH4+ and PO43- In aqueous solution without releasing counter ion, and this method gives great advantage over the other ordinary removal methods.

Jan 1, 2002

By Vadim J. Jabotinski

Electron beam processing is potentially very attractive for the high temperature treatment of hazardous materials. The very high power efficiency of the electron beam energy source (80- 90% of the power from the electric power line is converted to useable energy) is one of the positive features of this technique. This paper will consider advanced electron beam concepts for solid, liquid, and gaseous waste treatment such as stabilization of radioactive solid and liquid hazardous streams. Fundamental aspects and applications including an analysis of the economic potential of electron beam processing of waste treatment will be presented.

Jan 1, 2000

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 detennination 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 detennined 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 detennining the time of reduction.

Jan 1, 2003

By D. P. Cook, Jr. Jones, J. W. Evans

"It is well understood that the flow of liquid metal in the mold region of the caster can have a notable effect on the overall solidification behavior in aluminum casting. Previously our group has characterized the flow in this region in a water model, using particle imaging velocimetry. The flow is significantly effected by the specifics of the metal delivery system, i.e. size, geometry, used during the cast. Recently, a time-averaged 3D numerical model of the nozzle, combo bag and sump region has been developed and its validity has been tested against experimental data. Cases were run for different sized combo bags as well as bags that have been blocked. The results show satisfactory agreement between the physical and mathematical models.IntroductionFluid flow in the head of an electromagnetic (EM) and direct chill (DC) ingots has been shown to effect many important operational parameters in casting such as superheat removal, macrosegregation, and hot cracking. In most cases, the momentum from the nozzle is diverted through a delivery system, termed a bag, before entering the mold region. The specific geometries of the bags vary widely from operator to operator suggesting that there is still some question as to the optimum design. Several studies [1-4] have been carried out to understand the influence of the bag design on the solidification behavior in aluminum casters. However, few studies have included numerical prediction with experimental verification. Unfortunately, many simulations performed today still do not accurately account for flow in such devices.Recently, a significant amount of research into the flow resulting from the metal delivery systems has been performed [5-8]. The thrust of this research has been characterizing the flow patterns by a measurement technique called particle imaging velocimetry. The data suggest that the method of delivering the liquid metal into the mold region has a significant effect on the nature of the flow. With a detailed set of quantitative data from a water model, a numerical model can be built and tested to ensure a proper description of the flow field. The computational model used in these simulations is designed to represent a laboratory scale model of a caster in which ""combo"" bags were simulated. Such bags are mostly of a densely woven glass fiber material with low permeability to aluminum. ""Windows"", of a more open weave, permit aluminum to flow from the bag, see Fig. I. Two different sized combo bags were modeled, each subject to two different outflow window configurations. Furthermore, experimental measurements [9] were used to validate the model results."

Jan 1, 1999

By J. M. D. Wilson

An analytical program using a combination of SEM-based image analysis techniques is developed for automated modal analysis of ores containing silicate and other gangue minerals. Previous knowledge, gathered by means of either optical microscopy, X-ray diffraction, SEM, or electron microprobe analysis is used to establish discrimination criteria in the image analysis program. The program initially discriminates minerals on the basis of their relative grey values in a backscattered electron image. For those minerals which have overlapping grey levels the minerals are identified by the program using energy dispersive X-ray spectrometry with X-ray counting for twelve or more elements. This technique is useful to quantify ores in which the gangue minerals are numerous. Two cases of application are presented.

Jan 1, 1999

By Gervais Soucy, François Quesnel, Pierre Hovington, Wen Zhu, Karim Zaghib, Jocelyn Veilleux

The properties of lithium titanates anodes in Li-ion batteries are highly dependent on their secondary constituents. While their main phase is usually constituted of Li4Ti5O12, significant quantity of lithium titanates compounds of various stoichiometry are often present, due to either the processing, usage or aging of the material. These may go underreported, as many of these spectrums overlap or display low signal in X-ray diffraction (XRD). Samples of nanosized lithium titanates synthetized by inductive plasma were characterized by XRD and scanning electron microscopy (SEM), as they provide a regular yet typical crystallite size and shape including multiple phases. A Rietveld refinement was developed to extract the composition of these samples. Mass balance through further annealing and differential scanning calorimetry (DSC) enthalpy measurements from phase transformations were also used as identification and validation techniques.

Jan 1, 2015

By Norihiko Fukatsu

In order to use effectively the previously reported new sensing system for hydrogen and oxygen potentials in molten copper, the criteria of the potentials for getting sound castings have been determined in the laboratory experiment. The copper melt equilibrated with a given hydrogen and an oxygen potential was rapidly quenched in the crucible. The relations between the holding potentials and the gas porosity in the solidified sample were investigated by measuring the density of the sample and microscopic observations. It was found that the defects of the gas porosity became the maximum at the potentials where the dissolved amount of hydrogen and oxygen was in the mole ratio 2:1. The samples having the density more than 99% of the theoretieal value were obtained in the higher oxygen and lower hydrogen potential region or in the lower oxygen and higher hydrogen potential region. The criteria thus determined were examined by comparing with the measured potentials in the practical casting machine. In tough-pitch copper casting, the problem due to gas porosity was found to be serious when the hydrogen potential increased. In the. oxygen-free copper casting, the evolution of hydrogen was found not avoided. The gas porosity in the casting, however, was found eliminated when the oxygen potential was kept at a low value.

Jan 1, 2003

By M. B. Mesina

Mechanical separation systems are widely used nowadays for scrap metal processing, but they have natural limitations in product quality. The quality of the final product is considerably improved when sensors are used in the separation process. This paper describes new methods using sensors for scrap metal sorting and quality control. An example is the electromagnetic sensor, which uses the electrical and magnetic properties of materials to distinguish between different non-ferrous metals. The measurement results of two prototypes are reported. The benefits and the possibility to integrate such systems into practical applications regarding the processing of secondary raw materials are also described.

Jan 1, 2003

By Baicheng Liu, Houfa Shen, Wensheng Li

"In order to understand the formation of macrosegregation in steel ingots, a mixture model has been developed which accounts for coupled mass, momentum, species, and energy transport to describe the sedimentation of free equiaxed grains during solidification. In this model, the mushy zone is divided into the slurry and porous regimes according to a solid packing fraction. Settling velocity of equiaxed grains in the slurry regime is given by an explicit expression. The solidification of a binary steel ingot (Fe-0.36wt.%C) with a two-dimensional geometry is numerically simulated. It is demonstrated that the predicted macrosegregation patterns agree to some extent with classical experimental results. Further refinement of this model is still necessary for realistically simulating steel ingot solidification.IntroductionModeling macrosegregation in steel ingots is still a challenging study, mainly due to the length scale of the products and the complexity of global multiphase transport phenomena coupled with microscopic solidification kinetics [l]. The thermal-solutal convection and the motion of equiaxed grains are the two main mechanisms responsible for macrosegregation. But there are few models that deal with the motion of equiaxed grains, which is confirmed as the main phenomenon that explains the negative macrosegregation along the centerline of large steel ingots [2]. A model which takes into account melt convection and grain sedimentation was first proposed by Beckermann and co-workers ([3], and references therein). More recently, similar multiphase solidification models with advanced nature have been presented by Wu and Ludwig [1,4] and Combeau and co-workers [5,6]. It is known that the application of these sophisticated models to steel ingot casting is at its beginning.In this paper, a solidification model based on continuum mixture approach, using much less sophisticated relations to obtain the settling velocity of free equiaxed grains, has been proposed in order to predict the macrosegregation in steel ingots. The model is applied to simulate the solidification of a binary steel ingot with a two-dimensional geometry, and preliminary modeling results are presented."

Jan 1, 2011

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (Mf'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By Mao Chen, Baojun Zhao, Zhixiang Cui, Leonel Contreras

Viscosity is one of the important physiochemical properties of metallurgical slags which is important for slag tapping, metal loss in slag, freeze lining and fluid dynamics. High temperature viscosity measurements are time- and cost-consuming and the number of experiments is limited. Viscosity model is an effective way to predict the viscosities of the complex slags at high temperature. However, a reliable viscosity model can only be developed on the base of accurate experimental data. A unique high-temperature viscosity measurement apparatus developed at The University of Queensland enabled accurate viscosity data to be measured for the “FeO”-SiO2-CaO-MgO-Al2O3 system in equilibrium with Fe. An accurate viscosity model has been developed based on Eyring’s theory and extensive viscosity measurements. The viscosities of copper smelting, converting and cleaning slags over a wide range of compositions and temperatures can be predicted and applied in the process control.

Jan 1, 2016

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly. subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fumeless fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003

By P. Halsall

Smelters of medium or low grade tin concentrates must recover a high proportion of tin from iron-bearing slags or concentrates; the volatility of tin sulphide makes possible the production of iron-free tin fume. Laboratory work defined conditions which would promote the sulphidisation of tin slags and concentrates melted with them, to result in tin recovery as fume, and a residue of less than 0.5% Sn content, which could be controlled to vary with the value of tin. Subsequently pilot-plant work on 6-tonne and 15-tonne scale led to a commercial plant of 45 tonne. capacity (1962), for melting and fuming primary and secondary low-grade tin materials by submerged combustion. Some factors contributing to the rate of Working expressed in terms of the 'half-life and the amount of work done, the 'half-life-tonne' are studied, leading to the design and operation (1972) of the 100-tonne water-jacketed unit, presently in use, treating a wide range of slags and low tin-content ores and residues.

Jan 1, 1983

By Stig Petersson

Slag from the converting of copper matte is usually recirculated to the smelting furnace. This recirculation generally causes disadvantages as magnetite-build-up in the furnace, accumalation of impurities as antimony, lead, nickel etc in the process. The treatment of converter slag in a separate furnace in order to recover the copper and nickel content would be of advantage from several points of view. At the Mining and Metals Division, Boliden, testwork has been carried out to treat converter slag from the PS-converters in a separate furnace. The tests have been performed in laboratory and pilot plant scale. The pilot plant tests have been carried out in a TBRC with charges of 5 tons. Based on these tests a full scale TBRC has been projected in order to treat the slag from the PS-converters. This slag will be reduced with copper concentrates to give a matte and a final slag low in copper and nickel. The background and data from the testwork are presented. Also the lay out, technical data and flowsheets for the projected process are shown as well as some production data from the Rönnskär smelter.

Jan 1, 1976

By P. K. Jimack, C. E. Goodyer, A. M. Mullis, P. C. Bollada

"We review the application of advanced numerical techniques such as adaptive mesh refmement, implicit time-stepping, multigrid solvers and massively parallel implementations as a route to obtaining solutions to the 3-dimensional phase-field problem with a domain size and interface resolution previously possible only in 2-dimensions. Using such techniques it is shown that such models are tractable even as the interface width approaches the solute capillary length.IntroductionMulti-scale modelling impinges upon many areas of science, engineering and technology where the interplay between processes occurring on disparate length and/or timescales can affect the properties of systems in a complex, and sometimes unforeseen, manner. One such is the processing of materials where interactions at the atomic scale, through the nano- and microstructural scale can have a profound affect on the macro-scale response of engineering components. Here we focus on one such problem, the crystallisation of alloy melts, to illustrate how a range of advanced numerical techniques make the modelling of such systems tractable.The modelling of solidification structures, in particular the growth of dendritic crystals, is a subject of intense and enduring interest within the scientific community, both because dendrites are a prime example of spontaneous pattern formation and they have a pervasive influence on the engineering properties of metals. For alloy systems, which form the vast majority of engineering materials, solidification involves the rejection of both solute and latent heat from the growing solid, forming a coupled diffusion problem in which both the chemical and thermal diffusion equations should be solved. The multi-scale nature of this problem arises from the disparity between the thermal and solutal diffusivities for most liquid metals, which are typically 10-5 m2 s-1 and 10-9 m2 s-1 respectively. The ratio of these two, referred to as the Lewis number (Le =Dia), is therefore typically of the order 10,000 and gives a measure of the multi-scale nature of the problem. In fact, in many cases the thermal diffusivity is so much larger than its solutal counterpart that thermal diffusion is considered instantaneous, wherein the system can be approximated as isothermal such that the multi-scale calculation does not need to be performed. This is certainly a reasonable approach in most conventional castings. However, there is a class of solidification problem in which this approach is far from satisfactory, namely Rapid Solidification (RS). The application of isothermal phase-field models in such situations are highly likely to produce spurious results or to fail totally, particularly for temperatures below To (the temperature at which the free energies of the solid and liquid phases are equal at the concentration of the bulk alloy), wherein partitionless solidification may occur."

Jan 1, 2013

By Pekka Taskinen

The converter-less nickel matte smelting technology (DON) adopted more than 20 years ago in Boliden Harjavalta smelter has been since that applied successfully to the processing of large number of nickel sulphide concentrates of various Ni-to-Cu ratios and MgO contents. The operational point of the technology is far from the conventional primary nickel smelting in the smelting-converting route. Therefore, a careful scouting of distribution equilibria of the base and trace elements in the smelting conditions of DON process has been conducted, in order to obtain quantitative information about the equilibria and thermodynamic properties of the nickel mattes at low iron concentrations, less than 10 wt% [Fe] in matte. The series of investigations has included novel experimental and analytical techniques for increasing the reliability and sensitivity of the phase equilibria as well as the element distribution observations carried out in typical high-grade nickel matte smelting conditions.