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By W. D. Riley

Engineered Scavenger Compounds (ESCs), developed by the U. S. Bureau of Mines I are a novel class of compounds that can selectively recover a desired element from 'a solid or molten alloy. Lithium titanate (Li2Tip7 or Li20' 3TiO.) is being used as an ESC to recover lithium (Li) from Aluminum-Lithium (AI-Li) alloys. X-ray diffraction measurements have shown that lithium titanate undergoes a phase change from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of Li in the matrix of the material and the effect of temperature. Although both of the structures are metastable, the hexagonal phase that forms during the scavenging of Li from AI-Li alloys appears to be the more stable phase. Recovering Li from the ESC by electtodeposition does not cause the structure to revert to the orthorhombic phase. Both the orthorhombic and the hexagonal structures of Li.Til07 have similar scavenging capacities for Li. This paper proposes a new mechanism for the phase transformation.

Jan 1, 1991

By J. Y. Hwang

Microwave heating is an attractive alternative to conventional heating methods because heat is generated directly within the microwave absorbing materials. It has potential to be utilized for selective heating and removal of specified components from a materials mixture. This investigation was undertaken to explore the potential of selective heating and burning of binders for foundry sand reclamation. Selected raw materials and binders used in foundry operations were tested to determine their receptivity to microwave heating. Time needed to reach 600°C and/or the maximum temperature achieved for samples irradiated by microwaves for twenty minutes under 800 W microwave power are reported. The microwave heating characteristics of the selected materials are summarized and discussed. The interactions between microwaves and the raw materials used in a foundry. such as silica sand. chromite sand and bentonite (clay) binder were studied. The results showed that chromite sand coupled well with microwave energy at ambient temperature while silica sand did not. This was expected because the major component of chromite sand. iron chromite (FeCr2O4). is a good microwave absorber. while quartz, which is the major component of silica sand, is a microwave transparent material at ambient temperature. Bentonite absorbs microwaves well because it contains a hydroxyl functional group and water molecules in its structure. It was found that the structure of bentonite was changed through microwave irradiation. Microwave heating characteristics of silica sand mixed with different amounts of bentonite binders were investigated. The presence of bentonite in the mixture improved the microwave heating of silica sand significantly. and bentonite was deactivated by the microwave processing.

Jan 1, 1995

By W. K. Collins

Engineered Scavenger Compounds (ESCs), developed by the U.S. Bureau of Mines, are a novel class of compounds that can selectively recover a desired element from a solid or molten alloy. Lithium titanate (Li2Ti3O7 or L'20-3T'02) is being used as an ESC to recover lithium (Li) from Aluminum-Lithium (Al-Li) alloys. X-ray diffraction measurements have shown that lithium titanate undergoes a phase change from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of Li in the matrix of the material and the effect of temperature. Although both are metastable, the hexagonal phase that forms during the scavenging of Li from Al-Li alloys appears to be the more stable phase. Recovering Li from the ESC by electrodeposition does not cause the structure to revert to the orthorhombic phase. Both the orthorhombic and the hexagonal structures of Li2Ti3O7 have similar scavenging capacities for Li. This paper proposes a new mechanism for the phase transformation.

Jan 1, 1993

By Joseph Bloch

The hydriding of bulk metals and alloys is a gas-solid reaction in which a hydride product layer is initially nucleated adjacent to the gas-solid interface and continues to grow until a complete transformation of the parent (a) phase into the hydride phase. The combination of measurements of the overall hydriding kinetics of samples having defined shapes and dimensions, together with examinations of partially hydrided samples, enables the presentation of the reaction rate in terms of an appropriate reaction model. A common and important type of topochemical development of the hydride in bulk metals and alloys involves a hydride layer formed on the metallic surface. The continuity of the layer can affect the reaction rate. The rate of hydrogen absorption in a sample, in the presence of a hydride layer, is usually analyzed using a model combining several sequential steps in which the hydrogen is transferred from the gas phase into the reaction site. Coupling the flux equations across the layer under proper steady state conditions, results in a complex rate equation in which the steady state rate of hydrogen absorption (proportional to the hydride layer velocity) is expressed in terms of the pressure, temperature, the rate constants of the sequential steps and the critical concentrations of hydrogen in the hydride. Generally, the rate constants of the individual microscopic processes are comparable in magnitude, so that the overall rate is not controlled by any of the specific sequential steps. However, there are two limit cases related to the first stage, the adsorption, for which the general rate equation is much simpler, namely, the fast and the slow adsorption approximations. Using this limit cases, equations are derived for the steady state hydriding rate of a given system. These equations provide means to anticipate the pressure dependence of the steady state absorption rate under low pressures, close to Peq and under very high pressures. At the low pressure regime both the fast and slow absorption cases yield linear pressure dependence. For the very high pressure range, it is found that the rate become independent of the applied pressure. The rate is given then by a combination of the individual rate constants of the system and the critical hydrogen concentrations. The model is shown to apply in several real cases, such as ZrCo, LaNi5 and titanium.

Jan 1, 2002

By Peng Jianping, Feng Naixiang, Di Yuezhong, Wang Yaowu, Pan Xijuan

A vacuum silicon thermal reduction lithium process is developed in present work which used lithium hydroxide, alumina and calcium oxide as raw materials. The process contains two steps, which are that Li5AlO4 clinker is prepared in ambient environment, and that metal lithium is extracted from Li5AlO4 clinker with ferro-silicon alloy as reductant in vacuum. On the basis of thermodynamic analysis and investigative experiments, feasibility of this process is proved. The results show that Li5AlO4 can be generated by calcination lithium hydroxide and alumina, the burning loss is above 31% under the conditions of calicination temperature above 750℃ and time more than 90min. The main phases of calcination product are Li5AlO4 and CaO. When the calcination product is reduced by ferro-silicon alloy in vacuum, the lithium reduction ratio can be over 80% under the conditions of reduction temperature 1200℃ and reduction time 60min.

Jan 1, 2014

By Toshiyuki Kozuka

CdTe metal composite semi-conducting material has high potential in good performance of energy conversion efficiency for solar cell and there is much room for improvement of the performance by developing a process of making a thin CdTe film. In this paper, the imposition of intense magnetic field on CdTe electro-depositing surface is proposed, which is one of the possibilities for improving the energy conversion efficiency. In the experiment, cryogen-free super-conducting magnet up to 5T was used and CdTe film was deposited electrically in -o.nv vs. SHE The electrolyte was Cd and Te ammonia alkali solution with controlled temperature in the acrylic cell of 70mm diameter. Electro-deposition behavior of CdTe has affected by the imposition of the intense magnetic field due to microscopic convection in the vicinity of the depositing surface. Electro-deposited surface of CdTe becomes smooth due to microscopic convection around the surface, and the crystallization behavior is also affected, where crystallization temperature and the grain size is changed by the imposition of intense magnetic field.

Jan 1, 2003

In low carbon TRIP steels, the formation of carbide-free bainitic ferrite is crucial for the stabilization of austenite. Based on experimental investigations modeling the bainite reaction is examined adopting diffusional and displacive mechanisms, as well as the semi-empirical JMAK approach. Transformation tests were carried out to study the isothermal austenite decomposition into bainitic ferrite for a model steel containing 0.6wt%C, 1.5wt%Mm and 1.5wt%Si which replicates the composition of remaining austenite at the start of the bainite reaction in a classical C-Mn-Si TRIP steel. In the diffusional approach, classical nucleation theory is employed and subsequent growth of bainite plates is modeled using the Zener-Hillert theory. In the displacive approach, the autocatalytic nucleation of bairtite plates is assumed to be rate controlling. The predictive capability of all models is evaluated for temperature ranges where different morphologies of bainitic ferrite have been detected, The shortcomings and inherent challenges associated with either of these modeling approaches will be delineated.

Jan 1, 2003

By Bo Zhou

During secondary aluminum recovery, complex aluminum scraps are melted and refined often in a rotary melting furnace and the aluminum metal has to pass through a molten salt layer and melt down in a bottom aluminum bath. Previous experimental study and industrial observations have indicated that salt shell formation and re-melting on the metal solids in the early stage plays a critical role in the overall melting process of the scrap. In the present paper, mathematical models are developed to simulate the process of salt shell formation and its re melting, as well as aluminum melting in the molten melt. Influence of the salt layer properties, the residence time of the metal particles in the salt layer, the particle size, the temperature of bulk melt were investigated. Reasonable agreement with the measurement data was reached. The developed melting model will be used to construct a population balance model of the scrap melting behavior for a rotary melting furnace, taking into account the distributed characteristics of the scrap. Finally, an overall process model based on Computational Fluid Dynamics (CFD) for the rotary furnace will be constructed, coupling with the population balance model for the scrap melting.

Jan 1, 2003

Heap leaching with thiosulfate is only used in one location for the treatment of a refractory preg-robbing gold ore initially pre-treated with bio-oxidation. The chemistry of thiosulfate leaching is complex. Further work is required to develop a better control of the system. A mild refractory gold ore containing pyrite and chalcopyrite was used in this study to investigate the use of thiosulfate as an alternative heap leaching technology. Preliminary bottle rolls tests indicated that similar gold extraction was obtained with cyanide and thiosulfate. In the column leach test, effects of thiosulfate, copper and ammonia concentrations, and their ratio on both gold extraction and reagent consumption, were assessed. The range of reagent concentration were: 0.1 - 1.0M (NH4)2S2O3, 0.03 - 0.10M CuSO4*5H2O, 1.0 - 6.0M NH4OH. The solid-liquid ratio was in the range of 0.83:1 to 5: 1. Best results showed that 72% of gold was extracted in 50 days with 0.3M (NH4)2S2O3, 0.05M CuSO4*5H2O and 6M NH4OH or a combination of 1.0M (NH4)2S2O3, 0.03M CuSO4*5H2O and 3M NH4OH. The reagent consumption at solid/liquid ratio of 3:1 was 37 - 48.6 kg/t (NH4)2S2O3 and 0 - 0.62 kg/t CuSO4*5H2O. The results of thiosulfate leaching were also compared with cyanide leaching.

Jan 1, 1999

By S. J. Buckler

Many chemical and metallurgical processes use submerged gas injection to increase contact area between gas and liquid phases in order to promote faster overall reaction or refining rates. The total interfacial area produced by gas injection through lances, nozzles or tuyeres is both an important design parameter for new vessels and a measurement for estimating the maximum processing capacity of existing equipment. Estimating total interfacial area from submerged injection into industrial pyrometallurgical vessels from existing knowledge is a problem with two aspects. The first difficulty is the difference in behaviour of cold (aqueous) and hot (molten metal) systems, implying that existing models and correlations of gas-liquid behaviour developed in low temperature systems are not necessarily appropriate for estimation of high temperature behaviour. The second difficulty is the issue of scale-up of correlations from laboratory to industrial sized vessels. The work presented in this paper is part of an ongoing experimental investigation, at the GK Williams CRC for Extractive Metallurgy, to quantify the total gas-liquid interfacial area available in pyrometallurgical vessels using chemical measurement methods. The effects of three operating variables, injected gas flow rate, nozzle diameter and nozzle submergence, on total interfacial area are quantified in a IOOL aqueous system - the first stage of a three stage process in examining the implications for scale-up of high temperature, medium-scale results are discussed. The results of work at high, injected gas flow rates (up to 500/min) show that the submerged Froude number is not sufficient for use as the sole variable in a predictive model of total interfacial area. Further work is being undertaken to identify other dimensionless variables that will better represent the gas-liquid characteristics in submerged injection that influence the formation of total interfacial area. The second and third stages of the experimental investigation involve measuring the total interfacial area in a large-scale (1000L) aqueous sodium sulphite and small-medium scale molten metal baths.

Jan 1, 2002

By Natasa Mitevska

In order to ensure the minimal copper concentration in the reverb furnace slag, the graphical optimization method is used and the optimal slag composition of the reverberatory furnaces No.1 and No.2 in the RTB BOR, Copper Smelter and Refinery (Serbia) is obtained: (Si02) .. 38.0%; (FeO) .. 40.0%; (Fe3O4) = 5.0%; (CaO) = 5.0%; (Al2O3) .. 6.0%. Keywords: Optimization, Reverb Furnace Slag, Graphical Method

Jan 1, 2003

By Shaohua Ju

Siderite ore is abundant around the world, due to its inert properties of low grade, mudding when milling and low magnetic, and it is very hard to be beneficiated. Nowadays, decomposition by roasting becomes the main process for utilization of the siderite ore. The methods of energy input for roasting are normally electrical heating, coal or gas combustion. Because traditional roasting methods owns some disadvantiges, such as low energy utilization, high cost and/or large exhaust pollution, only about 10% of the siderite ores in China were used as iron concentrate. In this work, the possibility of roasting siderite ore with microwave energy is studied by both laboratory and pilot experiments. The result of laboratory experiments showed that the optimized condition is roasting for 20 min with a power density of 3 W/g, and the Fe content of the final sample obtained is about 59.12%. The pilot experiments result showed that the decomposition is thoroughly, and the main phases of the roasted material are magnetite and wustite, and the energy consumption of the roasting process is 695.8 KWh/t.

Jan 1, 2014

By Do-Hyeong Kim, Jong-Jin Pak, Jung-Mock Jang, Min-Kyu Paek

"Thermodynamic relations among Mn, Al and N in liquid iron were studied by measuring the effect of Mn on the solubility product of AlN in liquid Fe-Mn-Al-N alloys in the temperature range from 1773 to 1873 K. The critical Al and N contents for AlN formation were determined by the metal-nitride-gas equilibration technique over wide ranges of melt composition and temperature. The effects of Mn on N solubility in Fe-Mn and Fe-Mn-Al melts containing Mn up to 26 mass% were separately determined in the same temperature range. The experimental results were thermodynamically analyzed using the Wagner's formalism to estimate the critical Al and N contents for the onset of A1N formation. The validity was checked by the observation of inclusion evolution in Fe-20%Mn-1.5%Al-0.6%C-0.3%Si-0.012%N melt during cooling and solidification.IntroductionRecently, high manganese steels such as Twinning Induced Plasticity (TWIP) steels have been developed as next generation steels because of their high formability as well as excellent strength and ductility.[1•2l In these steel grades, a large amount of Mn (15-20 mass%) and Al (1-2 mass%) are added to liquid steels, and such high Mn and Al concentration bring the great challenges to the steelmaking and casting processes. Mn significantly increases the N solubility in liquid iron and the AlN inclusions can be easily formed at such high Al concentrations due to high affinity of Al and Mn with N in liquid steels. Although the AlN inclusion is known to be a dominating and considered as a detrimental phase for the hot ductility of steels,l3l thermodynamics of AlN formation in high Mn-Al alloyed liquid steels was not well known.Moreover, the melting point of these steels decreases down to near 1623 K as increasing Mn content up to 20 mass%. However, most of thermodynamic data has been measured at the steelmaking temperature around 1873 K. Even at steelmaking temperature, there are huge scatters in thermodynamic interactions of Mn and Al on N in liquid iron. The nitrogen solubility in Fe-Mn alloy melts has been measured using the Sieverts' method[4l and the samplinij method[5-7J in the temperature range of 1813 to 1973 K. In the authors' recent study,[8•9 the N solubility in Fe-Al alloy melts was measured using the sampling method in the temperature range of 1823 to 1973 K. However, the simultaneous effect of Mn and Al at high concentrations on Nin liquid Fe-Mn-Al-N alloys is still not known. Also, there remains uncertainty about the temperature dependence of the interaction parameter of Mn on N in liquid Fe-Mn alloys. Therefore, it is worthwhile to check the temperature dependence of this parameter at a low temperature near the melting point of Fe-Mn alloys. There have been few studies on the characterization of non-metallic"

Jan 1, 2014

By Marcos Aurélio S. Costa, Nilton F. Nagem, Andreia B. Henriques, Herman S. Mansur, Alexandra A. P. Mansur, Antonio E. C. Peres, Valeria G. Silva

The superfine material generated in the Bayer process was used in one innovatively way as a precursor to geopolymerization techniques because of the presence of Gibbsite. Gibbsite can play a role in system adjustment because of the SiO2/Al2O3 ratio. Furthermore in the geopolymeric system it was studied the influenceof the additives such as kaolin, metakaolin and sodium trisilicate in an alkaline media. Others conditions to form the geopolymer were also evaluated such as solid/liquid ratio, SiO2/Al2O3 ratio and total alkaline. The raw materials and geopolymeric products were characterized by several techniques e.g. XRD, DSC, FTIR and SEM. Through the FTIR technique it was observed an increase in intensity and bandwidth in the region centered at 1010 cm-1, which is related to the asymmetric vibration Si(Al)-O, this is an indicating of the possible geopolymer formation This broadening of the band promotes a relative disappearance (overlapping) peaks at 965 and 935 cm-1 associated with raw material (ESPDust).

Jan 1, 2015

By C. A. Silva

Ladle change-over, during continuous casting of steel, initiates transient flow in the tundish which influences the inclusion content and degree of mixing between two consecutive batches of steel. The mixing behavior in the tundish during this period is determined by the casting rate and the ratios of: inflow to outflow during the refilling period; and, the low liquid level relative to the nominal level in the tundish during the transiency. A 3:10 scale water-model of a typical one strand slab caster was operated in conjunction with a tracer technique to characterize the velocity fields for several combinations of these parameters. Steady operation, a limiting case of the transiency, provided a basis for comparison. High-order moments -- skewness and kurtosis -- of the residence time density function have been utilized as signature elements associated with a particular residence-time distribution for the system. A simple mathematical model incorporating the above parameters as well as a characteristic Peclet Number was successful in simulating the features of the transient period.

Jan 1, 1993

By Shijie Wang

In pressure oxidation leaching of copper anode slimes, than 65% of the tellurium is m' cxtraoted during decopperizing. About l0- 15% of the selenium is also dissolved simultane¬ously by severe leach conditions. Current operation for the treatment of the leachate is to constantly recirculate the leach solution through a bed of copper turnings. The tellurium and sele¬nium are precipitated from the leach liquor as copper telluride and copper selenide and sepa¬rated from the solution by filtration. In order to improve the reaction efficiency and reduce the process cost, viz, minimize the copper addition, cut retention time, and reduce the energy consumption; a chemical reducing agent is studied and the cementation process tested in the laboratory. In this paper, the test results are presented and the process chemistry is discussed.

Jan 1, 2003

By Reed M. Izatt

SuperLig® materials are capable of individually separating Rh, Pd, and/or Pt in highly purified form (99.95 to 99.99%) from a variety of chloride-based feed streams in a single stage operation. The hydrophillicity and associated kinetics of the supported materials allow for operation at relatively high flow rates of both loading and elution in a packed bed format. Pilot and commercial systems have been operated with Rh, Pd, and/or Pt present in the feed from single digit ppm (mg/l) to tens of g/l. A dual SuperLig® system for one pass Au(CN)2- separation followed by Cu and CN- recovery for CN- recycle has also been tested up to a pilot level,

Jan 1, 1999

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 C. Lupi

"The energy consumption of copper production by electrowinning, generally represents more than 1/4 of the total energy requirement in hydrometallurgical traditional process (roasting, leaching, purification and electrowinning). The considerable saving can be achieved just in this step that requires about 2.2 kWhlkg of the produced copper. To save energy the cell voltage, or more appropriately its anodic component, can be reduced: that is because the anodic voltage represents the main component of cell voltage and so it is largely responsible for the excessive energy consumption in copper sulphate electrowinning.In this work some ways are studied to lower the anodic voltage. First the cobalt ions were added to the sulphate solution in order to study the catalytic effect on oxygen discharge. Then lead alloys anodes (Pb-Ag, Pb-Sb-Ag and Pb-Ca) were used to promote a better oxygen evolution as a result of a different anodic surface. Their behaviour was compared with the PbSb traditional ones. Finally, as already pointed out by several authors for zinc electrowinning, ethylene glycol was employed as anodic depolariser in order to verify its effectiveness in the case of copper electrowinning. By combining all the above-mentioned ways, energy saving ranging from 20% to 27% is achieved.All the tests were carried out on a laboratory pilot-plant for long time to simulate the industrial conditions. The obtained copper deposits were observed by SEM to highlight their morphology."

Jan 1, 1997

By B. Mishra, W. A. Averill

"The application of various hydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, ego metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been investigated and suggested for dealing with some of these wastes and scrap material.The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EM] and decontamination and decommissioning [D&D].IntroductionThe high temperature carbothermic or metallothermic smelting reduction methods for metal production are associated with the generation of significant quantity of waste as slags, flue dusts, sludges, residues, effluent salts etc. Certain hydrometallurgical processes also generate lots of aqueous waste due to the inherent nature of the technique. Also, the gas-based reduction processes are not applicable to many stable metal compounds, such as alumina, titania, beryllia, lanthanide and actinide oxides, etc. due to thermodynamic considerations. All these methods cause substantial environmental hazard. There is a need to develop alternative processes which have low waste or ideally a ""zero-waste"" generation.Pyrochemical processes using molten salts provide a unique opportunity for the extraction and refining of many reactive and valuable metals either directly from the beneficiated ore (aluminum, beryllium, neodymium, plutonium, uranium, etc.) or from other process effluent that contain reactive metal compounds. The processes reduce metal compounds electrolytically (A12O 3 and BeCI2) on a carbon anode or by calciothermic reduction (Po, Nd). The by-product, in the latter case, is a calcium oxide saturated halide salt. The waste-treatment to recycle the halide has to be done as a separate step or stored as a contaminated waste. A successful separation technology can provide a new insight to the waste minimization strategy for the nuclear industry."

Jan 1, 1996