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By D. Neuschiltz, M. Witthaut, R. Cremer

"Metastable (Ti,Al)N coatings with fee structure have been shown to exhibit superior performance as compared to TiN under conditions of wear at elevated temperatures due to their better oxidation resistance and hardness. The oxidation resistance of these coatings increases significantly with increasing Al-content. However, the deposition of (Ti,Al)N films with Ti/ Al ratios below about 30/70 leads to a hexagonal structure which is not suitable for tribological coatings. Only little is known about the location of the cubic to hexagonal phase transition and hence about the optimum composition of (Ti,Al)N hard coatings.To determine the position of this transition, Tii-xAlxN films with different Ti/Al ratios were deposited on high speed steel at substrate temperatures between 100 and 700 °C by means of reactive MSIP. The composition of the films was determined by electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS), the crystallographic structure by thin film X-ray diffraction (XRD).It could be shown that in case of deposition temperatures of 300-700 °C a two-phase region exists in the metastable TiN-AlN phase diagram, which expands with increasing temperature, wheras at 100 °C substrate temperature no two-phase region was observed. But in opposition to the phase diagram known from literature, which is based on thermodynamic estimations, the detected two-phase region is narrow for typical PVD temperatures, thus allowing the deposition of cubic single-phase Al-rich (Ti,Al)N hardcoatings for tribological applications. Based on these results, a new Ti1-xAlxN film with x = 0.62 has been developed, which showed an increase of oxidation resistance by a factor of 4."

Jan 1, 1998

By I. Iwasaki

Platinum group elements (PGE) are often found in arsenide and sulfarsenide minerals as inclusions in copper-nickel bearing gabbroic rocks. Major losses of platinum in flotation have been attributed to the poor recoveries of the arsenic minerals. Flotation characteristics of a synthetic nickel arsenide and arsenopyrite were studied through rest potential and oxidation rate determinations, surface analyses, and micro-and batch-flotation tests. The use of nitrogen during grinding and flotation together with copper activation improved the PGE recoveries from Duluth Complex ores. The flotation behaviors of the sulfarsenide minerals are still unresolved. The role that electrochemical interactions play among arsenides, sulfarsenides, sulfides and grinding media on their f10atabilities is discussed.

Jan 1, 1988

By Stephen W. Paff

The EPA has estimated that there are over 3,000 sites across the United States contaminated with lead. Techniques to remediate these sites include standard stabilization/disposal technologies, reclamation of lead using secondary lead smelters, soil washing, and biological removal technologies. In this paper, the current technologies used for lead remediation will be reviewed. Factors affecting the use of each technology, such as range of applicable concentrations, soil types, interferences from other contaminants, economics, and current technology status will be assessed. The paper will also focus on the results of a recent study completed by the Center for Hazardous Materials Research (CHMR), in conjunction with a major lead smelter, which demonstrates that secondary lead smelters may be used economically to reclaim lead from a wide range of lead-containing materials frequently found at Superfund sites. Such materials include battery case materials, lead dross, and debris containing between 3 and 70% lead. The results of development work completed by CHMR on the Acid Extraction Treatment System (AETS), which has been demonstrated to extract Lead from soils containing up to 30,000 mg/kg lead, will also be presented. The use of these technologies will be compared with other options for the remediation of sites.

Jan 1, 1994

By K. J. Cathro

A hydrometallurgical process is described for the recovery of copper from chalcopyrite concentrates. The process is based on a cupric chloride leach, the concentrate having first been "activated" by heating it with sulphur at a temperature near 400°C. This activation process converts most of the iron of the chalcopyrite to pyrite, which is insoluble in the cupric chloride leachant. The copper is converted to the mineral idaite, which dissolves readily in hot cupric chloride: at 106°C, 98% of the copper is extracted in a three-stage countercurrent leach, the leaching tirqe being 1 hour per stage. The sulphur of the chalcopyrite appears as elemental sulphur, which is recycled for the activation of further concentrate, the final leach residue consisting of pyrite, plus the gangue present in the original concentrate. The copper extracted can be recovered by electrowinning, using a diaphragm cell. Current efficiency (one-electron basis) is about 70% but the cell voltage is only about 1 V, so that power consumption is three times lower than for the conventional sulphate electrowinning process. The leachant is simultaneously regenerated in the anode compartment. The behaviour of minor elements in the concentrate has also been studied.

Jan 1, 1976

By Du Sichen, S. Seetharaman, A. Jakobsson

"In the Present paper, the principles of oxygen potential measurements have been discussed along with the design details for oxygen sensors that are used in copper industry. A description of some of commercial probes is presented along with their salient features. The application of these sensors in flash smelting, converter and casting sections of copper production are discussed along with their implications on process optimization.I. IntroductionThe high temperature galvanic cells have come into prominence on account of their numerous applications in both fundamental as well as applied measurements. Since the inception of the oxygen-ion conducting electrolytes like ZrOrCaO·by Kiukkola and Wagner [1], the oxygen concentration cells have been extensively used in laboratories as well as in industries. In metal-production technology, these cells have been used to monitor the oxygen potentials in metallic, slag as well as gas phases and also to control and styr metallurgical processes. The pioneer among the various industrial users of such cells is the copper industry. To-day, high temperature solid electrolyte cells involving oxygen ion conducting electrolytes have become an integral part of copper pyro-refining and continuous casting. In the present paper some of the applications according to the industrial processes are described including the developments that are going on in the European scene."

Jan 1, 1997

By A. A. el-Geassy

High-grade iron ore fines rejected from the DRl plants (>96%Fe20) were isothermally reduced in 30-60%COIH2 gas mixtures at 973-1273K. The freshly reduced reaction products were then subsequently carburised in either H2/CO or H2/CO/S mixtures at 823-1073K for 30-120 min. The thermogarvimetric technique was used to follow up both of reduction and carburisation reactions as a function of time. The carburised samples were characterized by X-ray and Mossbauer techniques. Chemical and carbon analyses were also applied. The influence of temperature and gas composition on the reduction behavior was investigated. The calculated values of apparent activation energy, application of gas-solid mathematical formulations were correlated with the microstructures to predict the reduction mechanism, The influence of carburization time, temperature, CO contents in H2/CO or H2/CO/S were investigated. A conversion extent of Fe to Fe3C was taken as a measurable index for the efficiency of carburization reaction under the different experimental conditions.

Jan 1, 2003

By J. A. Bakken

Thermal plasmas are interesting for a wide range of metallurgical and chemical processing applications. The 300 kW experimental reactor PRESS, which has been in use since 1987, is operated in the transferred arc mode with three or one plasma torches . Tests include remelting of silicon fines and production of ultrafine silica. Work on a novel three stage process for production of silicon metal is under way. A 1:1 model of the plasma reactor is used to measure the wall heat flux distribution calorimetrically. The cold walls of this model are divided into several water-cooled sections. The same plasma torches as in the real hot-wall reactor are used. In parallel to the experiments and calorimetric measurements theoretical work is done on numerical modelling of one and three transferred arcs. A modified version of the flow simulation program FLUENT from Creare Ltd. is used.

Jan 1, 1991

By R. M. Taylor

Lime addition to acid mine drainage (AMD) leads to precipitation, predominantly of metal hydroxides and calcium sulfate, and is the benchmark for remediation by precipitation. Geo2 Limited of Melbourne, Australia has developed and patented a novel alternative precipitation scheme based on the formation of mixed valency, M(I1)-M(III), hydroxide sulfate salts. When the composition of AMD is appropriate, the Green Precipitate Process provides a useful and more effective alternative to conventional liming. The characteristics and utility of the Green Precipitate Process are described in terms of the underlying chemistry, and a case study where the Green Precipitate process outperforms conventional liming. A mobile pilot pipe reactor rig which was built by Geo2 to demonstrate the process, and used successfully in both Australia and the United States, is described.

Jan 1, 1998

The oxidation of zinc vapour plays a very important part in the operation of the Imperial Smelting Process. The kinetics of the reoxidation of zinc vapour by carbon dioxide and water vapour onto quartz and zinc oxide substrates is qualitatively understood and this pertains to the conditions found as the gases are being transferred from the furnace to the splash condenser. However, re-oxidation also occurs in the shaft of the furnace where the solid substrates are sinter and metallurgical coke. It was found that there was a threefold increase in the rate of oxidation on sinter, compared to quartz and a 30 to 300 increase in rate on the coke. This was attributed to the high surface area offered by these materials.

Jan 1, 2003

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 Tejs Vegge

The lack of suitable means of storing hydrogen for use in the transport sector is generally viewed as a primary showstopper for a hydrogen economy. Recent developments within solid state hydrogen storage in complex hydrides and metal ammines have sparked new hope of a long term solution, but as of now, no materials fulfill all the DoE targets for onboard storage [1]. A detailed physical understanding of the ab-/desorption processes and the role of the essential catalytic additives is an essential prerequisite for the development of new optimized hydrogen storage systems. Here, we illustrate the potential of utilizing the synergy of combining state-of-the-art in theoretical methods and experimental techniques in the analysis and design of materials for hydrogen storage. Recent advances in computer hard- and software has made it possible to treat many of the essential problems in such materials, i.e. structural stability, hydrogen dissociation and diffusion, with high accuracy methods like density functional theory. We rely on such results to guide our synthesis of new materials, and to interpret our experimental results from, e.g. time dependant in situ x-ray diffraction, synchrotron/neutron experiments, and advanced materials testing. Through a continuous feed-back optimization loop between theory and experiments, the obtained nano-scale insight is used to expedite the design and development of novel materials for hydrogen storage.

Jan 1, 2006

By Tao Zeng, Jianchao Li, Chang Jie, Jieyu Zhang, Jifang Xu, Kuochih Chou

"The densities of the selected quaternary Ca0-5%Mg0-Alz03-Si02 slag with low silica were measured by the Archimedean method in a wide temperature range from l 723K to 1823K. Slag compositions were chosen based on five different levels of Si02 content between 0.00 pct and 11.40 pct. The MgO content was equaled to 5.00 pct. The mass ratio of CaO/Alz03 was varied from 0.67 to 2.14. The effects of temperature, Ca0/Alz03 ratio and optical basicity were studied. It is shown that density decrease approximately linearly with an increase in temperature. With the same Si02 content, the density decreases with increasing of CaO/Alz03 ratio and optical basicity. Based on the experimental data as the boundary of the homogenous phase region predicated by F ACTSAGE software, the mass triangle model is used to calculate the density of selected limited homogenous phase region. The results showed that the mass triangle model is working well.IntroductionIt is of great importance to measure density of slag melt not only to the theory research for melt, which that is directly amenable to the structure correlations of molten slags, but also to the industrial application. Many metallurgy phenomena such as inclusion formation in molten melt and its removing, slag foaming, slag-metal reaction are closely related to the density of slag. Density is also required to estimate other fundamental properties, like surface tension, viscosity, and thermal conductivity from thermal diffusivity so that a relatively complete picture in regard to the behavior of high-temperature molten oxides could be made."

Jan 1, 2013

By V. A. Luganav

The behavior of arsenopyrite under heating has been studied by many scientists. It has been already established that under heating at more than 650°c and without air access the arsenopyrite dissociates with the formation of one atom arsenic. Under vacuum the dissociation process begins at 5500C with the formation of elemental arsenic. The residue of dissociation process contains pyrrhotite and throilite. In the presence of pyrite, arsenopyrite dissociates under lower temperature and with a higher velocity than without it. The industrial realization of fool scale processing of arsenic bearing raw materials is possible only by the use of standard equipment and oxygen containing blast. In this view the paper presents the results of the study on the effect of oxygen in the gaseous phase and its addition into the charge of pyrite in the process of arsenopyrite decomposition. Thermodynamic analyses showed that under thermal processing of arsenopyrite in the presence of pyrite and limited quantities of oxygen in the gaseous phase the formation of arsenic sulfides is possible according to the following reactions:

Jan 1, 2003

By Animesh Jha, Chris Dometakis

"Without the use of a flux, only a poor dispersion of ceramic phase can be achieved. A molten-flux-assisted ceramic phase dispersion technique for producing aluminium alloy metalmatrix composites has been developed. In this paper, we report the physical chemistry for the dispersion of TiB2 in molten aluminium. In particular, aspects of the interfacial energy and the thermodynamics of the dispersion reactions are briefly discussed for enhancing the volume of dispersion phase in the molten metal and for controlling their morphology. This investigation also addresses the role of molten flux in the fabrication of AI-alloy mmc using a casting technique. The morphological aspects of the dispersion are explained on the basis of the classical theory· of nucleation.IntroductionMetal matrix composites (MMCs), have long been recognised as an important class of material due to their greater wear resistance, specific stiffness and temperature capability when compared to conventional monolithic alloys. Particulate reinforced composites produced by melt casting techniques have been amongst the first MMCs to achieve commercial market viability. The advent of melt mixing techniques such as the Duralcan™ process have enabled low cost, easily fabricated composites based on the AI-SiC and AIAlz0 3 systems to be produced. In this process, uncoated ceramic particles with diameters 10ltm and larger, are incorporated into conventional monolithic alloys with reinforcement levels up to 25 volume percent. The AI-7Si-SiC metal-matrix composites have good wear resistance, high strength, low density and high thermal conductivity. The combination of these physical and mechanical properties has become a major attraction for the fabrication of light-alloy composite disc rotor brakes for the automotive sector2. However, in silicon-free alloys, SiC is thermodynamically unstable above the composite melting point and is extensively attacked by the melt to form aluminium carbide3 :"

Jan 1, 1996

By Ian M. Ritchie

Cementation or metal displacement reactions such as Cu2+ + Fe Cu + Fe2+ are among the oldest known hydrometallurgical reactions. They are still used in the recovery of some metals and in the purification of process liquors and waste water streams. However, they are often more complex than the stoichiometric reaction would suggest because they involve the simultaneous deposition of one metal onto a second which is dissolving. For example, sometimes a cementation will not take place, even though it is thermodynamically favoured. On other occasions, a cementation reaction will start but come to a halt as the depositing metal blankets the reacting surface. On yet other occasions, side reactions, catalyzed by the deposit, can be important. In this paper, the electrochemical basis of cementation reactions is described. The conditions for each of the complications encountered in these reactions are described and illustrated by examples drawn from a number of hydrometallurgical processes. The cementation reaction between activated carbon and gold thiosulfate is also briefly described, this reaction being unusual in that no dissolution of the carbon occurs.

Jan 1, 2003

By Daniel K. Kim

The charge for the copper refinery is a mixture of anodes produced at San Manuel from BHP source concentrate and copper purchased from external sources. Control of unwanted impurities in the tankhouse - is very important and beneficial. Currently available removal/recovery technologies were reviewed for the control of bismuth and antimony levels in the electrolyte. Recent studies have focused on solvent extraction (SX) technology and generated successful results for the removal and subsequent recovery of bismuth and antimony. The SX system employs the reagent, ACORGA SBX-50, in conjunction with a patented high chloride stripping system. The latter enables recycle of the eluant, avoiding the high costs associated with conventional systems, such as regeneration of resin. Concerns over potential transfer of organics and chloride ion to the electrolyte were readily addressed, solved and demonstrated using conventional, established technology. This paper describes the benefits of electrolyte purification, the flexibility afforded by the SX system, the operational practices necessary for maintaining adequate control of bismuth and antimony impurities in the electrorefining environment and possibilities for future development /exploitation of the Zeneca SX system at the San Manuel refinery.

Jan 1, 1998

By Jose Carlos D’Abreu, Edelink Efrain Tinoco Falero, Mauricio Marcos Otaviano, Helio Marques Kohler

Nowadays the most important Direct Reduction - DR processes in shaft furnaces has to deal with carbon fines precipitation and DRI carburization issues. Based in a cooperative research program joining Catholic University (PUC-Rio) and SAMARCO Mining Co, a project dealing with pellets reduction and those two phenomena was established. This work analyzes kinetically the three reactions mentioned before, considering typical values for the operational variables temperature, flowrate, pressure and gas composition, parameters commonly used to control the DRI formation in the Reduction Zone - RZ of the shaft furnaces. From laboratories experimental results, the kinetic equations for those reactions were established and, using the superposition principle, generated a specific global kinetic model for the iron oxide reduction and the soot formation. Finally, using those experimental results and applying a planned statistical factorial analysis for the experiments, the numerical coefficients for each equation were calculated and the correlation factor determined for the proposed global kinetic equation.

Jan 1, 2015

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 Mahesh C. Meyer Jha

AMAX has developed a chloride refining process to produce pure nickel and cobalt metals from mixed sulfide .precipitates, Metal chloride solutions, generated in a hydrochloric acid leaching step and purified in a solvent extraction circuit, are converted to metal oxides .and HCI gas by pyrohydrolysis. A pilot plant consisting of a 30-inch diameter fluidized bed reactor and other ancillary units was designed, constructed, and operated for over one year. Process design was aimed at minimizing energy consumption, maximizing conversion efficiency, and achieving simplicity of operation and control. The operation provided valuable information on process scale up parameters, process control strategies, and materials of construction., Several process variables such as bed temperature, solution composition, solution feeding system, bed particle size distribution, and fines recycle system were investigated to determine their effects on process efficiency and the physical and chemical characteristics of the product.

Jan 1, 1985

By J. M. Zhuang

Lignosulfonates, by-products of the sulfite pulping process, have been utilized in a process [1, 2] to treat acidic rock drainage (ARD). This process is referred to as the LignorTM process. In the present study, lignosulfonates were found to protect lime from developing an external surface coating, and hence to favor its dissociation. Further, the addition of lignosulfonates to ARD solutions increased the clotting and settling rate of the formed sludge. The capability of lignosulfonates to form stable metal-lignin complexes makes them very useful in retaining metal ions and thus improving the long term stability of the sludge against leaching. The LignorTM process involves metal chelation with lignosulfonates, ARD neutralization by lime to about pH 7, pH adjustment with caustic soda to 9.4 ? 9.6, air oxidation to lower the pH to a desired level, and addition of a minimum amount of FeCl3 for further removal of dissolved metals. The LignorTM process removes all concerned metals (especially Al and Mn) from the ARD of the Britannia Mine (located at Britannia Beach, British Columbia, Canada) to a level lower than the limits of the BC Regulations. Compared with the high density sludge (HDS) process, the LignorTM process has many advantages, such as considerable savings in lime consumption, greatly reduced sludge volume, and improved sludge stability.

Jan 1, 2003