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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 William Petruk

The development of automatic image analysers brought the application of image analysis into process mineralogy because the analysers can measure parameters more easily, quickly and accurately than by manual grain counting techniques, and can also collect data unobtainable by manual grain counting. Data from ore specimens and mill products are used to predict and to define the behaviour of minerals during processing. The analyses are generally performed on the basis of either surface areas or linear intercepts of grains in polished or thin sections, and the data are computer processed to give mineral quantities, liberations, size distributions, and characteristics of middling particles. For analysis, the minerals must be detectable and discriminatable from each other. An image editor is usually used when minerals are not easily discriminated. In addition BSE-8EM photographs have been used where the silicate minerals could not be discriminated from the mounting media. Methods of analysis, typical results, and their applications are discussed.

Jan 1, 1982

By Jonkion M. Font

An expression for the distribution ratio of arsenic between slag and copper matte or liquid copper was developed by both, an extension of the Reddy-Blander model for deriving a priori the arsenic capacity, and by a relationship between the arsenic capacity and the arsenic distribution ratio. In this study, the a priori arsenic capacities in the FeO-SiO2, CaO-SiO2, MgO-SiO2, FeO-CaO-SiO2, FeO-FeO1.5-CuOo.5-MgO-SiO2, FeO-FeO1.5-CuO0.5-CaO-MgO and FeO-FeO1.5-CuO0.5-CaO-MgO-SiO2 slags were calculated at 1573 K. The a priori arsenic distribution ratio between the FeO-FeO1.5-CuO0.5-CaO-MgO-SiO2 slag and copper matte (L s/m as), and between the FeO-FeO1.5-SiO2 or FeO-FeO1.5-CuO0.5-CaO-MgO slag and liquid copper (L s/Cu as) were calculated. The model calculated data are found to be in good agreement with the reported experimental data. The availability of reliable thermodynamic data for slag components and impurities in the slag-matte-metal system is essential for the accurate prediction of impurity capacities and distribution ratio data. The arsenic distribution ratio model developed here, can be extended for prediction in multi-component slags and mattes or liquid metal, and thereby may lead to the development of new slag systems for the efficient removal of arsenic in the copper smelting, converting and refining processes.

Jan 1, 2003

By M. D. Strachan

Technical & Procurement Services Limited (TECHPRO) in Ashford, Kent, UK, have been appointed as Project Managers for the major rehabilitation of the Copper Smelting complex of Nkana Division, Zambia Consolidated Copper Mines Limited, (ZCCM) Zambia. In outline, the overall scope covers three main areas: a) Transfer and implementation of new technology into Zambia for the production of primary copper. b) Replacement of gas collection and gas treatment circuits to guarantee high quality feed to the acid plants. c) Completion of a number of minor projects in the copper smelter and associated utility plants to complement changes in the primary smelting technique. This paper describes the Project Management methodology and style used by TECHPRO to tackle typical problems that arise in retrofit projects of this type. Reference is made specific aspects of the smelter projects to illustrate solutions to the problems. The subjects. addressed highlight the complexities not only of having a -Client 5,000 miles from the Project Office, but also the difficulty of co-ordinating and controlling the performance of min sub-contractors who are also geographically distant.

Jan 1, 1991

By Ray Y. Lin

This study explores the formation of sodium pyrosulfate in molten sodium sulfate resulting from dissolution of SO3 at temperatures between 1160 and 1250 K. Solubility of SO3 in Na2SO4 melts at temperatures between 1160 and 1250 K under gas mixtures of SO2, O2 and argon was investigated applying a thermogravemetric analysis (TGA) technique. The activity of Na2O in the melt was determined with a high temperature electrochemical cell (ECC). Results showed that the SO3 solubility in molten Na2SO4 increases with decreasing temperatures and increasing SO3 partial pressures. Enthalpy of SO3 dissolution in molten Na2SO4 was calculated to be -119 kJ/mol for infinite dilute solutions. Thermochemistry of Na2SO4-Na2S2O7 melts was analyzed based on information obtained from both TGA and ECC techniques. Detailed examinations of the earlier low temperature measurements in the Na2SO4-Na2S2O7 system along with data from this study reveal that the solution behavior between Na2SO4 and Na2S2O7 can be satisfactorily treated as regular with the interaction parameter, , being 2.7 kJ/mol. The phase diagram and the field of SO3 partial pressure has been generated with the thermodynamic calculation using a regular solution approach.

Jan 1, 2006

By Pengfu Tan

NiModel, a thermodynamic model, database and computer program, has been developed to predict the distribution behavior of Ni, Cu, Co, Fe, S, O, As, Sb and Bi, and heat balance in the nickel pyrometallurgical processes such as Outokumpu flash smelting, Outokumpu direct high-grade matte smelting, INCO flash smelting, and Peirce-Smith converting processes. In this model, as much as 16 elements (Ni, Cu, Co, Fe, As, Sb, Bi, S, O, Al, Ca, Mg, Si, N, C and H) are considered. The compositions of matte, slag and gaseous phases, and heat balance are calculated using the thermodynamic data and the activity coefficients of the components derived from the experimental data. The model predictions were compared with the known industrial data from Kalgoorlie Nickel Smelter in Australia, Outokumpu Harjavalta Nickel Smelter in Finland and INCO Metals Company in Canada, and an excellent agreement was obtained. In this paper, the applications of NiModel in the nickel pyrometallurgical industries have been presented. NiModel has been used by Jinchuan Group Limited in China.

Jan 1, 2004

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 Fathi Habashi

The recovery of uranium from wet process phosphoric acid was applied on industrial scale in the 1940's by using octylpyrophosphoric acid as an extractant. Later, more efficient reagents were used, e.g., di(2-ethylhexyl) phosphoric acid and actylphenyl phosphoric acid. In the 1970's the rare earths in Kola phosphate were recovered in Finland and recently (1997) in Norway using HNO, as a leaching agent and di(2-ethylhexyl) phosphoric acid as solvent. It was demonstrated later on laboratory scale that both uranium and rare earths could be extracted from the rock by tributyl phosphate but at different pH values provided that the rock is leached with nitric or hydrochloric acids instead of the commonly used sulfuric. This new concept opens the way to the possibility of treating phosphate rock by in-situ, dump, or vat leaching for the recovery of phosphate values as well as uranium and the rare earths. Another solvent extraction process is used industrially for the purification of phosphoric acid using butyl and amyl alcohols.

Jan 1, 1998

By XUEWEN WANG, Bowen Li, Mingyu Wang

A novel technology characterized by higher extraction of vanadium and recovery of valuable elements was developed to recover vanadium from stone coal. The brief flow of the novel technology mainly includes low temperature sulphation roasting, water leaching, recovering potassium, aluminum, copper and selenium, solvent extraction enrichment vanadium, precipitation of red vanadium, removal sodium from red vanadium and calcinations. The total recovery of vanadium reached 76.3%, which was higher than the current applied technology. The novel technology was environmentally-friendly and could extract vanadium from the stone coal, in which the content of V2O5 was less than 0.8%.

Jan 1, 2015

By G. R. Palmer

The success of future electric vehicles will depend greatly upon the power supply choices made today. Research is presently being conducted by automotive engineers and electrochemists to determine what battery type may be the most promising. Not only are product production and application efficiencies being evaluated but also environmental concerns of reclamation and recycling. Rechargeable batteries using nickel-metal hydride electrodes are strong candidates for these electric vehicle applications. The U.S. Bureau of Mines is investigating hydrometallurgical technology that separates and recovers purified metallic components present in nickel-metal hydride battery scrap. Sulfuric, hydrochloric, and nitric acids are all capable of dissolving the battery electrode alloys given the proper operating conditions. Solvent extraction of the leach solutions using D2EHPA removes iron, and selective precipitation shows promise of recovering the other metals in the H2SO4 and HNO, systems.

Jan 1, 1994

By L. A. Neumeier

The Bureau of Mines, U.S. Department of the Interior, is investigating the feasibility of partitioning complex sulfide minerals to simpler sulfide .phases by sulfldation reactions. Such partitioning can afford opportunity to improve selective extraction of mineral constituents of value. This report describes initial research involving sulfidation partitioning of chalcopyrite concentrates. Small chalcopyrite samples were sulfidized with elemental sulfur in glass capsules sealed after evacuating and backfilling with helium, by heating for 1 to 24 h at specific temperatures in the range of 250° to 500° C. which extends from below to above the boiling point of sulfur (-445° C). Above the boiling point of sulfur, the overall reaction with adequate sulfur (13.9 wt pct of CuFeS2) is 5CuFeS2 + 4S g ? Cu5FeS6 + 4FeS2.

Jan 1, 1989

By Yanhui Liu, Xuewei Lv, Chenguang Bai

A thermodynamic model for determining the surface tension of molten slag by considering the surface tension and molar volume of the pure oxide component, and their ionic radii was extended to the slag bearing high TiO2 (varying from 80 to 67%) at 1973 K. The iso-surface tension curves for the FeO-TiO2-Ti2O3 ternary system at 1973 K are almost parallel to the FeOTi2O3 line. TiO2 plays a role of surface-active solute, and its surface-active effect is attenuating with increasing the TiO2 content. The iso-surface tension curve shifts away from the TiO2 corner, indicating that the surface tension of the ternary slag decreases along with the addition of SiO2. The reasons include the addition of SiO2 with lower surface tension and the decrease of the total ion moment at the surface. Both CaO and MgO can bring about that the iso-surface tension curve shifts towards the TiO2 corner, indicating that the surface tension of the ternary slag increases along with the addition of CaO or MgO. CaO has a more pronounced effect on increasing the surface tension of the ternary slag than MgO at an equimolar amount addition. The increase of the surface tension results from both the compositional change and the variation of the slag structure.

Jan 1, 2015

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

By D. Mishra

Electric arc furnace dust (EAFD) generated during the recycling of steel- scrap is classified as a hazardous waste for landfilling. This is because it contains leachable heavy metals such as zinc, lead,... Recovery of these metals could result in both resources conservation and resolving waste disposal problems. A study of the thermal reduction of a sample of EAFD was carried out in an inert gas atmosphere using coke as a reducing agent. Preferential volatilization of zinc and lead was achieved during the reduction process at about 800 "C. More than 96 % of both zinc and lead were removed from the dust and were recovered in the condensates. The treatment residue was essentially composed of iron oxides and almost free from heavy metals.

Jan 1, 2002

A rotating-discelectrode system was used to evaluate the electrochemical behaviour of Eu(III) during its reduction in NaCl solutions. The solution pH and NaCl concentration have a great effect on the reduction kinetics. The thermodynamic modelling study also revealed that Eu(III) exists in various forms in NaCl solutions. At a low concentration of NaCl, the predominant species is the free Eu3+. Other Eu-chloro complexes become more predominant when the NaCl concentration increases.

Jan 1, 1992

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

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

Jan 1, 2012

By B. Mishra

The application of various bydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, eg. 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 [EMI' and decontamination and decommissioning [D&D].

Jan 1, 1996

By José Carlos Abreu

This work presents a kinetics study covering the effects of temperature over the reduction rates of a carbon composite briquette, aiming its use as burden in some of the new alternate ironmaking technologies, such as the Tecnored process. It is reported that increases in the temperature increases the reaction rate. Additionally, the morphology of the iron phase generated during the reduction of these briquettes is presented. It was possible to verify that three types of iron morphology occurred during the process: an external, dense and continuous iron layer, the presence of iron globules at the center of the briquettes and whiskers at the briquette's core. The measurement of the carbon content on the globules and the external iron layer is also presented.

Jan 1, 2003

By Y. K. Rao

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

Jan 1, 1995

By Mariane Costalonga de Aguiar, Carlos Mauricio Fontes Vieira, Sergio Neves Monteiro

"This work evaluates the effect of incorporation of an ornamental rock waste into an industrial clayey body used for roofing tiles fabrication. Formulations with 0, 10, 20 and 30 wt.% of waste were prepared by replacing the sand in the industrial clayey body. The plasticity of the formulations was determined by the Atterberg limits. Specimens were fabricated by 18 MPa press-molding and then fired from 850, 950 and 1050°C. The specimens were tested to determine the water absorption, linear shrinkage and three points bending flexural strength. The results indicated that the waste improves the extrusion performance of the clayey body by decreasing its plasticity. The use of the waste was beneficial to the water absorption and mechanical strength of the fired clayey ceramic at 1050°C.IntroductionOrnamental rock is a natural resource available in the municipal area of Santo Antonio de Padua and located 150 km from the city of Campos dos Goytacazes, northe of state of Rio de Janeiro, Brazil. Intense industrial activity related to ornamental stones, especially gneisses, is traditionally occurring in the region. After mining, the flagstone is submitted to sawing to obtain blocks and then, after a manual operation, the final products are small flagstones [1,2]. During the sawing operation, a sludge composed of water and fine particles of rock is generated. A monthly production of 1000 tons of ornamental rock waste is estimated to be produced at Santo Antonio de Padua. The final disposal of this waste has brought serious environmental problems. Since most industries do not have an adequate sludge treatment, the waste is contaminating the soil and underground waters as well as obstructing rivers and lakes.Ceramic bodies industrially fabricated in the municipal area of Campos dos Goytacazes, 280 km from the city of Rio de Janeiro, are still empirically elaborated using a mixture of local clays. These clays are predominantly kaolinitic mineral, associated with high plasticity. Due to the excessive plasticity of the ceramic bodies, it is common to have dimensional defects in the final products after the drying and firing processes. Moreover, the kaolinitic structure and the presence of aluminum hydroxide confer a refractory behavior to the local clays. This impairs sintering during the firing operation. In the case of clay ceramics for civil construction, this results in greater porosity associated with elevated values of water absorption [3,4]. To avoid this problem, it is necessary to reformulate the ceramic body composition. The addition of both non-plastic materials to reduce plasticity and fluxes to condition the refractoriness is a possible alternative."

Jan 1, 2011