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By David Cocke

Study of surface and subsurface interfacial chemistry of metallic and similar systems has its enormous technological importance. Copper, for example, is a common component of many alloys and bulk amorphous systems. It is being increasingly studied today because of its use for electronic interconnect systems where processing is done below 200 ºC. Since several types of copper oxides exist, and the degree of their formation is dependent on temperature, perhaps characterization by EDS-SEM depth profiling and EIS might delineate one type of oxide from another. In this paper, we described our work on transformation of copper oxides with temperature ranging from 70 to 350 °C and their characterization by SEM, EDS, and XRD. We also showed the use of the phase angle portion of the impedance as a means to identify the predominant structure and the transition through Cu3O2 between the predominant stable CuO and Cu2O.

Jan 1, 2009

By Y. K. Rao

In the carbonyl process for the refining of crude nickel CO(g) reacts with nickel in the 310-370K range producing nickel tetracarbonyl, Ni(C0)4(g). Iron and cobalt impurities also form gaseous carbonyls but their partial pressures are low. The carbonyl is led to a decomposer plant wherein the gas disproportionates in the 500-600K range depositing pure metal on nickel pellets that move countercurrent to the gas-flow. This system serves to illustrate the fundamental principles involved in the vapor phase mass transport of elements, against temperature-gradient, under the influence of chemical potential gradient. Unlike in the crystal growth, the source is at a lower temperature (say 350K) whereas the seed is in the hot-zone (say 550K) of the closed ampoule-type reactor. By assuming virtual gas-solid equilibria in the end zones, with diffusion of gaseous species between them acting as a slight perturbation, the quasi-steady- state mass-transport rates are computed for a range of CO-pressures and temperatures.

Jan 1, 1993

A novel process is being developed for metal recovery from waste electrical and electronic equipment involving a leach reactor coupled to an electrochemical reactor. Metals such as Ag, Au, Cu, Pb, Pd, Sn etc. are dissolved from shredded electronic scrap in an acidic aqueous chloride electrolyte by oxidising them with aqueous dissolved chlorine species. In the electrochemical reactor: (i) chlorine is generated at the anode for use as the oxidant in the leach reactor, and, simultaneously, (ii) at the cathode, the dissolved metals are electrodeposited from the leach solution. The extended Butler-Volmer equation was used to provide predictions of the electrode potential dependences of partial current densities and, hence, total current densities, current efficiencies and alloy compositions for acidic aqueous chloride electrolytes containing Ag(I), Au(III), Cu(II), Pb(II), Pd(IV) and Sn(IV) species, together with dissolved chlorine. With judicious choice of kinetic parameters, the predicted total current density ? electrode potential behaviour of such solutions was in good agreement with experimental data for a rotating Pt disc electrode. Reduction of dissolved chlorine at a Pt rotating disc electrode exhibited mass transport controlled behaviour, in agreement with Levich?s equation over the potential range 0.3-0.9 V (SHE). This could form the basis of a linear sensor, possibly using a microelectrode for measurement and control of the dissolved chlorine concentration in the efflux of leach reactors and inlet to electrowinning reactors in the envisaged process.

Jan 1, 2003

By Beate Ina Jenssen

Ferric iron removal from the nickel electrolyte at Glencore Nikkelverk AS in Kristiansand, Norway, is achieved by precipitation of iron hydroxide followed by filtration, and it is desirable to improve filtration properties of the precipitated iron hydroxide in order to decrease the filtration time. The effect of increasing the residence time from the current 45 min to 75 min and temperature from 65 °C to 90 °C on the filtration properties of the precipitated iron hydroxide (akaganéite) was studied by simulating the industrial process conditions in a continuous reactor setup operating at steady state, using ferrous-containing process solution as feed material. It was possible to decrease the filter cake resistance by both increasing residence time and temperature, but temperature gave the most pronounced effect and reduced the filter cake resistance by one order of magnitude.

By K. Yamada, T. Takaoka, A. Ozeki, M. Yamaga, Y. Kawai, S. Nishioka, Y. Kikuchi

"Recently, smelting reduction of chromium ore in BOF has been actively investigated as a key unit process for an innovative future stainless steelmaking. The prominent feature of this new process route is energy and process saving, and production cost saving. The development is already in the midst of application to the commercial production, however there still remain the following key technologies to be established for the full use of the process. One is a speed up of the reduction of chromium ore to match with sequential continuous casting, and the other is efficient combustion of carbonaceous materials in BOF to reduce their consumption, and hence to assure the steel quality. High degree of post combustion technology and new charging technology, i.e., ore-coal-flux-oxygen mixed injection, could be effective for those two subjects. In 2000 or beyond, the new process would have become quite popular owing to the establishment of those key technologies.Introduction Since stainless steel was invented, its production has continued to expand because of its attractive combinations of functions of excellent corrosion resistance, good formability, a pleasing appearance, and a wide range of strength levels. New types of stainless steels as well as new applications are continually being developed.Compared to the production of ordinary steels (1), stainless steel production (2,3) shows steady growth worldwide, while the former production remains on the same level, as Figure 1 shows. It can be estimated that future production would show further growth since materials consumer demands are more fashionable, or more functional, which could be satisfied by stainless steels.Thus market needs would be met, if it could be produced with reasonable production cost. The emergence of an innovative production technology is then potentially requested as VOD and AOD processes have emerged, which has saved substantial production cost. This paper describes a possibility of a future stainless steelmaking process, which uses the in-bath smelting reduction of chromium ore in BOF, and which would save production as well as energy cost."

Jan 1, 1988

By P. M. Prasad

The last two decades have witnessed the emergence of numerous hydrometallurgical and direct processing techniques for the extraction of some metals from pocketed/lean/complex sulfide ore deposits. A new approach with some inherent technological merits, investigated in recent years, is the lime-enhanced reduction of metal sulfides. Thermodynamic aspects relevant to the lime-enhanced reduction of metal sulfides by H2,C0 and C are discussed. A survey of the researches on the basic features of and factors influencing the lime-scavenged reduction of selected sulfides and sulfide concentrates reveals that lime tremendously enhances the sulfide reduction rates (up to 100 times) and drastically reduces the sulfur emission into off-gas to negligible levels. Further successful practice of lime-enhanced reduction requires only a moderate temperature of reduction (characteristic of each sul¬fide) and, in the case of gaseous reduction, relatively low gas flow rates. Relevant kinetic aspects of the concerned reactions that have a bearing on process development and its understanding are also briefly discussed. A conceptual scheme of general applicability for the processing of sulfide concentrates by the lime-enhanced reduction technique consists of three main steps: (0 lime-enhanced reduction by a suitable reagent (e,g., H,2, CO, gasified coal, water gas), (ii) separation of the product metal from the dry slag (CaS + unused CO) by mechanical separation, magnetic/gravity concentration or flotation and (iii) melting and refining by standard procedures. This novel approach, which is patently less complex, is expected to employ basically simpler flow sheets at comparatively lower operational temperatures and aid in pollution abatement. Potential for developing such a route for the small scale extraction of metals like copper, molybdenum and antimony is indicated. Possibility of utilizing this technique for the production of fibers/ filaments of some metals is also outlined.

Jan 1, 1983

By M. Moinpour, E. Liao, C. Y. Aw, D. J. Brown, P. W. Cheung

"Currently, silicon-based insulated-gate field-effect devices are being widely developed as the basic structural elements in a new generation of chemical microsensors. In this paper, we discuss some of the process considerations related to the fabrication of the Chemically Sensitive Field-Effect Transistor (CHEMFET). This ion-sensitive CHEMFET (or ISFET as it is often called) can be used for pH measurements (i.e., as a pH sensor) when the gate insulator of the electrolyte/insulator interface is made of Si3N4 obtained by the LPCVD method. Effects of processing parameters such as the Si3N4 deposition rate, gas composition, total flow rate, annealing treatment, etc. on Si/Si02, Si/Si3N4 and Si/Si02/Si3N4 structures are discussed in relation to the CHEMFET fabrication. Their effects on the electrical characteristics and chemical response of the sensor are also examined. Capacitance-Voltage (C-V) measurements and ESCA analysis have been used to interpret the results. The Si3N4/Si02 double dialectric layer provides improved ion blocking for the gate insulator in electrolyte solutions with enhanced pH sensitivity over time. The stability and performance of the fabricated CHEMFET sensors were tested by measuring the pH sensitivity in various storage conditions. The SEM analysis was used to evaluate the hydration effect at the ISFET's gate insulator with respect to different storage conditions.IntroductionThere has been a continuous interest in the development and fabrication of various chemical microsensors for chemical and biomedical applications over the last fifteen years. The application of semiconductor (particularly silicon) technology to the area of sensor fabrication has led to an emergence of a new generation of miniaturized, microelectronic, solid-state chemical sensors. There are numerous clinical situations where continuous monitoring of body electrolytes concentrations such as Na+, K+, Ca+2 , etc. and blood gases (pH, Po2 , and PC02) would be essential for the effective diagnosis and management of patients under critical conditions. Solid- state microsensors can be used for direct and continuous in vivo measurement of the above parameters in most instances."

Jan 1, 1988

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.

By A. Kontopoulos

The extraction of nickel and cobalt from low-grade greek laterites by sulfuric acid leaching has been studied. Batch and continuous mini-plant atmospheric leaching as well as pressure leaching techniques were employed. Atmospheric leaching at temperatures as high as 95 OC generally resulted in low Ni extractions (up to 82%), high acid consumption (650-850 kg/t ore or 80-100 kg/kg Ni) and high Fe co-dissolution (30%). Pressure leaching at 260 OC increased Ni extraction to over 98%, with minimal Fe co-dissolution (2.5%); acid consumption was 300 kg/t ore (31 kg/kg Ni). Detailed experimental results and conceptual flow sheets for atmospheric and pressure leaching are presented.

Jan 1, 1991

By A. Niedbalska

A technique was developed for low pressure diamond synthesis using a specially prepared glassy carbon. The glassy carbon is produced in the form of solid plates by slow carbonization process of phenol formaldehyde resin interrupted at temperatures of 1273° K, 1073° K, and 923° K. The diamond synthesis is performed using cobalt plates as a catalyst-solvent. Synthesis was carried out at applied pressures of 6.0 and 3.8 GPa and a temperature of 1970° K and 2170° K. The products were analyzed by the x-ray powder dyffraction method and by microprobe to identify the diamond crystallites. The samples were taken from the place of contact between the glassy carbon and the cobalt catalyst. They were separated from the charge by a chemical method. Diamonds of the best form and the largest size were obtained at pressures that were much lower than those used in the traditional graphite method of diamond synthesis.

Jan 1, 1989

By Zhitong Sui

Based on several case studies on the precipitating behavior of valuable nonferrous metal compounds (VNMC) in molten slags a green technology for the recovery of VNMC from molten slags was proposed. This technology involves three steps: (I) The selective enrichment of the dispersed VNMC into the designed mineral phase in the molten slag; (2) The selective coarsening of the designed mineral phase to a critical grain size in the molten slag; (3) The selective separation from tailing of the grown mineral phase in the solidified slag by dressing or hydrometallurgy processes. This is a clean and low cost technique and has a great capacity to deal with a large quantity of slags. The utilization of the recovered VNMC such as Titanium, Boron, Vanadium compounds was summarized as examples of application. It was confirmed by experiments that the precipitating behavior of the designed mineral phases like Perovskite(CaTiO3), Suanite(2MgO*B2O3) and Sincosite(CaOoV2O5*P2O5) in molten slags is obviously affected by operation factors such as temperature, chemical composition, heat-treatment, additives and so on. The precipitating kinetics and mechanism of the VNMC from molten slags during solidification processes were also investigated.

Jan 1, 2003

By Tianzu Yang, Weifeng Liu, Shu Bin, Lin Chen, Wanda Bin

"Vanyukov Process has been mainly applied for processing copper and nickel sulfide ore for more than 30 years. Based on the understanding of the Vanyukov Process, researchers from China introduced the technology into the areas of lead, antimony and bismuth extraction by changing the furnace structure and technical flow, which greatly extended the application area and raised the processing efficiency, thus developed the oxygen-rich side-blow bath smelting (OSBS) technology in 2000. This contribution reviews the history of OSBS technology from four respects: the quantity, the furnace structure, the process flow and the application area. Its potential research direction and industrial application are also summarized.IntroductionVanyukov bath smelting furnace and related bath smelting technology were developed by researchers from Soviet Union who devoted comprehensive research on fundamental theory as well as engineering technology [1,5]. Vanyukov process has been applied for large industrial production since the 1970s and it is still one of the major methods in modem pyrometallurgy process. The appearance ofVanyukov double district furnace and joint double furnace in the past ten years, which are applied for copper smelting, is the most valuable advances of the Vanyukov process [7,8,9]. However, the application ofVanyukov process was limited in copper and nickel sulfide ore smelting, and few countries adopted this process except Soviet Union."

Jan 1, 2013

By Chunlin Chen

Nickel-sulfide minerals are normally associated with copper and iron sulfides and often contain a minor amount of valuable metals such as cobalt and detrimental impurities such as arsenic. Metal losses in slag vary from process to process during the pyrometallurgical production of nickel and, depend on the feed composition, slag chemistry and operating conditions. Maximiz the metal recovery is one of major considerations to optimize operating condition for nickel smelting/ converting processes. At the same time, the deportment of minor elements between various phases during nickel smelting is of great importance by smelter operators. The Multi-Phase Equilibrium (MPE) is a thermodynamic package developed by CSIRO for simulating reactions between phases in multi-component and multi-phase systems [1]. Over the years the capability of the MPE model has been extended to cover the behavior of a large number of elements in high temperature systems. The sulfide smelting module of the MPE, which covers the minor elements such as As, Bi, Sb, Pb, Se, Te, Sn, Co and Zn, is capable of modeling the deportment of major and minor elements between various phases during nickel smelting. In this article the application of the MPE model in modelling the nickel smelting process is presented. The modelling results on the majors and minors are compared with the plant data. The deportment behaviour of arsenic in nickel smelting was analysed and the impact of slag chemistry on slag properties was modelled. These results can assist process metallurgists in exploring the optimum fluxing strategy for smooth operation and the potential practices for improving arsenic removal.

By I. D. Reznik

On blowing nickel matte in a converter without quartz, first the oxidation of metallic iron and a part of FeS occurs without evolving sulfur dioxide, the formed FeO dissolves in a sulphide smelt and form a homogeneous oxysulphide smelt. On further increasing the FeO content, the oxysulphide separates into 2 layers. Based on the laboratory investigation of FeO-(FeS+Fe°) - (Ni3S2+Ni°) ternary phase diagram we have identified the separation region at 1250°C. The boundaries of the separation region have the form of an arc and the composition of the separated oxysulphide layers is defined by the canodes. In the nickel or copper-nickel matte - silicacalcium oxide slag system at 1250°C three layers, namely sulphide, oxysulphide, and slag may be formed. A high slag basicity due to the presence of CaO can serve to enhance the activity of FeO; a low nickel content in the matte corresponds to a high concentration of FeS therein; FeO from slag and FeS from the matte form a homogeneous FeO-FeS solution, i.e. an oxysulphide layer. The investigation on the "Camebaks" apparatus and by the nuclear gamma-ray resonance spectroscopy method of the phase composition in a slowly cooled oxysulphide layer has shown the presence of four phases: wustite, troilite, ferronickel grains, and calcium oxide-silica inclusions. Knowledge of regularities in the oxysulphides formation makes it possible to use them in pyrometallurgy of nickel and cobalt or preventing their formation.

Jan 1, 1997

By M. K. Mohan

Lead recovery from process solutions contributes not only to the conservation of resources but also clean environment. Zeolites are natural aluminosilicates, which finds applications as catalysts and in wastewater treatment. In the present investigation, studies were taken up on the processing of Pb from process solutions by zeolites. Effects of pH of the solution, time and type of zeolite viz. chabazite, mordenite, erionite and clinoptilolite on the removal of Pb from solutions was investigated. Rate of sorption was found to depend on the pH of the solution and about 99 pct. recovery was observed at pH 6. Optimal conditions were established for the maximum recovery of lead from process solutions. Possible sorption mechanisms were proposed. The calculated adsorption constants calculated from Langmuir and Freundlich equations showed that the adsorption of lead on chabazite was strong.

Jan 1, 1999

By S. Ozbilen, B. Erdogan, M. Erdogan

To study by thermal analyses the response of precipitation hardenable alloys of Al-Cu-Mg and Al-Li-Cu-Mg system to natural and artificial ageing, a series of ternary and quaternary Al-alloys with nominal compositions of Al-l.13wt%Cu-0:65wt%Mg (alloy-I), Al-1.15wt%Cu-0.57wt%Mg-0.07wt%Li (alloy-2), Al-l.19wt%Cu-0.56wt%Mg-0.75wt%Li (alloy-3), Al-2.0lwt%Cu-0.89wt%Mg (alloy-4), Al-2.14wt%Cu"0.56wt%Mg-0.07wt%Li (alloy-5) were used in the present investigation. Samples in the form of rolled sheets are subjected to water quenching at 25EC after solution treatment at 530EC for 20 min. Alloys were aged naturally at room temperature (25EC) up to 2 months and artificially at 190EC up to 2 days. By using differential scanning calorimetry (DSC) in the temperature range of25-300EC, differential thermal analysis (DTA) in the temperature range of25-600EC together with Vicker's hardness measurements, the response to natural and artificial ageing of the alloys used in the present study were investigated. It was observed that in these alloys, GPB(Cu, Mg) zones [Guinier-Preston zones with Cu and Mg] do form during water quenching at 20EC following solutionizing heat treatment. Natural ageing of the same alloys causes formation of more GPB(Cu, Mg) zones, which results in hardening in the alloys. Artificial ageing at 190EC up to l day results in GPB zone dissolution causing preliminary decrease in hardness values while two days of artificial ageing in the alloys cause S' (Al2CuMg) precipitation confirmed by DSC/DTA analyses resulting in an increase in hardness values. Li addition up to 0.75wt% helps T1 (Al2CuLi) and T 2 (Al6CuLi3) phase formation together with S' precipitation as DSC/DTA analyses show after the same heat treatment.

Jan 1, 1998

By E. J. Peuraniemi

Primary copper production using suspension smelting techniques like Outokumpu Flash Smelting always causes some dust formation. Flue dust particles are formed when sulphide feed material reacts violently with oxygen inducing particle disintegration and total desulphurisation of fragments. In the process, flue dust follows the off-gases to the heat recovery boiler (HRB) where its sulphation takes place because of prevailing conditions. Sulphation releases heat and causes also a drop in particle melting temperature and, further, particle sticking to the walls and heat exchange tube banks. Sulphation of synthetic CU20 particles were examined using a laboratory scale fluid-bed reactor. This study aims to a better understanding of flue dust behaviour in a HRB and, thus, to a better operational practise and design of a HRB. The effect of PSO/PO2 -ratio and temperature on the sulphation kinetics were tested. Standard chemical analysis, light optical and scanning electron microscopy with energy dispersive spectroscopy were used to examine the samples.

Jan 1, 2001

By F. Elgersma

A high purity electrolysis solution is essential for hydrometallurgical zinc winning processes. For this reason ferric iron containing compounds such as jarosite are precipitated as iron and impurity collector during the calcine leaching. Jarosite thus forms a chemical waste and creates environmental problems. This research contributes to the development of a wet jarosite treatment process, where less contaminated jarosite is produced which can act as an iron source. The present work studies jarosite precipitation kinetics and the uptake of zinc cations in batch and continuous experiments. The distribution coefficient for zinc in continuous experiments is constant for a wide ratio of zinc over ferric ions in the solution. Addition of NH, + ions in batch experiments accelerates the conversion rate equivalent to the driving force increment. Addition of 50,2-ions above the stoichiometric ratio increases the conversion rate less then could be expected from the increase in the estimated driving force. Zinc ions tend to retard the conversion rate. An increasing reaction temperature increases the conversion rate. Below 75 ?C the conversion rate approximates zero.

Jan 1, 1990

By M. A. Cocquerel

The future economic necessity of mining copper ores with a high impurity content and increased environmental awareness will require closer examination of the distribution of arsenic within copper smelting processes. A generalized approach is developed which can be adapted to specific projects for the determination of an overall process configuration to satisfy all requirements in a cost effective manner.

Jan 1, 1983

By S Ivanaj

Oxidation of chalcopyrite from a copper concentrate in an electrochemical cell having separate-anodic and cathodic compartments was studied by potentiodynamic, potentiostatic and galvanostatic experiments. Oxidation of chalcopyrite particles was mainly realized by in-situ electrogenerated FeIII and Cull ions. The use of an ion exchange membrane, in this experimental set, avoids the reduction of the ferric and cupric ions. The effects of particle size, current feeder potential, current intensity and pulp density were studied to optimize the oxidation parameters. Selective complete oxidation of chalcopyrite was achieved. Oxidation of pyrite was negligible. Mom than 85 % of sulfur was obtained in its elemental form. This may allow selective extraction- of copper from the chalcopyrite concentrate without sulfur dioxide emissions.

Jan 1, 1995