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By David R. Sadedin

The highly negative Gibbs free energies of hydrogen atom reactions suggest that refractory oxides such as titanium dioxide should be easily reduced by hydrogen atoms. These reactions appear to be most favourable at low temperatures; oxides should be reducible even at room temperature. Since hydrogen atoms are produced in plasmas containing hydrogen a number of investigators have used hydrogen plasmas of various sorts to test these possibilities for reducing refractory oxides, in particular TiO2. None of these attempts has succeeded, a small degree of reduction being achieved in only a thin layer near the surface. A deeper consideration shows that several factors complicate the reactions expected on the basis of the negative Gibbs free energy. One factor is that the back reaction by water molecules produces molecular hydrogen, not hydrogen atoms, and the metal atoms that have been reduced may be immediately re-oxidised. In plasmas there are complications due to diffusion, thermal and charge boundary layers and charged particle reactions. Interpreting the results of hydrogen atom reactions is difficult. Hydrogen is not detectable by electron dispersive spectroscopy and amorphous products are not determinable by x-ray diffraction. Another consideration is economics. The cost of producing hydrogen atoms has a large bearing on the metals for which hydrogen atom reduction may be competitive. In this paper these factors are discussed, some necessary basic studies are highlighted and the general principles of a laboratory reactor are given, together with the results of tests using ZnFe2O4, ZnO and TiO2 as test oxides.

Jan 1, 2006

By M. Potesser

In the primary and secondary copper industry the anode furnace is the most important process step in the refining procedure to reach an enhancement in value and quality of the copper by a selective oxidation and reduction. By combining the advantages of the conventional tilting hearth anode furnace and the benefits of the drum type anode furnace a new aggregate was developed and patented. The cross-section of the furnace is elliptical and the whole unit is tiltable. During the melting period, the contact surface between the burners and the bath or the scarp is enlarged - an increased energy input is the consequence. For the refining period the furnace is rotated, whereby a high bath level is guaranteed. Due to the longer residence time of the gas in the copper melt, not only the gas consumption is reduced but also the efficiency/quality of the refining process is improved. This investigation shows a metallurgical comparison between the new anode furnace concept with the elliptical profile/cross section and the conventional, tiltable hearth anode furnace as well as the drum type anode furnace. The CFD modeling of the currents in these different furnaces delivered helpful data to compare the geometry of the different furnaces. The investigation covered the refining of blister copper from primary metallurgy, from secondary metallurgy as well as from a mixture of both copper melts. The paper underlines the possibilities for a reduction of the tap-to-tap time and for an increase in production capacity, which can be achieved by applying the new furnace concept in comparison to the conventional furnaces.

Jan 1, 2006

By Cameron Hams

Noranda's Process Reactor and Codelco's Teniente Converter are physically similar vessels, which leads to the commonly held misconception that the two processes are the .same. However, notable differences in chemistry, operating philosophy, and construction make them quite dissimilar. This paper compares and contrasts the Noranda Reactor and the Teniente Converter, and attempts to explain some of the apparent differences in behaviour and performance. The results of a worldwide survey of most operating Noranda Reactors and Teniente Converters, along with those processes that have ceased operation or are planning to be started-up in the future, are presented.

Jan 1, 1999

By Darryl Lovato, Ramiro Pereyra, Daniel S. Schwartz

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

Jan 1, 2008

By W. G. Davenport

A survey of world copper refining tankhouse .practices has been carried out. This paper compiles the results and examines changes in operating practices .since the similar 1987, 1991 and 1995 surveys. Continuing trends are the installation of ISA Process and Kidd Process stainless steel cathode technology, polymer concrete cells, anode preparation machines and automatic cranes. Instrumentation and automatic control are increasing, particularly for addition agent optimization; solvent extraction .and ion exchange techniques are being increasingly applied for electrolyte purification. The overall consequences of these changes have been 'improved cathode purities and enhanced tankhouse productivities.

Jan 1, 1999

By R. G. Haire

Studies of the f-elements under pressure provide important insights into their solid state chemistry and physics. From such studies, of the elements and their alloys, it has been established that the normally localized f- electrons of several of these elements can become, involved in bonding under pressure. The electronic behavior of f-element compounds under pressure tend to be more difficult to interpret, due to the variety and the nature of electronic orbitals that are present. The 4f-elements and some 60% of the 5f-elements have been studied under The systematic comparisons that have been established for these materials are discussed.

Jan 1, 1992

Four slag types covering the range of Fe-Ca-Si-O compositions and two iron blast furnace slags were melted at 1300 °C and doped with 1% of arsenic, antimony, cadmium, zinc and chromium. The melts were either slow cooled or quenched and the solidified slags were leached according to TCLP procedures. The morphology of the solidified slags was characterised using XRD, optical and electron microprobe techniques. Theoretical considerations showed that the capacity of the molten slag to hold the above toxic elements depended upon slag basicity and this was confirmed in practice. The experiments showed that the leaching of the toxic elements was a function of surface area and the phases present, both of which were affected by the mode of cooling. Iron silicate slags produced in nonferrous smelting operations and blast furnace slag from ferrous smelting operations both show promise of being suitable media for immobilising low levels of toxic elements and complying with current regulatory requirements.

Jan 1, 1994

By Roberto Parra

The selective reduction smelting of Cu2O in Cu2O-FeOx-SiO2 melts has been studied at laboratory level, using as a feed a dead roasted calcine from a copper concentrate. The purpose of the study was to evaluate the kinetic and mechanisms of the indirect reduction with CO and the direct reduction with graphite from 1260°C to 1350°C. The reduction rate by CO was found to be 10-2 to 10-1 mole Cu2O m-2s-1. The graphite reduction macrokinetics for FeO and. Fe2O3 containing melts, was found to be a first order reaction with respect to the Cu2O concentration, with a kinetic constant of 104 to 10-3 s-1. The reduction rate was not sensitive to temperature nor to stirring, in the range studied. The measured reduction rate is almost one order of magnitude larger than the observed rate for the direct reduction of FeO.

Jan 1, 1999

By B. R. Adams

This paper discusses the use of a reacting CFD model to determine chalcopyrite kinetics in a drop tube furnace and to predict the reaction of a chalcopyrite concentrate in the reaction shaft of an industrial smelter. Reacting CFD codes can be applied to determine the consequences of the interaction of gas with particles and therefore improve the ability to derive kinetic parameters that take into account the temperature and oxidation histories that different particles will see. This paper describes the application of such a model to derive improved kinetic parameters for the pyrolysis and oxidation of chalcopyrite. The reaction shaft model includes the effects of turbulent fluid mechanics, entrained flow mixing, turbulent particle dispersion, heterogeneous particle reactions, radiative and convective heat transfer, and' surface and bath deposition rates. Particle reaction and composition characteristics are predicted as a function of particle trajectory and deposition and are used to aid in evaluating shaft performance.

Jan 1, 1999

By G. A. Brooks

The problem of treating concentrates with increasingly higher levels of arsenic and antimony is compounded by the trend to stricter environmental guidelines regarding the disposal of smelter wastes. Much of the arsenic and antimony from non-ferrous processes is recovered as oxide fume. The options for handling these fumes include recycling them to the smelter, stabilising and disposing of them, and recovering values from them. Whilst arsenic oxide has little value, there is a market for antimony oxide and this provides an incentive for devising techniques for separating antimony oxide from arsenic oxide before disposal of the arsenic oxide. Arsenic can be separated from antimony oxide by selectively volatilising the more volatile arsenic trioxide from a mixed oxide sample or by selectively condensing the less volatile antimony tetroxide at high temperatures, leaving arsenic trioxide to condense out at lower temperatures. The results of selective volatilisation experiments at 379 to 587 °C indicate that it is difficult to achieve an arsenic content below 5.0 wt.% using air or nitrogen as carrier gas due to the formation of solid solutions between the two oxides. Injection of oxygen into a mixed vapor stream improved separation by selective condensation and antimony tetroxide containing as low as 0.23 wt.% was obtained in laboratory experiments.

Jan 1, 1994

By Yong Kuk Park

The horizontal cold chamber die casting process can produce a wide range of near-net shape, non-ferrous castings with small dimensional variation, excellent surface finish and very complex geometries. However, top quality die castings can be achieved only when optimal performance of the cold chamber and plunger is maintained during the molten metal injection phase of the process. Cold chambers (shot sleeves) are known to deteriorate fast and sometimes fail catastrophically because of poor design. Catastrophic fracture and wear due to deformation are leading causes to degrade quality, increase downtime and thereby decrease productivity and profitability. Therefore, a systematic approach to minimize irregular and adverse conditions which prevent an intended injection profile, is highly desirable. To eliminate them, design criteria for shot sleeves were developed using analytical tools and available experimental data. The correlation between design and mechanical failures of shot sleeves was shown by the data obtained from the die casting industry. Also, the relationship between die casting process parameters and deterioration/ failure mechanisms were carefully evaluated.

Jan 1, 1996

By Francis Vanbellen

Umicore Precious Metals Refining operates an integrated precious metals smelting and refining plant in Hoboken, Belgium. Once a smelter and refiner of complex concentrates, the plant today?s feed consists exclusively of industrial and consumer recycled products, making it the world?s largest recycling facility for precious metals. Unlike the fairy tale of the Frog Prince, it took much more than a princess? kiss to successfully realize this makeover. A completely renewed plant has been built over the past decade. The most visible technological innovation was the commissioning of the Pb-Cu smelter. Its flexibility towards very different types of feed makes it perfectly suited as main entry to the Hoboken flow sheet. A new Cu-leaching & electro winning plant and precious metals refinery make up the Precious Metals Operations (PMO) whose targets are fast throughput and maximized yields for gold, silver and the platinum group metals. The Base Metals Operations (BMO), flexibly process the by-products from the PMO, valorizing ?impurities? like indium, tellurium, selenium and others. Off gas and waste water treatments ensure compliance with strict environmental standards. Precious metals recycling is an art that goes beyond mastering a unique flow sheet. Umicore Precious Metals Refining offers a complete recycling service, taking care of sampling and assaying, metals management and logistics. The quality of this integral service is recognized through the attribution of ISO certifications for our operational activities, sampling and the environmental care. And it?s an art that follows Michelangelo?s experience: ?Art is 5% of inspiration and 95% of transpiration.?

Jan 1, 2006

By Susumu Imashuku

A pseudoternary phase diagram of the BaO?ZrO2?ScO1.5 system is established and the conductivities of the scandium-doped barium zirconate are measured in wet conditions. According to the phase diagram, the molar fraction of scandia in the barium zirconate phase that equilibrates with the cubic zirconia (ZrO2) and scandia (Sc2O3) phase is 0.03. On the composition line, where the molar fraction of barium oxide (BaO) is 0.50, the solubility of scandia into barium zirconate is 0.27 as a molar fraction of scandia. At around 500 °C, the conductivities of scandium-doped barium zirconate are estimated to be almost same as that of yttrium-doped barium zirconateThe activation energies for bulk proton conduction in scandium-doped barium zirconate (0.57 eV for BaZr0.90Sc0.10O3-d) are higher than that of yttrium-doped barium zirconate (0.44 eV for BaZr0.90Y0.10O3-d). In addition, the bulk conductivity of scandium-doped barium zirconate in this study is 10 times higher than the reported conductivities in the temperature range of 75 °C to 300 °C.

Jan 1, 2006

By Francis Vanbellen

Umicore Precious Metals Refining operates an integrated precious metals smelting and refining plant in Hoboken, Belgium. Once a smelter and refiner of complex concentrates, the plant today?s feed consists exclusively of industrial and consumer recycled products, making it the world?s largest recycling facility for precious metals. Unlike the fairy tale of the Frog Prince, it took much more than a princess? kiss to successfully realize this makeover. A completely renewed plant has been built over the past decade. The most visible technological innovation was the commissioning of the Pb-Cu smelter. Its flexibility towards very different types of feed makes it perfectly suited as main entry to the Hoboken flow sheet. A new Cu-leaching & electro winning plant and precious metals refinery make up the Precious Metals Operations (PMO) whose targets are fast throughput and maximized yields for gold, silver and the platinum group metals. The Base Metals Operations (BMO), flexibly process the by-products from the PMO, valorizing ?impurities? like indium, tellurium, selenium and others. Off gas and waste water treatments ensure compliance with strict environmental standards. Precious metals recycling is an art that goes beyond mastering a unique flow sheet. Umicore Precious Metals Refining offers a complete recycling service, taking care of sampling and assaying, metals management and logistics. The quality of this integral service is recognized through the attribution of ISO certifications for our operational activities, sampling and the environmental care. And it?s an art that follows Michelangelo?s experience: ?Art is 5% of inspiration and 95% of transpiration.?

Jan 1, 2006

By Antrekowitsch Jürgen

The recycling of residues from metal producing by-products has become a main field of interest in metallurgical investigations. Forced by a stricter environmental legislation and the resulting increase of landfilling costs, combined with the aim to recover as many valuable metals as possible, a lot of different processes have been developed in the last two decades. Because of the high yearly tonnage residues from the iron and steel industry like slags, dusts and sludges have moved in the center of interest. Dusts from the steel mill, containing heavy metal oxides and halides did not play a considerable role as secondary raw materials for a long time. They even contain a huge amount of leachable elements and compounds which cause noticeable problems in case of a dumping. Nevertheless, the implementation of a new landfilling regulation, including a prohibition of aboveground dumping without inertisation, caused a rising interest concerning recycling technologies for such residues. In addition, the zinc content of these dusts became higher and higher and began to play the most important role for the economy of dust recycling.

Jan 1, 2006

By Marco Pasetto

The possibility to re-use marginal materials (by-products) deriving from industrial activities in the construction of road infrastructures, as total or partial substitution of natural aggregates, successfully combines demands for economy and environmental sustainability. The paper presents the results of a laboratory study, conducted at the Experimental Road Laboratory of the University of Padova, to verify the suitability of a particular type of electric arc furnace slag to be recycled in the lithic skeleton of high-performance asphalt mixes (porous asphalt, high modulus mixes, stone mastic asphalt, nonskid surfacings) for road and airport flexible pavements. the process of transformation of iron and steel slag into a product that can be used in road building is described, along with the characterisation of the mixtures, plus an analysis of the results of a wide battery of mechanical-performance tests. This study forms part of wider theoretical ? experimental research being done at the University of Padova in order to improve knowledge of the characteristics of succedaneum materials and check their possible applications in road and airport construction.

Jan 1, 2006

By T. Lezhava

A new reactor model with rotating cathodes has been developed where various forms (dendrite, spongy) of metal depositions and their uninterrupted removal are accomplished by the realization of high current densities and low energy consumption. At the same time in contrast with the existing methods a high quality metal powder may be obtained from concentrated electrolytes without any specific organic or inorganic additives, which allows raising the intensity of the process. The reactor can be used for electrowinning of metals with low adhesive capacity (Pb, Ag, Cu, Zn, Ni, Co, etc.) and the powders. The obtained products may be utilized in general metallurgy as well as in powder metallurgy.

Jan 1, 2006

By P. Gray

Process and engineering development of the Warner Zinc Process over the past two decades has proceeded alongside the world-wide collection and analysis of operating and cost data of current processing practices from sulphide ores to refined metals. Study of these data shows that recoveries are dependent on mineralogical characteristics of the sulphide matrix and point to the inadequacy of differential flotation as a tool for preparing feed for smelters. The paid-for return at the mine on the combined metal values in zinc rich sulphide ores rarely exceeds 80% and increasingly runs as low as 50-60%. Surveying the possible alternative ways of improving these performances leads to the conclusion that the Warner Process is the only technology in sight that could meet a target of 90% paid-for recovery and that its development has now reached a point where it can be a fully practicable process for all mixed sulphide ores.

Jan 1, 2000

By Motoyasu Sato

Highly pure pig irons were produced in a multimode microwave reactor from powdered iron ores with carbon as a reducing agent in the nitrogen atmosphere. The grains in compacted powder absorb microwave energy selectively. Microwave-matter interaction creates thermal non-equilibrium state microscopically and enhances chemical reactions and the phase mixing at the grain boundaries very rapidly. The visible light spectroscopic techniques was used to monitor the progress of the reactions. Up to 650°C, the heated powders radiate the continuous spectrum of blackbody emission. The small non-equilibrium hot spots rise, move and finally burst in to brighter light emitting from all over the surface at 650°C. CN molecules and Fe (I) atoms were identified in the recorded spectrum. These bursts are similar to the ?ignition propagation? normally observed in chemical reactions. The line spectra originated from CO molecules have not been detected yet. The solid-solid reaction could be expected between the iron oxides and carbon to produce CO2 directly. A loss in the sample weight was accelerated during the excess-emission. These are the clear evidence that microwaves cause thermally non-equilibrium state and accelerate reduction process. The reduction of iron ore is completed at 1380°C and relatively very pure pig iron was produced. It should be noted that the impurity level of Mg, S, Si, P and Ti is only 5-10% of what is found in the pig irons produced by modern conventional blast furnaces in the steel industries. The necessary amount of carbon needed was 1/2 compared to conventional blast furnace to produce the unit weight of steel, if we applied renewable energy or nuclear power for the microwave excitations.

Jan 1, 2006

By Guo Chang Jiang

In order to improve the IIAZ toughness of X-60 pipe steel, the intragranular ferrite plate (IFP) technology was used. The characteristics of IFP is claimed to be much fine ferrite plates appear inside the original austenite grains. By means of suitable Re, Zr, Ti additions in a bath with a higher initial oxygen potential, a good control of the peak temperature and the cooling rate during welding simulation, one can get a %IFP in volume over 50%, and the toughness gets up from 55 J to 160 J. It was found that the inclusions most effective in nucleating IFP are some deformable complex silicates which either entrap Re, Zr, Ti oxides or contain these elements. The greater the number of the evenly distributed and effectively nucleating inclusions, the more the %IFP in volume, and the finer the microstructure of the HAZ, so the better the relevant toughness. Generally, these silicates bahave as fine spheres along a line. The present authors revealed that these fine spheres result from the remelting of the shuttle- like silicates due to heating in the process of welding simulation. These silicates used to get a higher sulphur capacity, so MnS deposits might be observed on the periphery of the silicates. IFP was proved to be directly rooted in the [Mn] depleting zone which locates beside MnS deposits.

Jan 1, 1997