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By Dale Zacherl, Andreas Buhr, Rainer Kockegey-Lorenz

"The microporous calcium hexaluminate insulating material SLA-92 has been introduced as an alternative to refractory ceramic fiber and other insulating refractory materials. Key properties associated with this product include: high chemical purity, long term high temperature stability up to 1500 °C, low thermal conductivity up to 1500 °C, and high thermal shock resistance. The properties of the new material and various applications in the steel and ceramic industries have been reported in previous papers. The current paper summarizes the industrial application experiences with innovative refractories based on SLA- 92 and discusses potential new applications in various manufacturing as well as energyrelated industries.IntroductionSLA-92 was introduced to the refractories industry in 1998 by van Garsel, et al. [1] as a new insulating raw material for high temperature applications, followed by investigations [2] of long term temperature stability for this new lightweight aggregate up to 1500°C.SLA-92 was developed as an innovative alternative to commonly used refractory ceramic fibers. It has unique properties regarding chemical purity and mineral composition and is a microporous, silica-free calcium hexaluminate (CA6 – mineral name: hibonite)."

Jan 1, 2010

By Peter K. Eriksson

Nanofiltration is very efficient in separating heavy metals from water solutions, even if they contain strong acids. Desalination System, Inc., has many years of experience in this area, and this paper deals with three different such cases. The first case deals with concentrating the heavy metals in the pregnant leach solution from a copper dump leaching site with a surplus water problem. The increased copper concentration in the pregnant leach solution increases the capacity of the following copper extraction stage. The nanofIltration permeate is polished with a biomass adsorption column to remove the small amounts of remaining heavy metals, before being discharged. This method eliminates sludge handling and disposal, which are quite costly with the alternative precipitation process. In the second case, a complicated precipitation method was used to remove heavy metals from the waste stream of a specialty metals manufacturer. Nanofiltration was installed to increase the metals concentration four times, which greatly simplified the precipitation process. The chemical consumption and sludge production decreased by more than 80 percent, and the labor cost decreased by 66 percent. In the third case, nanofiltration was used to purify waste sulfuric acid solutions containing heavy metals, to meet the specifications for technical grade acid. Sulfuric acid concentrations above 30 weight percent were successfully purified in a multiple pass membrane system.

Jan 1, 1996

By D. B. Dreisinger, V. van der Pas

Zinc sulphate electrolyte used for zinc electrowinning must be purified for cObalt ions. The cobalt is removed in a cementation stage by the addition of zinc dust. Copper arid antimony are frequently used additives which enhance the cementation of cobalt. This paper aims at a better understanding of how copper and antimony promote the removal of cobalt. Initial experiments were done in a batch cementation reactor. Copper and antimony precipitated in the early stages of cementation indicating that a preferential substrate was formed. The individual role of copper and antimony was further investigated in an electrochemical cell. On a microsca1e, the , growth process, morphology and the composition of the precipitates were examined with SEM and XRD. It was found that cobalt could not be deposited in its pure form but as a cobalt-zinc alloy with zinc as the prime constituent. Copper increases the cathodic surface area of zinc dust by precipitating as numerous dendrites. Antimony acts as a cathodic surface onto which a cobalt-zinc alloy with an increased cobalt content is deposited.

Jan 1, 1997

By A. W. Bryson, S. P. Fox, S. A. Godorr

"This work is an extension of a previous investigation on the development of surface roughness during electrodeposition of copper. A comprehensive model based on diffusion and migration in a force field together with surface diffusion and sticking probabilities is used to generate profiles which are compared to those produced experimentally. The roughness is characterized by using the technique of fractal geometry which is shown to describe both qualitatively and 9uantitatively the development of surface morphology during electrodeposition.The work is extended to the deposition of copper in the presence of various concentrations of thiourea. The development of roughness is observed experimentally on the edge of a thin copper disc mounted between two glass plates. This enables photographs to be taken at various stages during growth. The surface outline is digitized using an image analyzer which enables the fractal dimension to be determined as growth proceeds. As expected, the presence of thiourea at low concentrations produces a fractal dimension which is closer to unity (i.e. the surface becomes smoother).IntroductionThe development of surface morphology during electrodeposition has far-reaching implications for copper plating in the electrowinning and electrorefining processes. Short circuits as the cathode surface grows unevenly require operator intervention in a dangerous environment and imply processing delays, and the inclusion of electrolyte in small gaps in the plated cathode have implications in downstream processing of the cathode. Higher current densities are obviously desirable, as they result in greater production rates, but as shown by Ettel et. al.(l), Harvey et. al.(2), Cook (3), and Harvey et. al.(4), it is not possible to operate near the projected economically optimum conditions because the electrodeposition of copper from sulphate and acid solutions is a mass transfer controlled process. It has been shown (Ettel et. al.(l), Harvey et. al.(2)) that the closer a system operates to mass transfer limiting conditions, the poorer the resulting cathode quality. One solution is to use agitation techniques to increase the limiting current density. Another is to add surface active additives to the electrolyte which has been shown by Ettel et. al.(l), Harveyet. al.(2) and Afifi et. a1.(5) to allow higher rates of production without decreasing cathode quality. The second proposed solution is of interest in this work, since there is very little knowledge of the conditions under which these additives operate effectively, and little fundamental understanding of the mechanism by which they operate. The current work seeks to contribute to this field by correlating a simulation model with experimental results to describe the development of surface morphology in the electrodeposition process."

Jan 1, 1997

By Michael J. Nicol

This paper summarizes some of the results of a study of the reactions involved in the Caron leaching process and identifies the roles of the major dissolved species in the kinetics of dissolution of iron alloy particles formed during reductive roasting. Using rotating disk electrodes and synthetic leach solutions, the reduction of water with the evolution of hydrogen was found not to occur on a dissolving iron surface under typical leach conditions. It has been established that the oxidative dissolution is governed primarily by a reaction involving reduction of Co(III) to Co(II) ions. The reduction of oxygen was also found to make a significant but largely indirect contribution to the kinetics of the dissolution process. The dissolution rates of various iron-nickel-cobalt-copper alloys which simulate the dissolving alloy particles in a Caron plant were measured in synthetic leach solutions under aerobic and anaerobic conditions. The initial dissolution rates of iron, nickel and the iron alloys were found to increase in the presence of thiosulphate, whereas the thiosulphate had a negative effect on the dissolution rates of cobalt and copper. It is shown that the eventual passivation of the iron occurs sooner in solutions rich in Co(II) ions. Whilst these conditions are present in the quench slurry, on-site measurements have shown that due to the very high concentration of reduced dissolved species, passivation does not occur until the slurry is strongly aerated. In the light of these fundamental findings, options for optimizing the rate of dissolution and minimizing the extent of passivation of the iron and iron alloys are discussed. Keywords: Ammonia, leaching, alloy, kinetics, passivation.

Jan 1, 2004

By Robert H. Hsu

Palladium finely dispersed in a substrate of kieselguhr, Pd/k for short, has been successfully used for hydrogen storage, separation and pumping for a number of years at the Savannah River Site (SRS). Recently SRS has developed a new pd/k flow through bed (FTB) prototype for separating hydrogen from other gases and simultaneously storing the hydrogen on palladium. The FTB uses single-pass liquid nitrogen cooling during hydrogen absorption/separation/storage and electrical heating for desorption/unloading of hydrogen. Fourteen absorption-desorption or loading/unloading cycles using hydrogen have been conducted with the new FTB prototype. Test results show that all design performance objectives have been successfully achieved: recover 295% of hydrogen gas from feed gas, produce 99.9% hydrogen product gas and < 5% hydrogen in discharge gas. This paper will discuss characteristics of the palladium-coated kieselguhr or diatomaceous earth, design and operation of the FTB, and results of performance tests such as separation efficiency, hydrogen storage capacity and system heat transfer characteristics.

Jan 1, 2002

By R. E. Aune

In the present work, a critical assessment of the thermodynamic information available for the ternary system Ni-W-0 has been carried out; This was complemented by experimental measurements of the standard Gibbs energy of formation of the ternary compound NiWO, by solid state galvanic studies involving Zr02-CaO solid electrolyte. The assessed thermodynamic data, together with the phase diagram information available in literature, were employed to generate the ternary phase diagram for the system Ni-W-0 in the temperature range 1073-1273 K. The calculation of the phase diagram was carried out by computer optimization according to the "CALPHAD" method. The computed phase diagram has been confirmed at isothermal sections by identification of the phases present in samples equilibrated at defined temperatures.

Jan 1, 1994

By G. P. Chaudhari, F. Warchomicka, M. Dikovits, V. Pancholi, C. Poletti

"The hot formability of a microalloyed steel with 0.16 wt-%C modified with N is studied by using processing maps. Compression tests of cylindrical samples are carried out using a Gleeble®3800 simulator in the range of temperature between 750 -1000°C and strain rates between 0.01-100 S-1. For this alloy, an Ar3-temperature about 740°C is determined by means of dilatometry. Processing maps are calculated using the modified dynamic material model developed by Murty and Rao for different logarithmic strains. For the instability map, the parameter Kj developed by the authors in previous works is used and compared with other instability values. Softening in the flow curves provoked by induced ferrite during deformation at low temperatures and low strain rates is reflected in the n-value. Light optical microscopy (LOM) and electron back scattered diffraction (EBSD) measurements are used to study the microstructure of the hot deformed samples to determine the deformation mechanisms active and to verify the processing maps.IntroductionProcessing maps offer a good possibility to optimize thermomechanical process parameters and to avoid defects in the products. Prasad et al. [1] developed the processing maps using the dynamic material model (DMM) and Murty & Rao [2] modified it. Processing maps consist of two superimposed maps: the dissipation efficiency and the instability map. The processing maps can be used to detect areas with a good hot formability, which are normally related to restoration of the material by dynamic recovery/recrystallization. For a high dissipation efficiency value and no instabilities, a good hot formability is predicted. In the DMM no storage of energy takes place and so the material is considered essentially dissipative, this is only true for high temperatures and high strain rates [1]."

Jan 1, 2012

By Chi-Ming Chang

Alloy powders are commonly used in the purification of zinc sulfate solutions for use in standard electrowinning practice. The primary goal of this research was to study the use of zinc-lead alloys for similar reactions in the galvanic stripping of impurities from organic solutions. The effects of various parameters on the electrochemical behavior of commercially produced zinc-lead alloy powders were determined. A qualitative evaluation and summary of the influence of the more pertinent parameters on iron removal from di-(2-ethylhexyl) phosphoric acid (D2EHPA) by galvanic stripping is given. Water concentration, oxygen content and reaction temperature were the principal factors affecting the reaction rate and process efficiency. Activation energies were also calculated and indicated that the reaction changes from chemical to diffusion control .with increasing temperature in the range of 35" to 45°C. The results showed that zinc-lead alloy gave faster reaction rates with less sensitivity to process variables than SHG zinc as a reducing agent for galvanic stripping. The role of lead could be as cathodic sites for the reaction which enhances the zinc dissolution or anodic half reaction. The morphology of the zinc-lead alloy surfaces, before and after the reactions, supports this assumption.

Jan 1, 1998

By M. T. Ernett

Significant amounts of arsenic are often present in effluents arising from the mining of sulfide ores for the extraction of metals such as copper, gold, lead and zinc. The arsenic is usually removed from the process effluent by co-precipitation with iron because of its common occurence in the mined ore bodies and the excellent adsorptive property of the precipitated hydrous ferric oxide compound. There has been controversy, however, over the long-term stability of the arsenic-bearing ferrihydrite which is produced. This paper presents the results of laboratory studies which indicate that the cations of calcium, magnesium, zinc, cadmium and lead, increase the pH range of effective arsenic adsorption in the Fe-As precipitate from 4-7 to 4-9. The increase in the pH range is similar for all of the added cations investigated. Sulphate ions are shown to have a minimal effect on the residual dissolved arsenate concentration. Silicate ions reduce the adsorptive capacity of ferrihydrite if they are present before the arsenic is adsorbed.

Jan 1, 1994

By Terry Mandziak

Typical leach mine operations recover gold values through the application of a dilute cyanide solution onto ore within an engineered facility. Key to the success of mining operations is the, containment and management of the cyanide solutions within the facility. Properly engineered&apos; facilities will have containment systems that are both protective of the environment while enhancing solution recovery. This paper not only discusses general containment standards, but identifies state-of-the-art containment and monitoring practices;

Jan 1, 1998

By L. Petitnicolas

The experimental study of nitrogen absorption and its removal from a liquid Ni-20%Cr alloy at 1873 K has been undertaken, using an experimental, apparatus based on the Sieverts technique in order to determine the solubility of nitrogen in the alloy. as well as the kinetics of nitrogen transfer across the gas/melt interface. Experiments show that nitrogen solute equilibrium content can be calculated using the Sievens law. Measurements point out the nitrogen absorption reaction rate to be well described by first order kinetics, whereas experiments on nitrogen removal reveal that the rate is better expressed using a second order equation.

Jan 1, 1996

By John G. Reid

When the paper "Operations at the Greenvale Nickel Project Mine and Refinery" was delivered at the 1st International Laterite Symposium in February 1979, the Yabulu Caron plant had been operating for four years and production had just stabilized. The design had been based closely on the Caron plant at Nicaro, Cuba, built in 1944, also by Freeport. Yabulu had 10 Herreshoff ore roasters and production in 1978 was 18,682 tonne nickel as impure oxide sinter and 763 tonne cobalt in a mixed sulphide with a cobalt to nickel ratio of 1 :2.5. In the 25 years since the 1st Symposium, two more roasters have been added, but dry ore processing rate has remained relatively unchanged at 2.4M Uyr to allow a lower feed rate per roaster with associated higher recovery. The ore source has changed from the domestic Greenvale mine to imports from New Caledonia, Indonesia and the Philippines. Nickel production between 1978 and 2003 has risen by 67%, cobalt has risen by 146% and the products have changed to high purity nickel compacts and "ChemGrade" cobalt salt. The plant changes that have contributed to the increased recovery, production and product value are discussed. Keywords: Caron, Yabulu, nickel, cobalt, ammonia

Jan 1, 2004

By Erwin Flender, Preben N. Hansen, Peter R. Sahm

"Until now FDM-Techniques have been widely used for Modeling Solidification Processes in Castings. Often a rigid, regular type of enmeshment (cubes, , --) have been used. This has the advantage of low CPU-costs, but the disadvantage of a zig-zag presentation of the interface between the casting and the mold. The last point is the reason why FEM-Techniques, giving the possibility of a true presentation of the shape in the enmeshment, are increasingly used. The disadvantage is the high CPU-costs. In this paper, a technique is presented, which uses the FDM-Mesh with the zig-zag presentation of shape and ADI-Algorithms to calculate temperatures and gradients. The new idea is that the calculated parameters are not presented related to the mesh in which they are calculated, but displayed using the true shape of the casting. Such an advantage of both low CPU-costs and shape correct presentation of the calculated results are achieved. IntroductionThe main reason for using a regular type of enmeshment is that it gives the possibility, via ADI-Algorithms, of obtaining a very fast FDM-Technique. The technique presented by P.R. Sahm and P. N. Hansen (1984), and also used by E. Flender (1985), is numerically so stable that average time steps, at least 200 times larger than the limit given by the explicit FDM-Technique, can be applied. To obtain reasonably good results, average time steps in the range of 20 to 50 times the explicit limit seems to be applicable. It should be pointed out,however, that FDM-Techniques can be used on arbitrary nets, the disadvantages being the same as for the FEM-Techniques. This has, among others, been discussed by P.R. Sahm and P.N. Hansen (1984)."

Jan 1, 1986

By Cong Wang, Kexin Jiao, Yongan Zhao, Haibin Zuo, Jianliang Zhang

Traditional refractory materials for blast furnace hearth lining are mainly composed of carbon bricks and the ceramic cup. However, these materials can’t meet the demands for long service life design of blast furnaces. In this paper, a new refractory called carbon composite brick (CCB) was introduced, which combined the advantages of carbon bricks and the ceramic cup. In this case, the resistance of the CCB against corrosion was equal to the ceramic cup and the thermal conductivity of the CCB was equal to carbon bricks. From the results of more than 20 blast furnaces, the CCB could be well used in small blast furnaces and large blast furnaces. In the bad condition of low grade burden and high smelting intensity, the CCB gave full play to the role of cooling system, and effectively resisted the erosion of hot metal to improve the service life of blast furnaces.

Jan 1, 2015

By E. Kuzeci, R. Kammel

"Lately various voltametric methods have gained increased attention as an analytic tool in hydrometallurgy. Voltammograms with mercury drop electrodes or glassy carbon electrodes provide information about the electrocrystallization of cathodic deposits and allow calculation of kinetic data by means of characteristic parameters like the peak potential and peak current and their variation with the voltage scanning rate.Cyclic voltammograms are also suitable for identification of reaction sequences. Voltammograms with carbon paste electroactive electrodes containing metal sulphide additions reveal information about the dissolution behavior. The stripping voltammetry can be applied to analyze metal ions and organic additives (e. g., thiourea) in extreme low concentration. Typical application of the various methods studied with microcomputer controlled measurement system are explained by examples selected from copper hydrometallurgy.IntroductionThe use of electroanalytical methods in metallurgical process control can be dated back to the starting period of industrial copper refining, when the deposition of the metal ions was followed electro-gravimetrically by weighing the electrode with deposits (1). The principles of metal deposition and dissolution have not changed but the methods to follow these phenomena were subjected to noticeable developments and especially the introduction of polarographic investigations by Heyrowsky (2) has greatly contributed to the progress in electro-analysis. A review about the fundamental work on the electrochemical kinetics in earlier time is compiled in a monograph of Vetter (2). With the steady improvements in the instrumental techniques, it is nowadays possible to apply several current and potential modulations for measurements with improved selectivity and sensibility. There is however, still a lack in theoretical interpretation of the data obtained. More theoretical information are already available for linear voltametric methods for systems where reduced as well as oxidized species are dissolved in the electrolyte (4, 5). Some recent investigations have also shown the reliability of these techniques to study electro-crystallization (6, 7). Main fields of the application in the hydro - and electro-metallurgy are:"

Jan 1, 1989

By H. Sieber

Multilayer samples of tantalum and aluminum with the composition of Al-25Ta were prepared by cold rolling of elemental foils. The microstructure and phases were characterized by XRD, SEM and TEMISAED and the reactive phase formation was examined by DSC and DTA measurements in multilayer foils rolled for different deformation levels. The rolling procedure yields a decrease of the Ta particle size in the Al matrix and also results in the formation of a multilayer structure with a thickness of the elemental foils down to 200 nm in average. No phase formation is observed during the cold rolling procedure. While XRD and DSC measurements show no phase formation up to the melting of aluminum for samples rolled up to 40 F&R (fold and rolling) passes, in samples rolled for 50 or more F&R passes a first phase formation reaction yield an interfacial layer of TaAl3. Contrary to former studies in the investigated cold rolled Al- 25Ta multilayers the reaction starts at temperatures as low as about 340°C. The first stages of the reaction are associated with two exothermic maxima, that increase in amplitude and shift to lower temperatures with increasing number of F&R passes. At higher temperature the TaA13 reaction layer thickens very sluggishly and yields a third exothermic maxima at about 600°C. Isothermal DSC scans show the reaction is not finished for samples containing elemental particles larger than 1 pm after annealing at 550°C for 5h. In all the investigated samples no Al- Ta phase other than Tad3 was observed to grow for heat treatments up to 800°C. Multilayer samples heated up to 1400°C show a morphology consisting of small AITa2 particles embedded in a single phase TaA13 matrix. The multilayer microstructure and reaction product morphology are characterized by SEM and TEM investigations in cross-section and plan view geometry.

Jan 1, 1998

By Yanxia Lu

Porous silicon carbide (SiC) has been the top selection for diesel particular filters (DPFs) since 2000 because of its high thermal diffusivity and strong body, which help it to survive in the harsh environment of a diesel exhaust system. However, the process to produce SiC DPFs is a costly one. The work presented herein describes more cost effective composite materials for this application, namely Si-SiC and Si₃N₄-SiC. Both composites have shown excellent filtration efficiency, low back pressure and outstanding survivability of regeneration at high soot loadings. Since the composites are batched from silicon metal, they can be prepared by a low temperature process that is impossible in the production of pure SiC PDFs. In fact, fabrication of SiC composites simply involves reactions between nitrogen gas and silicon metal, or silicon metal bonded with SiC, and as such uses a much less costly process when compared to the one employed to make SiC. In addition, the pore structure of the composites can easily be tuned by selecting raw materials and changing the ratio of two components. A typical pore structure consists of well connected pores with a median pore size of 5-20 µm and a porosity of 40-55%. This talk will describe the exothermic behavior as well as the mechanical and thermal properties of SiC composites in comparison to those of SiC filters. It will also show the superior thermal shock resistance of Si₃N₄ bonded SiC which is due to the unique combination of these phases that lowers the thermal expansion and elastic modulus relative to pure SiC.

Jan 1, 2006

By S. K. Varma, Miriam Regalado, Daniel Salas, Erica Corral, Erika Esquivel

"Age hardenable 2014 aluminum alloys and composites containing 0.10 and 0.15 volume fractions of alumina particles (VFAP) have been solutionized at 540 and 550°C for up to 20 hours. The solutionized samples, heat treated for 5 and 20 hours, have been subjected to room temperature rolling until cracking develops. The work hardening curves have been compared to determine the effect of solutionizing time on the rolling characteristics from both hardness and the microstructural evolution points of view. Solutionizing at two different temperatures results in differences in the extent to which the composites can be rolled until fracture. The microstructural characterization by TEM has been performed to understand the room temperature rolling behavior.IntroductionThe effect of solutionizing on the age hardening response of 6061 and 2014 aluminum alloys and composites reinforced with 0.10, 0.15 and 0.20 volume fractions of alumina particles (VFAP) have been reported in the literature [1-4]. A comparison of the monolith and composites indicates that particles promote the aging process through differences in the microstructures in solutionized condition. The first effect of solutionizing is to produce a grain growth process which follows a grain growth law (square of grain diameter as a function of solutionizing time). It appears that it is possible for vacancies to be emitted during grain growth period as they try to minimize the total grain boundary surface area by increasing their diameter. This may be common to both the monolith and the composites. However, the second effect must be exclusively considered for the composites. The particles generate dislocations during the solutionizing process due to the differences in the values of the coefficient of thermal expansion (CTE) between the particles and aluminum base metal. It has been determined [1] that the dislocation density increases with increase in solutionizing time in the composites of 6061 aluminum alloys reinforced with 0.10, 0.15 and 0.20 VFAP. The improved bonding between particles and matrix can give rise to additional generation of dislocations due to curvature effects [1] with the result that the dislocation density continues to increase with increase in solutionizing time even after the CTE effect is considered to have been stabilized."

Jan 1, 1998

By Jennifer Murphy, Brad S. Schake, Karol Holmes, John R. FitzPatrick, Mike H. West

"The separation and purification of uranium from either nitric acid or hydrochloric acid media can be accomplished by using either solvent extraction or ion-exchange. Over the past two years at Los Alamos, emerging programs are focused on recapturing the expertise required to do limited, small-quantity processing of enriched uranium. During this period of time, we have been investigating ion-exchange as a method for extraction/purification of uranium from acidic media. In addition, waste stream polishing is associated with this effort in order to achieve more complete removal of the uranium prior to recycle of the acid. Extraction chromatography has been demonstrated to further polish the uranium from both nitric and hydrochloric acid media thus allowing for a more complete recovery of the actinide material and creation of less waste during the processing steps.We will discuss contact experiments for evaluation of eleven different resins for uranium removal from nitric acid, the evaluation (again by contact experiments) of uranium elution from the ion-exchange media by various chemicals, and small-scale experiments for the removal of 235U from nitric acid. Larger-scale (1 DO-gram) flow experiments, using depleted uranium, were done after the small-scale evaluation of the selected resin. A discussion is also included concerning the shortcomings of the contact experiments and how the flow experiments were modified in order to overcome these problems. We will also discuss the application of ion-exchange for some specific process needs at Los Alamos.Contact experiments were used to evaluate some commercially available solvent-impregnated resins in addition to evaluation of several resins of this type synthesized in our laboratory. These experiments involved both nitric and hydrochloric acid media. The data from these experiments will be used to determine the column size and amount of resin required to polish the waste stream produced by the ion-exchange process described above. Small-scale flow experiments will be described and data given on the mass balances achieved using this two step process.Future work for evaluation of new ion-exchange and solvent-impregnated resins as well as the search for new eluants will be discussed. Other future experiments for both processes, including large-scale experiments, will be discussed in detail."

Jan 1, 1996