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By J. E. Murphy

Neodymium was electrowon into a Mg-Cd molten cathode at 650 °C from NdC1,-KC1 electrolyte. With the chloride system, neodymium was deposited into the molten alloy cathode until the neodymium concentration reached 20 wt pct. The alloy was then vacuum melted to remove the Mg and Cd. The current efficiency exceeded 80 pct under optimum conditions and the purity of the metal was 99.9 pct after vacuum melting. As an alternative approach, neodymium was electrowon at 1,030 °C from Nd,O, dissolved in a molten fluoride eleotrolyte. With the oxide-fluoride electrolyte, the metal was electrowon in a molten state with current efficiencies up to 60 pct. The purity of the metal was 99.8 pct with oxygen and carbon as major impurities. A number of problems were encountered including anode effect, low oxide solubility in the electrolyte, high neodymium metal solubility in the electrolyte, and reactivity of the metal with the cell materials. Approaches to improved cell, operation and prospects for commercial adoption of the electrolytic production of neodymium metal are discussed.

Jan 1, 1995

By Jin Liu

The mechanism and rate of carbon reduction of each of the phases that are formed in the flash flame, i.e. sulfide (matte) and oxysulfide, was investigated. Graphite-slag reduction was conducted for comparison purposes. The objective of these tests was to measure the rate of solid graphite reduction of respectively matte, oxysulfide, slag, and matte+slag mixture at different temperatures. More in particular, these tests were expected to permit understanding and explaining the reduction mechanism of each material by comparing the respective reaction rates, product reaction gas compositions and CO/CO2 ratios, reduced material assays, activation energies, and other relevant parameters. Direct visual inspection of the test crucibles would provide additional information.

Jan 1, 2006

By Douglas Robinson

This paper describes technical work done to develop a Spouted Bed Electrode Cell into a commercially viable Electrowinning Cell; (a previous paper has been presented at the ECS meeting in Paris in May of this year, with a more general overview of the cell, [1]). The studies have included hydrodynamic tests to understand the criteria for the circulating flow of metallic beads in the cell, particularly in the region at the entrance to the draft tube, and electrochemical tests to find a suitable diaphragm for extended time electrolysis. Various patent pending features were developed including a double nozzle to allow for automatic stopping and restarting of the bed, an arrowhead shaped draft tube to control the flow of beads into the entrance to the draft tube, a roof-top shaped device to control the flow of beads out of the top of the draft tube, an overflow weir to allow the continuous recovery of beads from the cell, and a family of diaphragm fabrics for extended operation. Prior to the identification of the diaphragm material, short circuits would develop within a few hours. A pilot scale cell was operated for three days, with continuous operator attention, and then for ten days with operator attention only on day shift. The cell is currently advancing to the next stage of development which will involve continuous testing in a commercial copper electrowinning facility.

Jan 1, 2003

By Naoki Hiroyoshi

It is generally accepted that ferric ions are effective for leaching chalcopyrite as an oxidant and ferrous ions contribute to the leaching only as a source of the oxidant ferric ions. However, this paper shows that ferrous ions are more useful for leaching chalcopyrite than oxidant ferric ions in sulfuric acid solutions in air at ambient temperatures. Leaching experiments and dissolved oxygen consumption measurements were carried out with a very pure chalcopyrite and 0.001 - 1 mol dm-3 sulfuric acid solutions containing 0 - 0.1 mol dm-3 ferric or ferrous ions at 303 K. Chalcopyrite oxidation with dissolved oxygen was promoted by ferrous ions but suppressed by ferric ions. As a result, the amount of extracted copper was larger with ferrous ions than with ferric ions. Effects of Thiobacillus ferrooxidans on the ferrous promoted chalcopyrite leaching were also investigated and discussed based on the experimental data.

Jan 1, 1999

Lance based copper-nickel matte converters have become an established technology in the field of base metal sulphide smelting and converting. An Ausmmelt® converter is currently being constructed at Anglo Platinum in South Africa to convert a nickel-copper rich matte containing platinum group metals (PGM's). The accurate prediction of the matte chemistry is required to control the composition at the endpoint which influences segregation of PGM's during the subsequent slow cooling and magnetic separation processes. A hybrid modelling approach is introduced in this paper that incorporates both the effect of thermochemistry and system dynamics. It will be shown how the model relates to fundamental conservation laws, while still providing enough flexibility to adapt to changing operating conditions. It will also show how off-line modelling can be incorporated into a robust on-line model. Based on the data from many pilot plant trials, the model prediction performance is shown to be within the accuracy requirement set by industry and therefore constitutes a reliable basis for model based control. The final generic model structure takes on the form of an thermodynamically integrated ARMAX hybrid model. The final model has the advantages of being dynamic, adaptive, robust and it can be related to thermochemical fundamentals.

Jan 1, 2002

By L. B. Tsymbulov

At present data on thermodynamic properties of metallic melts, containing copper and ?iron family? metals, is rather limited. Determination of the activity of metallic melts components under high temperature by experimental methods requires high level of labour inputs. With this it is not always possible to obtain the results with high level of accuracy. Due to that in a number of cases it is more appropriate to apply different methods of analysis, with the help of which there can be calculated thermodynamic properties of ternary and even more complicated systems, prominent thermodynamic properties of binary systems being used as a basis for these calculations. This work presents the results of calculations of different components activity and activity ratio in such ternary system melts as Ni-Cu-Fe, Ni-Cu-Co, Fe-Cu-Co and Fe-Co-Ni. Good compliance of calculations results with those obtained in the course of reliable experimental investigations fulfilment is demonstrated. There are presented the results of activity and activity ration analysis for some compositions of Cu-Ni-Co-Fe system.

Jan 1, 2006

By Ronald J. Roman

The shrinking core model for coarse particle leaching has been generally accepted as describing the leaching of a copper oxide or sulfide ore. However, when a mixed oxide/sulfide ore-is leached this model can not be used in its simple form because at least two and possibly three separate leaching processes are occurring simultaneously (dissolution of oxide copper minerals, secondary copper minerals and primarily copper minerals). It has been impossible to isolate their individual leaching curves from the recovery/time curve generated by the column leach test. This paper describes a tests program carried out at the Groupo Mexico, Mexicana de Cobre's La Caridad operation in which the individual recovery/time curves for the leaching of copper oxide mineral, secondary copper mineral and primary copper minerals were developed from standard column leach tests. Once the individual recovery/time curves were developed scale-up of the column leach test results to the commercial heap leaching operation is possible by using the shrinking core model.

Jan 1, 1999

By Jeffrey F. Adams

Gypsum fouling is a common problem in the hydrometallurgical industry. It is a particular problem in free sulphuric acid neutralization, or iron removal operations where sulphates are removed from aqueous solutions by the addition of calcium-containing bases. Previous work revealed a strong correlation between the degree of gypsum supersaturation in the reactor and the rate of scale growth indicating that scale formation and growth are primarily controlled by chemical phenomena. However, the chemical behaviour of gypsum is variable and unpredictable with solution chemistry and temperature. Many of the "rules of thumb" that are used to predict its behaviour (and avoid fouling) are in fact based on gypsum solubility in water, rather than on real mixed metal sulphate systems. However, despite this unconventional solubility behaviour, we have been able to accurately model it in Ni, Mg, and Zn containing solutions over a wide range of temperature (25°C-90°C) and solution concentration (0-6 m) using the OLI simulation software. Furthermore, by studying fouling rates in a simulated continuous neutralization reactor, the relationship between process conditions and fouling rates were explained for the first time. This has led to an understanding of how techniques for minimizing gypsum fouling work.

Jan 1, 2003

By Heikki Jalkanen

Oxygen converting of hot metal (LD/BOF) is contemplated as an object of simulation. Oxygen converting is a highly complex thermo-chemical process comprising a series of matter and energy transformation and transportation steps that makes the simulation very challenging. The basic principles of CONSIM 5 oxygen converter simulator are presented. Simulator is a comprehensive combination of a physical model with several empirical submodels describing all properties and processes that affect the final result of a converter blow, final mass and composition of steel, slag, dust and converter gas as well as the end temperature of steel. CONSIM simulator is used for simulation of series of high and low carbon steel blows. Simulated steel temperatures, oxygen consumption, blow time and iron oxide content of slag are compared with measured values. Problems of simulation and requirements for quantitative simulation of oxygen converter process are discussed.

Jan 1, 2006

By Xiangru Chen, Qijie Zhai, Wei Zhang, Haicheng Li, Chao Yang

In this paper, ductile iron material with different content of niobium was prepared by a scientific melting method. Image Analysis Software was used to studied the effect of niobium microalloying on both pearlite content and pearlite lamellar spacing in ductile iron quantitatively. The results showed that the addition of a small amount of niobium could increase the pearlite content and decrease pearlite lamellar spacing of ductile iron effectively.

Jan 1, 2015

By Wen-Ming Chien, Vamsi Krishna Kamisetty, Amrita Mishra, Ivan Gantan, Prathyusha Mekala, Dhanesh Chandra

"The phase equilibrium and characterization studies by using high temperature X-ray diffraction (XRD) and differential scanning calorimetric (DSC) methods have been performed for binary organic thermal energy storage materials. The organic thermal energy storage materials undergo a solid-solid state phase transition before melting which stores large amounts of thermal energy. Two materials [tris(hydroxymethyl)aminomethane(TRIS) and 2-Amino-2-methyl-l, 3- propanediol(AMPL)] were used for this study. Binary samples of AMPL-TRIS were prepared to perform high temperature XRD characterization and DSC studies and the binary AMPL-TRIS phase diagram was developed. The high temperature solid-state phases of AMPL and TRIS were characterized as a disordered BCC structure. It was found there is virtually no solubility of TRIS in AMPL or vice versa below -75 °C. The maximum solubility of TRIS in AMPL is 11% TRIS at 75 °C. The eutectoid transformation was shown at 19%TRIS-81%AMPL composition and at a temperature of 75°C. Lattice expansion calculations on single phase of TRIS and AMPL have been performed.IntroductionThermal energy storage materials can store a large amount of heat due to the presence of thermal transitions from the orientationally ordered to disordered phases occurring before melting. These molecules (such as amine and alcohol derivatives of neopentane) can reorient as a whole about the central carbon atom to form orientationally disordered crystals (ODIC) and their spherical shape makes them reorient relatively easier. Thermal energy storage materials are becoming increasingly important as a renewable energy resource. These molecules undergo large changes in enthalpies at solid-solid transitions. The presence of these compounds with large enthalpy changes are identified as potential thermal energy materials and some of die applications are solar cell systems [1-3]. Binary mixtures have been found as a way to adjust the transition properties in addition to pure compounds [4]. Tris(hydroxyrnethyl)aminomethane (TRIS, C(CH2OH)3NH2) and AMPL, CH3C(CH2OH)2NH2) are two important thermal energy storage materials."

Jan 1, 2012

By Nagahiro Saito, Takashi Nishimura, Takamichi Ichikawa, Akio Fuwa

"Yttria-stabilized zircohia (YSZ) has high potential to be used as solid-oxide fuel cell (SOFC) electrolyte. However, the high efficiency of SOFC has not been yet achieved due to the high internal resistance of bulk electrolyte. The resistance becomes lower with the decrease in the electrolyte thickness. Thus, the decrease in electrolyte thickness leads to lower internal resistance. . The aim of this study is as follows: (a) to prepare the thin films of YSZ by inductively-coupled RF plasma-enhanced metal organic chemical vapor deposition (PEMOCVD) process using Zr(t-OC4H9)4,Y(DPMh and oxygeil, and (b) to reveal the relationship between the structural characterizations and the process parameters.1. IntroductionYttia-stabilized zirconia (YSZ) has, been widely used as not only heat-resistant materials but also the components in automotive oxygen sensors, electrolytes of solid-oxide fuel cell (SOFC)(1)(2) and the buffer layers for the high-temperature superconductor because of its low thermal conductivity, good mechanical properties and high ionic conductivity. However, it is said that the internal resistance of the bulk electrolyte is too high to be appropriate as a solid electrolyte for high-efficient SOFC. The authors believe that the thin YSZ electrolyte can give a high performance to characteristics SOFC, since the internal resistance becomes lower with the decrease of electrolyte thickness. Thus the process technology to prepare YSZ thin films is desirable and must be established.In recent years, the YSZ thin films have been reported by chemical vapor deposition (CVD), thermal CVD using metal chlorides (MC) of ZrCl4 and YC(3)(4), thermal CVD using metal organic compounds (MO)(5)(10) Zr(t-OC4H9)4 and Y(C11H19O2)(11) and plasma-enhanced (PE) CVD using MO. Here, these methods are called MCCVD, MOCVD and PEMOCVD. MCCVD has two disadvantages; a large quantity of chlorinated impurities in deposited films and high processing temperature (> 1273K). This high processing temperature leads to damage of substrates in particular, so the application of this technology is limited. On the other hands, the processing temperature by MOCVD becomes and is lower. Unfortunately, the accurate vapor pressures of these metal organic compounds have not been, known so: that it is difficult to control the composition and the film thickness by MOCVD method well. Moreover, the large amount of carbonic compounds in the films prepared by MOCVD method is produced. However, plasma-effect has been reported to decrease large amount of the carbonic impurities by PEMOCVD. However, PEMOCVD has many reaction parameters in plasma processing; the geometry of experimental apparatus, radio frequency, electronic power input and so on. Thus, the general understanding about the relationship among reaction parameters, the composition and crystal structure of thin deposit film by this method has not yet been established."

Jan 1, 2000

By Junji Shibata

Extraction behavior of Ti(IV) and other metal ions, such as Fe(III), Fe(II), Cu(II), Zn(I1) and Co(I1) from acidic solutions like sulphuric acid and hydrochloric acid was studied in order to recover titanium from the waste solution in Ti02 production. Extractant used was tri-alkyl phosphine oxide whose trade name was Cyanex 923. Then, a study was made of the idea of simulating a countercurrent multistage extraction system, using the results of batch extraction. The simulation was camed out on extraction and saipping behavior for a Ti(1V)-H$O,-Cyanex 923 system. From the simulation result., the optimum operating condition of the system was considered.

Jan 1, 1994

By Abhishek Asthana

The incineration of Municipal Solid Wastes (MSW) is an attractive process for reducing the volume of the wastes and recovering their energetic value, which, however, requires to be strictly controlled in order to limit its impact on the environment. In this context, we have undertaken the mathematical modeling of the different sections of a typical incineration plant. The combustion of the waste bed, usually carried out on a moving grate, is at the core of the process. This paper presents the 2-dimensional, steady-state model that we have developed for simulating the MSW combustion. The model describes gas flow through the porous waste particle bed, the gas-solid reactions, conductive and radiative heat transfers, drying of the feed, its pyrolysis and the emission of volatile species, combustion of the pyrolysis gases, the formation of char and its gasification by water vapor and carbon dioxide, and the consequent reduction of the bed volume. Pyrolysis kinetics distinguish between cellulosic and non-cellulosic materials and are experimentally derived from our laboratory measurements. The calculated results give a deep insight into the various involved phenomena, an example being the complete consumption of oxygen in a large zone of the bed and the related appearance of a char gasification zone. The influence of various operating parameters, like the temperature and flow rate of primary air, is presented and explained. Finally, the effect of stirring the waste bed on the moving grate is also analyzed.

Jan 1, 2006

Silver has the highest electrical conductivity of all metals and consequently this property is an attractive feature which makes it a leading candidate for use in electronic devices. The research conducted was focused primarily on the development of a process for obtaining a deposited silver-coating onto alumina, for applications related to electrical-conducting devices and, ancillarily, catalysts. Alumina balls and plane substrates were utilized for the investigation. The coating process employed an aqueous arnmoniacal silver-nitrate electrolytes with a formaldehyde solution as the reductant. Modifying additives - an activator which would be expected to promote good deposition-characteristics onto the (dielectric) substrate and an inhibitor which would obviate homogeneous reduction (precipitation) of silver was observed when the activator-containing silver-electrolyte reductant constituents were combined. However, the silver-electrolyte/reductant system with inhibitor could be employed (at 80°C) to achieve a viable (subject to future research optimization) coating on alumina. The influence of the processing temperature on the deposition process was delineated during the course of the research. The morphology of the deposited-silver on the alumina balls was assessed by SEM imaging. A tape-peel test was employed, with the plane substrates, to semi-quantitatively characterize the adhesion to the alumina.

Jan 1, 1998

By D. C. Cupertino

Oxime based solvent extraction provides the user with a selective concentration process for copper prior to electrowinning. The selectivity required is largely for copper(II) over iron(III) and this is achieved by the preferential formation of the square planar copper-oxime complex in the organic phase. The copper/iron selectivity of oximes can however, be altered by modifiers or other types of oximes and may be enhanced in the presence of certain esters. Whilst the oxime based SX processes is important for operations leaching copper from laterite ores, the high selectivity will also be significant in processing streams arising from other leaching regimes which are currently under development, for example leaching of sulfide mineral ores. This paper presents some initial results using Molecular Modelling techniques to further our understanding of the nature of the copper/iron-oxime complexation processes together with some plant studies undertaken at a number of different mine sites investigating selectivity, and other properties, for some modified reagents. Some studies of the interfacial properties of the these systems are reported to explain in part the practical observations.

Jan 1, 1999

By Felipe P. D. Lopes, Jr. dos Santos, Sergio N. Monteiro, Frederico M. Margem

"Continuous and aligned fiber composites provide the highest possible reinforcement for a polymeric matrix. In particular, the impact resistance is significantly increased in comparison with a low energy absorbed brittle polymer. For this reason, investigations have been carried out with both synthetic and natural fibers as a way to improve the toughness of polymeric composites. Among the natural fibers, ramie was not yet been studied for its reinforcement effect to make tougher polyester composites. Thus, the present work assesses the impact toughness of polyester composites incorporated with different amounts of ramie waste fibers.IntroductionIn most engineering and other technological areas, the use of materials associated with low energy processing conditions is gaining attention for the possible environmental benefits. This offered an incentive towards the substitution of natural renewable and biodegradable materials for the traditional energy intensive synthetic materials [1]. Natural fibers from both origins: animal, such as silk and wool, and vegetable, such as cotton and jute, are typical examples of those environmentally friendly materials. Low cost and highly reduced processing machinery wear are important advantages of the natural fibers over the most common synthetic ones such as glass fiber and nylon. For these reasons, polymeric composites reinforced with natural lignocellulosic fibers have nowadays been the subject of investigation [2,3].The mechanical strength is one important property of lignocellulosic composites to access the possibility of uses like structural materials for building parts such as doors and panels, as well as furniture. In this case, mechanically strong fibers like sisal, jute, curaua and ramie [4-7] are most convenient. Moreover, the relatively low fiber/matrix interfacial shear stress in these composites is associated with higher impact energy. In fact, a greater energy has to be expended for the rupture of a weak interface. The many cracks that are formed by impact tend to branch during the fiber pullout from the matrix [8]. A larger number of cracks correspond to a greater fracture surface and consequently higher toughness."

Jan 1, 2008

By V. M. Paretsky

Recent developments made in the Gintsvetmet Institute in the field of autogenous smelting processes have confirmed that autogenous smelting continues to be the main prospective technology for pyrometallurgical processing of sulfide raw materials. This technology ensures energy conservation and environmental safety conforming to the current world standards for production of heavy non-ferrous metals. Two alternative processes of single-stage autogenous smelting producing white metal as well as high-basic ferrite-calcium slags have been developed and can be recommended for technical modernization of Russian copper smelters.

Jan 1, 2002

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 Jae-Chun Lee

Di-2-ethylhexyl phosphoric acid (D2EHPA) is widely used for separating rare-earth elements. In commercial plants, rare-earths are usually stripped from loaded extractant streams using mineral acid, then precipitated as oxalates. Many rare-earth uses demand specific powder characteristics, which are obtained by secondary processing. This paper demonstrates the feasibility of combining the stripping, precipitation and powder processing stages, thereby achieving considerable savings. MEHPA solutions were loaded with yttrium, then emulsified with oxalic acid-HC1 solutions to precipitate yttrium oxalate, which was readily calcined to yttrium oxide. The precipitation kinetics and yield were sensitive to process conditions. The morphology and size of the yttrium oxalate powders varied with the concentrations of D2EHPA and oxalic acid, and the presence of SPAN 60, which affected nucleation, growth, and the emulsion characteristics.

Jan 1, 1992