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By Cesimiro Fabian

The crystallite size of copper electrodeposits was determined by X-Ray powder diffraction analysis using a General Area Detector Diffraction Solution (GADDS) diffractometer. Crystallite size was calculated for copper thin films which were deposited on a 316 stainless steel rotating cylinder electrode (RCE) in the presence and absence of additive ?A?. The crystallite size was calculated from a corrected full width at half maximum (FWHM) of the [110] peak profile using the Scherrer equation. The test of significant difference on crystallite size was derived using Kruskal-Wallis method. It was found that in the absence of the additive the median crystallite size was 426, which decreased to 364 in the presence of the additive. As the additive degraded, the crystallite size increased to a size similar to that observed in the absence of additive.

Jan 1, 2003

By Lanre Oshinowo

The trend in process engineering is to design compact, more efficient processes, there is the paramount requirement to get the job done right the first time going from the drawing board to full-scale commercial operation. To accomplish this goal, there is also the need for tools beyond the traditional engineering toolkit to evaluate designs through virtual prototyping, thereby reducing the risks associated with making design decisions. One of the most important tools that has recently come to the forefront of process design and development is Computational Fluid Dynamics (CFD). CFD has been used at HATCH to address the key process parameters that drive the design of hydrometallurgical unit operations. This paper will detail the role of CFD at HATCH in achieving a superior level of confidence in the process design of autoclave circuits. Specifically, the optimum application of multiphase modeling including hydrodynamic, heat and mass transfer to hydrometallurgy operations, the impact of non-Newtonian slurry rheology on autoclave performance, and the challenges of optimizing the mixing of key reactants into slurries in autoclave reactors, is discussed.

Jan 1, 2003

By Brian G. Thomas

Quality problems in continuous casting of steel can be identified as they occur by monitoring mold signals (level sensor, thermocouples in the mold walls, friction etc.) and taking appropriate action (such as slowing casting speed, changing taper, changing a clogged nozzle, or later visual inspection of the surface for possible downgrading. Surface depressions and groups of deep oscillation marks form at meniscus and reduce local heat transfer as they move down the mold at the casting speed. This slows shell growth, increases shell surface temperature, and causes characteristic dips in mold thermocouple signals. More importantly, they are also associated with longitudinal cracks. Characteristic thermocouple signatures have been identified for many defects, including sticker breakouts, transverse depressions and deep oscillation marks, narrow-face bleeds, transverse comer cracks, longitudinal cracks, mold level fluctuation defects, and other problems. With the help of computational models, these mold signals should be used to troubleshoot defects, and to take appropriate corrective action. Keywords: Continuous casting, defect detection, thermocouple signals, on-line control

Jan 1, 2003

By P. A. Manohar

This paper describes an implementation of the Potts model for simulation of grain growth in 2D on a distributed-memory parallel architecture. The simulation scheme utilizes a continuous-time, asynchronous parallel version of the n-fold way algorithm. Each Processing Element (PE) carries a piece of the global simulation domain while the virtual topology of the PEs is in the form of a square grid in 2D and Torus in 3D. Different PEs have different local simulated times. Inter-processor communication is carried by the Message Passing Interface (MPI) routines. Sample results for grain growth simulation in 2D are presented for a 840 x 840 global domain size distributed over 16 PEs. The grain growth kinetics obtained in the simulation of pure, isotropic systems is in good agreement with the theory. Grain size distributions obtained in the parallel simulation are well described by the lognormal distribution, thus validating the simulation procedure. Keywords: Metropolis algorithm. n-fold way algorithm, asynchronous parallelization, grain growth

Jan 1, 2003

By David Hughes

The paper covers the utilization of on-line analysis in process control of solvent extraction in nickel leach solvent extraction processes in Finland and Australia and in copper heap-leach and solvent extraction in Chile. The goals of and requirements for controlling the solvent extraction stages of the processes are reviewed. The applications at three plants are compared. The development of the technology used is reviewed and design considerations are discussed. Requirements for on-line control and analyzer performance are compared. A new generation of analyzers and its effect on the set-up process of a project is introduced.

Jan 1, 2003

By Hiromichi Ohta

Precise thermal properties of molten materials are essentially required for analyzing the metal production process. These properties are also important as a clue to consider the dynamic structure of liquid materials. However, it is difficult to obtain the precise thermal diffusivity values of molten oxides at high temperature because of the experimental uncertainties arising from the bubble formation or the severe separation of radiative and conductive heat components. Recently a novel laser flash method has also developed for measuring thermal diffusivity of molten oxides at high temperature. In this new technique, the sample is melted in a metal crucible and heated to the desired temperature. A single laser pulse is flashed on the bottom of the metal crucible and the infrared ray irradiated from the same bottom surface is measured for obtaining the temperature decay, from which the thermal diffusivity of the liquid sample can be estimated. The usefulness and validity of this new laser flash technique have been confirmed by obtaining the thermal diffusivity values of silicate melts in the wide temperature range between 773 and 1673 K.

Jan 1, 2003

By Carla Lupi

In this work, nickel-cobalt electrodeposition under galvanostatic conditions was investigated. Ni-Co alloy was electrowon from an acid sulphate bath containing 40 g/L Ni and2-8 g/L Co.. The effect of electrolyte composition, current density, temperature, solution pH and presence of buffers such as H3BO3 and (NH4)2SO4 on Co content of the binary alloy has been investigated. In particular, current densities ranging from 180 to 400 A/m2 and temperatures ranging from 27 to 60°C were tested. The composition of Ni-Co alloys may be diversified through the selection of process parameters. The experiments show that the highest cobalt content of the alloy is reached by using a buffer free electrolyte without solution pH control. Though, in these conditions, the most homogeneous, fine and regular deposit morphology is obtained, energy requirements are the highest in tests lasting just two hours.

Jan 1, 2003

By Subagyo

The condition of slag in a pyrometallurgical reactor is vital to ensuring control of the process. A new technique based on multivariate image analysis (MIA) of digital images has been developed to provide an online measurement of important slag characteristics, such as the presence of exposed metal, the presence of solid phases, and temperature. This paper shall describe the technique and provide some results from analysis using industrial plant data.

Jan 1, 2003

By Jitka Jandová

In this study, hydrometallurgical processing of waste ZnO flue dust arising during zinc removal from galvanized low-alloy steel sheets was investigated on a laboratory-scale to obtain electrolytic zinc. The flue dust was separated from flue gases, generated during heating waste galvanized steel sheets in an electric furnace under air atmosphere at temperatures of about 1000oC. The dust, comprising tetragonal ZnO and insignificant amounts of SiO2, was contaminated by Fe, Mn, Pb, Al, Mg, Pb, Cu and Ca. The dust was leached in 0.5 and 1.0M H2SO4 and/or in 20 and 30% NaOH at different temperatures and different liquid-to-solid ratios to determine the optimum conditions leading to the highest possible selectivity of leaching and efficiency of Zn extraction in minimum time. The subsequent electrowinning process was performed with refined zinc sulphate leach liquors and/or with untreated zinc caustic solutions. Zinc sulphate leach liquors were purified using a combination of a hydrolytic pH-controlled precipitation, cementation and carbon refining. Effects of operational variables on Zn electrowinning have been studied for both sulphate and caustic electrolytes. The conventional plate-plate electrowinning cell has been explored in this study. Comparison of results obtained for both zinc electrowinning from acid sulphate and alkaline solutions is presented contribution.

Jan 1, 2003

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (Mf'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By Y. F. Jia

Arsenic constitutes a major contaminant for the hydrometallurgical industry. Its removal and immobilization from process effluents typically involves lime neutralization and co-precipitation with ferric iron (Fe (III)/As(V)>3). Alternatively, precipitation of scorodite (FeAsO4?2H2O (cr)) may be applied to arsenic fixation. The mechanism of arsenic fixation in the former process has been suggested to be surface adsorption. Unequivocal characterization of these products is difficult because of their amorphous nature hence a variety of methods need to be applied including the particularly powerful method, extended x-ray absorption fine structure (EXAFS) spectroscopy. In this study, we have investigated the preparation of arsenate-adsorbed ferrihydrite with the purpose to compare its structure to that of Fe(III)-As(V) co-precipitates and scorodite (both amorphous and crystalline). Furthermore the solubilities of these Fe(III)-As(V) solids are measured as a function of pH. Their structures are elucidated and correlated to their solubilities and thereby the application of these findings to the practice of arsenic removal and disposal is assessed.

Jan 1, 2003

By S. N. Ashrafizadeh

Nowadays, hard carbides have found various industrial application in the manufacture of cutting and drilling tools as well as metal forming devices. About 60% of the world tungsten production is consumed in the manufacture of hard carbide pieces. Regarding the high economic value of hard carbide components, i.e., Ni, Co, TaC, TiC, and WC, their recovery from scrap species is attracting much interest. In the current research, the cobalt and tungsten content were recovered from scrap cemented carbide pieces through the application of high voltage electrolysis in nitric acid media. By this method, cobalt and tungsten were initially recovered as cobalt nitrate and tungstic acid, respectively. The precipitate of tungstic acid was calcined at 800ºC after being washed twice with distilled water. A pure tungstic oxide was obtained. The effects of current density, electrolyte concentration, speed of agitation, and the surface area of the anode on the efficiency of the electrolysis process were investigated. The optimum conditions of current density of 1500 A/m2, an acid concentration of 1.5 M, and a cell temperature in the vicinity of 60 to 80ºC were obtained. At the optimum conditions, an acceptable rate of collapse for the anodic carbide pieces of about 3.1 g/h was achieved, which remained constant up to the completion of the recovery process without any passivation .

Jan 1, 2003

By W. K. Rankin

Achieving continued economic growth with social equity within the natural limits of the Earth's eco-systems is the major issue facing the world today. The material and energy needs of the world cannot be met with the current ways of addressing this issue. The need for metals, an important class of materials, will continue into the future because their unique properties make substitution by other materials impossible in many applications and this need will continue to be met from primary metal production and recycling. However, the recycling rate will increase and the usage pattern of metals will change to reflect the environmental impact of their production and use. Pyrometallurgy has an important role in meeting the metal needs of the future since some metals can only be produced pyrometallurgically; the energy required to produce some metals pyrometallurgically is significantly less than by other methods; most metals are most efficiently recycled pyrometallurgically; and the release of harmful and toxic elements into the biosphere can sometimes best be controlled through pyrometallurgical processing. The development of strategies for pyrometallurgical processing for the future lies in the recognition that sustainable development calls for large step improvements in value delivered per unit of environmental impact over the entire supply chain. Pyrometallurgists can respond to this challenge by contributing to reducing the environmental impact of meeting metal needs using three broad strategies: "end-of-pipe" approaches to convert emissions into benign materials for storage or disposal; flowsheet redesign to limit or eliminate emission production; and improved recycling technologies. A number of examples are discussed to illustrate how the sustainability driver is already influencing the technological development of pyrometallurgical processes, and how these will develop further as the sustainability driver strengthens.

Jan 1, 2003

By Hector M. Lizama

A new technology, known as the HydroZinc? process, is described for the recovery of zinc from sulphide ores that includes heap leaching, neutralization, solvent extraction and electrowinning. Unit operations were scaled up from bench-scale to a 1-t/d zinc cathode demonstration plant. Bench-scale studies defined the process chemistry and a process flowsheet. Column tests were used to design full-scale heaps for zinc bioleaching, and mini-pilot equipment was used to design a solvent extraction circuit. The characteristics of the process required development of a bleed circuit for water and impurities. The complete integrated process was tested on a demonstration plant scale for two years, with about 10 000 t of zinc sulphide ore being bioleached in two 6-m-tall test heaps. In addition to 1 t/d of zinc cathode, iron hydroxide and gypsum residues were produced. The process also generated a small effluent bleed. Over the course of the two-year demonstration test, a number of technical hurdles were overcome and several improvements were made. Some of the more significant ones are presented along with process descriptions and experimental and demonstration plant data. Some engineering aspects and economic evaluations of the new process are also discussed.

Jan 1, 2003

By F. J. Tavera

The column flotation technology, at first developed for application in mineral dressing, has received special attention in processing of non-mineral dispersions as a result of its low cost, high efficiency and relatively simple operation. This paper presents the results from the operation of a laboratory flotation column for the separation of vegetable oil and soap from aqueous industrial effluents, The flotation system was operated under continuous countercurrent conditions without and with additions of a cationic collector. The experiments show that it is possible to separate about 80% of the organic phase in a rougher flotation stage. These results suggest that the recovery of the organic phase is highly dependant on the dispersion characteristics (i.e. bubble size, gas holdup and bubble surface area flux) and the existing an optimum bubble size from which either smaller or larger, the recovery of the organic decreases.

Jan 1, 2003

By T. C. Tseng

Austenitization is a critical stage in heat treatment of steels. The available kinetic data in reference to various initial microstructures are very limited, particularly at high heating rates. In this study, integrated experimental and computational approaches have been conducted to quantify the progress of austenitization and the attained microstructure. In particular, the study is concentrated on cementite and carbide dissolution in two steel grades. Various computational methods are developed to facilitate the study: (l) an algorithm for direct determination of kinetics data as well as progress of transformation from high-rate dilatometer tests; and (2) a suite of mesoscale computational models for particle dissolution, elements diffusion, mechanics, thermodynamic and the resulting kinetics of transfonnation. Critical exprimentation is carried out using advanced techniques in microstructure characterization, chemical analysis, and Gleeble thermal-mechanical simulator on specimens of well-controlled initial microstructures. Keynotes: Cementite, Carbite, Dissolution, Steels, Austenitization

Jan 1, 2003

In low carbon TRIP steels, the formation of carbide-free bainitic ferrite is crucial for the stabilization of austenite. Based on experimental investigations modeling the bainite reaction is examined adopting diffusional and displacive mechanisms, as well as the semi-empirical JMAK approach. Transformation tests were carried out to study the isothermal austenite decomposition into bainitic ferrite for a model steel containing 0.6wt%C, 1.5wt%Mm and 1.5wt%Si which replicates the composition of remaining austenite at the start of the bainite reaction in a classical C-Mn-Si TRIP steel. In the diffusional approach, classical nucleation theory is employed and subsequent growth of bainite plates is modeled using the Zener-Hillert theory. In the displacive approach, the autocatalytic nucleation of bairtite plates is assumed to be rate controlling. The predictive capability of all models is evaluated for temperature ranges where different morphologies of bainitic ferrite have been detected, The shortcomings and inherent challenges associated with either of these modeling approaches will be delineated.

Jan 1, 2003

By A. Cullaj

Several industrial sites suffer from the contamination of soils from heavy metals, which are emitted among others by anthropogenic mining and metallurgical activities. Effective and economic physicochemical technologies for remediation of these sites remain complicated and costly. A new alternative remediation technique is the so-called phytoremediation. This is based on the ability of some plants to accumulate very high concentrations of metals from soils and thus providing the basis for a remediation of the contaminated sites. This technique as an emerging branch of natural biotechnology, has several advantages compared to the sophisticated physicochemical techniques of soil remediation. It is not only environmentally friendly but also its costs are quite low since it is solar driven. Furthermore plants can accumulate metals to such levels that the mineral recovery maybe feasible even in conventional Ni refinery or smelting operations. n this work, the potential of many plants to accumulate nickel has been investigated in order to identify the species which offer the best phytoremedial potential for nickel contaminated soils in Albania. Field surveys have been made in five nickel-containing sites in order to identify the nickel tolerant species that have spontaneously grown in contaminated soils. Atomic Absorption Spectrometry measurements were carried out on 145 different plants collected. 16 of them were identified as having an hyper ability to accumulate nickel since they contained more than 10 000 mg Ni per kg (OW). Seven taxa are of Alyssum genus and one of BornmueIIera genus of Cruciferae. The highest accumulation of nickel was present in aerial parts of Alyssum murale var. chlorocarpum Hausskn (25 500 mg/kg or 2.5%) and Alyssum markgrafii O.E. Schulz (23 700 mg/kg or 2.37%). The seeds germinated are more evidenced at A.m.var. chlorocarpum, about 63%. These plants are suggested as the most promising species to be used for phytoremediation purposes in nickel contaminated soils and phytoextraction of nickel.

Jan 1, 2003

By K. Watling

Vibrational spectra of surface and solution compounds formed during cyclic voltammetry of a gold electrode in a deoxygenated 0.01 mol dm-3 NaCN solution have been examined using surface-enhanced Raman scattering (SERS) spectroscopy. The presence of cyanide at the electrode surface was indicated by Raman bands characteristic of the carbon-nitrogen stretch, CN.. Chemisorption of cyanide on the gold surface was evidenced by the presence of vibrational modes due to gold-carbon stretching, AuC, and gold-carbon-nitrogen bending, AuCN. Prior to the disappearance of the surface cyanide stretch band, a limiting value of the CN was obtained, the same as the value reported for adsorbed cyanide. Effects upon the voltammetry and vibrational modes of surface species due to additions of silver and lead to the gold-cyanide system have been observed.

Jan 1, 2003

By Nobuaki Sato

The electrical conductivity, k, of pure and sodium doped sulfur melts was measured with and without ultrasonic waves at temperatures ranging from 140 to 340° C by the two probe method using an ultra high resistance meter. The II: value of the pure sulfur melt with irradiation jumped at around 170°C by an order of 102 after which it monotonically increased from 10-5 to 10-4 (omega) 1cm-4 with an increase of the temperature. The addition of the sodium metal to the sulfur melt was found to cause a larger jumping in the II: value. The II: value increased with the increase of Na proportion in the melt. For a 10 mol% Na doped sulfur melt it was as high as max. ~30 (omega) 1cm-1 above 180°C under the irradiation of ultrasonics.

Jan 1, 2003