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By V. A. Luganav

The behavior of arsenopyrite under heating has been studied by many scientists. It has been already established that under heating at more than 650°c and without air access the arsenopyrite dissociates with the formation of one atom arsenic. Under vacuum the dissociation process begins at 5500C with the formation of elemental arsenic. The residue of dissociation process contains pyrrhotite and throilite. In the presence of pyrite, arsenopyrite dissociates under lower temperature and with a higher velocity than without it. The industrial realization of fool scale processing of arsenic bearing raw materials is possible only by the use of standard equipment and oxygen containing blast. In this view the paper presents the results of the study on the effect of oxygen in the gaseous phase and its addition into the charge of pyrite in the process of arsenopyrite decomposition. Thermodynamic analyses showed that under thermal processing of arsenopyrite in the presence of pyrite and limited quantities of oxygen in the gaseous phase the formation of arsenic sulfides is possible according to the following reactions:

Jan 1, 2003

By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carned out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XQ >10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

By Anders Salwén

In 1975 T. Nishizawa and A. Chiba reported on observed deviations from the ferrite-austenite local equilibrium in several diffusion couples based on the Fe-Cr system. In order to try to verify these results the austenite-to-ferrite transfonnation in a Fe-20 %Cr-Invalid Code [Fe-]-%Cr diffusion couple held at 1100 for 100 hours has been simulated. The simulation model is based on the postulated principle of maximum dissipation rate of Gibbs energy during transformation, which allows non-equilibrium interface conditions. Keynotes: Computer Simulation, Austenite-to-Ferrite Transfonnation, Diffusion Couple

Jan 1, 2003

By O. Morfín

The most probable source of Pb contamination in the perennial reach of Aravaipa Creek, Arizona, has been determined using Pb isotope ratios and total metals analyses of samples collected from the ephemeral and perennial reaches and mine wastes located in the Aravaipa Mining District . Previously, elevated levels of Pb, Cd and As in fish in the perennial reach of Aravaipa Creek, a protected wilderness area,, were assumed to be due to off-site transport from abandoned flotation tailings piles located at Klondyke, Arizona upstream of the wilderness area.Our work replaces this inference with isotopic data that allows us to confirm this hypothesis. The Pb/Zn deposits of the district were mined between the late 1890s and the late1960s, with the most significant ore production coming from one deposit in a rhyolite dike swarm on the Western front of the Santa Teresa Mountains, a granitic pluton of Cretaceous-Tertiary age (~65 ma). Mineralogy has been well constrained across the length of the lode system: Pb and Zn sulfides predominate in the NW sector, and a mixed suite of hypogene/supergene Pb sulfide and Pb oxide minerals comprises the majority of its SE corner. Total metals analyses and comparison of metals ratios serve to constrain the source and transport of certain metals within different parts of the system. Pb isotope ratios in samples, obtained by ICP-MS analysis, define two distinct contributors. The first end-member (208Pb/204Pb = 38.513 to 38.721 and 207Pb/204Pb= 15.550 to 15.598) is characteristic of the mixed, oxide/sulfide ores at the SE end of the deposit. A second end-member (208Pb/204Pb = 38.855 to 38.946 and 207Pb/204Pb = 15.610 to 15.625) characterizes samples taken from the NW, purely Pb sulfide end of the lode. Pb isotope ratios from perennial reach sediments are closely correlated with ratios given by samples from the Klondyke tailings site and by Pb sulfide samples from the NW sector, the primary source of ores processed at Klondyke.

Jan 1, 2003

By William Ewing

Copper is rapidly being adopted by the semiconductor industry as the interconnect material of choice. The aqueous processing techniques used generate wastes such as spent electrolyte from electroplating, electroplating rinse water, copper solutions from removing copper from the back of the wafer and CMP waste streams. We are examining the use of chelating resins as a means of recovering copper from these streams within the processing plant, thereby allowing recycling of process water and minimizing hazardous waste disposal costs. We have examined the effect of model plating additives (and other organic complexing agents) on the efficacy of Dowex M4195. Although these might have had a significant effect, commonly used electroplating additives polyethylene glycol (PEG), benzotriazole (BTA), thiourea, glycine, and 3-mercapto-1-propanesulfonate (MPSA) each had little or no effect on the ability of the resin to chelate copper and remove it from solution. This suggests that Dowex M4195 could be useful for treating waste solutions of rather variable compositions.

Jan 1, 2003

By Hideaki Tokuyama

Recovery of Ni from acidic wastewater of metal surface treatment has been investigated for reuse of the metal and water. Ion exchange equilibria between Ni ion and a strong acid cation resin, DIAION SKIB, and effective diffusivity in resin particle have been studied and they related to the concentration of HCI. The amount of adsorbed Ni for unit quantity of resin decreases with the increase in HCI concentration. This trend is remarkable for acid concentration above 0.1 kmol/m3,. The exchanging ratio of Ni2+ to H+ in resin particle is I/2 and the values of equilibrium coefficient K and maximum exchange capacity Q are I.62 and 3.16 keq/m3 -dry resin, respectively. Effective diffusivity D. determined from the observed breakthrough curve increases with increasing concentration of DC!. A prototype of moving bed has been developed and applied for the recovery of Ni from model solutions of wastewater prepared by mixing HCl and NiCl2. This apparatus allows us to control the resin flow rate by changing the cross sectional area of hole I the Teflon plate installed at the bottom of resin bed. Characteristics of Ni recovery have been clarified under various liquid flow rates. In any case for Q1, Ni ion has been effectively recovered on SKIB resin and the removed fraction was more than 99.5 %. Higher loading ratio of ion is attained at larger liquid flow rate.

Jan 1, 2003

By H. Masuda

The lijima Zinc Refinery started operation in 1972, and has today an annual capacity of 200, 000+-Zn. The hematite process was employed for the first time and the ideal of waste-free refinery has been pursued for 30 years. In recent years, however, only half of the hematite produced would be sold to the cement industry and hence a reduction of arsenic level has been necessary in order to sell the entire amount produced, The arsenic cementation process with zinc powder, developed through a long time laboratory research was found among some options as the best for the hematite process. The construction work started in 2000 and the facility was put into operation in 200 I. As a result in the same year all hematite were sold to the cement industry. The outline of this project, present operations and technical issue are reported in this paper.

Jan 1, 2003

By Levente Becze

The zinc bottom dross is obtained as a by-product from hot dip galvanizing operations and contains at least 92 % zinc, which is recycled mainly by pyrometallurgical processes. The overall costs of such a treatment, however, are often relatively high, and the very strict environmental protection regulations might also cause additional difficulties for the high temperature procedures in the future. Therefore, a novel hydro-electrometallurgical process has been developed in our laboratory, by which one can reclaim zinc of high purity, while attempting to achieve low energy consumption and making allowances for all the environmental restrictions. This aqueous processing technique, based on electrolytic refining in a cell equipped with anion-exchange membrane to separate the anode and cathode compartments, allows the indirect purification of the anolyte. Zinc is dissolved from the anode along with some of the impurity elements, while the intermetallic compounds (Fe-Zn, Fe-AI- Zn) are accumulated in the anode slime.

Jan 1, 2003

By Jonkion M. Font

Due to the known disadvantages of the use of iron silicate slag in the nickel converting stage, i.e., high metal losses, high magnetite content, and low fixation of impurities in the slag, the development of the new proposed "ferrous calcium silicate slag" for smelting and converting processes of nickel is very promising. Hence, considering the successful experimental results of using CaO base slag for the nickel smelting process, a study based on a detailed comparison for the phase equilibrium, and the minor elements distribution between the Ni3S2-FeS matte with either FeOx-CaO or FeOX-Si02 base slag was investigated. The main results are summarized as: no difference in the nickel losses between both slags was found at high nickel content in the matte, and the fractional distribution analysis for arsenic and antimony pointed out their preferential fixation in the calcium ferrite slag rather than in the iron silicate slag. Considering the energy and pollution issues, the technical feasibility of using calcium ferrite slag in a converting process of the Bessemer matte will have a prominent future for the nickel industry.

Jan 1, 2003

By Junzo Hino

Most of the waste that contains a small portion of copper is landfilled. The recycling process of copper from the waste, such as shredder residue, should be developed in order to save mineral resources and prevent environmental pollution. Shredder residue, generated from disposed automobiles and electric appliances, consists of many types of plastics, glasses and metals. The combustion heat of plastics is efficiently used for smelting in the recycling process that consists of melting and reduction. Because the waste contains numerous components the knowledge of the distribution behaviors of the main components is necessary to develop the recycling process. The distribution behaviors in the recycling process are evaluated by using the thermodynamic calculation program, HSC Chemistry. The calculation results are compared with the practical operation data of the recycling process and discussed.

Jan 1, 2003

By Kenji Matsuzaki

A mathematical simulation model of the Imperial Smelting Furnace operation has been developed for purpose of improving the furnace operation. The model consists of top, shaft and bottom regions, Analysis in the shaft region is based on differential heat and materials balances taking account of reaction kinetics and heat transfer rates, and those in the top and the bottom regions are based on heat and materials balances under a steady-state condition, Longitudinal distributions of process variables such as temperatures of gas, sinter and coke, gas composition and fractional conversion under a practical operating condition were calculated, With this model, the furnace performance under various operating conditions also can be shown reasonably predicted,

Jan 1, 2003

By M. A. Neri

A lead-free solder alloy Sn-57.5Bi-0.5Ag has been developed by mechanical alloying and foundry processes, and has great potential as a lead-free solder system, to low temperature applications. The mechanical alloying powders show a microstructure different to the microstructure obtained by the foundry process for the same alloy. Its melting point of 142°C is slightly higher than that of eutectic tin- bismuth solder. Examination of the microstructure revealed that eutectic microstructure is refined by the mechanical alloying process Ag additions. The lamellar structure of tin-bismuth gradually disappeared with the process of mechanical alloying, while intermetallic compounds AgaSn phase was formed. The Cu-Sn intermetallic compound layer formed at solder-copper interface is the Cu6Sn5 phase. Keywords: Lead-free solder, Microstructure. Mechanical alloying

Jan 1, 2003

By J. Jakumelt

The coupled simulation of mold filling and solidification for an investment casting process presents difficult. This is due to the complexity of the carious physical process and the geometry, To achieve this task in a precise way, the CFD program FLUENT and the casting simulation tool CASTS were closely coupled. Any physical quantity, such as velocities or temperatures, can be exchanged via files after each time step of the simulation. The communication and operating sequence of the programs is controlled by PERL-scripts. This enables the expertise of FLU ENT for flow simulation and the strength of CASTS, for casting simulation to be combined. The coupled simulation was successful applied to an aerospace investment casting. Several physical models were tested for correct treatment of the casting filters, the porosity of the mold and the viscosity of the liquid metal. The results demonstrate that even complex investment casting geometries can be investigated using CASTS-FLUENT.

Jan 1, 2003

By Bruce R. Conard

Consideration of environmental and human health issues in metallurgy is growing rapidly. While not all metallurgists need to have detailed expertise in environmental and health questions, they should be aware of the challenges the metals industry faces, be able to interact with colleagues in other sciences and contribute to sound metal resource management. Hydrometallurgists occupy a unique position among metallurgists because of their knowledge of the behaviour of metals in aqueous systems, which are of fundamental importance in understanding environmental chemistry and human toxicology. As a result, hydrometallurgists should more frequently and passionately lend their expertise in assessing environmental and health risks of metals and in helping to develop effective global guidelines, regulations and process and product stewardship strategies, thereby enabling metals to continue their beneficial service to society.

Jan 1, 2003

By Patrik Fredriksson

Thermodynamic data concerning FeO-containing slags is of importance in ladle refining of steel. With a view to generate a set of reliable and self-consistent thermodynamic data for these slags, experimental determination of the activities of FeO in binary and ternary slags was carried out using the gas equilibration method involving CO-C02-Ar gas mixtures at steelmaking temperatures. The slag samples in Pt crucibles were quenched after the equilibration and subjected to chemical analysis. The thermodynamic activities of "FeO" in the slags were calculated from the experimental data. The results are incorporated into a thermodynamic description of silicate melts in the present laboratory. The model is based on a Temkin-Lumsden approach and is able to compute the thermodynamics of higher order systems from the lower order ones.

Jan 1, 2003

By E. V. Verhoef

The proposed EU directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment promotes the substitution of lead in consumer electronics to reduce emissions from lead in the end of life phase. In this paper, the consequences of substituting lead in solders is assessed using the Eco-lndicator-99 method for the examples. The base metal production system is considered as an interconnected network modeled dynamically in Simulink 4 and Matlab 6 (Mathworks Inc 2000), where the recovery and production of metal components of the assessed product partially overlap. This approach requires global modeling of metal production processes and mass balances and resulting allocation choices. It also reveals the susceptibility of LeA scores to different choices in the modeling and data availability and uncertainty. Besides the comparison between lead-free and lead-containing solders, other side effects are revealed. Lead is carrier material for the recycling and production of many co-elements in the interconnected production and recovery system. Substitution may have adverse effects such as temporary shortages of other connected metals that are often not considered in normal LeA assessments, thus leading to erroneous results. The suggested approach provides directions for including these external effects and for further assessment of the environmental effects of substituting lead. This paper shows that in order to assess the environmental aspects of metallurgy, dynamic modeling of the total system is required based on the fundamental thermodynamics in each metallurgical reactor, the basis of this dynamic model. With this the true environmental impact of metallurgy can be explained. In the case of lead free solder, it is shown that the mining of substitutes has a very much larger impact.

Jan 1, 2003

By Moelans. N.

A method using an ex-situ electrochemical measurement device was developed to determine the oxygen potential of non-ferrous metallurgical slags. The electrochemical cell consists of the molten slag sample, an inert Ir electrode, a stabilized Zr02 solid electrolyte and a NilNiO reference electrode. Different slags from non-ferrous pyrometallurgical processes were analysed at I 100 and 1200 °C and pO2values between 10-3 and 10-12 bar were obtained. The measurements were evaluated with thermodynamic calculations and using processing considerations. It was found that the reproducibility and stability of the measurement was significantly improved by shielding the molten slag from the atmosphere by a thin layer of carbon, especially for slags with a low oxygen potential.

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 k value of the pure sulfur melt with irradiation jumped at around 170°C by an order of 102 after which it mouutuniocally increased from 10-5 to10-4 A' 1 cm-1 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 K value. The k value increased with the increase of Na proportion in the melt. For a 10mol% Na doped sulfur melt it was as high as max ~30 A 1cm -1 above 180 C under the irradiation of of ultrasconics.

Jan 1, 2003

By A. A. EI-Geassy

High-grade iron ore fines rejected from the DRI plants (>96%Fe2O3) were isothermally reduced in 30-60%CO/H2 gas mixtures at 973-1273K. The freshly reduced reaction products were then subsequently carburised in either Hz/CO or H2/CO/S mixtures at 823-1 073K for 30-120 min. The thermogarvimetric technique was used to follow up both of reduction and carburisation reactions as a function of time. The carburised samples were characterized by X-ray and Mossbauer techniques. Chemical and carbon analyses were also applied. The influence of temperature and gas composition on the reduction behavior was investigated. The calculated values of apparent activation energy, application of gas-solid mathematical formulations were correlated with the microstructures to predict the reduetion mechanism. The influenee of carburization time, temperature, CO contents in H2/CO or H2/CO/S were investigated. A conversion extent of Fe to Fe3C was taken as a measurable index for the efficiency of carburization rcaction under the different experimental conditions.

Jan 1, 2003

By Chetan P. Malhotra

This paper describes an online control system and simulation environment for reheating furnaces. The system can be configured for implementing manual control as well as automatic control using either look-up tables or online model predictions. The simulator is also used for offline generation of optimized normal operation and delay setpoints for look-up tables and generating ideal heating curves for model-based control. Finally, it is employed to compare the performance of the above control strategies over a typical period of operation of a pusher-type reheating furnace. Keywords: Reheating furnace, control strategy, model-based control

Jan 1, 2003