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By Guojun Qi

This work relates to wafer bumping technologies for flip chip packaging applications in the electronics industry. Nickel and its alloys are alternative under bump metallization (UBM) materials because of their slower reaction rates with Sn-based solder as compared to Cu-based UBMs. In this study, we compared the morphologies of the intermetallic compounds (IMC) formed between Sn-bearing solders (Sn3.5Ag and eutectie Sn-Pb) and two types of nickel- based UBMs, electro less Ni-P (EN) and sputtered nickel. Both chunky-type and needle-type of intermetallics were observed between the EN UBM and the solders. In the case 'of sputtered Ni UBM, there is only a layer of scallop-type intermetallics formed, The morphology change and growth kinetics of the IMC in thermal aging process were analysed. Kirkendall voids were noticed from samples ofSn3.5Ag solder vs Ni-P UBM that have undergone prolonged thermal aging at high temperature.

Jan 1, 2003

By V. M. Paretsky

The basic work conducted by Prof. A.Yazawa has demonstrated that in order to ensure single-stage white metal production by autogenous smelting of copper sulfide raw materials, it is most favorable to use highly basic slags, in particular oxide systems CaO-FeO-Fe2O3-Sio2. he special studies have been conducted in the Gintsvetmet Institute to investigate the composition and structure of slags produced on a semi-commercial scale when testing the KFP and FBP processes for white metal smelting, as well as the slag obtained in a full-scale KFP furnace at the Almalyk copper smelter. The investigations conducted have demonstrated why production of high-grade matte or white metal is associated with lower loss of copper in slag in a series: silicate slag I silicate-calcium slag I ferrite-calcium slag.

Jan 1, 2003

By V. I. Lakshmanan

Whilst the prices of metals in nominal terms have largely remained static over the past forty years, in real terms, the primary metals industry receives very much less today for its products than in the past. Yet, it has largely managed to remain competitive, despite the fact that ore reserves are not only diminishing, but are of lower grade and higher complexity, and that there are much greater pressures on companies to be good environmental stewards. This paper examines how hydrometallurgical processing has shown itself to be highly innovative in order to remain viable both economically and environmentally. Aspects of process chemistry are discussed, and the lessons to be learned from having a good understanding of this chemistry are highlighted with reference to a number of case histories such as HPAL for nickel laterites, the Avmin/Chambishi Cosac Project, use of chloride chemistry for titanium extraction, and plant effluent treatment and recycle.

Jan 1, 2003

By Grigore Matei

The thermodynamic properties of CU2S-FeS system are important not only in the case of copper smelting but also in the case of general pyro-mctallurgy, However there are not many reported activity data In this study, activities of FeS and CU2S in the CU2S-FeS system were calculated using the Darken's method from the activity data of the CU2S-FeS-Sb2SJ systems measured by the transportation method at 10S0°C. The activities of CU2S and FeS in the CU2S-FeS system showed negative deviation from the ideal behaviour and satisfied the relation of the Gibbs-Duhem equation,

Jan 1, 2003

By Marcel Sturzenegger

Though the extraction of copper is well established, generation of sulfur dioxide (S02) is still a troublesome issue. Conventional processes are further challenged by the increasing amount of impurities in the concentrates. Direct decomposition of the metal sulfides into the metal(s) and elemental sulfur under concentrated solar radiation offers a promising path to solve both problems. Thermogravimetric measurements under inert atmospheres have shown that synthetic chalcocite or chalcopyrite yield copper at temperatures as low as 1773 K. Even though optimum reaction temperatures might be somewhat higher, such temperatures are straightforwardly accessible in solar chemical reactors. The absence of oxygen will reduce the extent of slag forming reactions and thereby alter the evaporation characteristics of volatile impurities such as arsenic or antimony. Chemical equilibrium calculations for a chalcopyrite-enargite feed, e.g., have shown that under inert atmospheres arsenic compounds are completely evaporated at temperatures above 1000 K and an effective separation of arsenic from the matte is expected. An important step towards a solar production of copper is the design and testing of prototype solar chemical reactors for this reaction. Numerical modeling is a key tool supporting a rational design but it requires data of the high-temperature properties that prevail in these processes. Development of techniques for determining the essential quantities such as decomposition rates or radiative properties at temperatures up to 2000 K is therefore a main activity in our laboratory in order to control and optimize the process. Though developed in the frame of high-temperature solar technology, the experimental techniques are also suited to advance the understanding of conventional high-temperature processes. Keywords: Solar technology, Sulfur dioxide, Solar Radiation, Thermogravimetry, Chalcocite, Chalcopyrite, Numerical modeling.

Jan 1, 2003

An EAF dust generated in a Swedish steel mill has been leached in hydrochloric acid at The solution obtained has been subjected to purification by cementation followed by precipitation of zinc with sodium carbonate. The thermal decomposition of the precipitate was studied using thermal analysis and X-ray diffraction. The results show that during the calcination of the precipitate three different reactions occur. The decomposition of the solid phases Zn5(CO3) (OH)6, CaZn(CO3)2 and CaCO3 occur completely at 370°C, 560°C and 940°C respectively, yielding a final product containing 61.9% ZnO and 38.1% CaO. Methods to minimize calcium and manganese in the final product are discussed.

Jan 1, 2003

Hazardous waste has often very complicated chemical compositions in a variety of physical forms and is normally processed in rotary kiln incinerators. Due to large variations in waste types and difficulties in feed characterization, the complex transport processes within the incinerator are not well understood, and the incineration process meets challenges in a smooth operation, and expects various uncertainties in the process chemistry and emission control. For better understanding of the incineration process, simulation was carried out by using Computational Fluid-dynamics (CFD) to characterize temperature and species distribution in the incinerator. In order to catch certain aspects of thermal and chemical behavior, a novel approach is proposed to represent approximately the waste streams and the subsequent combustion process. Hazardous waste in various forms from an industrial-rotary-kiln waste incinerator is firstly converted to a hydrocarbon-based virtual fuel mixture with approximately the same HIC molar ratio and calorific value. The simulation of the combustion process of the simplified hazardous waste was proceeded with a combustion model. The distribution of temperature and chemical species especially the remaining CO in the system is preliminarily investigated. Distribution of CO concentration, as a good indicator of emission level for the incineration process, could be used to evaluate the emission control. The predicted temperature distribution has been compared with available measurement data from an operating rotary kiln waste incinerator at AVR-Chieme, in the Netherlands. Reasonable agreement has been reached between the measured and predicted temperature data. In the next step, measurement of species distribution in the system is planned to further validate the combustion model.

Jan 1, 2003

By M. Oliazadeh

The present study was performed to develop a process for solvent extraction of molybdenum and cobalt from an acidic solution generated by an electrodeposition process of nanocrystalline cobalt alloys. Solvent extraction is a common practice in hydrometallurgical and refining processes to produce metals; however its application for separation of molybdenum and cobalt from this specific solution is new, because molybdenum and cobalt are not commonly associated together in nature. Five commercial organic extractants were examined for extraction of cobalt and molybdenum from synthetic acidic solutions with pH ranging from 1 to 5. Preliminary results showed that at pH 2, any of the Cyanex 923, Alamine 336, Aliquat 336 and Hostarex A327 could be used to extract 99% of molybdenum from solutions, while from pH 3 to 5, Aliquat 336 was able to extract about 100% of molybdenum. Cobalt extraction, on the other hand, varied from 15% to 23% at pH 3 and 30% to 53% at pH 2 using different extractants. Based on results obtained, Aliquat 336 was applied on mixed solutions of cobalt and molybdenum at various pHs. The results showed that molybdenum could be extracted as much as 99% from a mixture of molybdenum and cobalt at acidic pHs, while less than 1% of cobalt was separated at pH 2 to 4 simultaneously.

Jan 1, 2003

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of873 OK is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composItion formed under roasting of concentrates with particle sizes less than 0.02 J..lm (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CufeSz) each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forehamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By B. Zilbergleyt

Current understanding of chemical equilibrium is based exclusively on the probabilistic considerations that are correct for isolated systems with only one chemical reaction to take place. For the systems with multiple chemical interactions, current paradigm of chemical thermodynamics promotes the idea of openness, artificially flavored with coefficients of thermodynamic activity. Recently introduced thermodynamics of chemical systems and the Method of Chemical Dynamics (MCD) offer explicit accounting for the multiple chemical interactions within the system. In the new theory, thermodynamic equilibrium of the j-subsystem obeys the logistic equation derived exclusively from the currently recognized concepts of thermodynamics. Having the only one new parameter -the subsystem's reduced chaotic temperature 'tj to describe external interactions, and reaction extent Ilj as independent variable, this equation covers the whole domain of the system's possible states from true thermodynamic equilibrium through the open equilibrium to bifurcations and chaos depending on the 'tj value. The MCD brings new opportunities to thermodynamic simulation of complex metallurgical and chemical systems, allowing for the analysis of their domains of states and the area limits, and for more accurate calculation of the equilibrium compositions. Its usage is exemplified in this paper by several applications. Keywords: chemical thermodynamics, open systems. complex systems, chemical dynamics.

Jan 1, 2003

By Junji Shibata

The waste acid mixture whose main component is phosphoric acid, is discharged from the etching process in the liquid crystal production industry. In order to separate impurity acids from the phosphoric acid, trioctyl phosphate (TOP) is used as an extractant. TOP can extract acetic and nitric acids selectivity. The extraction and stripping operations are carried out for the acid mixture by beaker-scale experiments and countercurrent multistage operations with mixer-settler equipment. TOP selectively extracts the acetic and nitric acids in the acid mixture. From the results of the McCabe-Thiele analysis obtained by beaker-scale tests, the extraction for acetic and nitric acids are approximately 100%, respectively, by 6-stage extraction with a phase ratio (A/O) of 0.4. On the other hand, almost all of acetic and nitric acids are stripped with water from the organic phase by 4-stage stripping with a phase ratio (A/O) of 1.0. About 95% of acetic and 98% of nitric acids can be removed from the acid mixture without extracting phosphoric acid in case of the mixer-settler equipment operation. There are several steps such as slicing, lapping, chemical etching and mechanical polishing in the silicon wafer production process. The chemical etching step is necessary to remove any damaged layer caused in the slicing and lapping steps. The typical etching liquor is the acid mixture comprising nitric acid, acetic acid and hydrofluoric acid. The waste acid is treated by a neutralization method with a high alkali cost and balky solid residue. A solvent extraction method is applicable to separate and recover each acid. Acetic acid is first separated from the waste liquor using 2-ethlyhexyl alcohols as an extractant. Then, nitric acid is recovered using TBP (Tri-butyl phosphate). Finally hydrofluoric acid is separated with TBP solvent extraction. The expected recovered acids in this process are 2mol/L acetic acid, 6mol/L nitric acid and 6mol/L hydrofluoric acid. The yields of this process are almost 100% for acetic acid and nitric acid. On the other hand, it is important to recover and reuse the metal values contained in various industrial wastes from a viewpoint of environmental preservation. Most industrial products are made through processes to separate impurities in raw materials, solid and liquid wastes being necessarily discharged as industrial wastes. Chemical methods such as solvent extraction, ion exchange and membrane separation, and physical methods such as heavy media separation, magnetic separation and electrostatic separation are considered as the methods for separation and recovery of the metal values from the wastes. Some examples of the application of solvent extraction to the treatment of wastes such as Ni-Co alloy scrap, Sm-Co alloy scrap, fly ash and flue dust, and liquid wastes such as plating solution, the rinse solution, etching solution and pickling solution are introduced.

Jan 1, 2003

By Patrick R. Taylor

In the search for the development of more "environmentally friendly" and more intensive waste disposal approaches to meet more and more stringent environmental regulations, thermal plasma-based processes are considered one of the most promising alternatives to well- established technologies such as incineration. This paper presents an overview on the research and development status of thermal plasma-based waste remediation technologies. The properties of thermal plasma are described. Due to its unique feature of high-energy intensity and super high temperature, thermal plasma is particularly capable of destroying organic- containing wastes. Its potential and promising application to waste remediation may include: treatment of incinerator ashes; metallurgical dusts (especially, electric arc furnace dust); medical wastes; radioactive wastes; and other Resource Conservation and Recovery Act (RCRA) listed hazardous wastes. Many research institutes and vendors have been involved in the development of thermal plasma-based waste treatment technology encouraged by the cleanup programs supported by the Environmental Protection Agency (EPA), the Department of Energy (DoE) and the Department of Defense (DoD). More recently, thermal plasma-based waste treatment technologies (sometimes called plasma-enhanced pyrolysis) are focused more and more on not only just destroying organic wastes but also on how to practically, and economically recover energy contained in the organic waste materials in addition to the recovery of metals in order to offset the high operating costs.

Jan 1, 2003

By Nickolas J. Themelis

Nearly thirty two million tons of municipal solid wastes (MSW) are combusted annually in over one hundred U.S. Waste-to-Energy (WTE) power plants, thus reducing the use of fuel oil by about 1.6 billion gallons of fuel oil One of the advanced WTE processes is the 0.9-million ton/y SEMASS facility at Rochester, Mass. Most of the combustion in the three giant combustion chambers occurs while the injected shredded wastes are in suspension, i.e., in flash combustion mode. The velocity, temperature, and concentration profiles in the SEMASS combustion chamber were simulated by representing the combustible fraction of MSW by the simplified formula C6HIO04 and using the CFD program Fluent to solve the turbulent energy and mass transport equations. After validation against plant data, this model will be used to examine options for increasing the productivity of WTE combustion chambers, such as optimum distribution of primary and secondary air and oxygen enrichment.

Jan 1, 2003

By Asmo Vartiainen

Background of Direct-to-Blister Flash Smelting is discussed; especially slag chemistry relating to copper solubility, slag fluidity and impurity behavior. In December, 2000, Mini-pilot Flash Smelting test runs were carried out at Outokumpu Research Oy to produce blister copper from Chilean concentrate and white metal and from a mixture of them. Tested slag types were iron silicate slag, ferrous calcium silicate slag and calcium ferrite slag with different slag compositions and different concentrate/white metal ratios. The test runs were successful. The fluxing effect of copper oxide was clearly demonstrated and ferrous calcium silicate slags remained fluid on a very wide liquidus range. The distribution of arsenic between ferrous calcium silicate slag and blister copper is much higher than between iron silicate slag and blister copper. This successful test run with the new slag type offer new possibilities in Direct-to-Blister process design.

Jan 1, 2003

By Pragna Bhakta

The use of microbes for sulfide oxidation was investigated as a potential treatment option for low-grade refractory gold ores at Newmont Mining Corporation. The resulting patented technology for heap biooxidation maximizes oxidation rate by distributing the microbial population on the ore before placement on a heap. This paper presents data on global oxidation rates based on oxygen uptake in a 50-kg column for sulfidic refractory ores from the Gold Quarry mine. The oxygen uptake data was converted to a global oxidation rate. The calculated global oxidation rate was used to determine heap cycling times for Newmont?s commercial heap biooxidation facility.

Jan 1, 2003

By F. Kongoli

Nonferrous and ferrous smelting industries have recently faced the unavoidable necessity of changing and/or improving the smelting technologies as a result of the use of new raw materials which are becoming available from different geographical areas. These new feed materials usually contain different ore composition and higher level of minor components, which adversely affect the smelting process. Due to the problems encountered in several processes as a result of this feed diversification some work has been undertaken in order to make uniform the feed and avoid later surprises in the smelting process. However this has proven to be very difficult and sometimes almost impossible. In this work a more viable approach is undertaken to deal with this problem. It consists of controlling not the cause of the problem i.e. the feed composition but instead the results of this feed change, i.e. the end-point of smelting technologies. It is shown that this approach, when carried out through advances physicochemical modeling and simulation tools is not only easier and less costly but it also helps the control optimization and automation of the smelting processes. Several examples are given and future work is underlined.

Jan 1, 2003

By José Carlos Abreu

This work presents a kinetics study covering the effects of temperature over the reduction rates of a carbon composite briquette, aiming its use as burden in some of the new alternate ironmaking technologies, such as the Tecnored process. It is reported that increases in the temperature increases the reaction rate. Additionally, the morphology of the iron phase generated during the reduction of these briquettes is presented. It was possible to verify that three types of iron morphology occurred during the process: an external, dense and continuous iron layer, the presence of iron globules at the center of the briquettes and whiskers at the briquette's core. The measurement of the carbon content on the globules and the external iron layer is also presented

Jan 1, 2003

By Tapani Järvinen

Non-ferrous metals and metals in general are considered as being non-renewable natural resources. Metals are needed because of their excellent and irreplaceable properties. The consumption of metals, with the exception of carbon steel, is steadily growing by 1-3 % annually, and that of stainless steel as much as 3-6 %. This is a general trend, which is periodically disturbed by cyclical variations. In recent years so-called "New Economy" has become prominent in the public media and the market value of the traditional industry has been well below its real value and importance. Nevertheless, the modem society requires metals today and also in the future, and the companies using the most modern technology in a responsible way and innovative solutions not only in technology, but also in everything they do will survive. This paper describes the role of Europe as a producer of primary base metals and as a supplier of technologies in the base metals industry. It concentrates on the development and commercialization of technologies and project implementation in the metallurgical industry. As one example ofa European approach to these matters the paper presents Outokumpu's response to the future challenges in the base metals industry. Outokumpu Oyj is one of the leading metals and technology companies in the world of stainless steel, copper, zinc, and sales of technology in metals and minerals businesses. Outokumpu applies its knowledge of metals and processing to generate value for its customers and shareholder. Everything we do, we do in an economically, environmentally and socially responsible way.

Jan 1, 2003

By Fumito Tanaka

The Mitsubishi process is the sole pyrometallurgical process for the continuous production of blister copper from Copper concentrates and has been successfully operated around the world. The development of calcium ferrite slag (CaO-FeOx-Cu10), the so-called "C-slag", has enabled continuous converting from matte to blister copper in the commercial scale operations. Commercial interests in the slag led to many papers over the CaO-FeOx slag. However, Cu2O bearing slag has not been studied well due to experimental difficulties. The authors have quantified the thermodynamic properties of the CaO-FeOX-Cu2O system. The results have been utilized to analyze various issues related to the converting furnace, such as the magnetite precipitation from the slag or from blister copper and to develop better controlling criteria for the continuous converting operation. -

Jan 1, 2003

By Huang Kai

Uniform needle-like and spherical nickel oxalate particles were prepared by the chelating precipitation process, which was based on the reaction of oxalate acid and the solution of ammonia nickel chloride. The molar ratio of ammonia to nickel ion in the mixed solution is essential to determine whether the spherical or needle-like particles are formed, which means actually the concentration of ammonia is the key to determine the growth mechanism. When oxalate acid is added in the form of solid, it may act as the nucleation interface for the eariy-precipitated substance and so induce the formation of spherical particles. The PVP agent can improve the dispersing degree of the needle-like particles and higher reacting temperature leads to larger particles. The composition of the needle-like particle consists of ammonium and nickel oxalate instead of the pure nickel oxalate.

Jan 1, 2003