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This report presents overview of the authors' results of thermodynamical investigation of some important metallurgical processes and phenomena. Among them: carbo thermal reduction of silica, and boron oxide, silicon carbide obtaining from different precursors, investigations on copper and manganese ores processing, investigations on pollution from different sources. Special attention is paid-to thermodynamical approach to investigation and estimation of multi component multi element compositions stability, developed by the authors. Also are discussed some auxiliary but' important for the thermodynamical investigations issues.

Jan 1, 1997

By W. E. Wallace, J. A. Warren, D. Josell, D. Wheeler

"We present the results of experiments and modeling of flip-chip geometry solder joint shapes under shear loading. Modeling, using Surface Evolver, included development of techniques that use an applied vector force (normal and shear loading) as input to determine a vector displacement of the pads connected by the solder joint (standoff height and misalignment). Previous solutions solved the converse problem: fixed displacements used to determine required applied force. Such solutions were inconvenient for applications, where the applied force (chip weight) is known. Also, for geometric and materials studies of solder joint shapes involving multiple parameters, determining the equilibrium displacement from applied force by bracketing solutions could become computationally expensive. Measurements of solder joint standoff height and misalignment as functions of the applied force (normal and shear), solder volume and pad diameter are presented. Experiments were carried out for solder ball diameters from 0.38 mm (0.029 mm3 volume) to 0.15 mm (0.0019 mm3 volume) on pads of diameter 0.64 mm and 0.35 mm. Fitting of simulation to experimental results gave optimized values for the contact angle and surface tension of the solder which were consistent with measured and literature values. IntroductionIn packaging technology flip-chip has become an important method for attaching semiconductor devices to substrates. Generally, the chip and substrate are bumped with solder and then the chip is flipped onto the substrate and the solder reflowed to form conductive interconnects. An epoxy underfill is normally flowed between the substrate and chip to reduce the thermal fatigue on the solder joints. A flip-chip assembly is illustrated in Figure 1.In flip-chip applications, the use of an integrated underfill/solder bump system [1, 2) removes an extra process step, namely infiltration of the underfill. However, the presence of an underfill will retard the self-alignment of the flip-chip. A first step in understanding and predicting this retardation is to develop a model to describe normal and lateral force-displacements curves when underfill material is not present. At this stage it is unclear whether static surface tension theory is sufficient to describe a complete model for flip-chip realignment even without underfill."

Jan 1, 2001

By C. T. Philipp

Recycling of waste is much preferred over disposal. This paper discusses the Enviroscience, Inc. (ESI) process, now being commercialized by MetWool, Inc., to recycle hazardous wastes using an extractive metallurgical process which is followed by vitrification of non-reducible metal oxides. In this process, volatile and reducible metals are reclaimed as their respective oxides and elements.

Jan 1, 1995

By G. H. Khoe

Neutralisation of acid uranium mill tailings with lime or other alkaline materials is usually practised to reduce the dissolved concentration of heavy metals and radio nuclides. Computer modelling of this process was carried out using the geochemical equilibrium code MINTEQA2. Computed dissolved metal and sulfate concentrations were compared with laboratory-based experimental data. It was found necessary to include the modelling of adsorption of trace metals (such as uranium and lead) by the precipitated ferric hydroxide in order to obtain acceptable concentrations in the neutralised liquors. There were limitations of the modelling exercise due to important aspects which were not addressed or properly accounted for such as chemical reaction kinetics and the effect of high ionic strength. These are discussed in the paper.

Jan 1, 1991

By Demaerel. J. P.

Arsenic plays a major role during electroreflning of copper. Both the arsenic content in the anode and the arsenic concentration of the electrolyte have, in conjunction with other impurities such as lead, antimony, bismuth and oxygen, a direct influence on the quality of the cathode. The mechanisms are currently slime. inclusion and precipitation of insoluble compounds in the bulk of the electrolyte. Arsenic has also been reported to have a depassivating effect on the anode. An influence on the anode slime adhesion has also been found. A literature survey is given and these data are compared with and completed by our own results based on lab and pilot scale experiments as well as on Olen tank.house practice.

Jan 1, 1987

By G. Haesebroek

In L969 Metallurgie Hoboken-Overpelt started an industrial plant for the separation of iron and zinc from a concentrated CoCL2 solution. Iron and zinc are extracted in column contactors by a solvent containing 12 vol % of tertiary amines in xylene. The extracted metals are stripped from the pregnant organic phase by precipitation with a NaOH solution at pH LL. In this paper an overview is given of the industrial process. In order to overcome some drawbacks of this process (low flash point of the diluent, reagent consumption, batchwise stripping) an alternative solvent extraction process has been examined. In this alternative process, iron and zinc are extracted with an or¬ganic phase containing 50 vol % of TBP in Escaid 110. The pregnant solvent is stripped with water in conventional mixer settlers. Despite the ability of this process to overcome most of the inconveniences due to the use of tertiary amines, it suffers from the poor stability of TBP in concentrated chloride solutions, resulting in unavoidable and inacceptable precipitation phenomena in the stripping section.

Jan 1, 1988

By Grant Wallace, Rod James, Larry Twidwell, Ed Rosenberg, Courtney Young, Sean Dudley, Hsing-Hsin Huang, William Gleason, Jerome Downey

The use of applied chemistry in the production and optimization of leach solutions from Rare Earth Element (REE) ores and concentrates is being investigated. Ore and concentrate samples were characterized using scanning electron microscopy/mineral liberation analysis (SEM/MLA), X-ray diffraction (XRD), and Atomic emission inductively-coupled plasma spectroscopy (ICPAES). Multiple leach tests were performed to analyze the effects of temperature, residence time, and reagent concentration on the leaching of REEs. Analysis of leach solutions was carried out using ICP-AES. Modeling and statistical analysis of extraction behavior was carried out using DesignExpert 9. Modeling data for cerium extraction indicates that extraction is greatly influenced by temperature and reagent concentration, while leaching time plays a much less important role. Experimental design techniques are being utilized to optimize REE recovery. Results, conclusions, and directions for future studies will also be discussed.

Jan 1, 2015

By Yang Hong-ying, Yu Juan

Electrochemical behavior of natural chalcopyrite in electrolyte solution at pH value of 6.97 was studied by cyclic voltammetry, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy. The results showed that the electrochemical processes occurred on electrode surface were controlled mainly by the growth of sulfur species at lower applied potentials (<0.35Vvs.SHE), and the oxidative dissolution of sulfur species and the hydroxylation of iron at higher applied potential (>0.45V). The EIS spectra of oxide product layers could be illustrated by the equivalent circuit of Re(QdlRct(QfRf)), and the degree of hydrophilicity for chalcopyrite was higher when the value of charge transfer resistance Rct. was greater. The optimum potential range for the floatation of chalcopyrite in collectorless solution at pH value of 6.97 was between OCP (0.165V) and 0.35V.`

Jan 1, 2015

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 R. Schuhmann

The thermodynamic data and calculations which underlie the design of the Q-S process for coppermaking are summarized. The efficient production of crude copper and slag of low copper content in a single con¬tinuous converter requires the establishment and control of gradients in oxygen activity and other physico-chemical variables throughout the reactor. These gradients are established by stagewise introduction of oxygen and solid feed materials to provide: (a) flash oxidation of sulfides above the bath, utilizing the great bulk of the oxygen, (b) conversion of high grade matte or white metal to crude copper by bottom blowing with restricted bath turbulence, (c) close approach to equilibrium staging of converting and deconverting reactions along the length of the slag layer, from a maximum oxygen activity near the metal discharge end to a minimum at the slag discharge end, and (d) completion of slag cleansing by deconverting. In terms of the Phase Rule, the Q-S process involves a system with a minimum of 5 components (Cu, Fe, S, O, and SiO2) and several liquid, solid, and gaseous phases. Accordingly, basic data from previously reported studies on simpler systems are utilized to prepare an equilibrium diagram for the 5-component system and to generate a quantitative thermodynamic model for the Q-S process. This model shows in particular the ranges of oxygen activities (measured by equivalent CO2/CO ratios) involved in the Q-S process and the relations of oxygen activity to temperature and other important physico-chemical variables of coppermaking.

Jan 1, 1976

By T. E. Warner

In order to detect arsenic and antimony in zinc, various electrochemcial experiments were performed involving the electrochemical introduction of sodium atoms into molten zinc using a solid electrolyte. Under high rates, the formation of the intermetallic phase NaZn13 was assumed to form. Under more moderate injection rates of sodium, employing a symmetric "zinc/zinc cell", a qualitative relationship between the current generated during cyclic voltammeuy and the arsenic and antimony concentrations in molten zinc was observed.

Jan 1, 1999

By R. S. Celmer

The distributions of cobalt, molybdenum, copper, and selenium between nickel matte and silica-saturated iron silicate slag have been determined in the region of the metallic saturation boundary, at 1523 K. Results are given as a function of the composition of the coexisting Fe-Ni alloy and the activity of iron in the system. Under strongly reducing conditions, these minor elements display a marked preferential accumulation in the sulphide phase. It is shown that the dissolution of cobalt and molybdenum in slag follows an oxidative mechanism, and distribution equilibria are correlated with the oxygen potential. From these data, the thermodynamic properties of cobalt in nickel matte are computed. Further, comparisons of minor element partitions are made between the nickel and copper matte smelting cases under metal saturation conditions.

Jan 1, 1988

By Beate Ina Jenssen

Ferric iron removal from the nickel electrolyte at Glencore Nikkelverk AS in Kristiansand, Norway, is achieved by precipitation of iron hydroxide followed by filtration, and it is desirable to improve filtration properties of the precipitated iron hydroxide in order to decrease the filtration time. The effect of increasing the residence time from the current 45 min to 75 min and temperature from 65 °C to 90 °C on the filtration properties of the precipitated iron hydroxide (akaganéite) was studied by simulating the industrial process conditions in a continuous reactor setup operating at steady state, using ferrous-containing process solution as feed material. It was possible to decrease the filter cake resistance by both increasing residence time and temperature, but temperature gave the most pronounced effect and reduced the filter cake resistance by one order of magnitude.

By Ma Ying

The continuous directional solidification technique of five kinds of special ZA alloys with eutectic, peritectic and eutectoid transfonnation under the condition of continuous casting by heated mold was studied. The mechanism of surface defects appearing in ZA alloy line was discussed and the structure of some defects were analyzed by SEM. The results show that only when the fitting of various technique factors, pressure head, outlet temperature, pulling speed and cooling condition are reasonable under a certain range, can the ZA alloy smooth line be continuously pulled out. Unreasonable techniques will result in hot tear, rough surface, mush outlet, leaking and other defects. The shape and location of solid-liquid zone have an important influence on the formation of the above defects. When the solid-liquid zone is located in the mould outlet or inner mould, the surface of solidification will protrude into the inner mould. If the remaining liquid cannot counteract the solidification contraction, a rough surface will appear. If the solidification surface further into the mould, the ingot in the mould will have a great friction force when pulling and will form a hot tear. When the solid-liquid zone is moved out of mould, the solidification surface will turn into a plane, which easily results in leaking. A vibration or unstable operation will cause an ingot winding during pulling.

Jan 1, 2003

By Kezhuan Gu

Data on the kinetics and thermodynamics of dephosphorization are analyzed in terms of the dynamic partition ratio, determined by a combination of slag thermodynamic properties and the balance of oxygen supply and consumption. A recently developed phosphate capacity correlation is combined with data on kinetics to quantify the most significant parameters in controlling the interfacial oxygen potential. The role of slag composition, entrained gas fraction and temperature are discussed in addition to metal carbon and sulfur content. It is demonstrated that the mass transport of oxygen in the slag is enhanced by factors increasing conductivity and inhibited by entrained gas. The mass transfer of phosphorus in the metal is described considering surface renewal induced by CO bubbles.

By V. Blet

Rare earth elements (REE) are regarded today as highly critical raw materials but currently lack suitable recycling processes. A combined hydro- and pyrometallurgical process aimed at REE recovery from used NdFeB permanent magnets was recently developed by the CEA. The process integrates the physico-chemical treatment of magnets, followed by a solvent extraction step for the recovery and intra-REE separation using a selective extractant. A subsequent pyrometallurgical treatment via molten chloride salt electrolysis allowed the isolation of pure Dy metal. Technical-economic assessment and life-cycle analysis were also conducted. Following this first successful demonstration, a new project aimed at the recovery of REE from end-of-life nickel-metal-hydride batteries is currently being developed in association with industrial and academic partners. The project aims at evaluating from an experimental and economic perspective different processes converging at the production of value-added products such as cermet materials for catalytic applications, purified REO concentrates, or metallic alloys.

By Junwei Han, Wenqing Qin, Dawei Wang, Fen Jiao, Wei Liu

The removal of iron impurity from zinc calcine was studied by magnetization roasting and magnetic separation. The effects of roasting temperature, magnetic intensity, ore grinding, and leaching pretreatment on iron grade and recovery were investigated. The results indicated that iron recovery increased with the increase of roasting temperature or magnetic intensity, while iron grade was always less than 22%, depending on the fact that the magnetite were not liberated completely. The good liberation was difficult to be achieved by ore grinding but was easier by acid leaching, since the magnetite grains were very fine. After the leaching pretreatment, the recovery of 76.31% with iron grade of 53.24% was obtained by one roughing and cleaning. The SEM/EDS analysis showed that a part of sphalerite, zinc ferrite and other gangues were mixed into the iron concentrate, while some of fine magnetite was reported to the tailing.

Jan 1, 2016

By W. G. Davenport

Chapters 7,8and 9 calculated three combinations of: blast composition (mass% O2, mass% N2) oil quantity per tonne of concentrate blast temperature that will steadily produce molten 65% Cu matte from pure chalcopyrite-concentrate. The combinations are:

Jan 1, 2001

By Jiann-Yang Hwang

A study on microwave assisted chalcocite leaching was carried out with a microwave hydrothermal reactor. The leaching was conducted with thick mineral slurries (50-100 g/l). The leaching media is a mixed solution of CuCL2 and NaCL The investigation included the effect of leaching temperature, quantities of the minerals per unit slurry volume as well as the initial concentration of cupric ions were investigated. The results were discussed and compared with that using conventional leaching method.

Jan 1, 2003

By Florian Kongoli

Slags and fluxes are important interchangeable dimensions of pyrometallurgical processes. They can increase the efficiency of the smelting, converting and refining processes and improve the quality of the final products. A good slag should have appropriate physicochemical properties such as low liquidus temperature, optimal viscosity, maximum ability to attract undesirable elements, minimum potential of attracting valuable elements, etc .. A good flux, on the other hand, when properly used, can considerably improve the physicochemical properties of the slag since by modifYing its chemical composition it could decrease the liquidus temperature, improve viscosity etc.. Consequently, the choice of a good slag and the corresponding fluxing strategies has become indispensable in most of industrial processes. However, the properties of multi component slags as well as the effect of several fluxes are known only empirically and confusion exists in the literature and in the industrial practice. In today&apos;s reality of frequent changes in the composition of raw materials and that of the fluxes themselves, in the existing or new developing technologies, the quantification of the thermophysicochemical properties of multicomponent slags and the effect of fluxes becomes indispensable. This paper reviews some of the work carried out by the author&apos;s group during the last ten years on the quantification of the thermophysicochemical properties of multicomponent slags and on the effect of fluxes in several smelting and converting processes in close relation to their individual characteristics. Several examples have been given in order to demonstrate the fact that when taken outside the context some fluxes can become in fact anti-fluxes.

Jan 1, 2003