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By J. D. Sunderkötter, M. F. Stroosnijder, V. A. C. Haanappel

"TiAI-based intermetallic compounds have attracted considerable interest as structural materials for high-temperature applications due to their low density and substantial mechanical strength at high temperatures. However, one major drawback hindering industrial application arises from the insufficient oxidation resistance at temperatures beyond 700 °C. In the present contribution some general aspects of high temperature oxidation of TiAI-based intermetallics will be presented. This will be followed by a discussion of the influence of alloying elements, in particular niobium, and of the effect of nitrogen in the oxidizing environment on the high temperature oxidation behaviour of such materials.Extended AbstractIntroductionTiAI-based intermetallics are being considered as construction materials for high temperature components, e.g. in aircraft and car engines, due to their low density and substantial mechanical strength at high temperatures, see e.g. [1,2]. The best ductility can be attained with alloys consisting of y-TiAI with around 5-15 vol.% Q2-Ti3AI. However, one major hindrance to industrial application arises from the insufficient oxidation resistance at temperatures beyond 700 aG. In spite of their high aluminium content, TiAI-based intermetallics do not generally form long-lasting protective alumina scales. After longer exposure times the scales, which are initially rich in alumina, deteriorate and scales consisting of mixed alumina and titania predominate, with high growth rates similar to pure titania.It is not the intention of the present paper to present a general overview of the high temperature oxidation behaviour of TiAI based intermetallics, for which the reader is referred to the literature [3,4]. In the present contribution some general aspects of high temperature oxidation of TiAI-based intermetallics will be presented. This will be followed by a discussion of the influence of alloying elements, in particular niobium. The effect of nitrogen in the oxidizing environment on the high temperature oxidation behaviour of these intermetallics will also be considered."

Jan 1, 1996

By Esther Carrera Martinez

Caraiba Metals is the sole brazilian copper custom smelter. The sulfur present in the various concentrates processed is recovered as sulfuric acid and oleum ,which are sold in the local market For quality assurance purposes, a study was carried out in order to determine how to control the arsenic content in the acid, allowing the continuous processing of concentrates with high levels impurity, The study was based on the process parameters of the washing towers and mist precipitators, Others process variables were investigated and their effects were used in support to confirm the results, After many analyses performed some interventions to improve the quality of the acid were implemented in the plant, which proved to be successful even by using a conventional purification system,

Jan 1, 1996

By A. Mikula, S. Karlhuber

"Unique physical and mechanical properties made the Pb-Sn solders attractive for low temperature joining of electronic parts. But since lead in solder materials has become a great enviromental problem and health concern, lead will be slowly replaced by other materials in soft solders. Some of these materials which are currently under investigation are ternary tin alloys. Many different physical properties like wetting behavior, electrical and thermal conductivity and surface tension are measured on these alloys, but on the thennodynamic properties and the phase diagram of the alloys under discussion there is only little information available. We investigated the (Ag, Au, Cu)-Sn-Zn systems and determined the thermodynamic properties over the whole composition range by emf-measurements. From these measurements we also got some information on the liquidus. In the Sn-rich corner the phase diagrams are still under investigation.IntroductionSoldering is technically defined as the joining of two base materials, mostly metals or metal coated nonmetallic substrates, with a third metal. The melting temperature of the third metal or metal alloy should be well below those of the substrates. Solder alloys can be categorized in soft and hard solders. Soft solder alloys usually contain lead, tin, bismuth, indium or cadmium and hard solders gold, zinc, aluminium or silicon. The difference between soft and hard solders is the melting temperature of the soldering material. This temperature is around 350°C.An interesting brief history of solders is given by Vianco and Frear [1]. They report, that in 4000 B.C. solders were already used in Mesopotamia. From archaeoligical evidence those solders were gold-based hard solders.Tin-lead soft solders and their use are not easily found, because in course of time tin has been reduced to stannic acid, making the identification quite difficult. Well preserved soft solder artifacts were discovered in King Tut's tomb dating from 1350 B.C. In ancient time Pb-Sn solders were used primarily for the manufacture and repair of cooking utensils and metal tools. The Romans used lead-tin solders extensively in the construction of the aqueducts."

Jan 1, 1996

By A. Treverrow, G. A. Brooks, H. K. Worner

"The work by H.K Worner and co-workers at CRA in the 1960s, and early 1970s, established that molten metals could be refined continuously utilising counter current flow of metal and slag. Womer also demonstrated that counter current refining could produce highly refined metal products. These developments coincided with the advent of high intensity metallurgical reactors in both the ferrous and non-ferrous industries (e.g. BOS, Q-BOP and later Sirosmelt) that utilised high levels of gas injection to produce rapid stirring and very fast reaction. These new generation of high intensity metallurgical reactors allowed high tonnage rates through relatively small volume vessels.Whilst, it is well known that the counter current flow of reacting phases offers the potential of efficient mass transfer and high purity products, the application of counter current reactors to molten metal/slag systems has been criticized on the basis that they suffer from either low intensity or, alternately, from poor refining due to excessive dispersion. These criticisms relate to the balance between intensity and the refining capacity of a reactor. That is, whilst high levels of mixing transversely to the direction of flow promotes high mass transfer, longitudinal mixing (dispersion) is detrimental to refining. Of course, mixing in one direction invariably leads to mixing in other directions, thus creating a playoff between high mass transfer and excessive dispersion.This balance between intensity and refining has been the subject of recent studies overseas, and at"" the University of Wollongong, using cold modelling techniques to evaluate the effect of mixing on dispersion in a counter current refining launder. These studies have shown that for a given geometry and mixing regime, dispersion decreases with increasing flow of liquid phases. This means that whilst high mass transfer cannot be achieved in a refining launder without sacrificing the degree of refinement, there is no impediment to achieving high productivity through such a system, in fact, high through puts may favour good refining. Thus, it may be possible to match a high productivity smelting operation with a equally productive counter current refining stage."

Jan 1, 1996

By N. Choi

The distribution behavior of selenium and tellurium in nickel sulfide smelting was investigated in the temperature range of 1250-1300 °C under an inert gas atmosphere and various oxygen partial pressures. The distribution coefficients of selenium and tellurium between nickel-copper-iron matte and silica-saturated iron silicate slag were detennined in terms of matte and slag compositions, temperature, and oxygen partial pressure. The effect of slag additives such as CaO, MgO, and Ah03 on the distribution coefficients of those elements was also investigated. It was observed that the distribution coefficients of selenium and tellurium increased with increasing matte grade and temperature. The solubility of selenium and tellurium in the slag decreased with increasing the partial pressure of oxygen within the range investigated in this study. The distribution coefficients of selenium and tellurium increased with the amount of CaO and MgO. Tellurium distribution coefficients also increased by the addition of Ah03. Meanwhile, the addition of Alz03 decreased the distribution coefficients of selenium at high matte grade.

Jan 1, 1996

By H. Yin, T. Emi

"Advantages of gas/flux injection technology as materialized in the main stay unit processes for steelmaking are depicted covering hot metal pretreatment through secondary refining. Current status of micro-kinetic issues involved in the injection technology are reviewed including gas-in- metal, gas-in-slag, flux-in-metal, metal-in-flux and three-phase dispersion systems with reference to macro-kinetics. Key problems are briefly addressed to further develop injection technology for steelmaking processes.1. FROM PAST TO PRESENTApplication of gas injection to steel industry started in early 1950's when inert gas bubbling via stopper rod, lance, or porous refractory plug was practiced to make the temperature of steel melt in ladle uniform The gas bubbling in ladle was then extended to slightly removing hydrogen ti'om the steel melt tapped from Electric Arc Furnace (EAF) and Basic Open Hearth Furnace (BOH) when vacuum processing facilities were not popular. Later, oxygen gas injection via calorized steel pipe into molten steel bath in BOH Furnace was also put into operation to promote the decarburization to increase the productivity of the process. This line of development has been made in parallel with more profound processes, i.e, top blowing Basic Oxygen Furnace (BOF) for primary steelmaking and side blowing Argon Oxygen Oecarburization (AOD) vessel for decarburizing stainless steels.On the other hand, injection of fluxes into steel bath was first industrialized in Germany in 1960's, Primary objective was to desulfurize steel melt in ladle by injecting CaC2 or CaCrCaO mixture via lance under neutral slag cover with good success. Difficulties in injecting fluxes without clogging and rippling at a desired flux/gas ratio, and durability of injection lance were resolved in due time to bring forth many injection facilities to flourish for versatile refining operation. Top injection of fluxes from main oxygen lance to BOF was also industrialized as LDAC to promote early slag formation. A new process then emerged which injects oxygen gas and fluxes together through concentric annular tuyere, installed at the bottom of the BOE into steel melt. This process, developed in Germany [Oxygen Bottom Maxhutte (OBM)] and brought into maturity in USA (Q-BOP) and Japan in a large scale operation, became the predecessor of the combined blowing (top and bottom blown) BOF which dominates modern steelmaking."

Jan 1, 1996

By Jack Thibodeau

During the past six years, most states have promulgated water quality regulations which contain numerical aquatic life standards for heavy metals. In addition, the Environmental Protection Agency (EPA) promulgated national water quality standards in 1992 which also include numerical aquatic life criteria for heavy metals. Numerous wastewater discharge permits have been issued by the states and EPA to industrial facilities which include low microgram per liter heavy metal limitations. In many instances, the limitations are below detection limits or treatability limits using state-of-the-art analytical methods or treatment technologies. This paper will discuss options for conducting studies, including the use of water-effect ratios, metal partitioning coefficients, and recalculation procedures to develop site-specific metals criteria and higher permit limitations. The installation of expensive metal treatment systems to remove trace metals may be avoided if higher permit limits are indicated by the site-specific studies.

Jan 1, 1996

By Ian Baker, Xavier Pierron

"Iron aluminides hold great promise for intermediate temperature applications (to ~ 600°C) because of their excellent oxidation and sulphidation resistance and good strength. However, they have poor low temperature ductility, a feature which is exacerbated by water-containing environments. This paper presents an overview of the effects of environment on the ductility of iron aluminides, including the effects of iron aluminum ratio; ternary alloying additions, particularly boron; strain rate; and temperature. The mechanisms involved in water-induced embrittlement are discussed.IntroductionOver the last few years, it has became increasingly evident that the ductility and fracture toughness of many intermetallic compounds, particularly aluminides, are reduced dramatically if they are mechanically tested in either air or in hydrogen-containing atmospheres (1-5). For FeAI and Fe3AI, it has been shown that water vapor, for example in air at room temperature, can form atomic hydrogen by reacting with the Al atoms (1, 2). As a result in iron aluminides, the environmental embrittlement process is quite similar to traditional hydrogen embrittlement. This can be easily demonstrated by either testing an iron aluminide in an environment free of the deleterious species or by testing at high strain rates, both of which result in greater ductility. The purpose of this paper is to review recent progress in understanding environmental embrittlement in FeAI and Fe3AI, and to consider possible environmental embrittlement mechanisms. Greater understanding of this phenomenon will lead ultimately to remedies to this problem which is a major reason for preventing the practical application of these materials. First, some background on the iron-rich aluminides."

Jan 1, 1996

By Richard J. Abitz

Thennodynamic geochemical models have been applied to assess the relative effectiveness of a variety of reagents added to aqueous waste streams for the removal of radioactive elements. Two aqueous waste streams were examined: effluent derived from the processing of uranium ore and irradiated uranium fuel rods. Simulations of the treatment train were performed to estimate the mass of reagents needed per kilogram of solution, identify pH regions corresponding to solubility minimums, and predict the identity and quantity of precipitated solids. Results generated by the simulations include figures that chart the chemical evolution of the waste stream as reagents are added and summary tables that list mass balances for all reagents and radioactive elements of concern. Model results were used to set initial reagent levels for the treatment trains, minimizing the number of bench-scale tests required to bring the treatment train up to full-scale operation. Additionally, presentation of modeling results at public meetings helps to establish good faith between the federal government, industry, concerned citizens, and media groups.

Jan 1, 1996

By P. R. Khangaonkar

The industry of tin ore mining, beneficiation and smelting gives rise to a number of waste products like the beneficiation plant wastes (called amang), tin smelting slags, refinery dross etc. Some of the wastes deserve treatment to obtain economically useful products or to recover the metal values. The paper describes studies conducted on two materials, viz., struverite-middling (struverite-magnetic tin), which is an intermediate product of beneficiation circuits of tin tailings, and tin-smelting slags. The struverite middling was studied for treatment by chlorination using carbon tetrachloride, so as to yield vapour products separable by convenient condensation. The treatment was also found to lead to a tin-rich product amenable for treatment by known hydrometallurgical routes. The tin smelting slag was studied by alkali-leaching so as to avoid any dissolution of iron and it was possible to obtain an iron-free product solution suitable for high purity tin recovery.

Jan 1, 1996

By D. E. Karvelas

Argonne National Laboratory is conducting research to develop a cost-effective and environmentally acceptable process for the separation of high-value plastics from discarded household appliances. The process under development has separated individual high purity (greater than 99.5%) acrylonitrile-butadiene-styrene (ABS) and high-impact polystyrene (HIPS) from corruningled plastics generated by appliance-shredding and metal-recovery operations. The process consists of size-reduction steps for the commingled plastics, followed by a series of gravity- separation techniques to separate plastic materials of different densities. Individual plastics of similar densities, such as ABS and HIPS, are further separated by using a chemical solution. By controlling the surface tension, the density, and the temperature of the chemical solution, we are able to selectively float/separate plastics that have different surface energies. This separation technique has proven to be highly effective in recovering high-purity plastics materials from discarded household appliances. A conceptual design of a continuous process to recover high-value plastics from discarded appliances is also discussed. In addition to plastics separation research, Argonne National Laboratory is conducting research to develop cost-effective techniques for improving the mechanical properties of plastics recovered from appliances.

Jan 1, 1996

By Steven R. Pittman, Colin McCullough, Peter Galuska

"Traditionally Continuous Fiber Aluminum Matrix Composites have been fabricated using high strength fibers and high strength matrices, often commercial alloys, with the goal of producing high strength composites. However the specific role of the choice of matrix alloy on composite properties has not been well established. One way to control composite tensile strength is to use coatings to introduce a low strength interface between fiber and matrix which tends to reduce the importance of the matrix selection, but unfortunately renders the transverse strength unacceptably low. Thus using a system with strong bonding between fiber and matrix is desirable, such as an alumina fiber / aluminum alloy matrix system. In this case the transverse strength is a strong function of the matrix strength. However the longitudinal strength then depends largely on the characteristics of the matrix. The important role of the matrix is discussed using examples of alumina fibers in various aluminum alloy matrices. The key attributes are matrix constituent phases, alloy chemistry, alloy reactivity with the fiber, and matrix strength. From the understanding developed in these systems a set of design rules may be established for selecting an optimum matrix. IntroductionAluminum matrix composites (AMC's) reinforced with continuous fibers offer very attractive property gains over AI alloys, such as strength, stiffness, and fatigue resistance. These gains are magnified when specific mechanical properties are compared which make them attractive candidates for replacing steel, nickel, titanium and aluminum alloy parts in weight critical applications (1). Many systems have been tried in the past; B/AI, C/AI, SiC/AI, Si-Ti-C-O/AI and AI203/AI. Technically B/AI was a very good system but was expensive in regard to both fiber cost and fabrication and SiC/AI and C/AI systems are still plagued with reactivity problems. The Si-Ti-C-O/AI appears to be a good strength system but with lower stiffness. Until recently, the AI203/AI was a low strength system, in part due to a lack of a high strength fiber. Recently 3M introduced a high strength AI203 fiber - Nextel™ 610, which leads to high strength composites (1,2) and may also be both low cost and also compatible with less expensive casting approaches for fabrication."

Jan 1, 1996

By Suswnu Makino

Sumitomo Metal Mining developed a new nickel refining process ( Matte Chlorine Leach Electrowinning process) based on chlorine leach and electrowinning technologies. After the pilot plant study, the commercial plant with design capacity of 24,000 tonnes per year was constructed and has been successfully operated since August, 1992. During the practice of the past three years, great deals of improvement have been achieved. Through these operations the MCLE process has been demonstrated to be one of the most superior processes in the world with nickel recovery, productivity, cathode quality and working environment. Today the refinery product capacity is increased to 30,000 tonnes per year. This paper describes the equipments and operation of the Sumitomo MCLE process.

Jan 1, 1996

By A. Elizabet Serna

The weak acid is a by product obtained in a pre-treatment of gases from a copper smelter prior to sulfuric acid manufacture and the main components of this weak acid are: sulfuric acid. copper, arsenic. antimony, bismuth and iron. Usually, this effluent is neutralized with lime and the solid residues are stored in a landfill as a hazardous waste. This work was directed at determining the optimal conditions to recover copper from weak acid using a cementation process before the neutralization of the effluent. The variables investigated are: Effluent temperature, iron scrap amount and acid concentration versus reaction time. The results of these experiments show that the cementation process of copper and the co-cementation of impurities such as arsenic, antimony and bismuth were in accord with the theory of the electrode potentials.

Jan 1, 1996

By Keuncheol Choi, Yonghack Lee

"The new lead smelter based on the QSL technology was started operation from May 1992 at Onsan Refinery of Korea Zinc Co., Ltd. The smelter is designed to treat not only various types of lead concentrate but also secondary materials coming from the zinc plant without special pretreatment.Shortly after the start-up of the operation, it has demonstrated that the smelter have a capability to treat wide range of raw materials. Continuous modifications and improvements of the plant are still under way to increase the feed rate and also the ratio of secondary materials to the feed.In this paper, the operating experience and results of QSL smelter, especially the injection of gases and coal to the melt, will be presented with major operation parameters and data.INTRODUCTIONThe QSL lead smelter based on new injection technology was commissioned at the Korea Zinc's Onsan plant from May of 1992. After starting the operation, the QSL lead smelter faced various kinds of mechanical and metallurgical troubles. However, these were gradually worked out by the continuous improvements and efforts.At present, the QSL lead smelter is operated stably at the total feed rate of 57 tonnes per hour with an increased amount of secondary materials."

Jan 1, 1996

By Du Sichen, S. Seetharaman, J. A. Bustnes

"The present study deals with the kinetic studies of reduction of some selected transition metal tungstates with hydrogen. The measurements were carried out by the isothermal thermogravimetric method. Shallow powder beds were employed in order to avoid the effects due to transport phenomena affecting the reaction rate. In this way, the chemical reaction rates could be selectively studied. The experiments were carried out in the temperature range 873 - 1173 K. From the experimental data, the activation energies were evaluated and were found to be around 88 kJ / mol in the case of both iron as well as cobalt tungstates indicating the similarities in W-O bonds in both cases. The activation energies obtained are discussed in the light of the position of the transition metal in the periodic table as well as the thermodynamic stabilities of the various tungstates.IntroductionThe tungsten containing hard metals, characterized by high density, belong to a class of two-phase metal matrix composites. While these types of materials have traditionally found their applications within the defence industry as armour-piercing projectiles, counterbalance in helicopters and military aircrafts, outer casings of hand-grenades, etc., commercial applications for this class of alloys also exist, including radiation shields, penetrators for the oil industry, turbines for turbo-jet engines and a wide range of sports related parts. A possible route to the production of these alloys is to reduce the tungstates such as FeW04, Co W04 and NiW04 using a reductant like hydrogen or carbon monoxide. In order to have a better understanding of the processes involved in the production, it is important to have a knowledge of the reduction kinetics for these tungstates. According to the knowledge of the present authors, while the reduction ofNiW04 by hydrogen gas has been investigated earlier in the present laboratorypl no systematic reduction study has been carried out previously for the tungstates of iron, cobalt."

Jan 1, 1996

By Milton Manrique

The thermal decomposition of zircon concentrates in a non-transferred arc thermal plasma flow reactor was investigated. The plasma torch was operated using argon-helium and argon-nitrogen mixtures as plasma gases. The effect of power, feed rate and zircon particle size was studied. Products were characterized by XRD, SEM, TEM and chemical analytical techniques. The average size of the product was in the submicron range. Free energy minimization plots were used to predict the behavior of the system under different operating conditions. A kinetic model to describe the different stages of the thermal decomposition process is proposed. The results of this investigation showed a significant segregation process where the zirconia-rich product is collected in the reactor while the silica-rich product is collected in the filter. TEM analysis indicated that silica vapor is condensed on the surface of the zirconia particles.

Jan 1, 1996

By Luis W. Pommier

The wastes of the plating industry are generated in the process of rinsing the plated objects and during the cleaning of the plating shops. High volumes of hazardous waters are neutralized on site producing recyclable water, generating a metal rich, hazardous, filter cake. Occasionally, a complete plating bath has to be discarded which increases the metal content of the filter cakes. These filter cakes are discarded as hazardous at a cost of over $ 250 per ton. The metals found in the cakes are generally copper, nickel and chromium or zinc, lead and cadmium, assaying from 2% to 15% or even higher content of each metal The metals and their contents are highly variable. Some plating shops discard their products directly to hazardous waste sites, others, have them collected by companies which consolidate wastes from several producers prior to discarding. These wastes, richer in metal content than mine ores, need neither mining nor crushing and grinding for concentration. The commonly found impurities in the mine ores, i.e.: pyrites, arsenic, and valuable metals which are present in minute quantities, are absent in the filter cakes. The processes available to selectively recover the metals from the filter cakes, are discussed based on their technical and economic merits. The flow-sheets include leaching, solvent extraction when required, and electrolytic refining. Examples, showing the separation of copper, nickel and chromium and also of zinc and lead in pilot plants, show the technical and economic viability of the processes.

Jan 1, 1996

A modified Cuprex Metal Extraction Process (CMEP) leach process was used to extract Cu. Ni and Co from a complex sulphide concentrate. The standard leach was modified to a two-stage countercurrent leach which provided emf control of the copper SX feed and minimized iron dissolution. A flowsheet was developed to recover the base metals and silver from the leach solution and gold and platinum group metals from the leach residue which was predominantly elemental sulphur. Techniques required to maintain an iron balance in the system including pressure oxidation and solvent extraction are described.

Jan 1, 1996

By Matthew C. Binsfield

The simultaneous electro winning of zinc and manganese from waste water treatment plant sludge was studied as a part of the overall research program, which was conducted to develop the methods for removal of environmentally hazardous metals from the Bunker Hill Superfund Site. This paper discusses the electrolytic method for recovery of zinc and manganese from the solution produced by leaching of sludge with S02 + H2S04. After three stage purification of the leaching solution, zinc and manganese were electro won simultaneously in an undivided electrolytic cell. Zinc was deposited on an aluminum cathode, while manganese was simultaneously produced (as Mn02) on a lead silver anode. The electrowinning parameters studied were the effects of: temperature, current density, electrode material, spacing of electrodes, composition of electrolyte, and electrolyte additives. Anodic and cathodic efficiencies were 30 and 91%, respectively. In light of the process design parameters discussed in the paper, which are affecting the electrowinning, these efficiencies were found as acceptable with regard to the quality and marketability of the products.

Jan 1, 1996