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By Joseph Bloch

The hydriding of bulk metals and alloys is a gas-solid reaction in which a hydride product layer is initially nucleated adjacent to the gas-solid interface and continues to grow until a complete transformation of the parent (a) phase into the hydride phase. The combination of measurements of the overall hydriding kinetics of samples having defined shapes and dimensions, together with examinations of partially hydrided samples, enables the presentation of the reaction rate in terms of an appropriate reaction model. A common and important type of topochemical development of the hydride in bulk metals and alloys involves a hydride layer formed on the metallic surface. The continuity of the layer can affect the reaction rate. The rate of hydrogen absorption in a sample, in the presence of a hydride layer, is usually analyzed using a model combining several sequential steps in which the hydrogen is transferred from the gas phase into the reaction site. Coupling the flux equations across the layer under proper steady state conditions, results in a complex rate equation in which the steady state rate of hydrogen absorption (proportional to the hydride layer velocity) is expressed in terms of the pressure, temperature, the rate constants of the sequential steps and the critical concentrations of hydrogen in the hydride. Generally, the rate constants of the individual microscopic processes are comparable in magnitude, so that the overall rate is not controlled by any of the specific sequential steps. However, there are two limit cases related to the first stage, the adsorption, for which the general rate equation is much simpler, namely, the fast and the slow adsorption approximations. Using this limit cases, equations are derived for the steady state hydriding rate of a given system. These equations provide means to anticipate the pressure dependence of the steady state absorption rate under low pressures, close to Peq and under very high pressures. At the low pressure regime both the fast and slow absorption cases yield linear pressure dependence. For the very high pressure range, it is found that the rate become independent of the applied pressure. The rate is given then by a combination of the individual rate constants of the system and the critical hydrogen concentrations. The model is shown to apply in several real cases, such as ZrCo, LaNi5 and titanium.

Jan 1, 2002

By S. Abe

Various copper anodes to be electrorefined were subjected to a heat treatment comprising annealing at a temperature in the range of 700 °c to 1,000 °c followed by a slow cooling preferably on the order of about 150 °c, and using these heat treated anodes , a series of dissolution experiments were conducted under conventional electrorefining conditions. The results obtained have indicated that the above annealing/slow cooling process dramatically improves the dissolution activity regardless of the type of anodes. As an example, passivation times of l to 3 minutes in a standard test have been increased to more than 80 minutes by this innovated heat treatment. Other advantages sterning from the improved anodic activity include reduced electrical short circuiting which results in substantial labor effort in the tankhouse, reduced energy requirement, and reduced cost of processing anode slimes because the amount of anode slimes is reduced. In addition, this process gives rise to a dramatic change in the nature of anode slime layer formed in such a way that a comparable final cathode copper product can be achieved even from high-impurity copper starting material.

Jan 1, 1987

By Yoji Imai, Akio Watanabe, Masakazu Mukaida

"To clarify the feasibility of alkoxides and acetylacetonates as precursors for laser CVD of metal oxides, vapors of tantalum or titanium alkoxides and zirconium acetylacetonate were irradiated by KrF excimer laser and deposits were characterized by XRD and XPS measurements. As for tantalum and titanium, non-stoichiometric crystalline oxides grew nearly phototropically, however, zirconium oxides deposited showed only halo-pattern by XRD measurements. Electric conductivity measurements of tantalum oxides implied the improvement of the insulating properties by the addition of activated oxygen to the ambient.IntroductionThere has been renewed increasing attention to the metallic oxide thin films because ofits promising usefulness in many applications, such as high-Tc superconductors and ferroelectric devices. A variety of thin film preparation techniques have been studied such as sputtering, chemical liquid deposition (sol-gel and metalorganic decomposition), pulsed laser deposition and chemical vapor deposition (CVD). Among them, we think CVD is the most promising method because it offers a high controllability of morphology and good step coverage at relatively high growth rate. Preparation of oxide films by CVD can be achieved using a precursor containing metallic element and oxygen containing gas such as N20 at the same time. However, metalorganic (MO) compounds which contain both metallic element and oxygen, directly bonded to metallic element, seems to be more favorable because some of MO has a good properties for CVD such as a rather high vapor pressure, stability in ambient and low toxicity."

Jan 1, 1998

By Wade L. Karlsen

"Revision surgery to replace joints in the human body requires materials that are strong, long-lasting, and biocompatible. Metallic implants made of cobalt-chromium-molybdenum alloys are already popular because of their proven corrosion and wear resistance properties, but there is an on-going effort to economically improve their performance. Alloying with inert nitrogen can enhance the mechanical properties of the alloy, enhance its corrosion resistance, and elevate the temperature at which the metallic implants can be thermally treated, without increasing the threat to the human body. The current work has produced a high-nitrogen Co-Cr-Mo alloy through HIP consolidation of metal powders that have undergone nitriding in a mechanically fluidized bed. The already fine microstructure of the powders combined with the increased nitrogen content resulted in significant property gains in the consolidated materials.IntroductionMetallic implants made of cobalt-chromium-molybdenum alloys are already popular because of their proven corrosion and wear resistance properties, but there is an ongoing effort to improve their performance. Research on a Stellite 21 cobalt-chromiummolybdenum alloy has shown that nitrogen alloying can be desirable from several standpoints [l]. Firstly, it has indicated that nitrogen can enhance the mechanical properties of the alloy, which could allow more demanding implant designs. The same work also demonstrated that nitrogen can elevate the temperature at which the metallic implants can be thermally treated, which is desirable in situations in which surface textures are to be sintered to the implant to enhance its fixation properties. Finally, that research work discovered that, not only does nitrogen not harm the corrosion resistance of the cobalt-chromium-molybdenum alloys, but it may in fact enhance it. Combining this with the fact that small amounts of nitrogen are not considered a threat to the human body, makes nitrogen alloying an attractive alternative for enhancing the properties of Co-Cr-Mo."

Jan 1, 2000

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 Huyang Xie, Rishi Raj, Vera A. Versteeg

"A new method for MOCVD has been developed in which a precursor solution is directly injected into a reaction chamber. The vaporization of short pulses of liquid is facilitated by atomization with a piezoelectrically-operated nozzle. The system has been used successfully to grow oriented, thin Ti02 (rutile) films on sapphire substrates with the crystalline relationship (101)[010]R I (1120)[0001]s. A growth rate of approximately 2 monolayers per pulse was achieved at 650°C for a reactant impingement rate of about 800 monolayers per pulse. Also, epitaxial LiTaO3 thin films were grown on (0001) sapphire from a single source, bimetallic precursor, lithium tantalum hexa-t-butoxide as the precursor. X-ray diffraction shows that the LiTaOa c-axis is normal to the sapphire surface. The x-ray pole figure and crosssection TEM diffraction show that the films were also in-plane oriented, with sapphire [1010] parallel to lithium tantalate [1010]. These films are shown to have extremely low optical attenuation, and refractive index that compares well with bulk values.IntroductionMetalorganic chemical vapor deposition (MOCVD) techniques have come into increasing use in recent years, due to the growing versatility and availability of precursors and improved environmental advantages over the halogenated compounds used for conventional CVD. Most commonly, the films are deposited by dissolving the metalorganic reactant (typically a metal alkoxide) in a carrier gas, which is carried through heated lines to a heated substratel . The metal alkoxides decompose by pyrolysis, leaving the films on substrates. While this method has been used to produce excellent epitaxial and heterepitaxial films, it has the disadvantages of complexity: the precursor must be heated to fix its vapor pressure, the gas flow rate carefully controlled, and the carrier lines heated to prevent condensation before reaching the reactor. Additionally, this conventional method cannot be used with certain low-volatility precursors that decompose upon heating."

Jan 1, 1994

By J. Rastas

The recovery of lead, silver and gold from existing and potential zinc process residues using a sulfidization-flotation method was investigated on a laboratory scale. The following residues were tested: neutral leach residue, high acid leach residue, and hematite residues. The sulfidization of lead and silver is carried out at low pH by the addition of a stoichiometric amount of sulfide at a controlled rate. To increase the particle size of the sulfides, seeding with synthetic lead and silver sulfides -is employed. The flotation is carried out at pH 2-4 using low pH-collectors such as dithiophosphates and dithiophosphinates. Special attention must be paid to the role of oxygen in the conditioning stage. The effect of different parameters on both the sulfidization and the flotation has been evaluated. Recoveries of 85-90, 90-95 and about 80 % were obtained for lead, silver and gold, respectively. Typically, concentrates containing 50-60 % lead, 3-5 kg/t silver and 10-15 git gold were produced.

Jan 1, 1990

By T. J. White

Each year, thousands of tons of toxic concentrates are produced as the unwanted byproducts of industrial operations and smelting activities. The fate of these materials remains open, as in general their consumption is limited and potential markets contracting. Xtaltite (pronounced crystal-tight) is a Synthetic Mineral Immobilization Technology (SMITE) optimized for the concentration, detoxification and consolidation of toxic metal wastes. In this approach, we seek to mimic nature to produce durable synthetic minerals that survive for aeons in well characterized geological settings. This approach has high public acceptability because the concept is easily understood by the layperson and the long term stability of the waste form may be predicted with confidence. In addition, where Xtaltite is used for mine backfill, a system of ecologically sustainable mining development is established. This paper details the design and fabrication of Xtaltite under oxidizing and reducing conditions. To illustrate and contrast these stabilization regimes, specific reference will be made to the treatment of thallium, chrom~um and arsenic wastes. Waste form performance under TCLP, dynamic boiling water tests and in other leaching media will be compared and discussed with respect to their relevance to different disposal options.

Jan 1, 1995

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 Thierry De Nys

A direct leaching process of sulphidic zinc-based concentrates in aqueous sulphuric acid solutions has been developed by the V.M. R & D Department. By a very accurate control of the oxidation potential of the leach solution, this process enables a separate recovery of the zinc, copper, silver, lead and sulphur of the concentrate and makes it extremely attractive for treating more complex ores. The iron, solubilized during leaching, is eliminated out of the zinc solution by means of the V.M. goethite process. Alternative flow sheets for a conventional zinc electrolysis plant are presented.

Jan 1, 1990

By Jean Goldschmidt

Recycling of fine oxidized particles of non-ferrous metals usually cannot be carried out by pyrometallurgical methods. 'Hydrometallurgy provides an alternative technology to reintroduce? the resulting products as secondary raw materials into the industrial cycle, thereby saving resources and energy while keeping the environment a little cleaner. The paper summarizes the methods employed by Hydrometal to achieve these objectives and? stigmatizes the latest counterproductive international regulations which create ever more obstacles to environmentally sound recycling.

Jan 1, 1995

By Claudio Parra De Lazzari

The determination of the governing step of the deoxidation rate and the effects of the hydrogen content of the mixtures (C), the diameter of the delivery orifice (4) and the Reynolds number of the orifice (Re.) on the product Av kjg were investigated. A,, is the total surface area of the interface between the bubbles and the melt and kjg is the mass transfer coefficient in the gas phase. The design of the experiments was based on a two level statistically fractionated, factorial planning. Oxygen in the melt was measured as a function of time. It was found that the governing step of the deoxidation rate was the transport of hydrogen in the gaseous phase and that {Ay kjg} increases with C, {o} and Reo.

Jan 1, 1997

By Ari JokiIaakso

Three different sulphidic raw materials were treated in a laboratory scale laminar flow fur-nace simulating suspension smelting conditions. The materials were a pure chalcopyrite concentrate, a high-antimony concentrate (tetrahedritic), and crushed copper mattes. The gas preheating temperatures were 500 -1 100°C ana the atmospheres ranged from N2 to N2 -75 % O2, Two particle size fractions were used for the concentrates with x = 20 -38 um and x = 62 -74 um, and three for the granulated copper mattes with x < 37 um, x = 62 -88 um, and x = 125 -177 um. Scanning electron microscopy combined with energy dispersive analysis and backscattered electron analysis was used for determining the morphology and the mineralogy of the reacted particles. Fragmentation of the particles were observed in all materials during the flash oxidation, the conditions depending on the iron and sulphur content and the original particle size fraction of the material. The melting and/or reaction stages of the particles in different conditions were studied from powder samples. Polished sections were examined in order to follow the development of porosity and the mineralogy of the particles.

Jan 1, 1989

First, a classification of the various primary sources of feed materials for the production of cobalt is presented from a mineralogical point of view : sulfides, arsenides, sulfo-arsenides and oxide minerals. Each of these cate- gories will be characterized by its behaviour towards concentration methods, taking account of the presence of the associated minerals of other metals and of the nature of the gangue minerals. Then, for each category of cobalt bea- ring ores, typical flowsheets of treatment will be presented and discussed and the characteristics of the cobalt concentrates produced will be under- lined having in view their subsequent processing by pyro - and (or) hydrome- tallurgical methods.

Jan 1, 1988

By Nickolas J. Themelis

The flash oxidation and smelting of mineral sulfides is a very prominent metallurgical achievement of the second part of this century. Its initial industrial implementation owes much to the work of Petri Bryk, in Finland, and Paul Queneau, in Canada. However, attempts to develop flash reduction pro- cesses, such as the reduction of iron oxide concentrates with hydrogen, have not yet been successful. The author, on the basis of experimental studies on both kinds of flash reaction systems, examines the respective rate controlling phenomena and the relative rates of flash oxidation and flash reduction.

Jan 1, 1993

By Petrus Christiaan Pistorius, Farzin Fatollahi-Fard

The production of synthetic rutile—a common starting material for most titanium production processes—from iron-rich titanium minerals such as pseudorutile and ilmenite is described. The process for “upgrading” the mineral to synthetic rutile is by carbothermal reduction of the mineral while immersed in a molten salt at high temperature, followed by magnetic separation of the reduced iron. A variety of factors are also investigated, such as particle size of the mineral, the type of mineral, and the molten salt used. The solubility of iron(III) oxide in different molten salts is also experimentally determined.

Jan 1, 2016

The high pressure acid leach process (HPAL) is being commercially used in four plants around the world to treat limonitic laterites. The two major operating costs of the HPAL process are the sulphuric acid and the energy required to heat the pulp to the desired temperature (>240°C). As an alternative to acid injection and steam heating, the in-situ generation of sulphuric acid and heat, produced during the high temperature pressure oxidation of sulphur-bearing materials blended with laterites, has been investigated at the laboratory scale. Various sources of sulphur have been examined, in particular, elemental sulphur, pyrrhotite and a Cu-Ni low-grade bulk concentrate. Under the proper blend ratios, all sulphur sources tested generated sufficient acid to result in equivalent nickel and cobalt dissolutions. A significant improvement to the process economics can result from the addition of sulphur sources containing valuable by-products, such as nickellcobalt andlor precious metals (gold and PGMs). This is especially true in the latter case, when the HPAL can be operated under Platsol conditions (i.e. with the addition of 5-10g/L of chloride), to dissolve the base metals and precious metals simultaneously in the autoclave. Various examples of the application of this concept are presented, together with a brief discussion of its implication on the autoclave design and the downstream processes to recover the values from the leach solutions. Keywords: limonite, co-treatment, acid consumption, sulphur, sulphur compounds, pressure acid leach (HPAL, PAL), Platsol process

Jan 1, 2004

By J. P. Evans

The modem copper smelter today utilizes tonnage oxygen for smelting concentrates, generating a high strength S02 off-gas leaving the smelter vessel. This gas stream, which also contains any unreacted oxygen, plus C02, N2 and H20, also carries with it the volatilized portion of heavy metals in the feed, plus partly oxidized sulfide concentrates. The time/temperature history and subsequent treatment of this off-gas stream emerging from the smelting furnace exit up to the acid plant can influence the partitioning and segregation of heavy metals in the off-gas circuit. Depending on this history, the type and characteristics of the chemical and physical reactions which. occur in the gas handling system can be influenced. This fact can also be used as a tool to adjust the separation of copper from heavy metals. In this paper, the impact of different time/temperature histories of the gas, due to different furnace geometries .and design, on the subsequent formation and characteristics of the smelter dust is examined. Based on the available data, several case histories drawn from examples using both bath and flash smelting technologies are analyzed from this perspective.

Jan 1, 1992

By A. A. Hejja

The effect of composition on electrical conductivity, viscosity and liquidus temperature of the slags was investigated in the temperature range of 1300" to 1450°C. The synthetic slags containing CaO, MgO, SiO,, A1,0, and FeO were similar to those employed in the electric furnace smelting of sulphide Cu-Ni concentrates containing PGM (Platinum Group Metals) from the Merensky Reef of South Africa. FeO and SiO, were found to affect the viscosity and conductivity the most while liquidus temperature depended on MgO content in addition to these. The activation energy for electrical conduction was found to vary from 67 to 159 kJ/mol and that for viscosity from 125 to 209 kJ/mol. Optimization of the slag composition was attempted on the basis of opposite trend of the viscosity-electrical conductivity relationship with slag composition.

Jan 1, 1994

By Fumitaka Tsukihashi

Increasing amounts of steel scrap are being used as resources for steelmaking. Therefore. there has been a growing interest in the removal of handful tramp elements such as antimony, zinc, tin, arsenic, bismuth, lead and copper from the molten steel. The problem that should be solved is the economic removal treatment of residual tramp elements in the steelmaking processes and the production of high quality steel by reducing the effect of the contaminated tramp clements and satisfying the environmental regulations. In this paper, the available thennodynamic data of the residual tramp elements in the molten steel are summarized and the possibility of the removal of residual tramp elements from the molten steel is thcnnodynamieally estimated.

Jan 1, 2003