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By Benjamin P. Hay

Complexation of a metal ion to a ligand often results in structural changes that introduce steric strain within the ligand. A design criterior:1 for ligands that will complex metal ions more strongly is to choose Iigar:1d architecture, that minimizes this strain. This paper describes how molecular mechanics models can be used to define the degree of ligand binding site organization in terms of' ,strain energies associated with conformational reorganization and distortion of the binding conformer. This approach yields a method to predict how modifications to ligand structure will affect metal binding affinity.

Jan 1, 1999

By Toshiki Kabutomori

In fuel cell powered automobiles, hydrogen is required to be stored in materials that have a hydrogen storage density of over 4 mass%; further, these materials should be capable of supplying hydrogen by using the waste heat from a fuel cell, which is at a temperature of 373 K, in order to match the mileage of gasoline-powered vehicles. A Ti-Cr-V alloy, which exhibits a BCC structure and forms a solid solution, is a promising candidate for onboard hydrogen storage materials. Although it has a large hydrogen storage capacity of over 3.9 mass%, the rechargeable hydrogen capacity is limited to approximately 2.6 mass%. In this study, the effects of fine pulverization of the alloy on PCT (hydrogen pressure-composition-isotherm) characteristics were investigated in order to improve the rechargeable hydrogen storage capacity of the alloy. From the PCT measurements of the finely pulverized samples of the alloy, a plateau in the absorption curve was observed to begin at a hydrogen concentration of 0.5 mass%; further, a rechargeable hydrogen storage capacity of 3.3 mass% was obtained. This was greater than that obtained from the sample that was not finely pulverized, i.e., 2.5 mass%. However, the plateau width in the desorption curve was 2.5 mass%, which was the same as that observed for the sample that was not finely pulverized. The increase in the rechargeable hydrogen capacity during absorption is attributed to the precipitation of the -hydride phase (MH~2) directly from the metal phase (phase). The precipitation of the phase (MH~0.5), which should be formed in low hydrogen concentrations, is suppressed as a result of a possible reduction in the internal defects such as dislocations, vacancies, and grain boundaries by fine pulverization and annealing of the alloy.

Jan 1, 2006

By C. P. Manning

This paper reports recent progress in the development of a unique metal extraction technology utilizing zirconia-based inert anodes for the electrolytic reduction of metals from their oxides. In this process, the target metal oxide is dissolved in an ionically conducting liquid solvent phase. An extended anode consisting of an oxygen-ion-conducting stabilized zirconia membrane in intimate contact with a catalytically active electronic phase and an inert electronically conducting cathode are inserted into the molten flux containing the oxide. When the appropriate electric potential is applied between the electrodes the target metal is reduced at the cathode and oxygen ions are selectively transported across the stabilized zirconia membrane and oxidized at the anode. When the process is conducted at temperatures between 1200-1400°C, the ohmic resistance drop across the stabilized zirconia membrane is low, and high current densities on the order of I A/cm2 or greater can be obtained. In addition, the process efficiency can be increased further by directly reforming hydrocarbon fuel over the anode. Laboratory experiments at Boston University have demonstrated the technical viability of employing zirconia-based inert anodes for environmentally sound production of metals such as magnesium, tantalum, aluminum, etc., directly from their oxides. Significant progress has been made in the application of this concept to the electrolytic reduction of magnesium at 1300°C. The research topics covered include stability of the zirconia membrane in the selected molten solvent (flux), volatility of the flux, electrochemical characterization of the electrolytic cell, and analysis of the metals produced.

Jan 1, 2003

By Renato G. Bautista

The solvent extraction separation of nickel, cobalt and their associated metals have been considered for industrial application since the early 1960's. This review of the solvent extraction processes is limited to the industrial applications, pilot plant and the more extensive bench scale studies reported in the literature. The processes with their significant chemical and technological contributions are discussed in detail whenever the information are available. The application of solvent extraction to the nickel-cobalt processing has so far been limited to the secondary separation of nickel-cobalt containing feedstocks derived from other primary nickel-cobalt separation methods.

Jan 1, 1993

By Carlos A. Nunes

V-AI alloys have been used commercially to produce pure vanadium by Electron Beam Melting (EBM), as well as to obtain Ti-based alloys (ex. Ti-6AI-4V). The aluminothermic reduction of vanadium pentoxide (V205) is the primary method to obtain these alloys. Concerning the obtention of pure vanadium, earlier studies have indicated alloys presenting Al content between 10 and 15wt% as the most suitable alloys for direct EBM. In the present work we investigated the aluminothermic reduction of V205 in order to define process parameters for the obtention of V-AI alloys with composition in the previously mentioned range. It was studied basically the effect of excess AI, CaO addition and reaction atmosphere (air, argon) on the alloy composition (AI, 0, N). In addition, microstructural analysis of selected alloys by SEM (BSE images) and EPMA (WDX) were also performed.

Jan 1, 1996

By Maria K. Kojo

The interaction between various slags and a nickel concentrate containing pyrite, pentlandite, and violarite were investigated by submerging concentrate pellets in molten slags. The slags were contained in MgO-A12O3 spinel crucibles. The slag oxidizes the iron sulfides in the concentrate, resulting in a nickel matte. The amount of S02 gas formed during reaction was measured to determine the oxidation reactivity of the slags. The experimental variables included temperature, the ferric/ferrous ratio of slag, and other slag properties such as the FeO/SiO2 ratio and the MgO and NiO contents. The reactivity of the slag depended in a complex manner on its oxidizing power, viscosity, and interfacial tension. The slag composition for the greatest reactivity was determined to be Fe3+/Fe2+ = 0.3, Fe/SiO2 = 1.3, and % MgO = 2. This slag, however, caused substantial foaming. Increasing the MgO content to 10% or replacing it by 5% MgO + 8% NiO eliminated at a slight decrease in reactivity. The implications of the findings from this work in the bath smelting of nickel sulfide concentrates are discussed.

Jan 1, 1995

By T. -M. Guo, M. J. Braun

"This paper presents an experimental and numerical study of melt flow near the solid-liquid interface and its effect on the interface curvature in a horizontal unidirectional solidification system with succinonitrile. Melt flow is introduced by increasing the ampoule channel thickness. Visualization techniques are employed to observe the flow field and the solid-liquid interface curvature. A numerical model is also developed to simulate the heat transfer, melt flow and phase change in the system. Quantitative information on the flow and temperature fields is generated. A good agreement is achieved between the experimental observations and model predictions. The results could be used for the study of the effect of the melt flow on interface morphology during solidification.IntroductionClassic unidirectional solidification experiments of transparent alloys are conducted with thin film samples sandwiched between two glass slides to investigate the development of interface morphology during solidification [1]. Samples with small channel thickness are usually used to suppress any melt flow due to natural convection and solidification in the channel would then be in the diffusive regime so that the solidification theory can be significantly simplified [2, 3]. Effects of melt flow, in particular due to natural convection, on solidification have also been studied extensively in those systems with large geometrical dimensions [4-6]. These studies indicate a strong effect of the melt flow on interface curvature during solidification [5, 6]. Only limited efforts were made to address the effect of the melt flow on interface morphology in horizontal unidirectional solidification, in particular for the cases when the channel thickness is not thin enough to suppress completely the natural convection [7]."

Jan 1, 2004

By Broggi Andrea

Condensates produced by SiO(g) and CO(g) have a crucial importance in silicon production. Condensation will follow the reactions 3 SiOðgÞ+COðgÞ→ 2 SiO2 + SiC and 2 SiO ðgÞ→Si+SiO2. Solid compounds generated during silicon production contain Si, SiO2 and SiC in different microstructures and amounts. In industrial systems, condensates limit the SiO(g) escape to the off-gas system. On the other hand, they can block the gas flowing from the high temperature zone, hence the necessity of studying an optimized condensation process. This review discusses SiO(g) condensation and its interaction with CO(g). The report gives an overview of the condensates found both at laboratory and at industrial scale. The two main compounds are the Si–SiO2 and the SiOx–SiC mixtures. The hypothesis on the mechanism of formation of SiC–SiOx condensates is presented through a wide selection of performed works. The advantages and disadvantages of the former experimental procedures are discussed.

By Itsuki Uehara, Hiroyuki T. Takeshita, Tetsuo Sakai, Nobuhiro Kuriyama, Hideaki Tanaka

"AB5 type hydrogen storage alloys (A: rare earths, B: transition metals) are extensively applied to a negative electrode of a nickel metal hydride (Ni-MH) rechargeable battery for portable electric equipments, electric vehicles, hybrid vehicles etc. Performance of a hydrogen storage alloy electrode is affected by various factors, microstructure and surface composition of the alloy and structure of the electrode as well as composition of the alloy. Control of those factors enables us to commercialize the Ni-MH battery in various field.IntroductionA Nickel-metal hydride (Ni-MH) battery has been extensively developed because of (1) good compatibility with a nickel cadmium (Ni-Cd) battery, (2) high energy density (1.5-2 times higher per unit volume than a Ni-Cd battery) and high dischargeability, and (3) low environmental pollution. The charge/ discharge reactions can be written as [l, 2,3]:(+) Ni(OH)2+OH- = NiOOH+H2O+e· (E=+0.490V NHE),(-) l/6LaNi5+H2O+e-· = 1/6LaNi5H6+OH- (E=-0.828V NHE),where E° is a standard potential of an electrode vs. normal hydrogen electrode (NHE). Because of the above advantages of a Ni-MH battery, the battery have been widely used as a power source of portable computers, cellular phones, electric vehicles (Toyota ""LAV4L EV"", Honda ""EV Plus"" etc.) etc. Some hybride vehicles (Toyota ""Prius"" and Honda ""INSIGHT"") and fuel cell vhehicles (Toyota ""FCEV"") are power-assisted by a high-power Ni-MH battery. In 1999, the production of Ni-MH batteries reached 870 million cells in Japan. Most of commercialized NiMH batteries are incorporated with rare-earth-based AB5-type hydrogen storage alloy as a negative_ electrode. The production of rare-earth-based alloy is estimated to be approximately 8000 tons.The battery performances of the Ni-MH battery, for example, capacity, durability (cycle life), dischargeability (kinetics) and selfdischarge, ate closely related to the metal hydride· (MH) electrode, especially, the hydrogen storage alloy in the electrode. Substitution of alloy components, heat treatment, and surface treatment in order to change surface and bulk structure of hydrogen storage alloys have been examined by us and many reseachers in order to improve the performances of MH electrodes. This paper is a review of our and their efforts to improve performances of MH electrodes."

Jan 1, 2000

By S. Agatzini-Leonardou

The objective of this work was to prove repeated loading capacities and investigate the selectivity of physically stabilized algal biomass from Spirulina platensis and Chlorella sp. for the removal and recovery of cobalt, nickel and chromium from laterite heap leach liquors. The testwork was carried out on a bench scale in small glass columns and proved that it was possible to immobilize the biomass on the highly porous surface of pumice stone (kissiris). Nickel and cobalt could be removed from pure aqueous solutions of each metal by the immobilized cyanobacterial biomass. Nickel and also cobalt biosorption was sensitive to the initial solution pH. Cobalt recoveries up to 80% were achieved after 5 loading cycles, from low concentration solutions, at pH 6.0. Nickel removal was complete under the same conditions, whereas chromium sorption was ineffective. Desorption of the metal loaded columns was effected by dilute sulfuric acid. The algal species giving the best adsorption capacities for the metals under consideration was selected for further experimental work with real laterite heap leach solution produced by column leaching. A statistical analysis of all obtained results was conducted using the fraction of metal removed as response. The ratio "mass of metal removed to mass of protein contained in the immobilized cells" was determined as well. The described method might be applicable for recovery of cobalt and nickel from diluted laterite heap leach solutions, such as heap wash waters, or for their removal from waste streams of a hydrometallurgical extraction process.

Jan 1, 1997

By James C. Withers

There is no production of rare earth metals in the U.S. in spite that the U.S. is the largest consumer of rare earths in some form that includes consumer and Department of Defense (DoD) devices. The one U.S. mine has been purchased by the Chinese that even enhances their monopoly on rare earths. A research effort has demonstrated rare earth oxides can be extracted from bastnaesite ore as well as coal ash at efficiencies in the upper 90s percent. The rare earth oxide can be carbothermically treated to produce an oxycarbide which is highly electrically conductive. The rare earth oxycarbide can be used as an anode in anhydrous fused salts electrolysis to produce a highly purified rare earth powdered metal. It is also possible to electrofractionate the individual metals which can be combined with co-deposition of iron and boron to produce the highly magnetic alloy Nd2Fe14B.

Mar 1, 2018

By M. Opler

Presently, only a few large copper refineries are able to produce Grade A cathodes from copper scrap. Today's technology needs large plants for smelting, converting or refining the main impurities and casting the anodes for electrolytic refining. A new ECUPREX® PROCESS, by-passes all pyrometallurgical operations and produces directly copper cathodes starting from copper scrap with high lead and tin contamination. Copper scrap from chopped cables, copper cements and electronic scrap are suitable feed for ECUPREX® PROCESS. This process uses a non-conventional electrolyte and produces a surprisingly high quality, smooth cathode assaying only few ppms of total metallic impurities. Bench-scale work followed by a successful mini-pilot plant run, has led to the construction of an operating pilot plant equipped with a 1,000 Ampere cell. The results of the operations of this pilot plant are presented and described in this paper.

Jan 1, 1995

By Graham Cooke, Abhishek Lahiri, Animesh Jha, E. Jeya Kumari

"CO2 reduction by alternative energy devices such as wind-power, electric vehicles utilize rare-earth elements (REE) in several forms; such as in piezo-electric devices, batteries and magnetic materials. In 2010, the 95% of Rare Earth supply is controlled by China, compared to USA being dominant supplier in the 1980s. The dependence upon a single source of lanthanides has prompted the utilization of lower grades of titaniferous mineral concentrates, which often have rich seams of REE. We propose a new methodology, which utilizes the low-grade minerals for the extraction of synthetic rutile and also significant quantities of REE. We demonstrate the alkali roasting of lower grades of mineral concentrates and subsequent leaching in an aqueous medium for preferential flocculation of REE during the extraction of synthetic rutile. Changes in mineral structure during alkali roasting and leaching determine flocculation of REE and permit their separation at the front end of unit process.The physical chemistry and crystal structure of minerals in equilibrium with alkali and aqueous medium play an important role, which we explain by demonstrating the changes in the crystal structure. The quantification of separation of RE oxide via chemical analysis suggests that it may be possible to separate rare-earth oxides between 50 and 80% of the initial concentration in the non-magnetic fractions of ilmenite, for example. The microstructural and X-ray diffraction analysis points out that the presence of alumina and roasting with potassium based alkali enhances the separation and flocculation of rare-earth elements at the front end of the process after roasting. The process allows the recovery of CO2 generated by recycling into the process for the regeneration of alkali."

Jan 1, 2011

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothermic reduction, hydro metallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

Two pilot-plant investigations were conducted in which strong-base resins were compared with activated carbon for the extraction of gold cyanide from leached pulp from the Golden Jubilee Mine. The results show that gold can be recovered with carbon, but that the extraction efficiency is poor, probably because high concentrations of humic and fulvic acids are. present m the pulp. .However the extraction of gold cyamde from this material with strong-base resins JS very effo:1ent, and the overall efficiency of extraction is better with resin than with carbon, even when the concentration of resin is one-third that of carbon, and the flowrate of resin is one-third that of carbon. The results of the pilot-plant campaign reported in this paper led to the conversion of the Golden Jubilee plant from carbon-in-pulp to resin-in-pulp in February 1988.

Jan 1, 1989

By László I. Kiss, Verena Mackowiak, Alexandre Perron, Dominic Toulouse, Alicia Liedtke, Sándor Poncsák

"Bubbles play a very important role in different metallurgical applications like for example in electrowinning. During heterogeneous nucleation, the maximal size of the bubbles growing at the nucleation sites as well as the nucleation frequency is determined by the so-called detachment condition. Detachment occurs when the external forces acting on the bubble exceed the retaining forces along the solid-gas-liquid triple interface line. The phenomenon depends strongly on the shape and orientation of the solid surface and on the nature and strength of the external buoyancy and drag forces. In the present study the detachment conditions of bubbles from downward facing horizontal and inclined plates were studied experimentally under the effect of gravitational and hydrodynamic forces. The results show the deformation of the bubbles under the effect of the external forces and the detachment conditions as function of the bubble volume.IntroductionIn heterogeneous nucleation bubbles are generated at the so-called nucleation sites along the solid-liquid interfaces. They continue to grow there and after they reached a certain size they detach from the solid surface and leave the nucleation site. This scenario is well known both in boiling and electrolysis. During the growth period a stable equilibrium exists between the forces that retain the bubble at the nucleation site and the forces that try to remove it. This equilibrium evolves with the increasing volume of the bubble to the point when the detachment forces overcome the retaining forces.The life of a single bubble generated by heterogeneous nucleation can be divided into two periods separated by the detachment - or in other words by the departure - of the bubble: first the growth at the nucleation site and then the movement away. The knowledge of the detachment conditions makes possible the determination of the maximal volume of the bubble at the nucleation site that, in tum, makes possible the determination of the nucleation frequency. This is why so many researches have been directed toward the clarification of the details of the bubble detachment in the past decades. The equilibrium between the attaching and separating forces depend on the presence of body, surface and flow induced forces in the liquid, on the geometry and orientation of solid surface, on the properties of the solid-liquidgas system etc."

Jan 1, 2004

By J. A. Sekhar

Solidification processing/casting is increasingly being adopted as the preferred manufacturing technique for the fabrication of net shaped complex geometry components. Modeling of solidification processes is important both for design purposes as well as for understanding the physics of morphological evolution of the solidification microstructure. A fundamental aspect of such modeling involves the precise understanding? of heat transfer through the two phase solid/liquid region. A scheme to do this will be presented where the nonlinearity of the fraction liquid with change in temperature can be incorporated into the numerical calculations. The importance of properly accounting for the non-linear mushy zone will be discussed. Typical processes like squeeze casting and electromagnetic stirring will be discussed to illustrate how precise modeling of the solid/liquid region can aid in the calculation of accurate heat transfer coefficients for these processes.

Jan 1, 1990

By E. Krystad, G. Tranell

"The kinetics of boron removal from liquid silicon during slag refining, as a process step in the production of solar grade silicon, has been investigated by means of small scale mass transfer experimental series at 1600°C, using a graphite crucible. The slags were SiO2-CaO based, with or without addition of approx. 19 wt% MgO. Experiments were carried out at slag-metal ratios of 1 or 2, where the silicon initially contained approx. 250 ppm boron. The metal-slag mass transfer coefficients for boron were found to be in the order of 1-3 · 10-6 m/s and were largely influenced by slag composition. The mass transfer rate was higher for the MgO-containing slag than the slags without MgO. The final equilibrium distribution of boron between metal and slag, LB, was determined to be in the order of 2.3-3.3.I. INTRODUCTIONRecent years have seen a race in industry and research aimed at obtaining a reliable metallurgical route for production of silicon for solar cells (SoG-Si) from metallurgical grade (MG) silicon. Metallurgical routes can successfully challenge the traditional chemical routes for production of SoG-Si if they generate metal of sufficient purity while being less expensive in terms of production cost and energy consumption. Efficient removal of boron is one of the greatest obstacles in the refining of silicon by a metallurgical route, because the segregation coefficient of boron in silicon makes directional solidification unfeasible; in addition, the vapour pressure of boron is not high enough for removal by vacuum refining. However, the thermodynamic properties of boron makes removal from silicon by oxidation possible, and thus the process of slag refining of silicon has been receiving increasing attention as a method for boron removal."

Jan 1, 2012

By J. L. Watson

The composite nature of titanomagnetites found on the west coast of the north island of New Zealand is an important parameter in the beneficiation of the black beach sands for export to Japan. To investigate this composite nature, borehole and plant samples from the Waipipi Ironsands Ltd property were subjected to a series of separations in heated Clerici solutions at densities varying from 3.2 to 4.6 g/cc. The resulting density fractons were analyzed magnetically and a set of distribution curves for composite grains proposed. In addition the experi¬mental data was plotted to produce titanomagnetite sand 'washability curves" which illustrate the possible problem areas in beneficiation that may arise due to composite titanomagnetite grains. From this data a set of guidelines are suggested for interpreting the curves in terms of ease of gravity concentration. The composite nature or liberation of titanomagnetite grains is shown to favor high and low grade composites with few intermediate compositions being isolated. The relationships between grain size, borehole depth and liberation are examined and related to beneficiation procedures for the black sand deposit.

Jan 1, 1982

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothemlic reduction, hydrometallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003