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By K. S. Han, M. Yoshimuura, H. Fujita, Y. Sato, S. W. Song

"Film of LlCoO2 as cathode material for rechargeable lithium microbatteries has been fabricated on the platinum metal substrate by electrochemical-hydrothermal method in concentrated LiOH solution at 200 °C as Soft Solution-Processing. The film fabrication has been understood in terms of dissolution of cobalt metal powders and subsequent oxidative deposition on the substrate. The film structure was characterized using scanning electron microscope, X-ray diffraction analysis; X-ray photoelectron spectroscopy and micro-Raman spectroscopy.IntroductionRapid growth of wireless communications and emerging integrated optoelectronic circuits caused the miniaturization· cif electronic devices, thus the demand for high energy density microbatteries as a power source for the microelectronics increases. In this regard, all solid-state lithium microbatteries including LiCoO2 and LlMn2O 4 [l-4], the most promising intercalation cathode material, have been developed. However, major difficulty of .fabrication of a lithium microbattery arose from the preparation of cathode film, according to a· recent report on Rare Metal News [5]. Although many attempts have been made to deposit the cathode films, all those methods are mostly chemical vapor deposiiton (CVD), various evaporation, sputtering techniques and spray pyrolysis. These methods require preparation of bulk cathode materials cir its precursor, then deposition with complicated instruments including high· vacuum system, and even postsynthesis annealing to obtain desire electrochemical 'properties. It is clear that all of these techniques are neither economic nor environmentally friendly. Compared to those methods, film form.ation from an aqueous solution is thought to be simpler and more economical, and requires much· less energy consumption. Our .group has demonstrated the utility of Soft SolutionProcessing [6,7], which is defined as environmentally friendly processing using (aqueous) solutions, to produce films of a variety of functional solid materials. According to the Pourvaix's diagram [8], some metal can be dissolved in an alkaline solution and consequently combined with hydroxyl group or oxygen anion forming metalate or metalite. Cobalt also seemed to form cobaltite, HCoOi in strong alkaline solution in the Pourvaix's pH-potential diagram. Based on this information, it was expected that LiCoO2 could be prepared using the cobalt metal in Li OH solution by Soft Solution-Processing. Recently, we reported the successful single step fabrication of electrochemically active LlCoO2 films on the cobalt metal substrate by hydrothermal methods without any post-synthesis annealing as Soft SolutionProcessing [9,10]. Film formation mechanism could be elucidated by the following evidences. . As expected from Pourvaix's diagram, cobalt metal was dissolved in concentrated LiOH solution forming dissolved cobalt species which was detected by an observation of absorption band in UV-VIS absorption spectrum [10]. Thus the reaction was assumed to be started from dissolution. Time dependent potential of Co electrode exhibited only one-step evolution with 0.6 eV from Co metal to LiCoO2 [10]. Another strong evidence was the finding of LiCoO2 powder precipitates at the bottom of tetlon beaker after the reaction [11]. Based on those experimental findings, it was understood that film is formed by dissolution-precipitation mechanism [9-11]."

Jan 1, 2000

By Himaki Nakano, Kenji Hara, Toshiaki Tsuru, Shunsuke Kawano, Takeshi Ohgai, Hisaaki Fukushima, Shigeo Kobayashi, Tetsuya Akiyama

"Electrodeposition of Fe-Ni and Zn-Ni alloys from aqueous solutions is one of the well-known examples of anomalous codeposition in which less noble metal deposits preferentially. In this paper, the electrodeposition behavior of these alloy systems was compared between the methanol and aqueous baths. In Fe-Ni system, the significant suppression of the deposition rate of more noble Ni was observed over a wide range of electrolysis conditions in both methanol and aqueous baths. However, the electrodeposition of Zn-Ni alloys showed the typical feature of normal type codeposition in the methanol baths, which was completely different from that in aqueous sulfate baths. The difference in the electrodeposition mechanism between Fe-Ni and Zn-Ni alloys was discussed on the basis of the alloy deposition behavior in the baths in which the activity of water was varied:INTRODUCTION'It has been well known that Fe-Ni alloys show an excellent soft magnetic property. Therefore, thin films of this alloy have been used to fabricate the'-various magnetic devices. For the production of Fe-Ni thin films, dry processes such as sputtering, PVD and CVD are 'employed frequently and the resulting films showed a preferable property as a magnetic material. Electrolyses as a production technique of thin films, on the other hand, has the advantage over other processes in its cheaper production cost due to the simplicity of the production unit The Zn-iron-group metal alloys such as Zn-Ni and Zn-Fe electrodeposited on a steel sheet ale known to exhibit excellent corrosion resistance and therefore the electrodeposition of these, alloys has been applied to the production of surface treated steel sheets mainly for automotive body panels.According to Brenner (1), the electrodeposition behavior of Fe-Ni and Zn-Ni alloys was' classified into the' 'anomalous type. In this type of codeposition, less noble metal, i.e. Fe for Fe-Ni and Zn for Zn-Ni system, deposits preferentially and the change in -the alloy composition- with the variation of electrolysis conditions was unpredictable because of their obscure deposition mechanism. Since most properties of the alloys mainly depend on their composition, the composition of the deposited' alloys must be controlled strictly. Therefore, it is neces5al)' to clarify the mechanism of anomalous codepasition in Fe-Ni and Zn-Ni systems: Several mechanisms have been proposed so fur, and among them the hydroxide .suppression mechanism (2), (3) has been regarded most plauslble depend on their composition, the composition of the deposited' alloys must be controlled strictly. Therefore, it is necessary to clarify the mechanism of anomalous codeposition in Fe-Ni and Zn-Ni systems: Several mechanisms have been proposed so far, and among them the hydroxide suppression mechanism (2), (3) has been regarded most plausible. According to this mechanism, it can be predicted that the codeposition behavior depends greatly on the characteristic of water solvent in this study, using methanol as a solvent, the electrodeposition behavior of the anomalous codeposition was investigated to discuss the validity of the hydroxide suppression mechanism."

Jan 1, 2000

By M. F. Hochella

Transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analysis have been used to study the mode of occurrence and mineral associations of gold in partially oxidized high grade gold ore from the Carlin sediment-hosted deposit. Rounded.gold particles have been observed that range in size from 0.03 to 0.1 p.m (300 to 1000 A) in diameter. The gold is associated with maghemite h-Fep3l and a K-Al-Si-bearing phase that is suspected to be illite. Detailed descriptions of gold and its mineral associations in 'Carlin-type' gold deposits are critical not only to understanding the mechanism of fluid transport and precipitation of gold, but also to developing improved metallurgical techniques for the recovery of gold from refractory ore. Direct observation of gold in unoxidized ore is rare due to its relatively high degree of dissemination and low average bulk concentration which averages 9 ppm according to Radtke (1). Hausen and Kerr (2) observed 1 to 5 p.m grains of gold directly in oxidized ore but these microscopically visible particles account for only a small percentage of gold present in the ore. The samples used in this study were selected from individual beds of high grade, partially oxidized ore (4.55 oz/ton or 156 ppm gold) that were collected in the Main pit of the Carlin mine. The samples were collected from several thinly laminated carbonate micrite beds within the top 50 meters of the Roberts Mountains Formation. The carbonate micrite has been altered by hydrothermal fluids to a calcite-absent, moderately silicified rock referred to as alteration zone #3 by Bakken and Einaudi (3). Based on petrographic and SEM studies, the samples contain carbonaceous matter, and both pyrite and iron oxide pseudomorphs after pyrite. The oxidation of pyrite may be a pro-duct of deep weathering, in which case limited remobilization of gold may have occurred. TEM sections of the rock were prepared by first embedding small chips in low viscosity epoxy. The epoxy blocks were cut with a Reichert Ultracut E ultramicrotome, producing thin sections less than 0.1 p.m thick. The sections were examined with a Phil-lips 400ST TEM at 120 keV in both imaging and selected area diffraction modes. Native golci*was easily detected in TEM bright field images due to the large electron density contrast between gold and all other phases that are present (Figs. 1 and 2), Gold was positively identified with high spatial resolution EDX analysis in the transmission electron microscope, although selected area diffraction of individual grains was not successful EDX analyses of the platy and massive minerals immediately surrounding the gold particles typically indicate the presence of Si, AI, K, and Fe, However, the d-spacings derived from selected area diffraction of these polycrystalline masses (as, for example, in Fig. 2) give an exact match for maghemite. As a result, there is no diffraction information to identify the K-AI-Si-bearing phase(s). The lack of a diffraction pattern could be due to either electron beam damage or to a poorly crystalline phase(s).

Jan 1, 1987

By I. Iwasaki

Flotation characteristics of pyrrhotite by itself and in complex sulfide ores are reviewed with respect to the effects of oxidation, grinding media and other electroactive minerals.

Jan 1, 1988

By L. E. Murr

Preliminary studies of bacterial attachment to MoSp (molybdenite) have indicated a low correlation between dislocation density in the (0001) basal plane and the density of attached microbes. In the present investigation, poly- crystalline thin sections of CuFeSp (chalcopyrite) have been ion-etched or carefully comminuted to electron transparency and observed in the transmission electron microscope. The thinned test sections were then immersed in a culture solution in which bacterial attachment occurred. The attached bacteria were biologically stained in a uranyl acetate solution and the entire thin CuFeSp sections or tiny particles containing thin, electron transparent edges with bacteria attached were observed in the transmission electron microscope, allowing the coincidence of bacteria and their density to be directly observed in relation to lattice dislocations and crystallographic orientations of the exposed surfaces. This technique has the advantage of exposing crystallographic orientations where dislocation lines intersect the free mineral surface, and the emergence sites of dislocations could in principle be directly investigated as a possible preferential attachment site for bacteria. Bacteria morphologies were also extensively observed in the scanning electron microscope. The implications of the results are that although a strong correlation between dislocation density and distribution and bacterial attachment, density, and distribution has not been established, systematic multiplication of dislocation densities in crystalline mineral particles to be leached could enhance leaching rates by increasing the reaction rates as well as the density of attached bacteria at crystalline, metal-rich phases. Techniques for dislocation production in mineral and ore bodies and the particular implications in chalcopyrite leaching are discussed in relation to in-situ leaching where comminution is attained by explosives and the generation of strong shock waves in an ore body. The present study demonstrates the use of microanalytical and microscopic techniques in the investigation of fundamental microstructural phenomena in hydrometallurgical processes.

Jan 1, 1976

By X. J. Wu

Effects of various factors such as diaphragm materials, composition of electrolytes and current density on copper electrowinning from cupric chloride solutions was investigated. It is found that the crux of this process is to prevent the dissolution of copper by cupric ion and the formation of suspended CuCl precipitate. A process with high difference of copper concentrations between the feed solution and the spent electrolyte was selected. With this process, in which the feed solution contains 90 g/dm3 [Cu"], 3M NaC1, and 10mg/dm3 bone glue, and the spent electrolytes contains 10 g/dm3 [Cul, a very smooth and dense copper cathode can be produced with current efficiency above 93% and energy requirement less than 1.7 kwh/kg Cu at 25°C with N2 sparging. If a slightly higher energy requirement is permitted, smooth and dense copper cathodes can be produced at the current density up to 800 A/m2 with the identical solutions.

Jan 1, 1991

By E. A. Thiers

The causes of structural changes in the markets for high technology alloying metals are discussed in terms of technological, economic, and financial trends. Recent market imbalances have affected producers in developed and developing countries differently. Possible response strategies for suppliers in the two types of countries are examined that may alleviate future market imbalances.

Jan 1, 1988

By L. W. Beckstead

The use of acid ferric sulfate solution as a lixiviant for chalcopyrite concentrates has been of little interest from a practical standpoint due to the formation of a tenacious layer of elemental sulfur which severely impedes the reaction progress. CuFeS2 + 4Fe+3 ?Cu+2 + 5Fe+2 +2s° For example, an acid ferric sulfate leach of chalcopyrite concentrate results in only 12% copper extraction in a three hour leach at 93°C. Experimental results suggest that particle size is the only controllable variable which has a significant effect on the rate of acid ferric sulfate leaching at ambient pressure. Size reduction of the concentrate prior to leaching was exam¬ined using various methods of grinding. Of the grinding methods considered, attrition grinding was found to be the most effective. Leaching of an attritor-ground product (median particle size 0.5 microns) resulted in approximately 90% copper extraction in a three hour leach at 93°C. Energy measurements suggest that the costs associated with attrition mill¬ing are not unreasonable. Evidence indicates that "activation" or stored strain energy is not responsibile for the enhanced reaction kinetics of the finely ground concentrate, but rather the experimental results can be explained simply in terms of the increased surface area due to size reduction. Leaching reaction mech¬anisms operative in the acid ferric sulfate system are discussed and the application of ultra-fine grinding technology to other systems is considered.

Jan 1, 1976

By John Nauman

Liquid ferrous silicates that are related to cop- per slags have been studied as media for the transfer of heat in pyrometallurgical processes. The effective thermal diffusivities have been measured from 1025Oto 1400°C, and values in the range of 0.004 to 0.007 cm2/ sec have been obtained. The heat-transfer characteristics of these slags have been determined by measuring the rise of temperature of a cold nickel sphere immersed in the liquid slag. The sphere is spun about its vertical axis to obtain a well characterized flow of liquid about the sphere. The principal barrier to the transfer of heat from the bulk slag to the metal sphere is a solid shell of slag that forms around the sphere and subsequently melts. It appears that the detailed nature of this shell is important to theheat- transfer process. A mathematical model is used to predict the rate of heating of the sphere, and to evaluate various aspects of the system that can influence the transfer of heat.

Jan 1, 1976

By J. Dille

Metallic cobalt exist in two allotropic forms : the hexagonal compact a which is stable at low temperature ( ( 420') and the cubic form 0 stable at higher temperature. This latest form is the only one which is ductile. During the electrode position of Co, in moderate acidic conditions, we noticed a code position of both a and B forms. The influence of several parameters on the B/a ratio in the deposit was investigated. High acidity and the presence of Fe increased its ratio; on the opposite, high temperature promote the a phase. No significant influence on the material were noticed. The differentiation of a and B forms of Co is rather difficult and the method of J. Scoyer was improved quite successfully.

Jan 1, 1988

By Donald I. Bleiwas

World primary nickel production in 1987 is projected to be 770,000 mt, slightly higher than that in 1986. Market economy country (MEC) production in 1987 is projected to be about 524,000 mt, an increase of almost 5 pct over 1986 production. Production cutbacks and closures at Japanese ferronickel plants in 1987 resulted primarily from the strong yen and higher energy prices. Cutbacks also caused reductions in ore production from Indonesia, New Caledonia, and the Philippines. Technical problems affected production, to varying degrees, in Botswana, Indonesia, and Yugoslavia. World primary nickel production for 1988 is projected to be 787,000 mt, of which 536,000 mt will be produced in MECs. Increased production is projected from Botswana, Canada, Cuba, and possibly Greece and Yugoslavia, while slight production decreases are projected for Indonesia, New Caledonia, the Philippines, and Zimbabwe. .. South African nickel production in 1988 could be severly curtailed by social strife. In the early 1990's Brazil and China could be major economic competitors to Western nickel producers.

Jan 1, 1988

By A. M. Strachan

The arising and behavioural pattern of polonium-210 in the Capper Pass & Son Limited non-ferrous metal smelting and refining circuit is briefly discussed. The process developed for the removal of polonium from lead, solder and bismuth is discussed in detail, together with the essential personnel safety and environmental protection precautions which must be taken during the refining and subsequent storage of the active dross.

Jan 1, 1992

By Hang Goo Kim

A mathematical analysis based on equilibrium modeling has been developed to describe the distribution behavior of minor elements such as Pb, Zn, Bi, Sb, and As among gas, slag and recovered copper phases during the reduction of copper oxide in slag cleaning with CO gas. The results show that large fractions of the impurities transferred to slag during smelting or converting are recycled to the recovered copper metal. It is also shown that there is a limit to the recovery of copper from slag because iron oxides are also reduced to form a copper-iron alloy at low oxygen potentials. The effects of various operating parameters such as temperature, the activity of FeO, the initial amounts of the elements in the slag and CO content in process gas, on the behavior of these minor elements are discussed. The predicted results were compared with the results of a pilot plant operation in which pulverized coal was used as a reductant. Consistent trends between the two cases were obtained.

Jan 1, 1992

By R. A. Alock

The character, occurrence and genesis of the three types of nickel deposits, sulfide, laterite and deep-sea nodule are described, highlighting the differences in mineralogy and chemical composition that effect the extractive metallurgy of nickel and associated byproducts. World nickel production and current resources by deposit type and geographic location are also reviewed.

Jan 1, 1988

By R. G. Robins

Metal separations based on the selective precipitation of phosphates have a potential application in many hydrometallurgical processes. This paper reviews the literature on the solubility of a number of both divalent and trivalent metal phosphates and presents the result of some additional experimental measurements. The systems examined have been modelled to obtain free energy of formation data for the various species. Computer generated solubility diagrams which are described can be useful in predicting a variety of metal separations.

Jan 1, 1991

By John C. Taylor

With growing emphasis on energy conservation and increased concern over the presence of heavy metals in the environment, it is fortunate that most metals are readily recycled. In this respect, metals have a significant advantage over plastics and similar materials used as metal substitutes. For many years a secondary industry has processed scrap copper, nickel, lead and zinc to produce refined metal which has, to varying degrees, influenced the price and displaced the production of primary metal. This paper reviews some of the challenges the industry will face and the changes in process technology which will be required as pressure mounts to increase the amount of metal recycled. In the case of most base metals, this will have an impact on primary metal production; as the tonnage of metal recycled increases, the requirement for primary production, or new metal, will depend more and more on the growth in consumption.

Jan 1, 1993

By E. Gutierrez-Miravete

A computational method for the simulation of mold filling processes is described. The method is based on the representation of the flowing or deforming medium as a collection of mutually interacting parcels of material. Instantaneous positions of individual material parcels are calculated by numerical integration of the dynamic equations, subject to appropriate initial and boundary conditions. So far, the method has been used to produce qualitative simulations of some flowing and deforming systems encountered in mold filling technology, and our findings are summarized herein. In all cases, individual material particle motions can be followed in detail, allowing critical examination of potentially problematic mold design features.

Jan 1, 1992

By T. Inami

The chlorine leach of the anode slime was studied in order to improve the treatment process at the Niihama Nickel Refinery. The anode slime originates from the nickel matte electrorefining and, contains 3-5% of nickel as sulfides. A comparative study has been conducted on the filter cake resulting from the sulfur filtration of the molten anode slime. The kinetic factors of the chlorine leach such as temperature, grain size were defined. Under the optimized condition, 70-80% of the nickel is recovered from the slime or filter cake. On the basis of these results, the chlorine leach process for the treatment of anode slime has been established. The leaching plant has been installed and successfully operated since 1986.

Jan 1, 1988

By Peter Brown

The present work involves the study of Chemical Vapor Deposition (CVD) of silicon carbide from the methyltrichlorosilane (MTS) - hydrogen system. A computer program, SOLGASMIX has been employed to calculate the equilibrium compositions of the gaseous and condensed phases in the MTS - H2 system. The results indicate the range of parameters such as temperature, pressure and species concentrations, required to deposit the single phase Sic under thermodynamic equilibrium conditions. A mathematical model for describing the transport phenomena and the rate of deposition of Sic onto a thin rod in a vertically-oriented hot-walled CVD reactor has been developed. Exper iments were conducted using the same operating conditions as those used in the model in order to validate the mathematical predictions. The predicted rates of deposition were found to be in good agreement with those obtained experimentally. The model can be used to study the effects of various operating parameters on the rate of Sic deposition on a fiber.

Jan 1, 1992

By Robert R. Grinstead

Two new ion exchange resins have been developed, which selectively absorb copper and nickel in preference to ferric iron from dilute sulfuric acid solutions of pH 1-3. The first absorbs copper and not nickel and can be readily eluted with 1-2N sulfuric acid. This resin is well adapted to the processing of copper leach liquors, including relatively low grade liquors obtained from dump leaching. The second resin absorbs nickel as well as copper in the same pH region, but only the nickel is eluted with 1-2N sulfuric acid. Elution of the copper requires much stronger (ca. ION) acid, altho both species are readily eluted with dilute (ca. lN) ammonium hydroxide. This resin, which should be useful in processing of certain types of copper-bearing solutions, may also be suitable for treating acidic nickel leach solutions of laterites and other non-sulfide ores.

Jan 1, 1976