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By C. J. Boreiko

Traditional patterns of lead and zinc utilization are being evaluated in accordance with new paradigms that seek to ensure the long-term compatibility of global industrial activity with precepts of sustainable development and sustainable consumption. As a consequence, both industry sectors are experiencing intense scrutiny from the international community, and numerous regulatory options are being considered that may impact upon international industry practice. This paper reviews the growing expectations being placed upon industry, and highlights some of the common regulatory concerns being expressed regarding both metals despite their differing toxicological profiles.

Jan 1, 2000

By G. Hanko, A. Lebleu, M. Sibony, J. Lecadet

The New Jersey distillation process is today the most important pyrometallurgical method for the production of zinc of very high purity. The flexibility of the pyrometallurgical zinc production process, especially its ability for recycling, makes it competitive, although it is energy intensive. A deeper knowledge of the New Jersey process is necessary to further increase its technical performance by ensuring its global safety. A project, integrated in the European research program EUREKA, has been started in order to define the process chemistry of distillation. Experimental measurements have been carried out with a column at the laboratory scale, and the results, linked with industrial measurements, support the development of a model based on material and thermal balances. The first conclusions indicate that the key parameters for process optimization are the column geometry and the distribution of the thermal losses.

Jan 1, 2000

By M. Okido, H. Yamamoto, T. Sakamoto, R. Ichino, K. Kuroda

"Hydrogen absorption alloy films have been produced by molten salt electrolysis. Lanthanum-Nickel alloy film can be formed on a nickel substrate in KCl-NaCl-LaCb molten salts by electrolysis diffusion process. LaNi5 alloy was formed by mutual diffusion between La ·and Ni after La deposition on Ni substrate. Though several kinds of La-Ni compound existed in deposits, the alloy compounds on Ni substrate changed by electrolysis condition. According to the open-circuit potential measurement in molten salts after La electrodeposition, the formed compounds had a relation to the potential. In the case of the substrate electroplated a cobalt thin film on nickel, LaNi4_5Co0.5 was formed by the electrolysis in the molten salts with lanthanum ions. This ternary alloy film showed better hydrogen absorption behavior in cyclic charge/discharge test in alkaline solution.IntroductionHydrogen storage alloys have attracted attention as the active materials for batteries with the charge/discharge property at ambient temperature. The alloy of nickel and misch metal, mainly consisting of La and Ce, has been commercially 'used as a metal hydride with rechargeable property. In recent years, researches have been developed many kind of new alloys with better hydrogen absorption properties. The hydrogen absorbing alloy ingots are commonly produced by melting method of both metals in furnace, otherwise, prepared by mechanical grinding and metallurgical sintering technique with metal powders. The film is also made by vapor-phase techniques such as sputtering method, ion plating method, etc. ·We have proposed a new method to produce hydrogen absorbing alloy films by molten salts electrolysis technique [1-3]. The hydrogen absorbing film, LaNi5, Mg2Ni and CaNi5, were obtained in this process through controlling the electrolytic condition. The active metals, La, Mg and Ca, are electrodeposited on Ni substrate, diffuse into the substrate and form various kinds of intermetallic compounds. This technique provides a direct process using metal chlorides as resources to produce functional films without using active metals such as La, Ca and Mg."

Jan 1, 2000

By Ryuhei Masuda, Kenji Oosumi, Yasuhiko Watanabe, Yutaka Nagakura, Tomoya Ohzono

"In order to promote recycling of aluminum scrap, it is required to remove inclusions that have a remarkable influence upon the product quality. An internal filtration technology using a new filter, which is made by coating an adhesive on the surface of the conventional filter, has been developed as a new removing technology for inclusions.The technology has made it possible to remove inclusions as small as 10-20µm in the molten metal, which have been impossible to be removed by the surface filtration technology using conventional filter, An inclusion removal rate of up to 90% has been attained.The technology will contribute not only to recycling of aluminum products but also to the improvement in the quality of current products."

Jan 1, 2000

By D. Kennis

"Union Miniere Precious Metal's (UMPM's) Hoboken Business Unit has a long tradition in complex Pb-Cu metallurgy, focussing on the recovery of precious metals from various types of secondary and recyclable materials. Although the old flow sheet, based on a traditional sinter plant, blast furnace, and lead refinery process was a very complete flow-sheet with the capability of dealing with almost every impurity, the weaknesses became clear:1. old and costly technology,2. too many unit operations,3. too much internal recycling, and4. dependency on concentrates for the sintering process.To maintain the competitiveness of the Hoboken Business Unit, the project ""Smelter 2000"" was born. This project represents a breakthrough in metallurgical processes and technology. A modem smelting technology was chosen together with the development of a new process. A lead-copper process combining lead slag and blister copper production, carried out in an ISASMEL T vessel, was the key to simplifying the Hoboken flowsheet. ISASMEL T smelting technology was chosen for its flexibility towards feed characteristics and process parameters.The new smelter was commissioned at the end of 1997. Although there were a lot of problems due to the high degree of technical innovations in the process, the new smelter came to design capacity within 1 year after start-up. During this period, however, UMPM had, a very difficult time because of the extreme clear-cut nature of going from the old to the new flowsheet.After two and a half years of operation, the new flowsheet has proven to fit with the strategy of UMPM, focussing on treating secondary Pb-Cu materials and a broad range of recyclable feeds such as electronic scrap (E-scrap) and catalysts. Together with the new Precious Metals Plant, efficient logistics, recognised world class sampling practices and a customer-focussed commercial organisation, UMPM Hoboken can definitely be considered reborn."

Jan 1, 2000

By Entov Vladimir M., Gilmer R. Burgos, Andreas N. Alexandrou

"Processing of metal alloys in their mushy state represents a new trend in metal processing. As part of this process, known also as thixocasting, a specially prepared slurry at a temperature in the mushy region is injected into a die. Parts produced using this technology offer better mechanical properties than those produced by casting, and comparable to those of forged alloys.In thixocasting, semisolid slurries are highly concentrated suspensions of rounded rosette-like crystals in eutectic liquid. The mechanical behavior of the slurry is determined by the structure and properties of the skeleton formed by the alpha phase particles. The skeleton structure is almost never at equilibrium, and its evolution is, governed by a number of kinetic phenomena of different c11'aracteristic time-scales. Therefore, the skeleton structure depends on the mechanical and thermal history of the material. As a result of these kinetic processes, the rheological properties of the material, such as effective viscosity and yield stress, decrease with structure breakdown, and increase with its development. In the present investigation, the behavior of semisolid slurries during processing is modeled using the conservation equations, and a Herschel-Bulkley fluid model. The rheological parameters are assumed to be functions of the solid volume fraction, and of a structural parameter that changes with processing history. The evolution of the structural parameter is described by a first order kinetic differential equation that relates the rate of build-up and break-down of the solid"

Jan 1, 2000

By P. R. Bruggink

"A quantitative tool has been developed to assess the impact of changes in recycling rates on the environmental impact of aluminum supply. It has been applied to the USA to forecast sources of aluminum scrap and to examine the impact of an increase in Old Scrap recovery on the USA supply system and the subsequent effect on the Life Cycle Impact of aluminum supply. The reported data for primary, secondary and import/export supply and product shipments for aluminum in the USA show a fairly good balance between supply and demand on average over the years. Therefore, it is reasonable to use the data, along with published estimates of average product lives, recycling rates and recoveries to draw conclusions about future aluminum scrap generation· and recovery. The Life Cycle Impacts of increasing post-consumer recovery rates to recover an additional 450,000 MT/yr (1 billion lb/yr) has been estimated using the model.The spreadsheet model upon which this work was based was developed in U.S. Customary units. Converting the figures to Metric units would have required converting the entire model and rebuilding the figures. I have chosen to leave the figures in U.S. Customary units. I apologize for any inconvenience this may cause."

Jan 1, 2000

By Noboru Masuko, Sachiko Ono

"The structure and composition of anodic films formed on aluminum in a borate solution have been investigated by using TEM and SIMS with respect to the effect of current density and electrolyte temperature. The film is composed of a boron-containing outer layer and a boron-free inner layer with disc-like crystals present at the interface. The thickness of the film formed at constant current density up to an identical voltage, decreases with increasing current density. The thickness increases remarkably with elevated temperature. The transport number of Al3+ estimated from the thickness ratio .of the cuter to the inner layers is 0.4 when the film is formed at the current density of 20 Am-2 at 60°C. It increases slightly with increasing current density and decreases significantly with increasing temperature. Content of boron in the outer layer increases 1.5 times when current density .increases 10 times. These changes in film structure and composition with electrolysis conditions must have a significant role in the determination of electric properties of anodic alumina films as a capacitor material.IntroductionThe growth of anodic alumina film in ·a neutral electrolyte proceeds at both film/electrolyte and film/substrate interfaces giving a duplex structure. The oxide layer formed at the former interface includes electrolyte anions while a-pure alumina layer is formed at the latter interface. The thickness ratios of each layer respectively represent transport numbers of Al3+ and 0 2 - (1). The film thickness and the incorporated anion content as well as transport numbers of both ions must affect the dielectric properties of the film as a capacitor material. However, the correlation between film structure and electrolytic conditions is not fully understood (2). For the further clarification of anodic film growth mechanism, more detailed characterization of anodic films in relation to electrolytic conditions is advantageous. In the present paper, therefore, the effect of current density and electrolyte temperature on the microstructure and composition of anodic barrier films formed in a neutral borate solution was studied. The films were characterized by direct observation using transmission electron microscopy (TEM) and depth profiles of constituent elements obtained by secondary ion mass spectroscopy (SIMS)."

Jan 1, 2000

By Takafumi Kondo, Satoshi Yamashita, Noboru Masuko

"Aqueous oxidation of phosphite ions to phosphate ions with dissolved oxygen was examined at 80° C and pH 4.5 mainly from the stichiometric point of view. Dissolved oxygen alone can not oxidize sodilim phosphite in aqueous solution, but when sulfur dioxide is coexistent, cooperative oxidation for both sulfite and phosphite can occur in aqueous solution. Sulfur dioxide itself is well known as a reducing agent, but it also reacts as an oxidation-promoting agent for other species under a certain condition. So sulfur dioxide is· a promising cheap reagent for waste phosphite processing.IntroductionIn a liquid-phase oxidation reaction using the dissolved oxygen gas, the eoexistence of a copper salt is required generally. Recently, it was reported that the oxidation reaction progressed by using mixed gas of sulfur dioxide and oxygen without the copper catalysis, and the attention has been collected1·3). The present authors also noticed the phenomenon since the early time and have been studying on the reaction mechanism of sulfur dioxide in liquid phase oxidation 4l. It was found that; by using the SO2-O2 mixed gas, the oxidation of phosphite ions to phosphate ions proceeded efficiently in sulfuric acid solutions. In the present report, the applicability of SO2-O2 mixed gas as a cheap oxidizing agent to the industrial processing of the waste solution of electroless nickel· plating is investigated. It is well known that the sulfur oxide dissolved in aqueous solution is oxidized ·by the oxygen in the air to sulfuric acid according to the following equation"

Jan 1, 2000

By Keizo Uematsu, Satoshi Tanaka, Nozomu Uchida, Anze Shui, Joaquin Lira, Cyril Lavelle, Midori Saito, Thierry Poirier

"Dispersed and flocculated alumina (non-spherical particles) slurries were prepared by pH controlling with HCL Spray-drying of these resulted in dimpled granules with a smooth surface and high density, and spherical granules with rough surface and low-density, respectively. Detailed characterization on granules and their compacts includes: SEM observation, density measuring (mercury porosimetry and Archimedes's Principle) and liquid immersion optical microscopy. Compaction of these granules originated a larger particles rearrangement in the samples made with the spherical granules than with the dimpled granules. This was verified through the orientation of alumina particles, which was pronounced in the compact made with the former granules.IntroductionOn immersing a ceramic powder in water, the surface usually acquires a charge by interaction with ionic species in solution. The charge is affected by pH and the electrolyte concentration of the water. 1 The dispersion in a slurry is achieved through the interaction of charges on the particle surface with the media. In the ceramic processing, especially in the process of casting, the dispersion of slurry has been one of the most important topics studied for many years. Recently the attention is paid on its role in the pressing. The granule characteristics are governed by the dispersion state of slurry. Takahashi et al2 , Tsubaki et al3 and Walker et al4 showed that the granules from dispersed slurry were dimpled and of high density, while granules from flocculated slurry were spherical and of low density. This variation in the granules characteristics should have a marked effect on the structure of compact.This paper presents the influence of the dispersion state of alumina slurry on the granules characteristics and also on the internal structure of compacts. Different dispersion states were elaborated by adjusting pH of the slurry. In this method, the particles are dispersed or flocculated only by the effect of surface charging, and thus some secondary effect such as the steric hindrance from an electrolyte dispersant is avoided. The characteristics of granules and compacts are examined with SEM, density measurements by mercury porosimetry and by Archimedes's Principle and liquid immersion optical microscopy. This novel microscopy provides various important information on packing structure of particles, such as their orientation. 5"

Jan 1, 2000

By R. W. Lee

The first prototype plant using the Imperial Smelting Process commenced operation in 1950. It is timely therefore to review the developments that have occurred with the process over the past half-century. A major advantage claimed initially for the process was its ability simultaneously to recover zinc and lead from bulk concentrates. This has remained a fundamental advantage, but it has been extended by the increasing treatment of secondary materials containing zinc and lead. This has been facilitated by the development of hot briquetting and tuyere injection. These techniques and their impact on the technology of the operation will be described. The other major advantage claimed for the process was its potential to achieve new levels of productivity in the pyrometallurgical smelting of zinc. This has been realised with operating furnaces producing up to 400 t/d of zinc. The technical developments that have enabled this scale of operation will be reviewed.

Jan 1, 2000

By Toshio Kurikami, Koichi Yamazaki

"Toho Zinc Co., Ltd Chigirishima Refinery has the production capacity of electrolytic lead for 95000t/y by sintering- blast furnace electrolytic process. Lead raw materials are lead concentrates, spent batteries and dusts that contain lead from other companies, and these are handled by existing smelting process. There are many circulation materials in the process, because the system has been constructed with improving the recovery rate and protecting the environment. This report describes material balance in each process, distribution of the lead and various components, and it examines present state of the processing. In addition, we report the result that we have tried to improve the work environment.IntroductionThe Chigirishima Refinery of the Toho Zinc Co., Ltd. is located in Chigirishima, an island 4km off the coast of Takehara-city, Hiroshima, Japan. The Chigirishima Refinery began lead smelting operations in 1951.The Chigirishima Refinery adopted the sintering-blast furnace-electrolytic process and has an electrolytic lead production capacity of 95,000 tons/year. The existing smelting process handles raw materials from lead concentrates, spent batteries, and lead-bearing dust from other companies. This system was constructed with the intentions of improving material recovery ratios and protecting the environment; therefore, there are many materials recirculating throughout the smelting process. This report describes the material balance in each process and the distribution ciflead and various components, and it examines the present state of processing. In addition, we report the results of our attempts to improve the work environment."

Jan 1, 2000

By I. A. Ibrahim, A. K. Ismail, A. A. I. Afifi

"Synthetic rutile for paints industry is conventionally produced by a combined smelting and leaching process. Smelting process is an energy intensive step and represents economic burden in view of the increasing energy costs. Egyptian ilmenite ore containing 40% TiO2 and 38% total Fe was thus directly leached with sulphuric acid to produce eventually synthetic rutile. The process-involves digestion of the ore with sulphuric acid whereby both TiO2 and Fe are dissolved. The solution was then treated with iron powder to convert Fe3+ to Fe2+ to avoid co-precipitation of iron during the hydrolysis step. After solid/liquid separation and clarification, Fe was crystallized as ferrous sulphate hydrate by chilling. The titanium pregnant liquor was concentrated by evaporation and then hydrolyzed to precipitate hydrated titanium dioxide which was then calcined to produce synthetic rutile containing 98.6 TiO2 and 0.58% Fe2O 3. The optimum conditions of all the processing stages were determined.IntroductionSynthetic rutile for paints, welding rods and other industries could be produced from ilmenite ore by sulfuric acid leaching process. This process is a batch process and nearly 80% of all TiO2 produced in the world is made by this process [1]. Figure l shows simple block flowsheet of the process. The process involves the following stages.Digestion: In this stage, ilmenite ore is treated with concentrated sulfuric acid where both iron and titanium are converted to their respective sulfates according to the following equations:"

Jan 1, 2000

By Masami Taguchi

"It is found that lead monoxide, PbO, has an ionic conductivity, and the all solid-state electrochemical cell using this oxide as an electrolyte has attracted the attention of battery researchers. In this study, thin film PbO2/PbO/Pb solid cells were produced on glass substrates and their discharge properties were investigated. The acti.ve material for the positive electrode, PbO2, was obtained by reactive sputtering of a Pb target in oxygen plasma. The PbO electrolyte and the active material for the negative electrode, Pb, were vacuum evaporated from /3 -PbO powder and a Pb block, respectively. The open-circuit voltage of the cell agreed with the theoretical value based on the thermodynamic data, and the close-circuit voltage was improved by the addition of a univalent impurity such as sodium or potassium to the PbO electrolyte. The connection of the cells in series and in parallel produced a higher electromotive force and a larger capacity. Also, the charge-discharge cycling test revealed that the cell could be charged and function as a storage battery.IntroductionGenerally, the ionic conductivity of a solid-state electrolyte is lower than that of a liquid electrolyte near room temperature. This has been a serious obstacle to using such electrolytes in an electrochemical cell. However, some solid-state electrolytes, which can preferentially pass a specified ion and have high ionic conductivity, have been found. Lead monoxide, PbO, which is an oxygen ion conductor, is such an example (1)(2). If a solid-state electrolyte is adopted for use in an electrochemical cell the problem associated with a liquid electrolyte such as leakage can be alleviated. The cell structure also can be simplified, because the electrolyte plays the role of separator to prevent the active materials from mixing. Thus, physical vapor deposition technology may make it possible to develop a very thin film cell, which consists of only solid phases (3)(4). In this study, the thin film PbO2/PbO/Pb solid cell with a thickness· of only a few micrometers, in which all the constituents were systematically deposited on a glass substrate by reactive sputtering and vacuum evaporation, has been produced and the charge-discharge properties were investigated. An attempt was made to improve the discharge properties by doping impurities such as Na2CO3 and Sb2O3 into the PbO electrolyte. Moreover, the connection of the cells in series and in parallel to get a higher electromotive force and a larger capacity, and the charge-discharge cycling test to determine its use as a storage battery were carried out."

Jan 1, 2000

By R. J. Wesely

Non-ferrous smelters traditionally have a hot gas handling system. In these systems, the dust is captured as a dry material which is often recycled to the process. Some smelters use wet gas cleaning methods with the recovery of the dust as a wet sludge. Although this sludge can be recycled to the process, in some cases it is preferable to dispose of the sludge. This paper will discuss the disposal methods available and specifically will deal with one type of sludge which has a high arsenic and high lead content. Problems with this sludge were investigated and methods were tested with the aim of stabilizing the sludge so that it passes the EPA TCLP test. Results of the laboratory tests are given.

Jan 1, 2000

By A. C. Cascalheira, L. M. Abrantes, M. Savic

This paper reports our results on the application of a novel process for the spontaneous and sustained reduction and recovery of elemental silver and gold on an electroactive polymer surface. This work incorporates the metal recovery from photographic films (silver) and goldsmith residues (gold), by direct contact of metal containing solutions with polymer. The performance on such process of electrochemically and chemically prepared polyaniline (P ANI) is evaluated. SEM coupled with EDX and XRD analyses confirmed the presence of metallic silver and gold deposited onto polymeric material.

Jan 1, 2000

By M. -V. Wang

Hydrotreating and hydrorefining (HT and HDS) spent catalysts contain molybdenum, vanadium, nickel or cobalt at concentration levels that can make metals recovery economically viable. Quanzhou Jing-Tai of China has developed, through many years of operating experience in metal recovery from spent catalysts, a simple process for recovery of these metals and the production of environmentally benign residues. The process first subjects the catalysts to a low-temperature calcination step, followed by grinding of the calcine. The ground material is then leached with 10-20% v/v hydrogen peroxide to recover metals such as Mo, V and Ni or Co. This step has a selectivity that is greater than 95% for the metals. The undissovled residue, which contains mainly Ah03 and Si02, can be dewaterd and used in the production of masonry bricks. The pH of the rich liquor is then adjusted to between 0.5 and 2.5 by adding dilute sulfuric acid to co-precipitate Mo and V, with a recovery rate of greater than 99%. The lean liquor contains mostly dissolved Ni or Co, which can be recovered through precipitation at a pH of between 8.5 and 9.5 by caustic additions. The final liquor is then sent to an ion exchange step for final recovery and cleanup of residual metals. The effluent is then discharged after a simple wastewater treatment process, which has been found to meet all environmental requirements. The entire process has been found to be simple, cost-effective with minimal environmental impacts while achieving the goal of complete resource recovery from spent catalysts commercially.

Jan 1, 2000

By John W. Pickens

The recycling of industrial wastes and by-products is an important component of ecologically responsible industrial management. Converting waste streams into value-added products or material and energy resources with a profit margin assures the continued viability and practice of recycling. The recycling of aluminum stands out as one of the best examples with major economic and environmental benefit. However, the benefits are compromised by landfilling of black dross and salt cake, waste streams produced from within the recycling process itself. This paper reviews Alumitech's strategy and progress in establishing a tertiary aluminum industry based on closed-loop recycling of black dross/saltcake; one which does not compete with the primary and secondary aluminum industries, but rather serves their needs to ensure the continued economic benefits of aluminum recycling and elimination of environmental liablJity associated with landfilling of black dross/saltcake. Alumitech has made significant progress toward that goal in operation of its new recycling facilities in Cleveland where recovered aluminum and nonmetallic residue from salt based drosses is being converted into commercial products, eliminating the landfilling of the greatest portion of dross/saltcake. The economic strategy for recycling saltcake and its progressive achievement is reviewed.

Jan 1, 2000

By N. Mizutani, S. Harada, Z. Asaki, T. Tanabe

"The development of lead-free solders is urgent in view of environmental standpoints. In this -work the wettability of tin-bismuth- silver solders on copper was studied. Three kinds of fluxes were used. The wettability of conventional eutectic tin-lead .solder exhibited an excellent level over the other solders of tin-bismuth systems. Poor wettability of the tin-bismuth solders may be caused by the growth or dendritic copper-tin compounds at copper/solder interface, in contrast to the case of tin-lead'· solder. The wettability was improved by the addition· of silver in the solder. In this tin bismuth- silver system, silver was abnormally concentrated at the copper I solder interface even in the initial stage of contact. The wettability of the solder and the thickness of compound formed on the copper have a good correlation; the solder containing 2% silver exhibited the best wettability and the formation rate of copper-tin· compound on the copper was slowest.IntroductionSocial demand to avoid lead use in the industrial fields has been recently promoted· (1) because of the environmental protection of water resources. Especially the lead-bearing solders have been widely used in electronics and automobile products, and it is urgent to replace them with nontoxic materials (2)-(4). Thus the development of lead-free solders becomes an indispensable subject to the new generations and many works (5)(6) have already been carried out on the research and development of new solders. New lead-free solders are expected to have some requirements, for example, moderate melting temperature, proper strength and integrity, and lower prices, as compared with conventional solders. There have been already several alloy systems developed. Among ·these alloy systems, tin-bismuth binary or tin-bismuth-silver ternary alloys have great advantages such as having a wide range of soldering .temperature by controlling con:ipositions, though they have such disadvantages as ""lift-off"" (7)-(9): It is said, on the other hand, that a frequently overlooked property of solders, or one that is typically ignored by the research scientist as an ""issue"" for the manufacturing or product engineer, is wettability (10), although a ·work on the wettability has recently been published (11). In this Work, therefore, the authors selected Sn-Bi-Ag solders and focused mi the effect of Ag-addition to wettability of the solder."

Jan 1, 2000

By R. Peterson, D. C. Popko, J. Y. Hwang, R. McChesney, A. M. Hein, R. C. Greenlund, M. Jeong

MTU is conducting a study to recycle and reuse the aluminum waste generated from various segments of the aluminum smelting industry. This research is supported by the U.S. Department of Energy and industry. A portion of this effort is to determine the operating efficiencies of Eddy Current Separation, comparing separating characteristics of white and black dross. The results of this effort will be presented here.

Jan 1, 2000