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By J. L. Holman

The Bureau of Mines is investigating recovery of Ni, Co, Cr, and other metals from mixed contaminated supera110y scrap. The scrap is melt-refined and cast into anodes for electrodeposition of recyclable Ni-Co alloy. Melt oxidation using roasted superalloy grinding sludge as oxygen source can divert the Cr to the slag but with excessive Ni-Co loss. Melt oxidation-carburization or direct melt carburization retains -95 pct of the Ni-Co in the anode alloy. With direct carburization, -90 pct or more of the Cr and other refractory metals report to the anode alloy, largely as carbide phases insoluble in electrolysis. Electrorefining data relate parameters such as controlled cathode potential, Fe and Cr impurities, pH, and compartmented cell use, to current efficiency and Ni-Co deposit quality. Recovery of -90 pct of the Ni-Co in the scrap can be achieved. Preliminary experiments to recover Cr, W, and other metals from the anode sludge and other byproducts are discussed. 347

Jan 1, 1987

By Z. M. Zheng

Cyclic voltammetry, potential step, and ac impedance techniques were applied to study the electrochemical reaction of arsenopyrite in chloride solutions. The relationship between anodic current density and time in potential step measurements indicates that the oxidation of arsenopyrite is irreversible. The results of the constant potential coulometry show that the stoichiometric factor of the total electron involved in the overall reaction is 14. It is proposed that the dissolution of arsenopyrite is retarded by coverage of sulfur produced in the reaction as an intermediate product. The measured results of ac impedance strongly support the proposition. The proposed reaction mechanism also explains satisfactorily the charging current density and Tafel slopes measured in potential step measurements.

Jan 1, 1995

By Yong .. Jun Wu

Laminated ceramics have received widely scientific and commercial attention because their properties, such as mechanical properties and electrical properties, can be tailored by adjusting the structure, thickness and composition of the different layers. For example, ferroelectric Bi4Ti3O12 (BIT) which has a positive temperature coefficient of dielectric constant (,E) can be used to modify the negative tE of typical microwave dielectric ceramic BaNd2Ti4O12(BNT), However, BaNd2Ti4O12/Bi4TiO12/Bi4Ti3O12/BaNd2Ti4O12 (BNT/BIT/BNT) laminated ceramics could not be prepared by the general method because the optimal sintering temperature of BaNd2Ti4O12 ceramic (around 1350°C) was much higher than that of Bi4Ti3O12 ceramic (around 1100°C). In this research, a new method of spark plasma sintering (SPS) combined with post-sintering was successfully proposed to prepare BNT/BIT/BNT laminated ceramics. It was divided into three steps. In first step, the BaNd2Ti4O12 ceramics were prepared by conventional sintering method. In second step, the calcined and pre-pressed Bi4Ti3O12 powders were sandwiched between BaNd2Ti4O12 ceramic pellets and spark plasma sintered at 900°C for 10min to synthesize BNT/BIT/BNT composite ceramics. In the last step, a post-sintering was employed to reoxidize the partially reduced BNT/BIT/BNT composite ceramics. The results of scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) showed that BNT layer and BIT layer were well bonded and no significant interfacial infiltration between them was observed. The sandwiched BNT/BIT/BNT ceramic with 10.7% BIT in volume has a dielectric constant of 92.85, a low dielectric loss of 01068 and a small temperature coefficient of dielectric constant of 35 ppm/°C at MHz.

Jan 1, 2003

By J. L. Hill, M. A. R. Sharif, J. Lin

"A numerical algorithm has been developed to simulate the movement, breakup, and entrapment of the oxide film inclusions encountered during the mold-filling processes of aluminum castings. The flowfield is solved using the well-known Marker and Cell (MAC) method by a time marching process. The Volume of Fluid (VOF) method is used to track the free surface boundaries. A kinematic approach is employed to track the movement and breakup of the oxide films on the free surface or in the bulk liquid metal. The computer program based on the proposed algorithm is able to model the flow behavior and oxide film movement, breakup, and entrapment in mold cavities for aluminum castings.IntroductionMetallographic and fractographic studies of the aluminum castings show tangled networks of oxide films in the castings. These oxide films can form in the furnaces or during the mold filling processes. Green and Campbell [I] concluded that the oxide film defects dominate the strength of aluminum castings. The main cause of oxide film entrapment into the bulk molten metal during the casting processes is the surface turbulence. In film-forming alloys, if the surface breaks, due to a drop, a fountain, or a breaking wave, then the surface film is folded over and incorporated into the bulk liquid. The incorporation of surface films leads to cracks in the casting and other defects that are nucleated by the presence of the folded films, such as porosity and hot tears. Campbell [2] estimated that up to 80% of scrap in light-alloy casting is the result of surface turbulence."

Jan 1, 1999

By George S. Dulikravich

An advanced semi-stochastic algorithm for constrained multi-objective optimization has been adapted and combined with experimental testing and verification to determine optimum concentrations of aJ10ying elements in heat-resistant and corrosion-resistant H-Series austenitic stainless steel alloys. The objective was to simultaneously maximize a number of alloy's mechanical properties. This research will result in a rigorous tool for the design of high-strength H-Series steels and other types of alloys unattainable by any means existing at the present time. Such a material-by-design tool will also be able to reduce or minimize the need for the addition of expensive elements such as Cr, Ni, Co, Nb, Ti, V, etc. and still obtain the optimum properties of an aJ1oy.

Jan 1, 2003

By J. G. Peacey, P. Hancock, R. -Q. Li

A pyrometallurgical process for the direct recovery of zinc from zinc concentrates and zinc/iron residues has been proposed and tested extensively by Noranda. The process consists of smelting bone-dry zinc containing materials (sulfide concentrates and secondary zinc/iron materials) in a molten iron oxysulfide bath to volatilize metallic zinc into a SC^-free offgas. Sulfur contained in the feed materials is fixed as an iron oxysulfide matte for disposal. Thus, this process not only is capable of treating zinc sulfide concentrates and secondary zinc materials simultaneously, but also eliminates the need of sulfuric acid production. Detailed thermodynamic analysis and experimental test work are described in this paper.

Jan 1, 2000

By Liming Wang

One of the steps in the extractive metallurgy of lead is a refining process called drossing. Hot dross is mixture of impurity compounds that form on the surface during the cooling of lead blast furnace bullion, and in Missouri, the main impurities are copper and sulfur. The slow cooling of bullion throws out of solution all other minor impurity elements (or their compounds) which are much less soluble at lower temperatures (mainly nickel, arsenic, iron, and zinc). The transfer of bullion from the blast furnace to the refinery and the subsequent hot drossing step cause fugitive emission of lead-containing fume and dust, which creates a plant hygiene problem. One cause of the emissions is the high vapor pressure of lead and its compounds during transmission of = 1000 °C bullion to the drossing kettle. Another cause is the lifting of dross dust during manual skimming of dross. The environmental problems associated with the traditional hot drossing process provided an incentive to investigate a new drossing process that avoids contact between plant air and hot bullion or dross. A key aspect of the process development was a detailed mineralogical examination of dross from two different bullions. The bullion samples were cooled at different rates, and the dross filtered out and examined. The morphology, phase identification, and composition of the dross was examined by optical and SEM microscopy. The principal dross phases were copper and cuprous sulfide, galena, a complex sulfide containing copper, nickel and lead, and speiss (containing nickel, cobalt, iron, copper, lead, and arsenic compounds). The copper was acicular, with nickel and arsenic in solid solution. The cuprous sulfide was largely digenite in a granular or dendritic form. A substantial part of the dross was solidified matte with a eutectic microstructure, consisting mainly of CU2S and PbS. Small particles (some of which had a eutectic microstructure) never floated to the surface of the lead during the slowest cooling rate, thus indicating that flotation of tiny matte droplets and dross crystals is exceedingly slow. The success in separating dross and lead by centrifugal filtration suggests its application in industry as a replacement for traditional hot drossing.

Jan 1, 1995

By Chuanfu Zhang

Based on Thermogravimetric and Differential thermal analysis (TGA-DTA), porous copper powder is prepared by thermal decomposition of complicated copper oxalate. The effects of various conditions on the morphology, crystalline grain size and specific surface area of copper powder were investigated, including temperature, duration, mixing ratio of nitrogen and hydrogen. Furthermore, composition and morphologies of the products were characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM) and BET adsorption isotherm. It is found that porous copper powder was produced under optimum conditions. The specific surface area is over 6.74 m2?g-1, and average pore size in particles is about 30.3 nm. After comparison of SEM images, the final product Cu well inherits the morphology of the precursor, thus a mechanism of in-situ decomposition is proposed.

Jan 1, 2009

Laminated ceramics have received widely scientific and commercial attention because their properties, such as mechanical properties and electrical properties, can be tailored by adjusting the structure, thickness and composition of the different layers. For example, ferroelectric Bi4T13O12 (BIT) which has a positive temperature coefficient of dielectric constant (TE) can be used to modify the negative of typical microwave dielectric ceramic BaNd2Ti4O12(BMT). However, BaNd2Ti4O12/Bi4Ti3O12/BaNd1Ti4O12 (BNT/BIT/BNT) laminated ceramics could not be prepared by the general method because the optimal sintering temperature of BaNd2Ti4O12 ceramic (around 1350°C was much higher than that of Bi4Ti3O12 ceramic (around /1100°C). in this research, a new method of spark plasma sintering (SPS) combined with post-sintering was successfully proposed to prepare BNT/BIT/BNT laminated divided proposed to prepare ceramics. It was divided into three steps. In first step, the BaNd2Ti4O12 ceramics were prepared by conventional sintering method. In second mop, the calcined and pre-pressed Bi4Ti3O12 powders were sandwiched between BaNd2Ti1O12 ceramic pellets and spark plasma sintered at 900'C for 10min to synthesize BNT/BIT/BNT composite ceramics. In the last step, a post-sintering was employed to reoxidize the partially reduced BNT/BIT/BNT composite ceramics. The results of scanning electron microscopy (SEM) and electron probe mircoanalysis (EPMA) showed that BNT layer and BIT layer were well bonded and no significant interfacial infiltration between them was observed. The sandwiched BNT/B1T/BNT ceramic with 10.7% BIT in volume has a dielectric constant of 92.8, a low dielectric loss of 0.0068 and a small temperature coefficient of dielectric constant v/35 ppm/C at 1 MHz.

Jan 1, 2003

By I. Gaballah

Spent hydrorefining catalysts may contain 4 to 6 % of COO and/or NiO, 8 to 16 % of Moo3 and up to 10 % V205 generally supported by alumina. Raw samples are roasted in order to eliminate carbon, sulfur and hydrocarbons contained in the spent catalysts. The roasting optimum temperature and time are 500 "C and 7 hours. Selective chlorination of roasted samples with Cl2 + air, Cl2 + N2 and Cl2 + CO is investigated in order to recover the valuable metals. Depending on the chlorination it is possible to recover more than 80 % of the Ni and Co about 95 % of the Mo and up to 80 % of vanadium compounds. Cobalt and nickel chlorides are obtained by leaching the chlorination residues' by acidified water. Molybdenum and vanadium chlorides and/or oxychlorides are obtained by selective condensation from the vapor phase. The chlorination of the catalyst support, Al2O3, can be limited to less than about 5 %. Besides the reaction temperature and time, the oxygen partial pressure of the chlorinating gas mixture appears to be the key factor for the reactions' selectivity.

Jan 1, 1993

By T. T. Chen

Hydrometallurgical products are difficult to characterize because of their fine grain sizes, heterogeneity, often amorphous structures and water soluble or hydrated constituents. Such products are advantageously studied using complementary mineralogical techniques including >50, ore microscopy, SEM-EDX, electron microprobe analysis, selective leaching and wet chemical analysis to determine the phases and their morphologies, to identify specific element carriers, and to elucidate the chemical reactions occurring during the metallurgical process. Sample preparation is an important consideration for these materials. For extremely fine-grained particles, or soft and brittle products such as elemental sulphur, the study of loose powder mounts provides information not available from the examination of polished sections. To demonstrate the application of the various mineralogical techniques, commercial zinc roaster calcines and leach residues, copper refinery anodes and anode slimes, and laboratory bornite leach residues were examined in detail. The various sample preparation and mineralogical methods are presented, and the use of these complementary and practical mineralogical techniques to improve the understanding of a particular hydrometallurgical system is discussed.

Jan 1, 1989

By Robert D. Rogers

The demand for phosphate will continue into the future, because phosphate is currently irreplaceable as a plant nutrient and in many chemical applications. Phosphate is not recycled, so the supply must be replenished through a process of mining and purification. Numerous microbial isolates. obtained from the environment were screened find those which demonstrated the greatest promise of solubilizing PO4 from the ore of interest. Screening was accomplished in a step wise manner an agar plate bioassay, shake flask studies, and semi continuous growth conditions. It was found that with the proper conditions of nutrient supply and solution pH; the bacteria and. fungus used in the semicontinuous process were able to solubilize in excess of 80% of an Idaho rock phosphate ore (RP) within nine days. A significant amount of solubilization occurred within the first six days. There was a 'reasonable correlation between the occurrence of soluble Ca and PO.4 during the processing of the RP thus providing evidence that the RP was being disintegrated by the organisms. In all cases, HPLC analysis of the solutions in which PO4 had been. extracted from RP showed that organic acids, which have been implicated as the mechanism of solubilization, were present.

Jan 1, 1991

By H. Yin, T. Emi

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

Jan 1, 1996

By Veena Sahajwalla

The cupola furnace is a coke-fueled shaft furnace used as a primary melting unit in iron foundries. Control of chemical composition of the iron tapped from the cupola is a key factor in productivity and quality control. In an effort to develop a control model for the cupola, a fundamental approach based on physical and chemical principles has been taken to describe the melting process. The behavior of oxidation of the solid charge in the stack of the cupola has been studied. Sulfidation of the charge materials by sulfur-bearing components released to the furnace gases from the coke has been described. Carburization of metal droplets of iron and of steel in separate molten streams has been characterized. Finally, reactions with alloying elements in the hearth (well) of the furnace have been defined. These reactions have been described in a computer-implemented model developed to predict the composition of the iron tapped from the cupola. The model has utilized the thermodynamics and kinetics of the oxidation, sulfidation, and carburization reactions, including temperature and physical aspects, in the various zones of the melting unit. The model predictions have been compared favorably with operating results.

Jan 1, 1992

By J. A. Innes

"""The oxygen, next uniting with the carbon, sent up an ever-increasing stream of sparks and a voluminous white flame. Then followed a succession of mild explosions, throwing molten slags and splashes of metal high up into the air, the apparatus becoming a veritable volcano in a state of active eruption.""IntroductionHenry Bessemer F.R.S(An autobiography, 1905)Thank you Mr Chairman for the opportunity to speak: at this, the opening session of your International Symposium on the subject of ""Injection in Pyrometallurgy"". Judging from the list of papers to be presented over the next three days, the Symposium promises to provide a most valuable addition to our existing knowledge base in what is now an extremely active area of R&D investigations. Whilst we have obviously come a long way since Sir Henry Bessemer's pioneering experiments of the mid-19th century, there is still much for us to learn.Most importantly, the Symposium offers a further opportunity to acknowledge the many significant technical contributions made in this field by the Organising Committee's special guest, Professor Howard Worner - one of this country's most respected research leaders.When first approached to give this talk I had two areas of concern. Firstly, I was not entirely clear just what injection metallurgy was meant to cover. How should the overall scope of this particular subject be defined?My second concern related to Howard Worner himself - a man for whom I have the highest personal regard and who, in fact, played a most influential role in respect of shaping my own career. Having already spoken about Howard's achievements on earlier occasions, I wondered what I could sensibly add.Notwithstanding these personal reservations, I am delighted to be here with you this morning. If my thoughts on the meaning and scope of injection metallurgy appear to be slightly off-course, and if Howard should perhaps recognise some repetition in my remarks, then I hope I can be forgiven."

Jan 1, 1996

By James Vaughan

Ionic liquids are solvents of interest for applications such as electro- plating, winning and refining of metals. Of particular interest is the possibility of processing reactive metals such as aluminium, magnesium and titanium that cannot be deposited from aqueous solutions. Aluminium has been electro deposited from AlCl3 : ionic liquid mixtures at low temperatures relative to conventional Hall-Héroult smelting. Imidazolium ionic liquids are have been used in the past due to their relatively high ionic conductivity and cation stability. The less studied and less expensive phosphonium ionic liquids systems may provide a viable alternative to imidazolium ionic liquids for certain applications. New information regarding the physical properties and electrochemical behaviour of phosphonium ionic liquid systems is presented.

Jan 1, 2006

By Jaeheon Lee

Gold-copper alloys are shown to form during the cementation of gold on copper in a solution containing 0.25M [S2O32-] at 25oC. The alloy composition is strongly dependent on the initial Cu:Au ratio in solution and ranges from Au3Cu to AuCu3. XPS results for Au, Cu, S, and O are reported as a function of depth through an entire deposited film with an initial solution containing 20 ppm [Au] and 30 ppm [Cu]. The deposit contained about 20 atomic % gold and was predominantly Cu3Au. Underpotential deposition (UPD) theory is discussed as a mechanism for explaining the formation of these alloys. Several other systems that produce alloys during contact reduction/cementation are also discussed.

Jan 1, 2003

By G. Riverin, C. Simard, W. D. Stevens

"An on-line technique to measure the efficiency of decoating I delacquering processes is being developed by Alcan' s Arvida R & D Centre. Decoating processes are used to remove moisture and coatings from shredded coated material such as Used Beverage Containers (UBC) before melting. Complete removal has been demonstrated to maximize metal recovery. Quantifying the weight of carbon and organic residue adhering to the shred surfaces is very difficult to measure directly, as the material can be highly folded. The technique developed indirectly measures the residue remaining by analysing the concentration of CO evolved in the decoater end zone exhaust gas.A commercial CEMS (Continuous Emission Monitoring System) incorporating an infrared type CO gas analyser was modified for on-line process exhaust gas analysis. Both pilot and plant trials had demonstrated that the CO concentration measured was inversely proportional to the efficiency of the organic removal achieved. As the quality of coated purchased scrap can be highly variable in moisture and organic content, continuous measurement should permit adjusting the feed rate and other decoater process parameters to the quality of decoating required."

Jan 1, 2000

By Wenzhou Yu, Cong Zhang, Wenhui Ma, Gang Wang, Kuixian Wei

"A novel technique was successfully developed for nickel further purification by vacuum directional solidification. The removal effect of impurities in nickel was studied based on theoretical analysis and experiments. High removal efficiency of impurities in nickel can be realized according to theoretical analysis. The experimental results show that the vacuum directional solidification treatment could increase the nickel purity from 99.96% to 99.996%. Since vacuum directional solidification could effectively remove the impurities from nickel with low contamination and low cost, it is a potential route to obtain high-purity nickel for commercial application.IntroductionNickel is widely used in metallurgy, machinery, petroleum industry, chemical industry, construction industry, light industry, and other industries for its ductility, medium hardness, ferromagnetism and high chemical activity. Nickel-based alloy is an important material for the key parts of aircraft, tanks, submarines, radars, nuclear reactors and aerospace fields [1-5]. Generally, nickel contains Si, P, S, Fe, Cu, Zn, As, Cd, Sn, Sb, Pb, Bi, Al, Mn, Mg and other impurity elements, which may hinder the commercial application of nickel. Therefore, it is necessary to refine the crude nickel for the high purity nickel."

Jan 1, 2014

By W. L. Dalmijn, J. M. Krowinkel

A recycling concept of end-of-life televisions starting with shredding will produce a complex material mixture, very heterogeneous in size, shape and degree of liberation. Basically all materials in television scrap are valuable, which means that recovery is important for either economic, environmental or sustainability reasons. However glass, plastics and metals are the materials with the highest potential for recovery. Non-magnetic materials from shredded television sets can be separated into three characteristic size fractions that need further separation for a high value-added recycling of the materials. This study investigated the potential of physical separation of these size fractions into valuable material streams using polyseparator, tlrldy current separator, dry and wet shaking tables and electrostatic separator. An overall mass balance of the mechanically processed televisions was calculated. Evaluation of the produced material fractions showed that heterogeneity in particle shape and size together with the presence of unliberated materials caused sever difficulties in separation when exclusively based on mechanical techniques. The results indicate that a certain degree of dismantling is necessary to achieve products of appropriate quality in physical separation. In order to improve recycling of electronic scrap through design for recycling cooperation between the electronics industry, the manufacturers and the recyclers of electronic goods is necessary.

Jan 1, 2000