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By T. DebRoy

In recent years rapid technological advances have been achieved in the application of high energy density heat sources such as lasers and electron beams in diverse metals processing operations such as metal refining, fabrication, coating, surface modification and alloying. However, our phenomenological understanding of these new and emerging processes has not kept pace with the technological achievements. Inadequate understanding of plasma-metal interactions, the complexity of the component physical processes, and the scarcity of thermophysical data at temperatures much higher than the melting points of metals are the main difficulties in the comprehensive analysis of these processes. Several unique contemporary issues related to metals processing with high energy density beams such as rapid evaporation of alloying elements during processing and the role of plasma in influencing vaporization rate interfacial tension and species solubility in metals are discussed in this paper.

Jan 1, 1993

By Adolf Mikula

Lead-tin solders are commonly used in electronic packaging due to their unique combination of electrical, chemical, physical, thermal and mechanical properties. Since it is known that lead and lead containing alloys cause great environmental concern and health hazards it is necessary to replace lead in solder materials. Besides the environmental concerns new technologies in electronic packaging require new and improved solders. In most cases the new solders will consist of ternary or quarternary alloy systems, the main component will be tin or indium and the second element could be bismuth, silver, copper and gold and to improve certain properties a third element will be added. For a third element zinc, nickel, antimony and aluminum can be considered. This report will concentrate on solders containing zinc as an environmental safe element.

Jan 1, 2003

By B. R. Baldock

The converting of high-grade nickel matte for production of low-sulphur matte or nickel metal is a process which has eluded metallurgists in the past because of the limitations of conventional converting furnaces. The high temperatures required and the refractory nature of nickel oxide has prevented practical success in a process which has been known to be theoretically feasible for a long time. The Ausmelt top submerged lancing system is capable of operating under close control of the smelting conditions. High temperatures and both rapid oxidation and rapid reduction can be achieved. These features have provided the basis for successful pilot plant trials of the desulphurisation of high-grade matte from the Kalgoorlie Nickel Smelter. Sulphur level in product was lowered from 20 to 25% to as low as 0.2%, with iron levels in matte in the range of 1.0 to 3.5%. The theoretical background of matte desulphurisation is surveyed and the pilot plant operations described. The implications of the results in relation to commercial plants and possible refinery operations are summarised.

Jan 1, 1993

By Animesh Jha, Chris Dometakis

"Without the use of a flux, only a poor dispersion of ceramic phase can be achieved. A molten-flux-assisted ceramic phase dispersion technique for producing aluminium alloy metalmatrix composites has been developed. In this paper, we report the physical chemistry for the dispersion of TiB2 in molten aluminium. In particular, aspects of the interfacial energy and the thermodynamics of the dispersion reactions are briefly discussed for enhancing the volume of dispersion phase in the molten metal and for controlling their morphology. This investigation also addresses the role of molten flux in the fabrication of AI-alloy mmc using a casting technique. The morphological aspects of the dispersion are explained on the basis of the classical theory· of nucleation.IntroductionMetal matrix composites (MMCs), have long been recognised as an important class of material due to their greater wear resistance, specific stiffness and temperature capability when compared to conventional monolithic alloys. Particulate reinforced composites produced by melt casting techniques have been amongst the first MMCs to achieve commercial market viability. The advent of melt mixing techniques such as the Duralcan™ process have enabled low cost, easily fabricated composites based on the AI-SiC and AIAlz0 3 systems to be produced. In this process, uncoated ceramic particles with diameters 10ltm and larger, are incorporated into conventional monolithic alloys with reinforcement levels up to 25 volume percent. The AI-7Si-SiC metal-matrix composites have good wear resistance, high strength, low density and high thermal conductivity. The combination of these physical and mechanical properties has become a major attraction for the fabrication of light-alloy composite disc rotor brakes for the automotive sector2. However, in silicon-free alloys, SiC is thermodynamically unstable above the composite melting point and is extensively attacked by the melt to form aluminium carbide3 :"

Jan 1, 1996

By S. E. Khalafalla

A method for preparing ferrochromium alloys containing less than 2 pct carbon has been devised in a single vacuum furnace reactor. This method can conserve chromium and should reduce the capital and energy requirements relative to chromite electrothermal reduction. Reduced products containing less than 2 and as low as 0.01 wt pct carbon were obtained by reacting pellets of chromite and carbonaceous reductant mixtures at pressures of 0.1 to 1 ton and temperatures of 1,230° to 1,320° C. The extent of reduction increased with increased temperature and decreased pressure; however, operating conditions were limited due to the onset of significant chromium vaporization at higher temperatures and lower pressures. Foundry coke, anthracite, and carbon black were found to be superior to graphite as reductants. The reduction of chromite to metallics was found to proceed via the carbide intermediates Fe3C or Cr3C2. Lime accelerates the. rate of solid state reduction of chromite and can shorten the furnacin1r time at 1,3000 C under vacuum from 13 hours to less than three hours. Additional lime and silica are added to the hot reduced chromite after releasing the vacuum and raising the furnace. temperature to 1, 700° C. Soaking the charge for about 20 minutes gave a button of low carbon ferrochromium alloy beneath a well-defined slag layer.

Jan 1, 1985

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 Kirsi M. Riihilahti

The oxidation characteristics of solid copper matte particles under simulated Kennecott-Outokumpu Flash Converting conditions are presented. The effects of feed matte grade, matte particle size, oxygen-to-matte mass ratio, oxygen content of the process gas and temperature on the particle oxidation rate, quality of conversion, particle size change and particle morphology were determined. The converting quality was highest (~68) with the 58% copper matte at 1100°C. At similar conditions, the 72% copper matte was more likely to produce copper oxides and leave unoxidized particles rather than directly produce sulfur dioxide at 1100°C, resulting in an average converting quality of 55. The quality of conversion was poorest for the 72% matte at 920°C (~45); the sulfur removal was extremely low even with a relatively high degree of oxidation. Fragmentation of the particles was significant in all cases with the 72% matte. A higher O2/matte .ratio and higher temperature, in general, resulted in increased fragmentation while oxygen enrichment had no significant effect. With the 58% matte, particle size was found to increase for the finest fractions rather than to decrease due to particle expansion.

Jan 1, 1998

By R. H. Crist

Reactive components of algal cell walls include uronic and alginic acids: In addition, many marine species have half ester sulfate groups which function as fixed anions. Associated metals vary with the media, eg., Ca and Mg in fresh water (FV) and Na, Ca, Mg in seawater. . These metals readily exchange with aqueous phase protons or metal cations. A plot of the total amount of metal cations displaced by protons vs .. pH shows one inflection at pH 4 for FV algae and' in addition a second inflection at pH 2, 3 for marine algae. The first inflection is interpreted as. Indicating the cations associated with carboxyl groups ,and the ,second with half ester ?Sulfate groups. The exchange capacities of various aigal ,species vary widely. When FV algae is placed in a Pb2+ solution,- the amount of Pb2"' deposited on the algae is. Equivalent to the. Total Ca2?, Mg2, and H+ displaced? thereby confirming the ion exchange mechanism. Ion exchange equilibrium constants are reported for the displacement of ca2+ from Vaucheria. With Mg2+, sr2+, Cd2+, Pb2+_ and Na+ as well as the reverse reactions. Cd2+ can .be removed partially from algae by precipitating it as CdS or Cd(OH) 2 Pb2+ and Cu2+ are also partially removed as the hydroxides. Rates of reaction for various alkali hydroxides decrease with increasing .unhydrated cation radius. It is concluded that theory is useful in predicting viable applications for algae in pollution abatement.

Jan 1, 1991

By I-Min Lu

An electric field was applied to a metal-bearing kaolinite specimen to investigate the efficiency of electro-osmosis in removing heavy metals from contaminated soils. The electric field induces a flow of water through the porous medium, called electro-osmosis, which is superimposed on the hydraulic flow. Because the electro-osmotic flow is relatively stronger in smaller pores, it can enhance the displacement of contaminated solution by fluid convection. Furthermore local changes in pH caused by the electrode reactions can affect adsorption equilibria and the distribution of solutes between the solution and the solid surfaces. The electro-osmosis experiments were conducted by applying either a constant current or a constant voltage across 8-cm inside diameter, 25 to 30-cm long specimens of kaolinite clay with graphite electrodes. Samples of the pore fluid and of the clay were analyzed to determine metal content, pH, and conductivity as functions of time and position. Results show that removal of heavy metals from soil can be accomplished effectively by electrokinetic treatment of sufficient duration. Approximately 95% of the lead was removed after 189 days.

Jan 1, 1996

By Thomas W. Chapman, Shi-Chern Yen, I-Min Lu

"An electric field was applied to a metal-bearing kaolinite specimen to investigate the efficiency of electro-osmosis in removing heavy metals from contaminated soils. The electric field induces a flow of water through the porous medium, called electro-osmosis, which is superimposed on the hydraulic flow. Because the electro-osmotic flow is relatively stronger in smaller pores, it can enhance the displacement of contaminated solution by fluid convection. Furthermore, local changes in pH caused by the electrode reactions can affect adsorption equilibria and the distribution of solutes between the solution and the solid surfaces.The electro-osmosis experiments were conducted by applying either a constant current or a constant voltage across 8-cm inside diameter, 25 to 30-cm long specimens of kaolinite clay with graphite electrodes. Samples of the pore fluid and of the clay were analyzed to determine metal content, pH, and conductivity as functions of time and position. Results show that removal of heavy metals from soil can be accomplished effectively by electrokinetic treatment of sufficient duration. Approximately 95% of the lead was removed after 189 days.IntroductionRemediation of soils contaminated with toxic chemicals is a difficult and expensive task. Washing or leaching are not particularly effective if the contaminate is sequestered in small pores; hydraulic flows of water pass through larger pores leaving the smaller pores relatively untouched. Electro-osmosis appears to be the most promising new technology for removing heavy metals and organic substances from contaminated soils (Segal, 1980; Hamed et al., 1991, Masliyah, 1994).Electro-osmosis is one of several electrokinetic phenomena that occur through the interactions among an electric field, fluid motion, solute adsorption, and the existence of a net charge on a solid-fluid interface (Newman, 1991, Masliyah, 1994). Electro-osmosis refers to the fluid flow in a porous medium that results when an electric field acts on the mobile region of the electrical double layer, the solution-side region of charge separation that exists at the pore walls."

Jan 1, 1996

By Filippos Patsiogiannis

Laboratory size (5 kg) aluminum killed low carbon steel melts were desulfurized with synthetic fluxes in zirconia crucibles. The sulfur, oxygen, aluminum, silicon, and manganese contents in the melt were determined as a function of refining time and temperature. With a good argon shield and synthetic flux cover, melt reoxidation was not observed. Sulfur removal followed first order reaction kinetics. The effectiveness of calcia saturated calcium-aluminate (12CaO.7Al2O3) based fluxes in desulfurizing the steel melts was evaluated. The effects of initial sulfur level of the melt, weight of the flux (slag), and additions of tellurium, fluorspar, and barium oxide to the melt on the kinetics of desulfurization were also studied.

Jan 1, 1993

By J. T. I. Poijärvi

Outokumpu Harjavalta Metals Oy operates copper and nickel smelters, three sulphuric acid plants and nickel refinery at Harjavalta and copper refinery and precious metal plant at Pori. The by-products of these plants are presented in this paper. The by-products of the smelters include products from slag cleaning of flash smelting furnaces and converters, flue dusts and smelter off-gases. Weak acid and sludges from cleaning of smelter off-gases and acids are the by-products of the acid plants. The by-products out of the copper refinery are crystallized metal sulphates and sludges from electrolyte purification, on which a co-production process of the copper tankhouse is based. The main by-products of the precious metals plant are products from anode slime treatment and platinum metal group concentrates in the recovery of precious metals. Sludges from nickel matte leaching and precipitates from solution purification are the by-products of the nickel refinery. The formation, treatment and processing as well as the research work done for the utilization instead of dumping of the by-products in the production of copper and nickel will also be discussed in this paper.

Jan 1, 1995

By Senlin Xie, Wanlin Wang, Lejun Zhou

"The innovative development of multiphase slag in hot-metal treatment has attracted considerable attention due to the reduction of CaO consumption and minimal environmental emission. In order to improve the efficiency of dephosphorization and to reutilize the waste-slag as an alternative source of phosphate ores, it is important to increase the distribution ratio of P2Os between the solid solution (2CaO· SiO2-3CaO· P2O 5) and liquid slag. An investigation was carried out to study the effects ofNa2O and B2O3 on the distribution ratio of P2Os, the results indicated that the increase ofNa2O would enhance the distribution ratio of P2Os with the formation of solid solution (2CaO·SiO2-Na2O·2CaO·P2Os), while B2O3 has the opposite function, and changes the morphology of solid solution. The study would provide an instructive way for the design of multiphase slag and re-utilization of waste-slag.IntroductionIn order to meet the increasing demand for high quality low-phosphorus steel, it requires a high efficient hot metal dephosphorization process. The current slag system for hot metal treatment contains large amount of solid CaO dispersed in liquid slag, which introduced a large amount of CaO consumption due to its low solubility, especially when CaF2 was restricted due to the environmental concerns. Therefore, new refming method to improve the utilization efficiency of CaO by using a solid/liquid coexisting multiphase slag was proposed, and the studies regarding to solid solution formation mechanism, mass transfer behavior of phosphorus and the phase relationship for multi-phase slag have been conducted. [1-6]Normally, hot metal dephosphorization slag consists of CaO--SiOz-FeO--P2O 5, and it has been approved that 2CaO·SiO2 forms a solid solution with 3CaO·P2Os at the hot metal treatment temperature over a wide range of compositions. [7] Kitamura et al [8] pointed out that the (2CaO·SiO2-3CaO·P2O 5) solid solution plays an important role in dephosphorization, and it has been regarded as an absorbents for phosphorus to lower the phosphorus content in liquid phase, which makes it more capable for future dephosphorization. l Besides, the multiphase slag has the potential to be recycled as a source of phosphorus, if the (2CaO· SiO2-3CaO· P2O 5) solid solution could contain high phosphorus content, and it can be separated from FeiO matrix 8hase due to the large difference of their magnetic properties under the strong magnetic field. [10, 11]"

Jan 1, 2014

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 Joon H. Jang

At a selected pH, hydrothermal oxidation of chalcopyrite was carried out under controlled F+,, at elevated pressures and temperatures (172-200°C) by balancing the rate of oxygen injection against the rate of consumption. Chalcopyrite was converted to covellite (CuS) and digenite (CU1.8S) with rejection of iron and sulfur to the solution. Covellite forms in the first stage, followed by nucleation and growth of digenite in the second stage. The effects of rapid and slow injection of stoichiometric quantities of oxygen are compared. Both the covellite and digenite form a porous layer occupying the same volume as the original chalcopyrite grain. An electrochemical kinetic model is presented to correlate the observed results.

Jan 1, 1993

By S. J. Buckler

Many chemical and metallurgical processes use submerged gas injection to increase contact area between gas and liquid phases in order to promote faster overall reaction or refining rates. The total interfacial area produced by gas injection through lances, nozzles or tuyeres is both an important design parameter for new vessels and a measurement for estimating the maximum processing capacity of existing equipment. Estimating total interfacial area from submerged injection into industrial pyrometallurgical vessels from existing knowledge is a problem with two aspects. The first difficulty is the difference in behaviour of cold (aqueous) and hot (molten metal) systems, implying that existing models and correlations of gas-liquid behaviour developed in low temperature systems are not necessarily appropriate for estimation of high temperature behaviour. The second difficulty is the issue of scale-up of correlations from laboratory to industrial sized vessels. The work presented in this paper is part of an ongoing experimental investigation, at the GK Williams CRC for Extractive Metallurgy, to quantify the total gas-liquid interfacial area available in pyrometallurgical vessels using chemical measurement methods. The effects of three operating variables, injected gas flow rate, nozzle diameter and nozzle submergence, on total interfacial area are quantified in a IOOL aqueous system - the first stage of a three stage process in examining the implications for scale-up of high temperature, medium-scale results are discussed. The results of work at high, injected gas flow rates (up to 500/min) show that the submerged Froude number is not sufficient for use as the sole variable in a predictive model of total interfacial area. Further work is being undertaken to identify other dimensionless variables that will better represent the gas-liquid characteristics in submerged injection that influence the formation of total interfacial area. The second and third stages of the experimental investigation involve measuring the total interfacial area in a large-scale (1000L) aqueous sodium sulphite and small-medium scale molten metal baths.

Jan 1, 2002

By Rodney L. Williamson

Optimal estimation theory has been applied to the problem of estimating process variables during vacuum arc remelting (V AR), a process widely used in the specialty metals industry to cast large ingots of segregation sensitive and/or reactive metal alloys. Four state variables were used to develop a simple state-space model of the V AR process: electrode gap (G), electrode mass (M), electrode position (X) and electrode melting rate (R). The optimal estimator consists of a Kalman filter that incorporates the model and uses electrode feed rate and measurement based estimates of G, M and X to produce optimal estimates of all four state variables. Simulations show that the filter provides estimates that have error variances between one and three orders-of-magnitude less than estimates based solely on measurements. Examples are presented that verify this for electrode gap, an extremely important control parameter for the process.

Jan 1, 2001

By D. L. Yopps

Platinum-group metal (PGM) flotation .. concentrate from the Stillwater Complex, MT, was subjected to biooxidation using Thiobacillus ferrooxidans in an effort to break down the sulfide minerals and liberate the ? associated PGM's for subsequent chemical leaching. Bacterial treatment oxidized up to 94 pct of the sulfide present, destroyed the PGM-bearing pentlandite [ (Ni,Fe),9Ss) mineralization, and dissolved most of the nickel in the concentrate. Results showed that increased sulfide oxidation during the biological stage led to improved PGH recovery in the subsequent. chemical leaching stage. cyanidation at 80° c proved to be the best chemical leachant tested. It removed 7.6 pct of the palladium, 94 pct of the rhodium, 97 pct of the gold, but only 34 pct of the platinum from the biooxidized concentrate.

Jan 1, 1991

By J. L. Johnson

Remediation of small-arms firing ranges is being investigated by the Naval Civil Engineering Laboratory and the U.S. Bureau of Mines. Scheduled closures of military installations, as well as the management of active ranges, require the development of methodologies for heavy metals removal to prevent their entering the surrounding environment. The impact berms contain high concentrations of metals, and the soil and vegetation surrounding the berms were found to have slightly elevated levels. The heavy metals characterized are in the form of whole bullets, a wide size distribution of free fragments, smeared lead on the surface of the soil grains, and very finely attached particles. Gravity beneficiation can remove liberated metal contamination effectively. Weak acetic acid leaching shows promise in lowering the final metal contamination to allow the soil to pass the Environmental Protection Agency's (EPA) Toxicity Characteristic Leaching Procedure (TCLP) criteria.

Jan 1, 1991

By J. Y. Hwang

Microwave heating is an attractive alternative to conventional heating methods because heat is generated directly within the microwave absorbing materials. It has potential to be utilized for selective heating and removal of specified components from a materials mixture. This investigation was undertaken to explore the potential of selective heating and burning of binders for foundry sand reclamation. Selected raw materials and binders used in foundry operations were tested to determine their receptivity to microwave heating. Time needed to reach 600°C and/or the maximum temperature achieved for samples irradiated by microwaves for twenty minutes under 800 W microwave power are reported. The microwave heating characteristics of the selected materials are summarized and discussed. The interactions between microwaves and the raw materials used in a foundry. such as silica sand. chromite sand and bentonite (clay) binder were studied. The results showed that chromite sand coupled well with microwave energy at ambient temperature while silica sand did not. This was expected because the major component of chromite sand. iron chromite (FeCr2O4). is a good microwave absorber. while quartz, which is the major component of silica sand, is a microwave transparent material at ambient temperature. Bentonite absorbs microwaves well because it contains a hydroxyl functional group and water molecules in its structure. It was found that the structure of bentonite was changed through microwave irradiation. Microwave heating characteristics of silica sand mixed with different amounts of bentonite binders were investigated. The presence of bentonite in the mixture improved the microwave heating of silica sand significantly. and bentonite was deactivated by the microwave processing.

Jan 1, 1995