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By A. Shemi

Tungsten carbide scrap (WC–Co) is material generated from the tungsten carbide manufacturing process and worn out or used carbide parts from industry. Tungsten (W) ores contain about 3 wt% WO3 and their W concentrates about 10– 75 wt% WO3. Tungsten carbide scrap typically contains 40–95 wt% W. The high intrinsic value of W and the fact that the least valuable scrap contains more W than the average tungsten ore makes tungsten carbide scrap a worthy material for re-use. This study has investigated the selective dissolution of the cobalt (Co) binder phase, and recovery of tungsten monocarbide (WC) and Co using an acid leach process. The Co component was selectively leached leaving the WC solid particles intact. Further investigation using a complexing agent-aided acid leach process that takes advantage of organic chelating agents that form a soluble tungsten complex in place of the passive insoluble tungsten oxide is envisaged. The optimal dissolution of the Co binder phase using an inorganic acid in conjunction with an organic complexing agent is a novel approach with the potential of reduced leaching times and possibility of regenerating the unreacted organic acid.

By Matthew John M. Krane, Christopher J. Vreeman, J. David Schloz

"A continuum mixture model of the direct chill casting process is used to model the transport phenomena and solidification behavior in the Direct Chill casting of an Al - 6 wt% Cu billet using Wagstaffs AirslipTM process. The model, which includes the transport of free-floating solid particles, can simulate the effect of a grain refiner on macrosegregation and fluid flow. Numerical predictions of sump profiles and composition and temperature fields are presented. Two 45 cm diameter billets were cast under production conditions with and without grain refiner. Temperature and composition measurements and sump profiles are compared to the numerical results. The comparison shows excellent agreement for the grain refined case. It is believed that an incorrect model assumption prevents good agreement in the non-grain refined billet. IntroductionDirect chill casting is a semi-continuous process in which molten aluminum enters the top of a water-cooled mold, is cooled, and forms a solid ingot drawn out below (Figure l(b)). The molten aluminum begins to solidify due to the cooling effect of the mold wall. As the ingot is withdrawn from the bottom of the mold, water jets impinge on the surface, directly cooling the billet and forming a solid layer around a liquid melt, commonly referred to as the sump.A particular defect that occurs in a wide range of casting processes, including the direct chill (DC) casting of aluminum alloys, is macrosegregation, the uncontrolled redistribution of alloying elements on the scale of the ingot during solidification. Macrosegregation in DC cast ingots can produce non-uniform mechanical properties [l], which affects the behavior of the metal during downstream forming and heat treat operations."

Jan 1, 2001

By Katsunori Yamaguchi

A new technique for the removal of tramp-elements from steel scrap has been required from the viewpoint of saving energy and protection of environment. In order to obtain fundamental information on the removal of copper, tin and zinc from molten iron, the extraction method by using of phase separation in the liquid Fe-Pb-C system was investigated at 1453K A mixture of iron, lead and carbon melted in a carbon crucible separates into two phases of lead and iron containing carbon. The compositions on the miscibility gap in' the Fe-Pb-C system are 95A%Fe-4.5%C-0.l %Pb and 99.9%Pb-0.1 %Fe. The distribution ratios of copper, tin and zinc between the lead and the iron phases, Lx=[masso/uX in molten Pb]/(masso/uX in molten Fe), are 2.2, 2.2 and lA, respectively. Seventy percent of copper and tin from iron scrap can be eliminated with comparable lead addition. Gold, silver and palladium are enriched in the lead rich phase, on the contrary platinum and rhodium are more distributed to the iron rich phase than to the lead phase.

Jan 1, 2003

By Richard D. Hagni

Although the economically important uranium minerals are difficult to recognize under the ore microscope, they can be identified by a combination of qualitative and quantitative techniques. Useful quantitative techniques include indentation hardness, percent reflectance, spectral reflectance curves, and color coordinates. The latter two properties are especially distinctive for the primary urahlferous minerals uraninite, coffinite, brannerlte, and davidite. Together with the quantitative properties of indentation hardness and reflectance, the character and color of internal reflections are distinctive for many of the secondary uranium minerals. Ore microscopic techniques also provide an excellent means for determining the intergrowths of these minerals with other ore and gangue minerals. Such intergrowths are important to an understanding of the genesis of uranium deposits, and they may be important to uranium extractions.

Jan 1, 1981

By Susanne Pignolet-Brandom

Reflected light microscopy, and scanning electron microscope energy dispersive spectroscopic analysis and backscatter electron images were used to determine if a "slick dross" with undesirable handling properties has an assemblage of phases distinct from normal dross. This study has found that in the normal dross the most abundant lead phases are lead sulfide and lead metal and the most common copper phases are copper-iron sulfide and copper sulfide. In the slick dross, the most abundant copper phase is copper-lead sulfide and the most common lead phases are copper-lead sulfide and lead sulfide. The resulting mineralogical information has provided additional insight into the causes of the handling problem and the reaction mechanism for the formation of normal and slick dross

Jan 1, 1988

By G. L. Peralta

Geothermal energy is an important source of power in more than 12 countries and is a potential source in 50 countries. However, the exploration and use of geothermal resources generate residues such as scale and sludge. The scale is from the steam distribution pipes while the sludge is from cooling ponds. These solids contain significant levels of elements which are of environmental importance notably, arsenic, sulfur, copper, zinc and lead that require safe treatment and disposal. The compositions, phases, textures, morphologies and size of scale and sludge particles have been studied by laser particle size analysis, light microscopy, scanning electron microscopy, X-ray microanalysis, and X-ray diffraction. In addition, their leachability was tested with protocol leaching procedures and sequential extractions. The detailed spatial relationships and speciation of the environmentally significant constituents have received particular emphasis. The information obtained is useful in understanding how the scale and sludge are formed, their leaching behavior if disposed of in a landfill and in developing appropriate treatment strategies.

Jan 1, 1994

By D. E. Karvelas

Argonne National Laboratory is conducting research to develop a cost-effective and environmentally acceptable process for the separation of high-value plastics from discarded household appliances. The process under development has separated individual high purity (greater than 99.5%) acrylonitrile-butadiene-styrene (ABS) and high-impact polystyrene (HIPS) from corruningled plastics generated by appliance-shredding and metal-recovery operations. The process consists of size-reduction steps for the commingled plastics, followed by a series of gravity- separation techniques to separate plastic materials of different densities. Individual plastics of similar densities, such as ABS and HIPS, are further separated by using a chemical solution. By controlling the surface tension, the density, and the temperature of the chemical solution, we are able to selectively float/separate plastics that have different surface energies. This separation technique has proven to be highly effective in recovering high-purity plastics materials from discarded household appliances. A conceptual design of a continuous process to recover high-value plastics from discarded appliances is also discussed. In addition to plastics separation research, Argonne National Laboratory is conducting research to develop cost-effective techniques for improving the mechanical properties of plastics recovered from appliances.

Jan 1, 1996

By R. Leiby

Prior to March 1992, the only component of the lead acid battery that was not recycled by East Penn Manufacturing Company was the sulfuric acid electrolyte. This acid was unusable in new batteries because the iron level was found to exceed new product specifications. The development of a liquid ion exchange process to remove the iron from the acid allows East Penn to currently recover over three million gallons of sulfuric acid annually. The process is based upon the use of an iron selective liquid ion exchange material or solvent to extract iron from the sulfuric acid electrolyte followed by regeneration of the solvent. Equilibrium and kinetic data for the extraction and regeneration steps were collected in order to scale up the process to commercial scale. An electrochemical process for the treatment of the acid used in the regeneration step was, also developed which significantly reduces the volume of strip acid required in the process.

Jan 1, 1995

By Yoshifumi Abe, Akinori Toraiwa

"Nippon Mining & Metals started a new copper anode slime treatment plant that processes slimes in a chloride media. The basic plan of the process was proposed by Mr. James E. Hoffmann and Nippon Mining & Metals modified and advanced to produce precious metals in acceptable qualities for the company. The process has a wet chlorination stage of decopperized slimes, a solvent extraction and a reduction stages of gold, a silver chloride reduction stage and separative reduction stage of its gold extraction raffinate. The new plant of this process started in 1997 and has been operated in good condition.IntroductionThe old anode slime treatment plant of Nippon Mining & Metals, located in it's Hitachi Refinery, processed anode slimes through a combination of pyrometarllurgical processing and electrorefining. There was a need to plan a future of the plant because the maintenance cost increased year by year and a new selenium registration was going to be applied to the plant. Some plans were discussed and the result was that the process proposed by Mr. Hoffmann was superior among them.Nippon Mining & Metals started 'to examine the process and the experimental result showed that the process had an ability to be its new process but further research should be necessary to produce precious metals in acceptable qualities. The final process flow has some modified and additional stages to be suitable for its requirement. Silver processing stage is quite changed. Gold extraction stage has a new step to polish gold loading DBC. Gold extraction raffinate treatment stage is advanced to be able to recover precious metals, selenium and tellurium, separately. Aeration under atmospheric pressure is employed in decopperizing stage.The basic design of the new plant started in 1995 and finished in 1997. The construction of the new plant began in April 1997 and finished in October. The plant has been operating well after the four months test operation."

Jan 1, 2000

By M. Opler

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

Jan 1, 1995

By Raymond M. Coveney

Bedded sulfide ores in Cambrian Chinese black shales typically contains at least 2% Ni, 4.5% Mo, 1% As and 0.2% Se. Thin laminae and replaced on colites from the ore contain intimate mixtures of fine-grained Ni-rich sulfides and jordisite complicating ore treatment. The ores contain abundant jordisite, vaesite, nickelian pyrite, and barite and lesser amounts of sphalerite, gersdorffite, millerite, tennantite, fluorite, chalcopyrite, and HgSe (probably tiemannite). At present only ores that are sufficiently rich (>4.5% Mo) for direct roasting are mined and treated to produce, ammonium molybdate. The ores contain Pt, Pd, and Au in amounts totaling up to -2.5 ppm, but these are not recovered.

Jan 1, 1993

By B. Q. Li, Y. Shu, K Lynn

"This paper discusses the effects of magnetic field and internal radiation on the melt flow and solidification morphology during solidification processing of oxide crystals for optoelectronic and remote sensing applications. The numerical solution of the integral differential equation characterizing the internal radiation and the magnetohydrodynamic equations describing the magnetic and transport phenomena is obtained by applying the combined discontinuous and continuous finite element method. The results show that both internal radiation and an externally applied magnetic field can have important effects on the melt flow and solidification behavior during the melt processing of oxide materials.IntroductionOptical single crystals are widely used in optical and electronic devices. These crystals are often grown from high temperature oxide melts under strictly controlled conditions. As in the well-known single crystal growth processes for semiconductor wafers, thermal gradient in the melt is a major contributing fuctor to the oxide melt pool. Unlike the semiconductor single crystal growth processes, however, the oxide melt is semitransparent and internal thermal radiation plays an important role in redistributing the thermal energy in the melt pool. Our recent experience with pilot-scale plant measurements also shows that the oxide melt is electrically conducting, although its electrical conductivity is considered much lower than the liquid metal or semiconductor melt.The fact that the oxide melt is absorbing and emitting in the thermal radiation frequency range makes it difficult to study the thermal energy transport in the melt pool. This is because thermal radiation is governed by a hyperbolic differential equation, which is different from those describing the transport processes in liquids. Also, our understanding of how thermal radiation interacts with other transport mechanisms such as convection and conduction is rather limited at point in time, in particular in high temperature oxide melts for optical single crystal processing."

Jan 1, 2004

By Animesh Jha

"Fine ceramic powders (<500 nm) exhibit exceptional physical and mechanical properties in engineered structural ceramics. The production of fine powders, in particular the non-oxide ceramics, via a cheaper route than the organic solvent route has been rather elusive. This paper examines the physical chemistry of sub-oxide vapour-phase reduction reaction for the nucleation of non-oxide ceramic phase. Well known vapour species eg SiO and BO in the production of technical ceramic powders (SiC, BN) are particularly discussed for understanding the nucleation process of SiC and BN ceramic phases respectively. The regimes of partial pressures and temperatures are particularly 'identified. The calculated nucleation rate as a function of the temperature is compared with the experimental results on powder morphology. The production of amorphous and nanocrystalline h-BN powders is discussed in the context of substrate structure and thermodynamic parameters.IntroductionThe physical and mechanical properties of ceramic components are strongly dependent on the powder particle size and morphology used for their fabrication. For example the strength (Os) of the structural ceramic components increases with decreasing average grain-size (d) in accordance with the Hall-Petch relationship: Os = 0""0 + k/(d)1/2. Here k is an empirical constant which can be established from the graphical relationship. However as the particle size approaches submicrometer-size range, the dependence of strength on the particle size becomes more complex [1]. The design of ceramic components based on nanometer-size particles have recently become an important field which can offer ceramic materials with properties comparable to their metal counterparts. Several materials based on these concepts have been developed and reported by Niihara [2]. For example, the Al2O 3-SiC nanocomposite, having average B-SiC grain size 0.3-2um with intragranular SiC particulates of 5-10 nm has unusually high strengths (1100 MN/m2) at low and elevated temperatures combined with enhanced fracture toughness (> 4 MN-ml.5) which is an unusual combination in structural ceramics. Besides mechanical properties, as the particle size of ceramic powders approaches the nanometer-size range, the charge transport properties also improve by many times. The effect of particle size on the electrical conductivity of Si3N4-TiN composites has been well documented [3.4]. The size of ceramic particulates without doubt plays a pivotal role in determining the properties of ceramic components."

Jan 1, 1996

By J. T. I. Poijärvi

The smelter off-gas cleaning and the weak acid treatment at Outokumpu Harjavalta Metals Oy are presented and described in this paper. The smelter consists of the copper and nickel smelters and the acid plant of three separate acid plants two of which are double contact and one single plant and of one liquid sulphur dioxide plant. The preliminary cooling and flue dust separation of the smelter off....,gases from the copper ?and nickel flash smelting furnaces and converters? in the waste heat boilers and in the hot electrostatic precipitators are described. The final cooling and cleaning of the gases in the scrubbers at the sulphuric acid plant and the treatment of the weak acid in the vacuum and in the submerged combustion evaporators for the removal of impurities are presented as well as the treatment of the condensates from the evaporators. The attention is paid to the generation of sulphur trioxide in the smelter off-gas.and to the treatment of that in the weak acid bleed-off and to the utilization of the treated acid.

Jan 1, 1992

By Patrick R. Taylor

Coatings of TiCIFe have been produced by Reactive Plasma Spraying using ilmenite ore concentrate as the feedstock powder and methane as the reactive gas. A free energy minimization analysis of the ilmenite-methane system is presented. The coatings have been characterized by x-ray diffraction and SEM. The microstructure of the coatings indicates good interparticle cohesion. The composition of the coating is deficient in iron compared to the initial Fe to Ti ratio found in ilmenite.

Jan 1, 1998

By Clemens Schmetterer, Patrick J. Masset

"The surface tension represents an important property for the modelling of high temperature processes. In this study the surface tension of two Al2O3 – CaO – SiO2 model slags and the influence of the admixture of 5 up to 30 wt.% FeO were studied. The surface tension measurements were carried out using the sessile drop technique on BN substrates under Ar atmosphere (10-6 atm O2) up to 1500 °C.IntroductionThe aim of VIRTUHCON1 is the virtualization of high temperature conversion processes, a task that requires thorough understanding of these processes. In many of these conversion processes slag plays an important role to control the properties of the product, to protect the reactor lining or simply as waste. Slag surface tension is one of the materials properties that is needed for the description of such processes, since it influences the interactions between the components in the reactor, e.g. at the slag – Fe interface in the blast furnace.Surface and interfacial tensions have thus received considerable attention in research, but the number of investigations in this particular pseudo-quaternary system is surprisingly low. Furthermore, the literature data are subject to different measurement conditions and techniques which complicates the data analysis and comparison.The slag atlas [1] offers a compilation of the available literature until 1986 (shown in Table I), but literature search has not revealed more recent studies of this system until now. For example, Elliott and Mounier [2] determined the surface tension of ACSF slags using the double tube maximum bubble pressure technique at 1200 °C. They kept their slags in contact with Cu-S-F mattes, and the slag therefore contained a certain amount of sulphur which acts as a surfactant and lowers the surface tension. The compositions of their slags were scattered over a wide composition range and they did not use a common ACS base mixture for their tests, either. The surface tension values vary between 417 and 446 mN/m, but due to the reasons just mentioned no trend in the measurements can be observed and the influence of FeO admixture on the surface tension cannot be deduced. Further information including the temperature dependence is available from Pavlov et al. [3], Ishchanov and Shushkov [4] and Murav’eva and Kaplun [5]; the diagram on page 446 in Ref. [1] has been drawn from these sources. Both positive and negative temperature coefficients are reported in these works. SiO2 is the only pure constituent that has a positive temperature coefficient [6], but a correlation of the temperature coefficient with the SiO2 content was not found to be conclusive."

Jan 1, 2011

By E. James Quinn

Solvent extraction technology using EHEHPA (2-ethylhexyl phosphonic acid, 2-ethyhexyl mono ester) is the norm for industrial separations of rare earth elements. This process has some shortcomings, including a large number of stages compared to most SX processes and high acid requirement for stripping of the heavy rare earths. In this work, we examine a number of alternative mixed solvent extraction systems: (i) Mixtures of organophosphonic and phosphinic acids such as EHEHPA/Cyanex 272 or Cyanex 572; (ii) Ionic liquid mixtures of EHEHPA with quaternary ammonium chloride (Aliquat 336); and (iii) Mixtures of carboxylic acids for yttrium/lanthanide separations. We discuss and compare the efficacy of these systems with reference to the Nd/Sm separation, which is of industrial significance. Based on the extraction chemistry and the use of modelling tools to define the counter-current solvent extraction circuit, we present a techno-economic analysis of a separation plant and discuss the impact of various solvent systems on the capital expenditure (CAPEX) and operating costs (OPEX).

By G. B. Harris

Much has been written over the past decade concerning the disposal of arsenic from metallurgical processes. In Canada, there are proposed regulations which would classify arsenic in the Primary Group of twenty one persistent, toxic pollutants to be banned or phased out. Since many nickel and cobalt ores, not to mention those of copper, gold and uranium, contain significant amounts of arsenic, it is pertinent to assess the current state-of-the-art of its disposal. The literature is reviewed, and it is demonstrated that from a purely chemical point of view, the family of ferric arsenates largely immobilize arsenic. There is clear evidence from laboratory studies that both crystalline ferric arsenate (scorodite) and amorphous ferric arsenates in which the molar Fe/As ratio is at least three (Fe/As = 3) have very low arsenic solubility; plant data are given to support this. The debate over the long term stability of these compounds continues however; the evidence presented for long term stability and for compound breakdown is critically reviewed in the light? of the recent structural studies, and the role of base metals in these compounds evaluated. Finally, conclusions are drawn as to the viability of a purely chemical process for the long term disposal of arsenic from metallurgical processes.

Jan 1, 1993

By Kumar P. Dharmasena, Haydn N. G. Wadley, Bill W. Choi

"Non-contact eddy current sensing methods have been developed and applied to Cd0.955Zn0.045Te crystal growth to obtain a better understanding of the melt, solid nucleation, and the growth process. The application of this sensor approach relies on a large difference in liquid and solid electrical conductivities near the melting point and requires knowledge of the relationships between the electrical conductivity, melt composition, and temperature. Using a multifrequency encircling eddy current sensor, the electrical conductivities of three different Cd1-xZnxTe (x=0.00, 0.045, and 0.08) alloys were measured as a function of temperature in a laboratory-scale vertical Bridgman furnace. The measured solid and liquid electrical conductivities were then used in electromagnetic finite element models to analyze the multifrequency responses of eddy current sensor designs during the simulated growth of a crystal. These eddy current sensors were fabricated and installed in a vertical Bridgman furnace and used to monitor many Cd0.955Zn0.045 Te growth runs. One sensor was placed in the vicinity of the ampoule tip to detect undercooling/spontaneous nucleation and two other sensors (""absolute"" and ""differential"" designs) placed to monitor the movement/curvature of the liquid-solid interface during crystal growth. The sensor data was used to characterize the initial melt state, detect the onset of nucle-ation, determine the growth velocity, and identify the shape of the interface.IntroductionSingle crystal CdTe and its solid solution Cd1-xZnxTe alloys (0.03<x<0.05) are used as infrared transparent substrates for infrared focal plane array (IRFPA) detectors [1-6] and as solid state y- ray detectors [7-9j. Cd1-xZnxTe substrates are normally ""mined"" from large polycrystalline boules grown by the unseeded directional solidification of Cd1-xZnxTe melts using either a vertical or horizontal Bridgman process [10-14]. The vertical Bridgman method is particularly popular for growing CdTe and its related compounds. In this process, a Cd1-xZnxTe ingot is produced by first melting a charge in the hot zone of the furnace and then vertically translating the furnace (with its associated axial temperature profile) relative to the stationary crucible to cause directional solidification. In spite of many experimental efforts to investigate the relationships between material purity, stoichiometry, the controllable growth parameters (furnace temperature profiles, ampoule geometries/materials, furnace translation rates and starting position) and the resulting material characteristics (grain structure, dislocation densities, IR transmission, macro-segregation etc.), the yield of Cd1-xZnxTe of a quality suitable for large area (e.g. 4 cm x 6 cm) substrates remains low (<10%). Since much of this poor yield is directly associated with the crystal growth process (e.g. melt stoichiometry, solidification velocity, interface shape, temperature gradients, cooling rate, etc.) intensive efforts are under way to improve this technology."

Jan 1, 1997

By Tetsuro Ohashi, Tooru Matsumiya, Yoshio Abe

"The three-dimensional deformation of a continuously cast slab was modeled into two-dimensional deformation by developing the solidified shell of the slab. The developed solidified shell was divided into rectangular elements. The thermal strain produced as the slab is wi thdrawn over one roll spacing in the casting direction was calculated from the temperature change during that time and the increment of the geometrical unbending strain during the time was calculated from the change in the radius of curvature of the slab by assuming that the neutral axis of bending is located at the mid-thickness of the slab and that the transverse section of the slab is kept in a plane during unbending. These strains were imparted to each element as initial strains. The interaction between the elements and the overall deformation of the solidified shell were analyzed by the finite element method.The analysis was performed on a slab being cast on a machine of the circular arc type with progressive unbending. The following findings were obtained as a result. The effect of unbending is spread in the upstream and downstream directions of the slab by the shear deformation of the narrow and wide faces. As the shear deformation increases, the strain in the unbending zone decreases and the strain outside of the unbending zone increases. The effects of secondary cooling conditions, slab size, radius of caster circular arc section, compression casting, etc., were also analyzed. IntroductionTo develop a method for preventing the internal cracking of continuously cast slabs, it is important to acurately analyze the deformation of the slab and this subject has been extensively investigated. Many researchers, including the present authors, have analyzed slab bulging. (1)- (11) Analysis has also been made of thermal deformation that assumes importance in continuous casting of small-section blooms.(12)-(18) However, unbending deformation, an extremely important subject for continuous casters of the circular arc type, has not been fully analyzed."

Jan 1, 1986