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By S. M. McDeavitt

Waste form alloys are being developed at Argonne National Laboratory for the disposal of remnant metallic wastes from an electrometallurgical process developed to treat spent nuclear fuel. This metal waste form consists of the fuel cladding (stainless steel or Zircaloy), noble metal fission products (e.g., Ru, Pd, Mo and Tc), and other metallic wastes. The main constituents of the metal waste stream are the cladding hulls (85 to 90 wt%); using the hulls as the dominant alloying component minimizes the overall waste volume as compared to vitrification or metal encapsulation. Two nominal compositions for the waste form are being developed: (1) stainless steel-IS wt% zirconium for stainless steel-clad fuels and (2) zirconium-8 wt% stainless steel for Zircaloy-clad fuels. The noble metal fission products are the primary source of radiation in the metal waste form. However, inclusion of actinides in the metal waste form is being investigated as an option for interim or ultimate storage. Simulated waste form alloys were prepared and analyzed to determine the baseline alloy microstructures and the microstructural distribution of noble metals and actinides. Corrosion tests of the metal waste form alloys indicate that they are highly resistant to corrosion.

Jan 1, 1996

By D. W. Collins

The uptake of gold from halide solutions by activated carbon has been investigated using various techniques. Halide systems typically exhibit combined adsorption-reduction type behavior. In an attempt to gain more information about the nature of these processes, samples of synthetic highly-oriented pyrolytic graphite (HOPG) were contacted with aqueous solutions of gold-iodide. HOPG represents a model structure for activated carbon comprising of basal- plane sites, edge sites, and various defect sites. Two basic instrumental methods were used to examine the uptake of gold by HOPG. The first was standard X-ray photoelectron spectroscopy (XPS). The other involved several scanning probe techniques. XPS clearly indicated a preferred uptake of gold at edge sites. However, iodine appeared to be distributed on both basal-plane and edge sites. At low iodine additions, tapping mode AFM showed that clusters were concentrated along steps and surface defects. At high iodine concentrations, the HOPG surface was uniformly covered by iodine.

Jan 1, 1998

By Fathi Habashi

In the past five years Cuba has been attempting to more than double its nickel production by constructing two new ammonia leaching plants. No metals are yet produced on commercial scale but a variety of oxides and sulfides. This report updates the Cuban nickel industry as a result of two visits : one at the invitation of the Cuban Ministry of Basic Industries in 1987 and the other as a consultant to the United Nations for the Cuban Laterite Project in 1989.

Jan 1, 1993

By Jinrong Zhang

Fresh cyanide solution was treated by near UV light with the assistance of photocatalysts. Cyanide was oxidized mainly to cyanate. Photochemical behavior of the anatase and rutile forms of TiO2 was compared. It is found that anatase has a much higher activity than that of rutile. Bubbling of oxygen in the reactor showed no appreciable increase in cyanide oxidation, implying that the reaction is surface controlling. A very interesting finding in this study is that a natural mineral, ilmenite, can replace chemical titanium dioxide as the photocatalyst. Ilmenite without any treatment did not catalyze the oxidation of cyanide. But, after being roasted at high temperature with oxygen, the oxidation was enhanced dramatically. The mechanisms of photooxidation of cyanide and the roasting of ilmenite are proposed.

Jan 1, 1991

By Cevat Serdar Kucukkaragoz

The kinetics of prereduction of Chromite by carbon was studied under argon atmosphere at temperatures between 1000°C and 1300°C . The compacted and agglomerated specimens were reacted by using a TGA system. The mixing characteristics and the degree of compaction of the chromite and coke particles were the main parameters influencing the reduction kinetics. The reduction rate increased with temperature reaching to 81% reduction at 1300°C. The metallization started as the metallic nucleation around the particles which was first observed at 1100°C. The particles were surrounded by the metallic phase at approximately 40 % reduction obtained at 1200°C. At 1300°C, the reduction proceeded with a high rate during initial stages and with a low rate at final stages. The reduction was found to proceed in the sequence of Fe3+to Fe2+, Fe2+ to Fe(metal) and Cr3+to Cr(metal) with the formation of carbides.

Jan 1, 2006

By R. M. Westcott

A two-electrode, direct current, slag resistance furnace (SRF) has been constructed and operated to selectively reduce the zinc and lead contents of non-ferrous slags. The experimental SRF is equipped with multiple methods of gas/solids injection for both mixing and reaction. A computer is used to position the electrodes and for data acquisition. A geometric factor correlation was previously developed at Columbia University for calculating the electrical resistance on the basis of furnace geometry and slag conductivity. The experimental SRF was used to test this correlation.

Jan 1, 1994

By Joo Hyun Park

A history of the research regarding the spinel in the community of the stainless steels has simply been reviewed, followed by the recent studies for the formation mechanism of the spinel in the ferritic stainless steel melts equilibrated with the highly basic slags and the crystallization behavior of spinel phase in the calcium aluminosilicate melts containing MgO and CaF2 during slow cooling cycles. It has been proposed that the content of aluminum and calcium in the steel melts as well as the basicity and the content of MgO and Al2O3 in the slags are quite important factors affecting the spinel formation in view of the formation mechanism based on the reduction of MgO (or CaO) and Al2O3 in the slags by the aluminum and silicon added to deoxidize the molten steel. The use of magnesia refractory was also recommended. The formation mechanism of spinel from the MgO inclusions readily formed in the steel melts equilibrated with the highly basic slags has newly been proposed on the basis of the ionic exchange reactions at the inclusion/metal interface and the crystal chemistry of oxides. The crystallization behavior of the spinel phase in the calcium aluminosilicate melts was enhanced by the Al2O3 based on the ionic reaction of spinel formation in the oxide melts, while the size of the spinel crystals in the oxide melts decreased by addition of CaF2.

Jan 1, 2006

By Fumito Tanaka

The Converting Furnace (C-furnace) of the Mitsubishi process has solely provided opportunities for producing blister copper continuously from molten matte. Continuous converting originates from the proven technology for controlling the behavior of magnetite in lime-ferrite slag of the CaO-FeOX-Cu2O system. Recent improvements in the C-furnace operation have included the slag controls reflecting the impact of minor oxides on magnetite behavior. Although previous investigations focused on magnetite behavior, sulfur has also affected the C-furnace operation because it is of practical importance to avoid the precipitation of gypsum from lime-ferrite slag and the separation of matte from blister copper. This paper will quantify the behavior of sulfur in C-furnace with respect to the gypsum formation and matte separation, and discuss better controls for C-furnace operation.

Jan 1, 2006

By Corby G. Anderson

Laboratory testing, interpretation and application of metallurgical technologies can be tedious, time consuming and costly. This paper outlines the use of proven statistical design of experimentation software for rapid optimization of laboratory testing and operating plants with limited representative sample utilization. This results in less costly required testing, a more thorough understanding of results and the ability to simultaneously optimize several variables and outcomes at once. At the Center for Advanced Mineral and Metallurgical Processing, this testing methodology has been used successfully in many metallurgical development and plant optimization projects thereby confirming its real world utility and application. Accordingly, several applied examples in flotation and hydrometallurgy will be outlined in this paper. This will include flotation testing of a copper gold ore, flotation testing of a copper, cobalt and gold ore, optimization of an industrial hydrometallurgical jarosite circuit and optimization of industrial nitrogen species catalyzed pressure leaching of a copper enargite concentrate.

Jan 1, 2006

By A. G. Guézennec

Electric Arc Furnace (EAF) steelmaking co-produces amounts of dust (15 to 25 kg per ton of steel), which require to be collected and stored in specific landfills. The collection, handling, and possible beneficiation of EAF dust depend on its composition and morphology. We first studied theoretically the chemical evolution of dust particles along the fume extraction system, from the furnace down to the filters, using thermodynamic calculations of the Fe-Zn-O system. We show how it would be possible to favor zincite formation in dust and therefore increase further zinc recovery. Then, we developed a new morphological model, based on population balances, for predicting the granulometric evolution of dust particles as a result of agglomeration and sintering in the fume extraction ducts. The contribution of the various mechanisms (Brownian, turbulent, and sedimentary agglomeration; thermophoretic deposition; coalescence and sintering) is assessed. The influence of the exhausting conditions on dust granulometry is detailed. For the extraction system studied, intense agglomeration of the sub-micronic particles and complete coalescence take place inside the furnace; micronic particles then undergo little evolution from the elbow to the water-jacket, whereas big agglomerates are formed downstream. These results are in good agreement with dust particle observations.

Jan 1, 2006

By Toshitaka Ota, Hisao Suzuki, Minoru Takahashi

"Perovskite-type lead zinc niobate (PZN) exhibits excellent electrical properties such as high dielectric constant, high electrostrictive coefficient and superior piezoelectricity. Therefore, PZN ceramics are very promising for high performance electronic devices. However, perovskite phase PZN is not stable under the ambient atmosphere. Accordingly, it is very difficult to prepare single-phase perovskite PZN ceramics. In this study, A-site cation of lead was partially substituted for barium to stabilize the perovskite phase of the PZN (Ba-doped PZN) powder. In addition, molecular design of an alkoxide precursor was controlled for a low-temperature processing. As a result, molecular design to suppress the lead-volatilization during calcination was preferred for a low-temperature processing. Processing temperature for a single-phase perovskite was depended on the amount of barium dopant. Doping of20 mole% of barium resulted in the single phase perovskite at 900 °C. The temperature for the single phase perovskite of Ba-doped PZN powder, which depended upon the amount of Ba-doping, was lower than that of the powder prepared by the atmosphere controlled conventional powder processing at least by 150 °C.IntroductionFerroelectric thin films and powders with perovskite structure are of renewed interest for micro-electronic applications, including ferroelectric random access memory (FRAM), dynamic random access memory (DRAM), and thin-layer capacitors integrated onto a silicon wafer [1-3]. In addition, recent advancement in micro-machine requires a high performance micro-actuator [4]. A perovskite type relaxor of Pb(Zn113 Nb213)03 is one of the promising materials for a high performance capacitor and microactuator because of their high permittivity and electrostrictive coefficient [5]. Therefore, this paper focuses on the low temperature processing of Ba-doped PZN powders.Chemical solution deposition (CSD) from molecular-designed alkoxide precursor solution is one of the most promising techniques for processing high-performance powders and thin films because it offers precise control of compositions on a molecular scale as well as a low processing temperature [6]. However, chemical solution deposition of perovskite type PZN powders and ceramics are very difficult because of the formation of stable pyrochlore phases. Therefore in the past, PZN powders and single crystal have been prepared by the hydrothermal method or flux method as well as the partial substitution method of a A-site cation [7-10]. In this study, a suitable molecular design for a preparation of perovskite type Ba-doped PZN powders with a chemical solution deposition process is investigated as well as the effect of A-site cation substitution. Chemical solution deposition from molecular-designed alkoxide precursor solution is expected to decrease the amount of a A-site substitution and/or a crystallization temperature for a single phase perovskite. This paper describes ""the relation between molecular-design and processing temperatures for a single-phase perovskite of Ba-doped PZN powders in comparison with the conventional oxides mixing method."

Jan 1, 2000

By R. Padilla

Enargite (Cu3AsS4) occurs normally associated with copper sulfides, mainly chalcopyrite. When the enargite content in chalcopyrite concentrates is high, direct smelting of the concentrate presents problems related to environmental pollution and contamination of the final metallic copper. Leaching processes are viable alternatives to treat copper concentrates with high content of enargite. Consequently, in this paper, the pressure leaching of enargite in sulfuric acid-oxygen system is discussed. The leaching rate was studied in the range 160 to 220 °C and partial pressures of oxygen of 74 to 200 psi. The enargite dissolution increased substantially with temperature increase. Complete dissolution of enargite was obtained at 220°C, and 100 psi of oxygen pressure in 90 min. The shrinking core model controlled by surface reaction was used to analyze the kinetics of enargite dissolution. Activation energy of 70 kJ/mol was obtained for the temperature range 160 to 220 oC.

Jan 1, 2008

By Teruo Tanabe

The hydrogen-absorbing materials are expected to have the following properties at moderate conditions, (a) a large capacity of hydrogen absorption, (b) the absorption rate of hydrogen is large and (c) hydrogen-absorbed materials can easily desorb hydrogen. Thus the three concepts of capacity, rate and reversibility seem to be indispensable to clarify the mechanism of hydrogen absorption by the materials. In this work, the amount of absorbed hydrogen, the absorption rate and the reversibility of hydrogen absorption- desorption reaction were measured for binary R-M systems (R = Y, La, Ce; M = Co, Ni). These experimental results were discussed by the following three physical properties that were calculated by the extended Hückel method, i.e. the density of states unoccupied by electrons, the cohesive energy and the energy fluctuation. The major results are as follows: (a) the amount of absorbed hydrogen increases with the density of states in the energy range between -9 and -4 eV, (b) the R-M compounds of which energy fluctuations are large show a large value of rate of hydrogen absorption, and (c) when the cohesive energy is large, the compound has a tendency not to easily desorb hydrogen, i.e. its reversibility is poor.

Jan 1, 2006

By Mieke Campforts

The usefulness of the water-cooled probe technique to experimentally study slag solidification and freeze lining formation in pyrometallurgical reactors is evaluated. With this technique a layer of solidified slag is formed on a water-cooled probe that is submerged into a liquid slag bath. The influence of the submergence time and the heat input is examined. The solidified layers are analyzed with light microscopy, electron microscopy, electron probe micro-analysis and X-ray diffraction. Thermodynamic software is used to interpret the solidification microstructure. The results demonstrate that the technique is useful to understand freeze lining formation.

Jan 1, 2006

By Leiv Kolbeinsen, Stian Seim, In-ho Jung

"The current work presents new experimental data in the iron-unsaturated region of the FeTiO3-Ti2O3-TiO2 slag system. The samples are prepared by melting pure reactants in a high frequency induction furnace that employs a cold crucible. A similar experimental set-up has been described in literature and proven suitable to investigate high titania slags. The FeO content of the samples range from 3.7 to 21.8 wt% and the Ti2O3 content range from 3.6 to 30.1 wt%. The liquidus temperatures of the samples are measured in-situ by a spectropyrometer and range from 1450 to 1645 °C.In addition, an improved thermodynamic database for the FeO-Ti2O3-TiO2 system has been developed. Ternary parameters have been included and optimized to fit previously published experimental data. This optimization minimizes the discrepancy between experimental data and thermodynamic calculations as previously discussed in literature. New liquidus projection plots are proposed for the FeO-Ti2O3-TiO2 and the FeTiO3-Ti2O3-TiO2 systems.IntroductionIlmenite (FeTiOs) smelting is a relatively small industry world-wide. However, a reasonable focus on the process has been applied in Norway due to the location of one such smelter in Tyssedal, which is located in the western part of Norway. The process is essentially carbothermal reduction, where most of the iron in the ilmenite is reduced to its metallic state, and the titanium oxide is concentrated in the slag product. The metallic iron is sold as a high purity pig iron and finds applications in cast products. The slag concentrate is further processed for the production of TiOvpigment and/or titanium metal. This further processing can be performed through different routes according to the purity of the slag concentrate."

Jan 1, 2012

By Corby G. Anderson

For over a century, the Sunshine Mine in Idaho has been a major producer of silver. An estimated 335,000,000 troy ounces of silver has been mined. This has established the Sunshine Mine as the largest single source of silver in the world. Because the dominant silver containing mineral is tetrahedrite, a copper and antimony sulfide, normal metallurgical treatments to recover the precious metal are not practical. Thus, over the course of the company's history, novel, hydrometallurgical technologies have been developed on-site to handle complex, precious metal containing materials. Recently, the use of Sunshine technology has been extended to the recycle of secondary materials. As well, the use of Sunshine technology by other organizations for treatment of both primary and secondary feedstocks containing precious and base metals is an area of growing interest. This paper will provide an overview of Sunshine hydrometallurgical technologies including the applicability of Sunshine technology to the recycling of precious and base metals.

Jan 1, 1995

By Joo Hyun Park, Kyu Yeol Ko

The viscosity of the CaO-SiO2-xMnO-yCaF2 slags (C/S=1.0; x=10, 40%; y=0 to 15%) was measured to clarify the effect of CaF2 on the viscous flow of molten slags at high temperatures. Furthermore, the Raman spectra of the quenched glass samples were quantitatively analyzed to investigate the structural role of CaF2 in a depolymerization of silicate networks. The critical temperature of the slags abruptly increased at 15%CaF2, which was confirmed to originate from a crystallization of cuspidine using XRD analysis. The viscosity of the slags continuously decreased by CaF2 addition in the 10%MnO system, whereas the viscosity of the 40%MnO system was not significantly affected by CaF2 addition. The effect of CaF2 on the viscosity of the slags was quantitatively analyzed using micro-Raman spectra of quenched glass samples accompanying with a concept of silicate polymerization index, Q3/Q2 ratio. A polymerization index continuously decreased with increasing content of CaF2 in the 10%MnO system, whereas it was not affected by CaF2 in the 40%MnO system. Consequently, the bulk thermophysical property of the CaO-SiO2-MnO-CaF2 slags was quantitatively correlated to the structural information.

Jan 1, 2014

By John Snowberger III, J. Brent Hiskey

The electrochemical dissolution of super alloys containing different amounts of rhenium was investigated. The initial part of the investigation focused on the anodic dissolution of rhenium from second-generation (3% Re) and third-generation (6% Re) nickel based alloys. Exploratory electrochemical tests were conducted to evaluate solution chemistries and to establish fundamental dissolution behavior of the alloys. These included rotating disc electrode (RDE) cyclic voltammetry, linear sweep voltammetry, and chronoamperometry tests. Electrolytes comprising sulfuric acid, hydrochloric acid, and ammonium sulfate were examined. Of these, a 0.1 M HCl solution proved to be extremely effective for electrochemical dissolution of samples of CMSX-4, CMSX-10, and SC-180 alloys. This paper discusses in detail the electrochemical behavior of these alloys.

Jan 1, 2014

By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carned out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XQ >10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

By Chen Zhang

Polycrystalline Ti-rich NiTi thin films have been deposited from a single NiTi target using a DC magnetron sputtering system. Free standing film was obtained by using a single crystal silicon substrate. Thickness ofthe thin films is controlled at around 12 pm. In this investigation, the effect of deposition temperature on the microstructure and transformation temperatures of the thin films is studied. Influence of post heat treatment temperatures on the properties of the thin films is also investigated. Transformation temperatures of the thin films are determined by differential scanning calorimetry (DSC). The surface microstructure of the thin films is studied using a scanning electron microscope (SEM), and the crystallinity is determined using x-ray diffractometry. It is found that the thin film deposited on a hot substrate is crystalline even when the substrate temperature is as low as 300°C, while the normal crystallization temperature for an amorphous thin film is around 500°C. The microstructure of the film deposited on a hot substrate shows a very fine grain size. The grain size increases with increasing substrate temperature during deposition. The effect of post deposition heat treatment on grain size is minimal.

Jan 1, 1999