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By Alicia E. Ares

316 L Stainless Steel samples were solidified directionally under conditions which produced the columnar to equiaxed transition. The position of the transition was located in each sample and the distance from the bottom of the ingot was measured. During solidification the distribution of temperatures were measured by means of thermocouples located strategically. From the measured temperatures the following parameters were derived; the local temperature gradient, the cooling rate and the velocities of the liquid and solidus fronts. Comparing the location of the transition and the values of these parameters it was found that the temperature gradient reaches negative values of as low as -13.44 "C/cm, and velocities of the fronts of around 0.1 cm/s. Also, a supercooling of 5.81°C were measured which was associated with the supercooling for the nucleation and growth of the equiaxed grains ahead of the columnar front. In addition the primary and secondary dendritic spacing was measured in both regions. The spacing was compared with the predictions from available models. The results are presented and discussed in the frame of the results obtained for other alloys

Jan 1, 2002

By Peter C. Hayes

"The high temperature reduction of solids through the use of reactive gas atmospheres has application in a wide range of industrially important processes. Whilst significant advances have been made in understanding and describing these processes, some key aspects of the chemical reactions and reaction mechanisms operating in these systems, for example, the transformation from metal oxide to metal, remain poorly understood. A number of different product morphologies have been identified in these reaction systems and the reaction rates have been shown to be critically dependent on the product structure.Theoretical examination of the elementary process steps taking place in the region of the gas/metal/metal oxide interface, combined with electron microscope studies of the resultant product microstructures, have enabled the key process and material variables responsible for the development of the various product morphologies to be identified. By considering i) established criteria for the stability of moving interfaces in a thermodynamic potential gradient, ii) the relative rates of chemical reactions on the oxide and metal surfaces, and iii) key process phenomena and physico-chemical properties of the solid phases, the mechanisms and conditions for the formation of various product morphologies are identified. Interestingly the analysis points to direct analogies between these phase transformations and, the phenomena and microstructures observed in metal solidification, and the potential to develop generic models of these fluid/solid reaction systems."

Jan 1, 2013

By Sarah Beutner Mavrogenes

The mineralogy of three slags from a domestic secondary copper refinery were studied by applied mineralogical techniques to determine the: 1) phases present, 2) phase chemistry, 3) phase abundance, 4) associations, 5) crystalline habit, 6) grain size, 7)microtextures, and 8) causes for certain metallurgical problems, such as metal losses to the slags. The slags were produced by skimming the bath prior to melt-down to allow heat from the flame to reach the bath. The first slag is highly viscous and all three slags contain a large amount of copper. The "first slag", which is skimmed prior to treatment of the bath with fluxes, contains metallic copper, cuprite, delafossite, magnetite, Mg-hercynite, common spinel-chromite solid solution, picrochromite-chromite solid solution, common spinel-picrochromite solid soiution, gahnite, cassiterite, silica-rich glass, and corundum. Its abundant solid refractory phases make the slag difficult to skim. The "soda-rich slag", skimmed after the treatment of the bath with sodium carbonate flux, contains cuprite, delafossite, magnetite, cassiterite, Na-Al-silicate, and Na-Al-Ca-silicate. It contains less metallic copper than the first slag and lacks the refractory minerals. The "phosphorus-rich slag", skimmed after treatment of the bath with a copper phosphide flUX, contains metallic copper, cuprite, delafossite, berlinite, cassiterite, silica, apatite, Cu-Fe-rich apatite, copper phosphate, Cu-Fe-phosphate, and a Pb-phosphate. In contrast to the above three copper-rich slags, recent charges have produced a silver-copper-rich slag. The "silver-rich slag", skimmed after the treatment of the bath with a copper phosphor ide-borax flux, contains, cassiterite, delafossite, cuprite, a Na-Al-silicate, magnetite, metallic copper, MgO, common spinel-chromite solid solution, and wollastonite. Silver ranging from 0.05 to 2.02% was found by atomic absorption and inductively coupled plasma spectrometry analyses in the metallic copper phase.

Jan 1, 1989

By Michael I. Morris

The U.S. Department of Energy's (DOE's) Transuranic and Mixed Waste Focus Area (TMFA), funded from fiscal year (FY) 1996 though FY 2002, was tasked with finding solutions for the mixed waste treatment problems of the DOE complex. During TMFA's initial technical baseline development process, three of the top four technology deficiencies identified were the need for amalgamation, stabilization, and separation/removal technologies for the treatment of mercury-contaminated mixed waste. The Mercury Working Group (HgWG), a selected group of representatives from DOE sites with significant mercury waste inventories, assisted TMFA in soliciting, identifying, initiating, and managing efforts to address these areas. Solicitations and contract awards were made to the private sector to demonstrate both the amalgamation and stabilization processes using actual mixed wastes. The goal was to develop separation and removal processes that will address DOE's needs. This paper discusses the technology selection process, development activities, and the accomplishments of TMF A through these various activities.

Jan 1, 2003

By Fathi Habashi

During the recovery of copper, nickel, zinc, and lead from their sulfide ores, large amounts of sulfur dioxide are generated. A fraction of this gas is captured and transformed into sulfuric acid and liquid SOl and the remainder is emitted to the atmosphere. Numerous proposals were made to solve this problem. Hydrometallurgy offers the only valid solution by which elemental sulfur instead of sulfur dioxide can be produced. Sulfur can be easily stored, transported long distances, or transformed into S02 and H2S04 when desired.

Jan 1, 1996

By Akira Yazawa

Experimental results for the distribution ratios of various elements between the slag, matte and/or copper in the silica-saturated copper smelting system were summarized. The experiments were carried out under an oxidative smelting condition with S02 gas flow, and also a reductive smelting condition equilibrating with metallic copper or iron. To evaluate the results thermodynamically, the availability of one atom cation base expression for the constituent compounds is emphasized from both of theoretical and practical standpoints. Both of oxidic and sulfidic dissolutions in slag are postulated for some elements such as copper, nickel and lead., and the experimental results are reasonably explained thermo-dynamically. The results for the mutual solubility between matte and ferrite slag and the distribution of minor elements between liquid copper and ferrite slag are also discussed.

Jan 1, 1983

By A. Mezei

A process has been developed to recover cobalt, gold and bismuth from the NICO deposit in Canada. The process consists of a bulk rougher flotation followed by an optional separation by flotation to produce a bismuth concentrate and a cobalt concentrate, grading on average 12.8 % Bi and 1.8% Co, respectively. Cobalt is leached by pressure oxidation at 97% efficiency, producing a pregnant solution suitable for further processing. Before optimization, about 38% of the bismuth is recovered in the selective concentrate, wherefrom it is recovered by ferric chloride leaching followed by cementation, at overall efficiencies exceeding 98%. The gold is recovered from the cobalt and bismuth leach residues by cyanidation, at 95% efficiency. Previous work described the results of the leaching of the concentrates, recovery of gold (Part I) and the recovery of bismuth (Part 11). This work describes the results of the cobalt recovery testwork and the resulting conceptual flowsheet. The sulfur dioxide-oxygen system was the most efficient for the oxidationlprecipitation of iron and arsenic from cobalt bearing pregnant leach solutions, producing purified solutions assaying <1 mg/L As and <8 mg/L Fe. The efficiency of cobalt solvent extraction (from the resulting purified PLS containing about 1 g/L Co) ranged from 9 1 to 98%; the co-extractions ranged from 88 to 100% for copper, from 28 to 33% for magnesium, from 6 to 7% for calcium and from 96 to 98% for zinc. Sulphide precipitation processes (using either sulfur dioxidelelemental sulfur or sodium sulfide) produced residual copper concentrations in the cobalt strip solution ranging from 0.1 to 2 mg/L Cu. About 90% of the calcium and magnesium were separated by scrubbing the organic with cobalt sulfate, producing residual concentrations of 12 mg/L Ca and from 180 to 330 mg/L Mg in typical feed solutions directed to cobalt carbonate precipitation tests. Cobalt carbonate precipitation efficiencies ranged from 75 to 78% when calcium and magnesium co- precipitations were restricted from 8 to 17% and 0.3 to 0.4%, respectively. The limits required by most stringent specifications on commercial grade cobalt carbonate products were met or exceeded.

Jan 1, 2002

Thermodynamics and kinetics? of the removal of Va elements (As,Sb,Bi) from copper were investigated 1n the fire relining by alkaline carbonate fluxes such as Li 2co3 , Na 2CO3 and K2CO3. The distribution coefficients of As, Sb and Bl between alkaline carbonate fluxes and mo) ten copper were ?obtained at 1200°C under the different oxygen potentials. As and Sb were easily removed from copper to fluxes as pentavalent oxide form. On the other hand, Bi was hardly removed except by a Ll2CO3 flux. The removal rates of Va elements from copper were also measured In the temperature range of 1150°C.- 1250°C. The removal rates of As and Sb were much higher than that of Bi. The removal rates of Va elements showed the same order of the distribution coefficients. The removal rate could be expressed by following equation. (1).

Jan 1, 1987

By M. S. Moats

Galvanic stripping, in conjunction with solvent extraction, has been proposed as a technical option to the challenging problem of iron removal in certain hydrometallurgical processes. The galvanic stripping process is based on the ability of a solid metal to directly reduce ferric ion to the ferrous state in an organic media. Stripping the iron into the aqueous phase is then easily accomplished. Previous work has shown the reaction kinetics and efficiency are affected by such operating parameters as water and oxygen contents, temperature, time and metal reductant. In this study, the optimum operating range for some of these variables was determined. Both zinc and iron metal were used in the separate stripping of iron from D2EHP A. Reasons for the differences in the extent of the reaction obtained using the various conditions are discussed.

Jan 1, 1996

Physical and chemical methods were investigated to tower thorium levels in Eneabba Ilmenite from the natural levels of 180-500 ppm to give Becher Process synthetic rutile with less than 100 ppm thorium. Chemlcal treatments, but not physical separations were successful. A pilot plant trial of a sodium hydroxide leach (25M NaOH at 75°C and 40 wt% solids for Ih) followed by a sulphuric acid leach (3M H2S04 at 90°C and 60 wt% solids for 211) confirmed that thorium could be removed to below 100 ppm. However, the activity of the ilmenite was not lowered to the same extent

Jan 1, 1996

By Kenneth L. Nash

The control of solubility of waste actinide ions, by conversion to highly insoluble mineral phases has been demonstrated in the laboratory. Actinide metal ions are removed from neutral pH solutions by a combined ion exchange-decomposition-mineralization process based on the application of the naturally-occurring hydrolytically unstable.polyphosphate organic compound phytic acid.

Jan 1, 1999

By Graham Cooke, Abhishek Lahiri, Animesh Jha, E. Jeya Kumari

"CO2 reduction by alternative energy devices such as wind-power, electric vehicles utilize rare-earth elements (REE) in several forms; such as in piezo-electric devices, batteries and magnetic materials. In 2010, the 95% of Rare Earth supply is controlled by China, compared to USA being dominant supplier in the 1980s. The dependence upon a single source of lanthanides has prompted the utilization of lower grades of titaniferous mineral concentrates, which often have rich seams of REE. We propose a new methodology, which utilizes the low-grade minerals for the extraction of synthetic rutile and also significant quantities of REE. We demonstrate the alkali roasting of lower grades of mineral concentrates and subsequent leaching in an aqueous medium for preferential flocculation of REE during the extraction of synthetic rutile. Changes in mineral structure during alkali roasting and leaching determine flocculation of REE and permit their separation at the front end of unit process.The physical chemistry and crystal structure of minerals in equilibrium with alkali and aqueous medium play an important role, which we explain by demonstrating the changes in the crystal structure. The quantification of separation of RE oxide via chemical analysis suggests that it may be possible to separate rare-earth oxides between 50 and 80% of the initial concentration in the non-magnetic fractions of ilmenite, for example. The microstructural and X-ray diffraction analysis points out that the presence of alumina and roasting with potassium based alkali enhances the separation and flocculation of rare-earth elements at the front end of the process after roasting. The process allows the recovery of CO2 generated by recycling into the process for the regeneration of alkali."

Jan 1, 2011

By Brian Balmforth

Solvent extraction has been applied successfully to the recovery of a range of metals from a variety of process streams. Particular benefits are derived from the use of new highly selective extractants. These will be exemplified by case studies including the recovery of zinc from sulfate and chloride media using ZENECA&apos;s new extractants which show a very high selectivity over iron and the recovery of antimony and bismuth from copper refinery electrolytes using ZENECA&apos;s strong and selective extractant DS5834. The conclusions are drawn that solvent extraction is a cost effective technology for metal recovery and recycling, even when used to treat relatively small volume/low concentration process streams, and that it can provide the essential enabling components of a larger system for waste minimisation programmes.

Jan 1, 1996

By A. González

Arsenic is one of the main contaminants present in Chilean copper concentrates and its abatement represents a challenge for the process metallurgy, particularly under the strong environmental requirements in the global community. The possibility to form ferric arsenate directly from a gas phase by means of a heterogeneous reaction between an arsenic gas bearing and iron oxide was studied at laboratory scale. A thermodynamical analysis for the system Fe-As-O-S has been initially made, in order to obtain the stability conditions for the ferric arsenate or other FeAsyO2 type compounds. Experiments were made using an hematite sample suspended in a thermogravimetric device. AS4O6 gas generated from solid AS2O3 that was passed through the iron oxide sample and its instantaneous weight change was recorded directly. A kinetic study for the AS4O6 volatilization was made to control the gas composition. A chemical control between 300 and 600°C with an apparent activation energy of around 14 Kcal/mol As2O3 was determined. The samples after the reactions were chemically and XRD analysed. Arsenates detected corresponds to complex compounds. Results shows a dependence on temperature and oxygen content in the gas phase. The kinetics for iron arsenates formation is slow, reaching an arsenic capture of 6% after 80 minutes of reaction when an oxygen content of 50% is fed continuously at 800°C and 3,56% As in the gas. Experiences made at the same temperature but under higher oxygen content in a closed reactor, allowed arsenic capture close to 60%. For higher temperatures the capture is considerably lower.

Jan 1, 2003

By Zhang Duomo

A novel homogenous precipitation method, including microwave heating, solution conductivity controlling and freeze drying, was developed for the preparation of US nanoparticles. The effects of the precipitation conditions on the structure and morphology of CdS particles were discussed individually. It was found that under the experimental conditions the particle sizes were controllable in the range of 14nm to 100nm. Blend-type CdS was obtained from nitrate or sulphate solution and the more stable wurtzite-type US was obtained from chloride solution, which was ascribed to the coordination of C1 and Cd2+ altering the supersaturation of the solution as well as the different growth units and their connecting patterns, In the precipitation process the surface of US nanoparticles were surface modified with CH3CHSCOOH. The results demonstrate that the bifunctional thiols of thioglycolic acid modified the surface through Cd-S coordination bonding and the induced counter ion AOT-SO3 as the balance charge further increased the stability and dispersity of US nanoparticles. This surface-modified US nanoparticles had been used to prepare nonlinear optics and self-assemble catalysts.

Jan 1, 2003

By L. A. Bertram, F. J. Zanner

"The goal of this paper is to present a tool to simulate transient melting of the electrode tip. This capability is needed to develop and test furnace control algorithms since experimental determination is difficult and expensive. Simulation incorporates parameters (including arc voltage, arc current, electrode gap and furnace pressure) from previous quasi steady experiments with 460 mm diameter Inconel 718 electrodes.Cathode heating rates (determined by classical as well as experimental arc models) are linked to these independent variables. After radiative loss adjustments to the heating, transient one dimensional melting is computed. IntroductionThe vacuum arc remelting (VAR) process attempts to improve the physical and chemical homogeneity of a static-cast electrode by remelting and solidification in a quasisteady manner. To achieve steadiness of furnace operation requires automatic controls based on inputs measuring physically relevant state variables of the process. Previous industrial scale VAR studies (1,2,3) involving stainless steels, superalloys, and other alloys have provided a basis on which control strategies of some generality can be proposed (4). Of these measurements, the data for Inconel 718 is the most complete, so discussion in this paper is restricted to this alloy.Studies of the In 718 alloy subjected to the VAR process have established that melt rate M (kg/hr) depends not only on the melt current 1m (kA) supplied to the furnace, but also on ambient gas pressure of CO, PCO (micron), and electrode gap ge (mm) as well (1):"

Jan 1, 1986

By S. Neven

The smelting of copper anode slimes, a material which contains mostly lead, silver, copper and selenium, has been practiced for many years with a view to recovering the silver and associated small amounts of gold. However, a theoretical understanding of the process has been lacking and this handicaps efforts to improve and intensify smelting operations. In the past few years work has been done in this area and this work will be reviewed in the paper. The underlying thermodynamics of the oxidation of silver-copper selenide mattes has been developed and used as a basis for the construction of a computational thermodynamics model which attempts to predict the composition of all condensed phases during the course of smelting. The model will be outlined and its successes in matching experimental data, as well as its current deficiencies, will be considered. Supporting work on the thermodynamics of silver solubility in slags, on activity-composition relationships in the Ag-Se system and work in progress on the oxidation state of copper in the slags will be reviewed. These projects are designed to provide further detailed data which will improve the robustness of the thermodynamic model.

Jan 1, 1999

By C. -S. Jiang

In most copper refineries, addition agents are added at predetermined rates with no further monitoring of their activity or concentration in the electrolyte. Increasingly stringent cathode quality requirements, and a desire for better process control in tankhouse operations, have recently directed a number of refineries to search for a better addition agent control strategy. Extensive development work has been carried out at the Noranda Technology Centre for the monitor in of glue and thiourea in copper refinery electrolyte using cyclic voltammetry (cv~. Data from both synthetrc and commercial electrolytes are presented, showing the ability of CV to produce reliable and easily identifiable fingerprints of addition agent concentrations in copper refinery electrolyte.

Jan 1, 1991

By J. D. Miller

Gold adsorption from cyanide solutions by activated carbon has been studied at great length during the past decade. Findings from past research are reviewed and discussed with respect to structural features of various carbons, including carbon black, activated carbon, graphite and diamond.

Jan 1, 1991

By P. Maraboutis

Iron removal by precipitation as jarosite from Fe-Ni-Co sulfate solutions, (synthetic or real, resulting from laterites leaching) has been investigated. Precipitation was carried out at 95 C, and at an initial pH 1.6, which was either kept constant with CaCO3 or Li2CO3 additions, or left to drift with the evolution of the reaction to lower values. The precipitation of K-, NH4- and Na- jarosite was initially examined using synthetic solutions. In all cases, hydronium ions were incorporated into the precipitate as well. Residual iron in solution was lower (0.2-1 g/1) and equilibrium was achieved faster (within 4-8 h) when precipitating K¬jarosite at constant pH, using CaCO3 for neutralization. Nickel and cobalt losses were small. Na- jarosite precipitation was also studied from real solutions with high initial iron content, under constant pH=1.5, controlled with CaCO3 additions, and it was shown that low residual iron concentration in solution (0.3-0.5 g/1) can be achieved again, with relatively small nickel and cobalt losses. The thickening and filtration characteristics of the precipitates were excellent in all cases examined.

Jan 1, 1988