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By M. Shevchenko

Integrated experimental and modelling research program on the phase equilibria and development of thermodynamic databases of the lead and copper metallurgical gas/ slag-matte-metal-solids systems (PbO-“Cu2O”-FeO-Fe2O3- ZnO-CaO-SiO2) is being undertaken to support improvements in the pyrometallurgical smelting and recycling processes. This is the first systematic investigation of phase equilibria of slag systems in equilibrium with Pb metal, providing information for systems in which copper coexists in slag with lead or zinc as major components. The experimental studies involve high-temperature equilibration of synthetic samples, rapid quenching, and measurement of the compositions of equilibrium phases using electron probe X-ray microanalysis (EPMA). FactSage-based thermodynamic database development is integrated with experimental research. Initial thermodynamic assessments are used to identify priority compositions and conditions for experiments, which are planned to provide specific data to assist thermodynamic optimisation. Significant improvement in the accuracy of the phase equilibria description is achieved. Continuous database improvement and extension to include new elements are targeted. Example of industrial application is given.

By David M. Davidson

Seven intrusive phases have been mapped to date in the 1 b.y. Red Bluff Granite Complex (RBGC) near El Paso, Texas. This batholith is 20 km2 in area and intrudes older supracrustal units as well as a trachyte ignimbrite cap. Two early microgranite sills are spatially separated 6 km from a porphyritic, three-phase "ring complex" by a tin-bearing, biotite granite which cores the RBGC. These units are intruded, in turn, by a riebeckite granite which locally exhibits lineated and pegmatitic textures as well as exceptionally high light REE and Zr values (800 ppm La; 3,000 ppm Zr). The riebeckite granite is exposed in three separate occurrences within the Franklin Mountains. REE values in the RBGC are depleted in HREE and show distinct negative Eu anomalies. Typical La/Yb ratios are 5:1-2:1 with Eu values ranging from 10-80 ppm. The mineral source of the high REE values in the riebeckite granite has not yet been specifically identified, but is believed to be zircon.

Jan 1, 1988

By Jing Lin, Yuan Xu, Qingcai Liu, Dengfu Cheng

"Smelting reduction technology has been developed greatly in recent years. But one of the key problems for this technology is about the refractory that used as lining material in the molten bath. Investigation and test shown that corrosion rate of refractory was much higher and the corrosion mechanism was much more complexity in the molten bath of smelting reduction with iron bath than that of the blast furnace and rotary furnace technology [l-5]. The corrosion behavior and corrosion rate of Al2OrC-ZrO2 series refractory in the melt of smelting reduction with iron bath have been studied by rotary immersion and quasi-static immersion test in this paper. The major factors that affect the interaction between the melt and refractory were investigated. The test results shown that the corrosion rate of AI2O 3-C-ZrO2 series refractory decreased with the ZrO2 increasing when ZrO2 content was from 3% to 10%. Ferrous oxides content, relative moving speed between the melt and refractory and temperature of the molten bath were the important factors that affect the corrosion rate. But the ferrous oxides concentration was the most important one. The corrosion rate was increased as a linear relation with the rising of ferrous oxides content of the melt. The corrosion rate in the quasi-static immersion was much less than that of the dynamic immersion (rotary immersion) for the Al2O 3-CZrO2 series refractory in the same testing condition. The corrosion mechanism of Al2OrC-ZrO2 series refractory is: graphite oxidized in advance, then interaction between the constituents of refractory and melt taken place and deteriorate layer of refractory and new compounds were formed, the properties of refractory was changed.IntroductionSmelting reduction with iron bath is a typical technology [3, 4, 6]. The obvious features of the melt for smelting reduction technology with iron bath are much higher ferrous oxides and much more complexity melt composition and structure than that of the blast furnace technology [2, 5-8]. The properties of the melt were changed dynamicilly and constantly in reduction process. On the other hand, the behavior of the melt depends on the activity and the reduction rate of ferrous oxides in the molten bath[9]. Because of the high concentration of ferrous oxides in slag and high reduction rate in the molten bath, the corrosion behavior and corrosion mechanism of the refractory lining by melt are an important factor in development of the technology of smelting reduction with iron bath. Up to now, improving refractory quality to anti-corrosion of melt and developing high quality and long term refractory used as the lining refractory materials in the molten bath of the final reduction furnace are also the most important questions for developing smelting reduction technology."

Jan 1, 2000

By D. J. Chaiko

Certain radionuclide ions (e.g., TcO4) exhibit unusually strong Affinities toward the polymer-rich phase in aqueous biphase systems generated by combinations of salt solutions with polymers such as poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG). Thus, aqueous. polymer ,phases could potentially be used to selectively extract these ions during pretreatment of radioactive tank wastes at Hanford. To help develop a fundamental understanding of the interactions between various ions and polymers in aqueous solution, interaction enthalpies between sodium -perrhenate and a random copolymer of PEG and PPG (UCON-50) were measured by microcalorimetric titration. An entropy compensation effect was observed in this system in which changes in enthalpic interactions were balanced by entropy changes such that the interaction free energy remained constant and approximately equal to zero.

Jan 1, 1999

By F. D. S. Marquis

An investigation of the mechanisms of formation of two types of porosity-primary and secondary-their characterization, evolution during processing, and effects on the mechanical behavior (fracture, fatigue, and failure) of 7X50 and 2X24 alloys has been conducted. The mechanisms of formation of three forms of primary or cast porosity were investigated, and each form was characterized: (a) macroscopic shrinkage porosity-MSP); (b) microscopic interdendritic porosity (MIP); and (c) hydrogen gas porosity (HGP) or primary hydrogen porosity (PHP). The mechanisms of formation of four forms of secondary or thermal/thermomechanical porosity were investigated, and each form of porosity was characterized: (a) high temperature oxidation (HTO). internal hydrogen precipitation (IHP), or secondary hydrogen precipitation (SHP); (b) preheating blistering porosity (PBP); (c) eutectic melting porosity (EMP);and, (d) dissolution micro void formation (DMF). The evolution and interactions of the primary and secondary types of porosity (w.ith special emphasis on PHP and SHP) during industrial and laboratory processing and their effects on the fracture and failure behavior of both types of alloys (with special focus on fatigue crack initiation and propagation) were investigated.

Jan 1, 1996

By Zhang Hengzhong

Based on thermodynamics of surfaces and a proposed two-dimensional state equation for surfaces, the relationship between the surface tension (Y) of a solution and the activity (a1) of its component (i) was derived: (1/Y)r2-.¬E (ai/Yl) The derived equation was verified with reported experimental data of water-alcohol systems and water-acetone system, the calculated results showed astonishing coincidence with experimental. Applications of the equation to the five matte systems Cu2S-FeS, Ni3S2-FeS, FeS-PbS, Cu2S-PbS and FeS-Cu22S-PbS also demonstrated that at given matte compositions the calculated surface tensions agreed with experimental fairy well.

Jan 1, 1993

By Xuan Cheng

The electrochemistry of sulfide mineral flotation is reviewed with particular emphasis on galvanic interaction among minerals and grinding media, and its relevance to flotation of complex sulfide ores is discussed. Surface alteration due to galvanic interactions among chalcopyrite, pyrrhotite and mild steel is analyzed in terms of voltammetric and chronoamperometric studies on individual minerals and through galvanic current measurements in 2- and 3- electrode combinations. The results are related to laboratory flotation behaviors of chalcopyrite-pyrrhotite mixtures simulating copper-nickel bearing Duluth gabbro.

Jan 1, 1993

By J. E. Clemson

The Black Pine sediment-hosted, disseminated gold deposit is located in Cassia County, Idaho. Gold mineralization occurs in flat-lying zones 50 to 100 feet thick. Total geological ore reserves are 5.6 million tons grading 0.049 oz/t. Ore types include: non-carbonaceous, oxidized ore; carbonaceous, sulfide ore; and carbonaceous, partly oxidized ore. In the oxidized ores, native gold grains commonly occur in porous hematite pseudomorphs that have replaced disseminated framboidal and euhedral pyrite, and this gold should be readily leached by cyanide solutions. Approximately 4 % of the native gold observed in the oxidized ores is locked within gangue and may be refractory to cyanide solutions. Native gold has not been observed in the unoxidized samples, all of which are characterized by primary sulfides. It is suspected that the bulk of the gold mineralization in the sulfide ore occurs as submicroscopic particles within pyrite and will be refractory to cyanidation. It is believed that much or all of the gold observed in the oxidized samples was originally in pyrite but was released and re-precipitated during oxidation. The degree of oxidation of the pyrite and the presence/absence of preg-robbing carbonaceous material is used as a guide in delimiting zones of mineralization amenable to heap leaching.

Jan 1, 1988

By Dmitri Nassyrov, In-ho Jung

"All relevant thermodynamic and phase diagram data in the CaO-Fe10-CaF2 system were critically reviewed. One set of model parameters describing the Gibbs energy of all phases has been obtained as a result of critical evaluation of the available data and optimization of the model parameters. The Modified Quasichemical Model was used to describe the interactions in the liquid phase. All calculations were performed using the FactSage thermochemical software.IntroductionSlags contaimng CaF2 are of significant interest to the steelmaking community. Notable examples of slags containing significant amounts of CaF2 include Electro-slag Remelting (ESR) slags [1] and mould flux for continuous casting [2]. The role of these slags is, among other things, to refine steel by absorbing inclusions and dissolved impurities. During slag-steel interaction, some iron from the steel will inevitably get oxidized and form iron oxides which will dissolve into the slag. With this in mind, it is important to understand the interaction between CaF2 and Fe,0 for accurate prediction of slag composition and process optimization. A thermodynamic optimization of the CaO-FetO-CaF2 was thus undertaken."

Jan 1, 2013

By D. F. Suarez

Spontaneous nodulation leading to growth of well developed glossy spheroids (generally hemispheres) of up to 0.06 cm width in 120 min has been observed during copper electrodeposition with certain levels of glue, thiourea and C1-. Thiourea alone can produce spontaneous nodulation but addition of glue and/or Cl- is required for rapid and sustained growth. In most cases once the glossy nodules develop they consume the majority of the copper deposited; thus, the specific current densities (and hence copper electrodeposition rates) on the glossy nodules are about an order of magnitude or, more greater than on the adjacent planar surfaces. The texture of the adjaoent planar surfaces is not glossy in appearance but is well faceted showing the usual deposition grain structure for such additives. Cathode potentials when spontaneous nodulation occurs are about TOO my more negative than with usual copper electroplating. This fact associated with evidence of extremely high levels of cathode surface passivation based on cyclic voltammograms indicates that the conditions which lead to spontaneous nodulation result from a very tightly adsorbed additive surface film. This film breaks down in specific points initiating the glossy nodules which then grow at extremely rapid rates. Current density is also important in spontaneous nodulation. At equal deposition times a current density of 21.5 mA/cm produced much larger glossy nodules than at 48 mA/cm2. The surface concentration of the glossy nodules was much greater in the latter case, however. The role of current density is still not well understood. The role of it as well as the relative roles of the three additives, thiourea, glue and Cl- in spontaneous nodulation is presented. Preliminary results and some possible correlations of these to help explain spontaneous nodulation are presented. It is believed that tankhouse upsets where cathode nodulation occurs may be related to this phenomenon.

Jan 1, 1987

In the new flowsheet for Inco Limited's S02, Abatement Project at the Copper Cliff, Ontario operations, a copper/nickel sulphide flotation concentrate will be flash smelted, then converted to Bessemer matte. As in current practice, this will be slow-cooled and separated into components by magnetic separation and flotation. The copper content will emerge as a chalcocite concentrate (impure Cu2S), containing some nickel. This copper sulphide will be converted to copper metal.

Jan 1, 1993

By Charles A. Sorrell

Two red muds, two fly ashes, and several aluminosilicate minerals were subjected to direct treatment with concentrated H2SO4 at temperatures of 175°C and below. X-ray analysis showed that virtually all the sulfate reaction products remained in the solid residue because of their low solubilities in x SO Substantial portions of the Al2O3 Fe2O3TiO2, Na2O, and K2O components of the materials reacted to form water soluble sulfates, which were then removed by H2O leaching at 55°C. The solid residue after water leaching consisted largely of amorphous silica and, in lime bearing compounds, CaSO4, The reaction and leaching processes were effective in removing all or nearly all the Al2O3. Fe2O3, TiO2, Na2O, and in lime components in the fly ashes, red muds, china clay, bentonites, the nephelioe fraction of nepheline syenite, and a plaster insulating brick composed of anorthite and mullite. Reaction with potassium feldspar and petalite took place, with formation of alkali aluminum sulfates, but the reaction rates and yields were extremely low. Potassium feldspar can be heated with Na2O and x O in air at 700°C for 24 hours, or with CaO at 1000°C for 24 hours, after which the reaction product kaliophilite, nepheline, and leucite-like phases, prove to be very susceptible to H2SO4, reaction and H2O leaching, providing yields near 100% of the Al2O2 content. An alternative method of H SO treatment consists of heating the sample in a silica tube and passing H2SO4 vapor over it. Preliminary results indicate that this method can be effective in enhancing the kinetics of reaction with the Al O component of potassium feldspar and offer the possibility that formation of Al2 (SO ) Fe2(SO4)3 and TiOSO4 can be accomplished selectively by taking advantage of the fact that the upper stability limits of the respective sulfates in the presence of H2SO4 vapor will be different.

Jan 1, 1982

By Guohui Zheng

The ever increasing quantities of solid wastes generated by various industries are at the source of the growing need for proper waste disposal methods. Thermal treatment of combustible wastes is a proven technology which permits the reduction of hazardous material having to be landfilled. However, this method is not universally applicable to waste disposal. For example, the transferal of heavy toxic metals into the thermal remediation products is a major issue of public concern. This paper focuses on the analysis of morphology changes from solid sludge to ash which is a product of the sludge combustion. The morphological parameters analyzed were particle size and external surface. They were determined using Jeol 840 Super Probe. The experiments were conducted in a computer-controlled high-temperature combustion system consisting of the thermogravimetric furnace coupled with Fourier transform infrared spectrometer (TGA-FTIR). Sludge particles were made of complex fibers trapped in the aluminosilicate matrix. At low temperatures, up to 680 K, the solid residue looked similar to the initial sludge. Between 680 K and 1180 K the sludge underwent intensive burning and steadily changed into powdered ash. At the temperature of 1050 K the ash was composed of separate, flat flakes with sizes ranging from 5 to 20 um. At 1470 K the flakes aggregated into large particles. The surface observed at 1670 K was a mixture of mullite crystals. Such structure could result from the solidification of the ash material after its melting. Morphological changes influenced the distribution of metals in the solid residue. For example, Cr was concentrated in small aggregates. Such distribution should allow for recovery of valuable metals from the solid waste residue.

Jan 1, 1996

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 Cong Wang, Siyang Long, Pengcheng Zhang, Haibin Zuo

This paper introduced the research progress of microwave treatment on coal. The mechanics of microwave treatment mainly include thermal effects and non-thermal effects. Thermal effects, which lead to cracks and changes of pore structure, attribute to the selective heating of microwave. Non-thermal effects involve the removal of oxygen functional groups, improvement of coal rank and decomposition of minerals. Therefore, microwave treatment of coal has a lot of potential applications, mainly including drying, desulfurization, improvement of grindability, enhancement of coal-water slurry property and change the combustion and gasification properties.

Jan 1, 2016

By Suzzann Nordwick

Over the past decade, significant advances have been made in the development of sulfate-reducing bacteria (SRB) technology to treat acid mine drainage (AMD). Bench-scale testing, field demonstrations, and engineered applications of SRBs for the treatment of AMD will be presented. Designs include an in situ bioreactor installed in the subsurface workings of the Lilly Orphan Boy Mine in 1994, the SRB bioreactors installed at the Calliope Mine from 1998 to 2001, the integrated biological reactors built at the Surething Mine in 2001, and the ongoing development of a replaceable cartridge system. SRB technology benefits include the reduction of dissolved metal ions to insoluble metal sulfides and the neutralization of the AMD resulting from the production of bicarbonate from the oxidation of organic nutrients. This paper will address engineering design criteria including the selection of organic media and system permeability and complete mitigation of AMD. Research was funded under Interagency Agreement No. DW899388-70-01-1 between the US EPA and the US DOE and was conducted by MSE Technology Applications, Inc., through the National Environmental Technology Laboratory (DOE Contract No. DE-AC22-96EW96405) at the Western Environmental Technology Office located in Butte, Montana.

Jan 1, 2003

By Jianxun Song, Hongmin Zhu, Qiuyu Wang, Jungang Hou, Shuqiang Jiao, Xiaobo Zhu

This work presents the results of a study on the Ti3+/Ti2+ couple redox potentials vs. Cl–/Cl2 at the temperature range (673 to 1073 K) in fused LiCl-KCl eutectic by direct potentiometric method. Initial concentrations of TiClx in solvents did not exceed 5.0 mol%. Basic thermodynamic properties of the reactions TiCl2+1/2Cl2(g)=TiCl3 were calculated using the temperature dependencies of apparent standard potentials of the couples E* Ti3+ /Ti2+.

Jan 1, 2014

By Moto Goto

Onahama Smelter of Onahama Smelting & Refining Co., Ltd. has two green- charge reverberatory furnaces; the old furnace was constructed in 1965 and the new one in 1973. This paper discusses the use of oxygen-oil burners in a green-charge reverberatory furnace and also compares the copper loss in slag between the two furnaces at Onahama Smelter. During the past ten years of operation, no shutdowns of the old furnace were necessary and the smelting capacity was increased by 25% by the use of two oxygen-oil burners. These burners are suitable for a green-charge reverberatory furnace to in- crease the smelting capacity without causing an increase of the exhaust gas volume and refractory erosion. After two years of operation of the old furnace, a bottom build-up in the charging zone of approximately 50 centimeters was experienced, and this build-up has stayed at this level since then. In 1973, a new additional reverberatory furnace was put into operation. Copper content in slag of the new furnace was lower by approximately 0.15% than that of the old one during the first several months after the start-up. Investigations were then made on the effect of the bottom conditions in the charging zone on the copper content in slag.

Jan 1, 1976

By D. E. Roberts

Over 425 million used automotive oil filters are discarded in the United States each year. Estimates prior to this research claim that 10% are recycled with the remainder typically being landfillcd. Surveys conducted with ferrous scrap users and oil filter processors as part of this research reveal that at least 15% are currently being recycled as ferrous scrap. Oil filter scrap is not being used by many operations because of concerns with scrap consistency and quality. These concerns stem from trials conducted in the infancy of the oil filter recycling movement. Consistent scrap quality depends both on the content of the used oil filters and the processing technique used to produce the scrap. Technology has advanced since the first recycling trials were conducted by steelmakers. Several different types of scrap are available, including pucks, bricks, cubes, and shred. This research conducted at the University of Missouri-Rolla investigated the content of used oil filters and compares the recyclability of different oil filter sizes and designs. Filters vary by application and vary between manufacturers for a particular application. An understanding of the scrap itself as well as the concerns and problems of both oil filter recyclers and oil filter processors is necessary to increase the number of used oil filters being recycled.

Jan 1, 1996

By Vaughan R. Voller

"Over the last ten years an increasing number of heat and mass transfer models of solidification processes have been presented in the literature. A key component in these models is the coupling between thermal and solute fields. This is achieved by developing relationships based on the behavior at the microscopic scale in the casting (typically a secondary dendrite arm space). An important class of models in this respect are models that describe the local scale redistribution of solute alloy components-collectively referred to as microsegregation models. This paper explores this class of models.IntroductionModeling takes a key role in processing materials for properties. This is particularly time in solidification processes where current computer techniques allow for a detailed treatment of the critical macroscopic phenomena. Typically these macro scale models consist ·of three main coupled components.1. A model of flow in the melt and solid + liquid mushy region.2. A model of heat transfer.3. A model of solute transport.The focus of this paper is the solute transport component, in particular the manner in which process scale transport is coupled to transport ·at the local scale of the solid-liquid interface. This step requires a modeling of the redistribution of solutes at the scale of the secondary arm spaces in the dendritic mushy region-a process referred to as microsegregation. Basic microsegregation models use the limit assumptions of no mass diffusion in the solid (Gulliver-Scheil [l]) or complete diffusion in the solid (equilibrium lever rule) in a fixed and space. Recently, however, more sophisticated microsegregation models that account for finite mass diffusion and coarsening of the arm space have been developed [2-19]. In this paper governing equations for a general microsegregation model for a multi-component alloy in a coarsening and spacing _are introduced. From these general equations various models for a binary system are developed and tested"

Jan 1, 2000