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By I. S. Escobar

Copper, particularly the oxygen-free grade Cu-OFP, is a candidate material for containers for the long-term isolation and disposal of high-level radioactive waste (HLW) in underground repositories. After having been buried for a few hundred years, all oxygen will have been consumed in the repository, and corrosion of the copper will be caused entirely by contact with dissolved sulfides. Chloride is another potential corrodant, but in deep repositories where groundwater is neutral or slightly alkaline, the effect of chlorides can be ignored on thermodynamic grounds. Thus, the corrosion of copper in the presence of sulfide ion and under reducing conditions has been studied using cyclic voltammetry and Tafel slope measurements. It is possible to determine the effect of sulphide ion on copper corrosion resistance which is minimized at low temperature and also at low sulphide concentration. The presence of anions such as HCO3 under environmental conditions produces a beneficial effect because these ions are inhibitors.

Jan 1, 1999

By Michael S. Moats, Daniel Kim, Shijie Wang

"The behavior and deportment of lead, arsenic, antimony and bismuth are critical in producing high quality cathode by copper electrorefining. A critical review of research related to these elements is presented along with a comparison to industrial data, where appropriate. These elements exist predominantly in the anode as complex oxides along die grain boundaries. Upon dissolution, Group 15 elements report both to the electrolyte and slimes while lead essentially enters the slimes. The deportment of the Group 15 elements appears to be influenced by several chemical interactions which are discussed. The effect of these elements on floating slimes and anode passivation is reviewed. Under normal electrorefining conditions, lead, antimony and bismuth are thought to enter the cathode through the encapsulation of slime particles. The literature indicates that arsenic enters the cathode predominately by electrolyte entrainment. Finally, areas for future research regarding these elements are presented.IntroductionControlling lead, arsenic, antimony and bismuth is critically important for the production of high quality cathode in copper electrorefining. The reasons for this are twofold. First, ASTM Grade 1 Cathode specifications [1] for these elements are low, as listed in Table 1. Second, they can affect the efficiency of the electrorefining process (e.g., through passivation, current efficiency, slime processing)."

Jan 1, 2012

By Line Hallgren

The fluid flow in the mold during up-hill teeming is of great importance for the quality of the cast ingot and therefore the quality of the final steel products. At the early stage of the filling of an up-hill teeming mold, steel enters, with high velocity, through the nozzle into the mold and the turbulence on the meniscus could lead to entrainment of mold flux. The entrained mold flux might subsequently end up as defects in the final product. It is therefore very important to get a mild and stable inlet flow in the entrance region of the mold. It has been acknowledged recently that swirling motion induced using a twist tape swirl blade, in the submerged entry nozzle is remarkably effective to control the fluid flow pattern in both the slab and billet type continuous casting molds, resulting in increased productivity and quality of the produced steel. From the above result, we propose, swirling flow generated through a swirl blade inserted into the entry nozzle, as a new method of reducing the deformation of the rising surface and the unevenness of the flow during filling of the up-hill teeming mold. The swirling blade has two features: (1) to generate a swirling flow in the entrance nozzle and (2) to suppress the uneven flow, generated/developed after flowing through the elbow. The effect of the use of a twist tape swirl blade was studied using both numerical calculations and physical modeling. Water modeling was used to assert the effect of the swirling blade on rectifying of tangential and axial velocities in the filling tube for the up-hill teeming and also to verify the results from the numerical calculations.

Jan 1, 2006

By Henk Dijkman

Existing metallurgical operations can be optimized by implementing engineered bioreactor systems in the process configuration. For instance, metals can be recovered safely and economically from process and waste streams using biogenic sulfide. This paper focuses upon possible applications of high rate biotechnology in metallurgy and mining. Metal recovery from liquid streams (process bleed streams, leach water, waste streams), integrated removal of (fugitive) SO2, treatment of acid blowdown and other options will be described. Practical examples are given. A large-scale application of biotechnology at Pasminco's Budel Zink refinery is described. Here, acid plant blowdown is treated together with electrolyte magnesium bleed. Concentrated zinc sulfide (10 tpd) is produced biologically, eliminating the production of gypsum and closing the refinery sulfur cycle. Recovery of metals from solution at Kovehute Pribram in the Czech Republic is the second practical example. In this case, H2S is produced on-site for metal removal from an alkaline slag dump leachate. At the Caribou mine in New Brunswick, Canada, acid mine drainage is treated with biogenic sulfide. This plant is situated upstream of a lime neutralization plant. As a result, reusable ZnS is produced, the volume of the sludge (gypsum and hydroxides) from the lime plant is reduced by 50%, the sludge is free of heavy metals and the final effluent concentration of heavy metals is in the ppb range. In the second phase of this project, metals will be recovered from stored tailings, resulting in significant revenues.

Jan 1, 2002

By Osvaldo A. Bascur

Several new hydrometallurgical plants have been built in the past years. They have implemented new processes to treat new type of ores. New technologies have been used to improve metallurgical performance from the start. The cycle times between knowledge generation and innovation are often neglected in the traditional capital expenditures and building of these new process plants. The paper reviews several implementations in which they have started with new ways of using information management from the beginning. The implementation of a real time performance management infrastructure is reviewed to assist in the implementation of mine to product strategies, metallurgical mass balances, solvent extraction composition statistical process control, methods to minimize organic losses, reduce variable costs and to improve metal extraction. Several examples are provided to improve operations by simplifying the access and analysis of information from assets and metallurgical processes. Continuous improvement and innovations have been enabled to minimize start times and for faster troubleshooting and resolution of operational problems.

Jan 1, 2006

By Rivera Jose Antonio Ore

Top Submerged Lance (TSL) smelting technology is currently used in a wide range of applications in the non ferrous and waste product treatment industries. The use of TSL technology for tin concentrates smelting has been successfully applied at the Minsur Tin Smelter and Refinery at Pisco, Perú. The process is based on the air-cooled top entry submerged Sirosmelt lance, developed by Dr. John Floyd at the CSIRO division of Mineral and Process Engineering in the 1970?s. Advantages of the process include flexibility to operate the lance, main burner of the Sirosmelt furnace, with different levels of combustion stoichiometry which allows us to get from highly reducing to highly oxydising atmospheres in the smelting reactor according to the type of feed we are processing, ability to utilize cheap energy sources such as natural gas, low capital cost and an environmentally friendly operation. This presentation summarises the application of the Submerged Sirosmelt technology for smelting tin concentrates and a variety of tin containing materials like iron dross, copper dross, tin residues, low tin/antimony slags by applying recent metallurgical developments at the Minsur smelter. The impact of new feed conditions and level of impurities on reactor performance with features of process and operation control are described. As a result of these recent advances in tin smelting using TSL technology, the Minsur Tin Smelter and Refinery improved its overall tin recovery, substantially reduced tin inventories and became the second largest tin smelter in the world, currently producing more than 40,000 metric tones of refined tin per year.

Jan 1, 2006

By Michael Stelter

Lead alloys are a typical material for anodes in technical electrowinning processes. The life time of those anodes differs from 2 years to more than 5 years in tankhouse practice depending on the type of alloy, the mechanical damaging and last but not least the chemical corrosion in the electrolyte. Different types of alloys, such as PbSb, PbCa, PbAg, PbSnCa or PbAgCa have been developed and used in the past, their rate of corrosion being more or less a philosophic discussion. Comparable investigations on the corrosion behavior in dependence of the concentrations of alloying metals, the grain structure and the mechanical and thermal treatment during production have not been conducted before. In the last years the Institute for Nonferrous Metallurgy and Purest Materials of the TU Bergakademie Freiberg investigated the corrosion behavior of the typical lead alloys for metal electrowinning under comparable conditions. Correlations between different alloys, mechanical treatments like rolling or thermal treatment like annealing to the rate of corrosion were made, leading to the conclusion that grain structure and grain size are of eminent importance for the rate of corrosion in technical electrolytes. From these results new and optimized lead alloy anodes can be produced with an increase in life time of the factor 3 ? 5. The optimized lifetime in terms of corrosion stability can not protect from mechanical damaging in tankhouse practice, but with a careful practice the increase in lifetime can save a lot of money and problems.

Jan 1, 2006

By Dieter Offenthaler

Catalysts used in petroleum industry often contain valuable amounts of PGMs. The typical recycling route for those materials is the pyrometallurgical one, but this treatment way offers limited flexibility with respect to small charge weights. A new process, combining a pyrometallurgical pre-treatment step of the ceramic carriers with a hydrometallurgical leaching procedure overcomes this disadvantage. It not only allows the economical treatment of even very small charge weights, but also gives the possibility to maximize the PGM yield by individually adapting the process to the different charge materials. Due to an ingenious process design, where all leaching agents and effluents are recycled in a closed loop and therefore no waste waters leave the process, process operation becomes very economical. However, the temperature-time-regime in the pyrometallurgical pre-treatment step is of major importance for the success of the whole process. Therefore various investigations have been done to identify how the different process variables in the pyrometallurgical pre-treatment influence the subsequent leaching procedure. It turned out, that the adjustment of the correct phase-modification in the ceramic carrier materials during the pyrometallurgical treatment is the key factor of this process step. Although it is a troublesome issue to exactly adjust the correct phase modifications, it is the prerequisite to take advantage of the benefits of this new process concept.

Jan 1, 2006

By Peter J. Koros

The current wave of interest in this topic is the result of increased use of titaniferous ores or ilmenite in blast furnace burdens for the purpose of repairing hearth damage. The titanium compounds that promote deposition of ?patching? materials in blast furnaces are the cause of downstream problems in the steelmaking shops. Steelmakers historically have objected to significant amounts of titanium in hot metal (>0.10 % Ti) for several reasons: 1) accretions caused by the TiC.TiN needles that float out of the iron as it cools in transit and in transfers make the accompanying slag sticky and crusty, causing problems in desulfurization and increasing time and Fe yield loss at the subsequent raking, 2) defensive measures have been taken in treatment, such as use of argon for carrier gas, but without technical rationale for this approach, 3) difficulty in removal of the ladle slag by the raker, with subsequent sulfur addition to the vessel charge, and 4) transfer into the BOF and/or formation of a very corrosive TiO2 containing acid slag during the early part of the BOF blow which, in addition to causing lining damage, results in loss of sulfur removal capability by the vessel slag. Based on a conceptual analysis of the metal-slag-atmosphere interactions during transfer ladle desulfurization treatment, a mechanism is postulated for the apparent effectiveness of the use of argon in reducing the deleterious effect of titanium and an alternate technique, possibly more effective, is proposed. As probably the use of argon causes increased exposure to atmospheric oxidation of the titanium carbonitrides contained in the ladle slag, the same benefit can be obtained by use of either oxygen or an air blast to oxidize the noxious reaction compounds. Validity of the concept has been demonstrated in a pilot plant setting. These issues, and related effects on testing the hot metal, are examined in detail with reference to the literature and plant and laboratory experience.

Jan 1, 2006

By Ashish D. Patel, Ramesh S. Minisandram

"Vacuum Arc Remelting (VAR) is the final and, hence, critical melting step for the production of a sound, segregation-free ingot for the manufacture of alloys used in rotating components in aircraft engines. A mathematical model for this process has been developed by the Specialty Metal Processing Consortium (SMPC). The model predicts temperature distribution in the solidifying ingot, flow in the molten metal pool, and the electromagnetic field in the ingot. These predictions may be used to estimate the effect of melting parameters on the pool profile in the ingot. In this paper, typical pool shapes and flow fields during VAR of Alloy 718 and Ti-6Al-4V are presented. The differences in the pool profile are primarily due to vastly different melting conditions. The model predictions are compared to the observed pool shapes from industrial-size VAR ingots.1. IntroductionVacuum Arc Remelting (VAR) is a process in which an electrode is melted in vacuum by the heat from a DC electric arc. Metal droplets from the electrode fall into the molten metal pool, which solidifies in a water-cooled copper crucible to form the ingot, as shown in Figure I. The ingot obtained from VAR is sound, and has superior cleanliness and chemical homogeneity. Hence, the process is the final melting process for most nickel-base superalloys and titanium alloys used in the manufacture of critical rotating components (discs & blades) of aircraft engines. Modeling of this process provides an insight into the effect of melting parameters on the molten metal pool in the solidifying ingot, which is a key first step in process optimization and defect prevention. In this paper, typical pool shapes, both measured and predicted, for VAR of Alloy 718 and Ti-6Al-4Vare presented. Alloy 718 is the most common VAR-processed nickel-base superalloy; whereas Ti-6Al-4V is the ''workhorse"" alloy for titanium-based alloys."

Jan 1, 2004

By Stavros A. Argyropoulos, Henry H. Hu

"The assimilation of exothermic additions in liquid metals exhibit an array of unique coupled heat, mass and momentum transport phenomena. These phenomena are further complicated by the presence of a moving boundary.This paper describes a) A mathematical model which simulates the complex phenomena, and b) An extensive verification of the mathematical model. The SIMPLER algorithm was employed to solve numerically the pertinent partial differential equations. The computational results indicated that the exothermic heat of mixing led to a rapid increase in temperature around the moving boundary, which produced an enhanced convective flow in the liquid phase. The intensification of fluid flow around the moving boundary resulted in an acceleration of the melting process.Verification of the model was carried out in two contexts. The first was, in a low temperature physical model consisting of ice immersion in different sulfuric acid solutions. In this physical model, both temperature and velocity measurements were carried out. The model results were compared with experimental measurements and they were found to be in excellent agreement. The second context employed high temperatures, involving the assimilation of silicon in high carbon liquid iron. The model was also applied to predict fluid flow, heat and mass transfer for these high temperature experiments and a good agreement was obtained.In addition new dimensionless heat transfer correlations that quantify these complex phenomena will be presented."

Jan 1, 2001

By C. K. Gupta

Electrometallurgical processes have a definite place in the extraction technology of rare earth metals and alloys. Some of the advantages of the molten-salt electrometallurgical processes include fast electrode reaction, providing accurately controlled large amount of energy to a relatively small reactor volume, negligible over voltage, simplicity of operation, and possibility of accomplishing continuous or semicontinuoue operations. This paper provides a vivid account of the theoretical and practical aspects of electrometallurgical processes for the production and processing of some of the rare earth metals and alloys. Reference has been drawn to the work reported on electrometallurgical processes as applied to the preparation of lanthanum, cerium and misch metal from author's laboratory.

Jan 1, 1992

By S. Kang, D. G. C. Robertson

Slag cleaning furnaces require extensive wall cooling because they involve the use of a superheated slag bath. This is in direct contrast to smelting furnaces, where the wall is usually (but not always) protected by "banks" of solid charge. In order to understand the heat transfer and flow in slag cleaning furnaces a number of model studies have been carried out using molten wax to simulate the slag. Wax is a good model fluid because, like slag, it has a high Prandtl number. Wax models cannot simulate the behavior close to the electrodes (DC arc or AC submerged), but they can and do give a good simulation of the flow and heat transfer at the wall. An understanding of these phenomena is of great importance for the design of cooling panels in the walls of the furnace. Since superheated molten slag will eventually wear away any refractory bricks over time, the wall cooling must be designed to form a frozen layer of slag, referred to as a "freeze lining". The heat flux density (Q/A) required to do this is given by Q/A = h* ?T, where h is the heat transfer coefficient in the slag phase at the wall, and Li T is the superheat (bulk slag temperature - liquidus temperature). Both Q/A and h vary greatly with position and both are usually a maximum at the slag line. In the experimental work, molten wax baths were heated by block heaters to provide similar energy densities to those encountered in commercial slag cleaning furnaces. This procedure was considered to be valid since most of the electrical energy into a furnace bath is dissipated as heat. Gas stirring was used to simulate the gas evolved at the electrode in real furnaces - the quantity of this gas could be estimated from a knowledge of electrode consumption. The similarity criterion was equal gas flow per unit area of surface, in model and prototype. Heat transfer coefficients were measured in the models as a function of power density, gas stirring, superheat, etc., and could be related to the full-scale operations by the use of dimensional analysis.

Jan 1, 1999

By J. Huot

It has been shown that magnesium-based metal hydrides such as Mg2Ni could be synthesized by high energy mechanical alloying. This process creates a nanocrystalline alloy that has enhanced hydrogen sorption properties due to the high density of defects and grain boundaries. Unfortunately, this process also requires a long synthesis time (up to 100 hours in some cases). In order lo reduce processing time and cost of synthesis, we have investigated the effect of milling at elevated temperature under an inert atmosphere. Milling at high temperature improves interdiffusion of the elements and reduces the number of structural defects such as vacancies, dislocations and internal strain. It was found that by milling elemental powders at 200°C. a complete synthesis of Mg2Ni could be achieved in 8 hours. This synthesis time is roughly an order of magnitude lower than that of the process conducted at room temperature. The hydrogen sorption kinetics and capacity of this material are comparable to Mg2Ni synthesized at room temperature.

Jan 1, 2002

By S. C. Flood, J. D. Hunt

"The columnar-equiaxed transition (CET) has been studied numerically under unsteady-state conditions using mathematical models that: (i) include a non-equilibrium undercooling at the columnar front;and(ii) describe the simultaneous evolution of the columnar and equiaxed zones.The results are discussed and compared with those produced by a steady-state analysis.IntroductionThe majority of the previous work on the columnar-equiaxed transition (CET) has concentrated on the production of equiaxed nuclei, regarding this as being the critical step in the formation of an equiaxed zone. Recently, the growth of equiaxed grains has been considered and this is not unreasonable because, for an equiaxed zone to be present, the grains must grow as well as nucleate. Since the growth rate of the grains will be determined by the thermal environment at and ahead of the columnar tips, it was decided to model the liberation and flow of heat during solidification to discover whether the various trends in the columnar range might be explained by their effect on the temperature profile throughout the casting. The models presented here for the solidification of a casting are the first to include the latent heat liberated ahead of the columnar front. Burden and Hunt (1) consider its effect only qualitatively, and although Lipton et al (2) adopt a criterion for the CET which is based on the thermal interaction of the columnar and equiaxed grains, they do not actually include the latent heat in their calculations.It can be argued that the latent heat liberated by the equiaxed grains in the bulk will retard the columnar dendrites in a casting: once the equiaxed grains are sufficiently well-established, the latent heat that they evolve could slow down the columnar growth to such an extent that the equi axed would dominate. Alternatively, the latent heat produced by the equiaxed grains might suppress further equiaxed solidification by raising the bulk temperature. The nature of the thermal interaction between columnar and equiaxed growth is not obvious, and because it is dependent on the material parameters and the dimensions of the system, it cannot be considered effectively in a qualitative way but has to be studied quantitatively: hence the need for the mathematical models discussed in the following pages. The results of the models are discussed in the light of a steady state analysis."

Jan 1, 1986

By Renato G. Bautista

"The development of processing methods for the preparation .of three electronic materials with rare-earth components is discussed. The resulting processing innovations are the results of a search for an economically competitive pilot scale or industrial production flowsheet without compromising the required properties of the final products. The three cases highlighted in this presentation are: 1) The preparation of high energy (Pr-Nd-Ce)FeB magnets for MRI application from a mixed-rare-earth oxide with a narrow range of composition directly prepared from the solvent extraction circuit of bastnaesite ore. 2) The kg production of the giant magnetocaloric effect Gds(SixGe1-x)4 magnetic refrigerant materials from commercial grade gadolinium metal (95 to 98 at. % pure) instead of high purity gadolinium metal (99.8 at. %); and 3). An industrial chemical synthesis flowsheet for the production of the superconductor precursor of YBa2Cu3O7.INTRODUCTIONIn the laboratory discovery stage, the synthesis of a new material is carried out using very high purity components, usually the highest purity available. As the new material is studied and characterized, the effectiveness of its desirable properties becomes better defined and understood. The evaluation of the effectiveness of the .property over the range of a given parameter and other interactions are further studied. Once it's potential application becomes clear, a practical and economical processing method need to be developed. The successful material processing flow sheet does not necessarily have to be a scale up of the laboratory procedure. At this stage, substitution of starting components and with lower purity materials is considered as the economics of the processing becomes a major issue. In addition, other approach to it's synthesis"

Jan 1, 2000

By Patrick R. Taylor

The synthesis of high-purity ultra-fine barium strontium titanate powders (BST: BaO6Sro.4TiO3) has been performed in a non-transferred are D.C. thermal plasma reactor. Slurries of aqueous solutions of dissolved barium and strontium nitrates and solid titanium dioxide powders were used as precursors. Oxygen and argon were used as carrier gases, and pure argon and combinations of argon and nitrogen were used as plasma gases. The plasma torch power was varied, as well as the oxygen flow rate and the total molar concentration of the precursors. A graphite plate was designed to protect the torch electrode and lower the level of impurities in the product. A thermochemical analysis of the Ba(NO3)2-Sr(NO3)2-TiO2-H2O-O2 system was performed to predict the conditions for the formation of BST and the feasibility of the reaction, The powders collected from the different sections of the reactor were characterized using Transmission and Scanning Electron Microscopy, X-Ray Diffraction, and ICP chemical analysis. The powders produced showed high conversion to BST, ultra-fine particle size (< 30 rim) and high purity, which makes this a potential process to produce ceramic materials for electronic devices.

Jan 1, 2003

By Xingye Guo, Yeon-Gil Jung, James Knapp, Zhe Lu, Jing Zhang, Li Li

La2Zr2O7 is a promising thermal barrier coating material due to its low thermal conductivity and superior high temperature stability. In this work, Bilayer La2Zr2O7 and conventional 8 wt% yttria stabilized zirconia (8YSZ) coatings were deposited using plasma spray technique. Both singlelayer La2Zr2O7 and double-layer 8YSZ/La2Zr2O7 coating architectures were designed. Thermal cycling and thermal shock tests were used to evaluate coatings’ thermomechanical properties. All La2Zr2O7 coats were delaminated in the furnace cycle test in less than 20 cycles. This is because residual thermal stresses accumulated during thermal cycling. In the jet engine thermal shock (JETS) tests, the SCL La2Zr2O7 and DCL dense 8YSZ/La2Zr2O7 coatings were fully delaminated. In contrast, the DCL porous 8YSZ/La2Zr2O7 coating sample only partially delaminated on the edge. This is because of the porous 8YSZ layer provides strain compliance. The findings will help to propose efficient thermal barrier coating systems.

Jan 1, 2016

By F. Chabchoub

A mathematical model has been developed to study the influence of process variables on the horizontal Ohno continuous casting process. The model simulates the heat transfer and fluid flow in a wide plate ingot of pure tin. A two dimensional numerical analysis based on a control-volume finite difference approach, the Semi-Implicit Method for Pressure-Linked Equations algorithm (SIMPLER), and an Enthalpy Transforming Model was used. The shape and position of the solid-liquid interface were calculated at different casting speeds, ingot thicknesses, and cooling device characteristics, as well as various mould temperatures. Results of the mathematical model were compared with

Jan 1, 1992

By Anil Saigal, Jr. Fuller, Said Jahanmir

"All-ceramic crowns, including glass-infiltrated spinel composites, are coming into widespread use because of their superior aesthetics and chemical inertness. This study investigates the residual stresses that are developed in these composites as a result of cool down from the glass-infiltration temperature to room temperature due to slight mismatch in the coefficients of thermal expansion and its effect on the mechanical behavior of these composites. Two-dimensional finite element simulations were performed using an object oriented finite element program OOF. The OOF program is a combination of two programs. The first program, PPM200F, is designed to read an image file such as a micrograph. The individual pixels that constitute the micrograph may be collected into groups and their material properties assigned. PPM200F is then used to create the finite element model/mesh that OOF then reads. The average residual stresses are found to be tensile in the spinel matrix and compressive in the infiltrated-glass. There is large variation in residual stresses and strains from location to location with presence of locations at which the glass is under tensile stress. The crack initiation and initial propagation in glass-spinel composites is at the glass-spinel interface in both the glass and the spinel. The presence of residual stresses can lead to lower crack initiation stresses and degrade the mechanical properties of the composites.IntroductionGlass-infiltrated spinel ceramics are in clinical use as core materials in all-ceramic crowns and as inlays and onlays (1-3). Advantages of ceramic composites include near net-shape forming with high strength in the infiltrated state. Besides, spinel is quite translucent and may potentially be used without a veneer. However, these ceramic composites are subject to damage accumulation from repeat oral contact loading and often fail after a few years of use (4). This paper examines the residual stresses that are developed in these composites, after cooldown from the glass infiltration temperature to room temperature, due to the slight mismatch in the coefficients of the thermal expansion of the two phases."

Jan 1, 2001