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By B. R. Westphal

The Integral Fast Reactor (IFR) concept being developed by Argonne National Laboratory is based on the pyrometallurgical processing of spent nuclear metallic fuel with subsequent fabrication into new reactor fuel by an injection casting process. During fabrication, a dilute scrap stream containing uranium alloy fines and broken quartz (Vycor) molds is produced. Waste characterization of this stream, developed by using present operating data and chemical analysis, was used to evaluate different uranium recovery methods and possible process variations for the return of the recovered metal. Two methods, comminution with size separation and electrostatic separation, have been tested and can successfully recover over 94% of the metal. Recycling the recovered metal to the injection casting process was evaluated for the different economic and process impacts. The physical waste parameters and the important separation process variables are discussed relative to their effects on the viability of recycling the material. A discussion of the criteria that is being used to establish the acceptable operating limits is also presented.

Jan 1, 1992

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 Ian Baker, Xavier Pierron

"Iron aluminides hold great promise for intermediate temperature applications (to ~ 600°C) because of their excellent oxidation and sulphidation resistance and good strength. However, they have poor low temperature ductility, a feature which is exacerbated by water-containing environments. This paper presents an overview of the effects of environment on the ductility of iron aluminides, including the effects of iron aluminum ratio; ternary alloying additions, particularly boron; strain rate; and temperature. The mechanisms involved in water-induced embrittlement are discussed.IntroductionOver the last few years, it has became increasingly evident that the ductility and fracture toughness of many intermetallic compounds, particularly aluminides, are reduced dramatically if they are mechanically tested in either air or in hydrogen-containing atmospheres (1-5). For FeAI and Fe3AI, it has been shown that water vapor, for example in air at room temperature, can form atomic hydrogen by reacting with the Al atoms (1, 2). As a result in iron aluminides, the environmental embrittlement process is quite similar to traditional hydrogen embrittlement. This can be easily demonstrated by either testing an iron aluminide in an environment free of the deleterious species or by testing at high strain rates, both of which result in greater ductility. The purpose of this paper is to review recent progress in understanding environmental embrittlement in FeAI and Fe3AI, and to consider possible environmental embrittlement mechanisms. Greater understanding of this phenomenon will lead ultimately to remedies to this problem which is a major reason for preventing the practical application of these materials. First, some background on the iron-rich aluminides."

Jan 1, 1996

By Natasa Mitevska

The statistical analysis of the slag composition influence on copper losses to discard slag in the reverberatory furnaces No.1 and No.2 in the RTB BOR, Copper Smelter and Refinery (Yugoslavia) is presented in this paper. The model for the slag basicity calculation is determined, and connected to the copper distribution coefficients between the matte and slag phase. The influence of all components on the slag structure is also illustrated.

Jan 1, 2003

By Sheng Dai, Yuan Lee, Haiming Xiao, J. P. Young

"There are numerous analytical applications of scatter-emission and/or absorption spectroscopy applied to liquids and solids in the temperature range of 0 to 350°C. In this paper an all-silica fiberoptic probe is described which is useful for spectral analyses from 0 to 1600 K and can be used in harsh chemical environments. The probe has been used for Raman spectral analyses of many molten salt and solid material systems to 1000°C. It has applications for such studies at higher temperature ranges. The instrumentation required along with the demonstrated and proposed applications of the all-silica probe are presented and discussed.IntroductionThere are many kinds of scatter-emission spectroscopies that are of value for analytical measurements. Fluorescence, reflectance, arc or spark emission are descriptors for some of these. Raman scatter spectroscopy is also quite a useful technique for analytical measurements.In Figure 1, we give a simplified explanation of the Raman effect. If one shines monochromatic light into a sample, light may be absorbed, exciting the sample to some virtual state. We know from experience that almost all of the light is re-emitted in the same wavelength range. This is called Rayleigh or Mei scattering and is designated in the figure by the arrows in both examples that point up and down from the same lower energy state. A very small percentage (the order of 10-4%) of the monochromatic light is re-emitted leaving the sample at a vibrationally-excited state. Thus, this light is at a distinctly lower energy compared to the exciting radiation. This is called a Stokes shift and is represented in the left-hand example by an arrow descending to a more energetic vibrational state. If the sample is not at a temperature of absolute zero, some of this vibrationally excited state will be thermally populated. That portion of the sample still absorbs and re-emits exciting radiation as Rayleigh scattered light, but a small percentage of the exciting light is re-emitted as the sample relaxes to the lower vibrational state. The energy of this light is of higher energy and is called an anti-Stokes shift, depicted in the example to the right. Notice that the energy separation of the Stokes or anti-Stokes shifted emission from that of the exciting radiation is the same, and expressed in ~cm-I. The intensity of either shifted emission is a function of the population of the vibrational energy states; therefore, the ratio of the intensity of Stokes to anti-Stokes signal varies with absolute temperature. We will come back to this point later."

Jan 1, 1997

By E. Dendy Sloan

An overview of hydrate properties is given, with emphasis on unusual deviations from ice, the most common solid water form. Reliable sample preparation and reproduction of in situ hydrates provide the foundation for all hydrate science and engineering. Relations are given to connect the three domains in the title: (1) micro-scopic properties measured with Raman, NMR, and diffraction spectroscopy, (2) meso-scopic properties measured with single crystals, and (3) macro-scopic properties measured with pressures, temperatures, volumes, etc. A principal illustration relates micro-scopic and macro-scopic domains. Experiments provides the basis for improving statistical thermodynamics model for these compounds. To date, this model is one of the most commonly used industrial statistical thermodynamics applications, based upon the classical model of van der Waals and Platteeuw (1959). Microscopic measurements and simulations indicate model assumption improvements, resulting in the next generation of the statistical thermodynamics for improved macroscopic property prediction.

Jan 1, 2002

By Frederick T. Wallenberger

"Laser assisted chemical vapor deposition (LCVD) is a new containerless fiber process whereby growth of small diameter fibers or microstructures (microsprings, microsolenoids) occurs directly from the vapor phase. The laser beam has a focal point adjusted to coincide with the tip of the growing fiber inside the reaction chamber. Since the growing fiber is not in contact with reactor walls or foreign materials, it is chemically pure, and suitable for optical uses and uses requiring high structural uniformity. Continuous fibers and multifilament yams are possible. The use -of high reaction chamber pressures (1-10 bar) and a small wavelength Nd-YAG laser made it possible to fabricate small diameter fibers at growth rates >1 mm/s. This paper describes the synthesis of single crystal, polycrystalline and amorphous fibers by LCVD, and provides a comprehensive analysis of phase transformations occurring during their fabrication.IntroductionLaser assisted chemical vapor deposition (LCVD) is a new containerless fiber process [1-10] whereby growth of small diameter fibers or microstructures occurs directly from the vapor phase. The laser beam has a focal point adjusted to coincide with the tip of the growing fiber in the reaction chamber (Figure 1). The diameter of the growing fiber corresponds to that of the laser focus. Depending primarily on the laser energy (Le., the temperature at the growing fiber tip), it is possible to obtain single crystal, poly crystalline or amorphous fibers by this method.Since the growing fiber is not in contact with reactor walls or foreign materials, it is chemically pure, and suitable for optical uses and uses requiring high structural uniformity. Laser assisted CVD is a potentially continuous process; continuous fibers and multifilament yams are possible."

Jan 1, 1994

By J. D. Scott

The counter-current jarosite acid wash circuit presently in operation in the zinc plant produces a combined jarosite plus Pb/Ag residue which is discarded. Extensive pilot-scale testwork, and some past in-plant operational experience, has shown that the zinc plant can be easily reconfigured to produce two residues during periods of high silver feeds and/or prices. Plant.optimized circuit configurations are available for silver recovery to a Pb/Ag residue and are in use for the prevention of Pb/Ag-jarosite formation in both the neutral and high-acid leaching circuits. Silver in the zinc plant undergoes several changes in state as it proceeds through these circuits. The roaster calcine is ~3:1 silver sulfate: silver metal, with metallic silver mainly as micro-Inclusions In an aluminosilicate phase. In neutral leach residue, the majority is as silver sulfide or Pb/Ag/Zn-sulfide coatings on unroasted sphalerite grains, with minor Pb/Ag-jarosite and some residual metallic silver in unreacted alumina-silicate grains. In high-acid leach residue, silver occurs as Se-rich silver sulfide particles in sulfur/jarosite ball aggregates, as silver sulfate impregnations in silica-gel masses and in solid solution in Pb/K/Zn~jarosite. Silver concentrations in solution range from 20 to 60 ppb.

Jan 1, 1990

By Michele L. Bustamante, Gabrielle Gaustad

In recent years, t h e future supply of tellurium has been called into question due to the anticipated rapidly increasing demand from thin film cadmium telluride photovoltaics. Since tellurium is produced as a byproduct of other extractive processes – principally, the electrolytic refining of primary copper sulfide ore – it is important to explore the dynamics of the parent metal extraction and processing – in this case copper – when attempting to answer this question. This research explores the changing landscape of global copper production; introducing system diagramming and the concept of byproduct intensity (BPI) to illustrate concerning downward trends in tellurium supply potential. Upon closer inspection, it is concluding that, while a likely contributor to these downward trends, the increased use of non- traditional copper production techniques alone are not responsible; other factors include market substitution and incomplete data reporting. Additionally, a review of literature on tellurium recovery processing reveals a promising outlook for future supplies; highlighting potential for improvements in yield, which allow producers to make better use of what is available, even in the face of suppressed BPI.

Jan 1, 2014

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to simulate nickel flash smelting process. In the nickel flash furnace, oxidation of concentrate occurs at one end, and reduction of slag occurs at the other. The model makes use two zones, namely the reaction shaft/settler zone and the appendage zone and accounts for 6 phases (matte, slag, silica, magnetite, Cu-Ni alloy and gaseous phase), 13 elements (Ni, Co, Cu, Fe, S, 0, N, C, H, Si, Al, Mg and Ca) and 33 chemical components in nickel flash smelting system. The compositions of matte, slag and gaseous phases in equilibrium are calculated by using the data of free energies of formation and activity coefficients of components. Two nickel sulfide species are used to allow for the modeling of sulfur-deficient mattes. The model predictions are compared with the known industrail data from Kalgoorlie Nickel Smelter, and excellent agreement is obtained. The model can be a very useful tool for monitoring and optimizing the actual industrial operations of nickel smelting process. The distribution behaviors of Ni, Co, Cu, Fe, S and 0 in the nickel smelting furnace depend on the process parameters such as smelting temperature, volumes of air, the content of the elements~ charge and oil.1. IntroductionThe nickel flash smelting furnace essentially consists of a reaction shaft where nickel sulfide concentrate is partially oxidized with air, a settle zone where matte and slag are allowed to separate, and a slag cleaning end where coke is added to provide for the reduction of the oxidized nickel from slag, and electrodes are used to provide heat.The theoretical model to consider a mass balance for copper flash furnace is developed by S. Goto and R. Shimpo[1][2J. However, this can not be true for nickel flash furnace as a whole since oxidation of concentrate occurs at one end (in the reaction shaft/settler), and reduction of slag occurs at the other (in the appendage). Despite these limitations, an acceptable pseudo-thermodynamic description of the furnace can be achieved using essentially two zones, namely the reaction shaft/settler zone and the appendage zone. Compositions of gas, slag and matte in two zones are calculated."

Jan 1, 1998

By Xi Dai

The LiFe1-xNixPO4(x=0, 0.05, 0.10) cathode materials for Li-ion battery were synthesized with Fe1xNixC2O4?2H2O(x=0, 0.05, 0.10) as Fe sources by high temperature solid-state reaction method. The Fe1xNixC2O4?2H2O(x=0, 0.05, 0.10) materials were produced by liquid co-precipitation method and crystal structure and morphology of cathode materials were characterized by X-ray diffraction and scanning electron microscopy. The composition contents and charge-discharge performances were measured by chemistry analysis and charge-discharge apparatus. The XRD patterns showed that LiFe1-xNixPO4(x=0, 0.05, 0.10) cathode material samples were well-crystallized homogeneous olivine-type phase, with only tiny trivalent iron impurities according to chemistry analysis results. Charge-discharge test showed that cathode materials possessed excellent charge/discharge capacities, about 150mAh/g at 0.1C rate and more than 120mAh/g at 0.4C rate. The polarization of cathode in charge-discharge process can be restrained effectively, for the potential offset between oxidative peak and reductive peak of doped LiFePO4 material was only 0.079V, lower than pure LiFePO4 markedly.

Jan 1, 2006

By O. Forsén

A new cell construction was designed for the study of the electrochemical behaviour of additives in conditions that simulate real copper, electrorefining. The behaviour of gelatine and thiourea was studied by applying different electrochemical methods, i.e. polarization resistance and voltametric measurements. In this study, individual galvanostatic electrolysis experiments were carried out for 120 hours. The organic additives were introduced to the electrolyte at certain intervals and their concentration was varied in the range &om zero to four ppm. An optical microscope was applied for the examination of copper cathode deposit microstructures. The results show that gelatine has a polarizing effect on the deposition potential of copper whereas even small amounts of thiourea depolarize the electrodeposition of copper. The maximum inhibitor efficiency of gelatine was obtained at a gelatine concentration of slightly lower than two ppm. When both gelatine and thiourea were present in the electrolyte, the depolarizing effect of thiourea exceeded completely the polarizing effect of gelatine. If chloride ions were added to gelatine and thiourea containing electrolyte, the electrochemical behaviour of the system was altered drastically. Chloride ions resulted in the prevailing of polarization effect caused by gelatine while the depolarizing effect of thiourea disappeared in this system. The polarizing effect of gelatine increased until chloride ion concentration of 30 ppm was reached. Also, the above electrochemical phenomena could be detected in the optical examination of copper deposit microstructure.

Jan 1, 1995

By T. T. Chen

Canadian Electrolytic Zinc has developed the "cement-stabilization of jarosite residue" Garofix) process to stabilize zinc plant jarosite residues for disposal. The cement-jarosite mixtures cure quickly, have good mechanical strength and low hydraulic permeability; they possess good neutralizing capability and chemical stability. In the jarofix process, Portland cement partly decomposes jarosite to form (SO4MOH)12.nH2O, ferric hydroxide and an alkali sulphate. Approximately 40% of the jarosite reacts in mixtures containing 30% cement. The jarofix product also contains various Ca-Al-Fesilicate-sulphate-hydrate phases and gypsum, which bond the individual particles together imparting mechanical strength and reducing the permeability. Most of the reactions take place in the first few hours of curing. Ammonium jarosite is slightly more reactive than sodium jarosite but releases NH3 gas; water-soluble Zn in the jarosite residue is stabilized in the cement reaction products.

Jan 1, 1996

By K. D. Peaslee, V. L. Richards, C. H. Rawlins, S. N. Lekakh

"Steel-making processes generate carbon dioxide air emissions and a slag co-product. The aim of this project was to develop a functional sequestration system using steelmaking slag to permanently capture carbon dioxide emitted in steelmaking offgas. A possible parallel benefit of this process would be rapid chemical stabilization of the slag minerals with reducing swelling or leaching.This paper summarizes the original results of the project, including mineralogical and structural features of carbon sequestration with steel making slag, mathematical modeling of reaction phenomena using a modified shrinking core model, METSIM modeling of several possible industrial applications, a thermo-gravimetrical study of the reaction between slags and different gases, and design and testing for a lab scale apparatus consisted of two reactors.1. IntroductionThe U.S. produces 9-14 Mt of steelmaking slag annually, which represents approximately 10-15 wt. % of crude steel output.1,2 Primary uses for steelmaking slag include high quality mineral aggregate, Portland cement, unconfined fill, soil conditioning, and pH neutralization of abandoned mine drainage.3,4 The key factor prescribing slag use is the alkaline-earth metal (e.g. Ca and Mg) oxides content, which contribute to overall basicity and cementitious strength. However, as-produced steelmaking slag is chemically unstable. Calcium and magnesium oxides readily form hydroxides and carbonates through reaction with atmospheric gases. Both hydroxide and carbonate formation produce substantial mechanical swelling leading to heave failure in confined construction applications, thus many states dictate stockpile aging for 3-6 months prior to commercial use.5,6 Sequestration of carbon dioxide is a natural corollary to forced carbonation. The conversion of CaO/MgO to carbonates serves both to stabilize the slag, and permanently capture and store the CO2."

Jan 1, 2008

By V. E. Antonov

Hydrides of iron and iron-based alloys are thermodynamically stable only at hydrogen pressures in the gigapascal range and rapidly loose hydrogen under ambient conditions. At low temperatures, however, these hydrides can be retained in a metastable state at atmospheric pressure after being cooled under the high pressure to liquid nitrogen temperature. This review will discuss the current state of studies on phase transformations in the Fe-H and related systems and also on the composition, crystal structure and physical properties of the hydrides, both under high hydrogen pressures and in the "quenched" metastable state at ambient pressure. The studies at ambient pressure include magnetization measurements, X-ray and neutron diffraction, Mossbauer spectroscopy and inelastic neutron scattering. In the sections on Mossbauer and structural investigations of hydrides of Fe-Cr and Ni-Fe alloys new experimental results will be presented.

Jan 1, 2002

By Ravi Vancheeswaran

The consolidation of ceramic fiber reinforced metal matrix composites is a key process step in the synthesis of high performance composite systems. A simulation tool has recently been developed for predicting the evolution of the composites internal state microstructural variables (eg. relative density, fiber microbendinglfracture, and chemical reaction layer thickness at the fiber-matrix interface) during the consolidation processing of spray deposited composite mono-tapes. A Generalized Predictive Control (GPC) scheme is used in conjunction with the simula-tion tool to design near optimal process paths that minimize fiber damage and reaction product thickness while simultaneously maximizing the composites relative density. The microstruc-tural evolution depends nonlinearly on the process conditions and therefore the scheme uses a constantly updated linearization of the model to optimize the input process variable vector. A control simulation is presented to illustrate the performance of the design scheme and to assess the feasibility of its use for the achievement of goal state microstructures at the completion of consolidation cycles.

Jan 1, 1996

By Gervais Soucy, François Quesnel, Pierre Hovington, Wen Zhu, Karim Zaghib, Jocelyn Veilleux

The properties of lithium titanates anodes in Li-ion batteries are highly dependent on their secondary constituents. While their main phase is usually constituted of Li4Ti5O12, significant quantity of lithium titanates compounds of various stoichiometry are often present, due to either the processing, usage or aging of the material. These may go underreported, as many of these spectrums overlap or display low signal in X-ray diffraction (XRD). Samples of nanosized lithium titanates synthetized by inductive plasma were characterized by XRD and scanning electron microscopy (SEM), as they provide a regular yet typical crystallite size and shape including multiple phases. A Rietveld refinement was developed to extract the composition of these samples. Mass balance through further annealing and differential scanning calorimetry (DSC) enthalpy measurements from phase transformations were also used as identification and validation techniques.

Jan 1, 2015

By Charles H. Rawlins

Reported is work done on processing of steel mill effluents in the areas of dewatering and separation. Much of the waste from these operations is in the form of sludges from scrubbers, in which the primary constituent is iron oxide. Recycling of the sludge&apos;s magnetic fraction has become economically attractive in order to reduce the overall volume placed in landfills. The objective of this research is to determine the effectiveness of combining magnetic and cyclonic forces, to recover iron oxide particles from waste water stream, while decreasing the volume to be disposed. Three different size hydrocyclones, operating within the field of a quadripole magnet, were tested using varying feed pulp densities of magnetite, magnetite/dolomite, blast furnace (BF), and basic oxygen furnace (BOF) slurries. In the first three cases, the percentage of magnetics recovered increased to greater than 95%. The limiting operational factors are; high pulp density for small cyclones, which can cause flow blockage within the magnet field, and extremely fine particle sizes (<2 microns), which cannot be recovered. The results indicate this technique can remove virtually all the magnetic particles from some steel effluents to a 40-50% weight percent solids pulp, on an in line continuous basis.

Jan 1, 1994

By M. J. Collins

A hydrometallurgical process has been tested at the Sherritt Research Centre for separation of zinc, lead, copper and precious metal values from the zinc oxide fume leach residue stockpiled at the HBM&S operations in Flin Flon, Manitoba. Zinc is found primarily as zinc femte and sphalerite in the residue, lead as lead sulphate and jarosite, and copper as sulphide and jarositic compounds. Gypsum and siliceous gangue are significant diluents. The separation process includes hot acid, atmospheric and reducing (sulphur dioxide) leaching; zinc, copper and lead flotation; and atmospheric iron removal steps. Zinc is recovered to a high strength zinc sulphate solution and to a zinc sulphide concentrate suitable for feed to a roaster or to a zinc pressure leach plant; lead to a high grade lead sulphate concentrate suitable for feed to a lead smelter, and copper to a high grade copper sulphide concentrate suitable for feed to a copper smelter. Precious metals are divided between the zinc, lead and copper concentrates.

Jan 1, 1993

By David G. Dixon

A mathematical model is derived in dimensionless form which simulates the effluent concentration response of reagents from spent heaps under both fresh and recycled water rinsing. The model is based on dispersion from isochoric pathways distributed in length and cross-section, oriented normal to convection channels in ideal plug flow. The effects of heap height, rinsate flow, and initial reagent concentration are examined. It is shown that the rinsing cycle undergoes a distinct shift between fast and slow rinsing at a certain time depending on the amount of stagnant solution in the heap, and the distribution of dispersion pathways. Results of preliminary column rinsing tests on both agglomerated and unagglomerated ores are presented which partially validate the model.

Jan 1, 1994