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By Phillip B. Messersmith, Emmanuel P. Giannelis

"A versatile in-situ polymerization approach is described for the synthesis of polymerceramic nanocomposites consisting of two-dimensional layers of mica-type silicate (MTS) within polymer matrices. Functionalized, organically modified mica-type silicates (OMTS) were used to promote delamination/dispersion of the host layers and initiate polymerization of organic rrionomer. Epoxy nanocomposites prepared in this manner exhibit substantial modulus reinforcement at low silicate loadings. The water vapor permeability of the poly(?-caprolactone) nanocomposite containing 4.8% silicate by volume was reduced by nearly an order of magnitude compared to pure poly (?-caprolactone).IntroductionPolymer matrix nanocomposites are a relatively new class of materials with dimensions typically in the range of 1-100 nm.1 In general, because of the ultrafine phase dimensions involved, nanocomposites exhibit new and improved properties when compared to their micro- or macrocomposite counterparts. We as well as others are currently investigating the design, synthesis and characterization of polymer-ceramic nanocomposites. Our effort, in particular, has focused on the use of mica-type silicates (MTS) with various thermoplastic and thermosetting matrices.2-5MTS's belong to the general family of 2: 1 layered silicates. Their crystal structure consists of layers of two silica tetrahedral sheets fused to an edge-shared octahedral sheet of either aluminum or magnesium hydroxide. Stacking of the layers leads to a regular van der Waals gap or interlayer.6 Isomorphic substitution within the layers generates negative charges that are counterbalanced by cations residing in the interlayers. Although the natural forms of MTS's usually contain hydrated Na+ or K+ ions, ion exchange reactions with organic cations (e.g. alkylammonium ions) can render the normally hydrophilic MTS's organophilic."

Jan 1, 1994

By Marco Olper

Zinc bearing materials containing chlorides and fluorides of alkali metals, such as EAF dust, Waelz oxides, galvanizing ashes, zinc & brass foundry fumes and converter fumes are little attractive, both technically and economically for processing in ISF plant or in a conventional zinc sulphate electrolysis works. The Ezinexm Process allows for the recovery of high purity zinc in cathode form, from these materials, regenerating the leaching liquor. The process is based on a new electrochemical system which depolarizes the anode reaction with reduction of the cell voltage, compared with the traditional sulphate electrolysis method. The electrolyte, based on a chloroamrnino complex, allows for the recovery of other valued metals present in the zinc bearing materials such as lead, copper and silver, these being recovered as a metallic cement consequently improving the economics of the process.

Jan 1, 1994

By R. S. Krarner

Fly ash, a by-product of coal burning power plants, poses a major problem for the utility industry since most fly ash must be landfilled. These quantities may represent as much as 20% of the total material going into landfills. A major problem with fly ash utilization is that although the ash consists of useable components, ash composition can vary depending on the types of coal burned and plant operating conditions. Ash is first characterized using SEM, image analysis, and chemical methods. Processing techniques were developed to separate ash into various components including cenospheres, magnetic spheres, carbon, and clean ash. These products are again evaluated for various utilizations before being used to produce valuable products such as mullite, activated carbon, fillers in plastics, and concrete.

Jan 1, 1994

By Richard A. Heckman

Destructive Thermal Technology (DTT) is used in the management of various waste streams. DTT includes Destructive Distillation, Pyrolysis and Classical Incineration. Recent work has more clearly defined the differences in these technologies based upon a more rigorous thermochemical approach. The U.S. Environmental Protection Agency (EPA) has chosen Classical Incineration as the Best Developed Available Technology (BDAT) for the management of hazardous organic wastes. Municipal Solid Wastes (MSW) and Sewage Sludges (SS) are also managed using Classical Incineration. Three environmental problems plague the use of Classical Incineration. Destructive Distillation, on the other hand, avoids these problems. It is an environmentally benign DTT for managing a wide variety of organic waste streams, including hazardous wastes. Thermochemical analysis of the available data on the performance of three types of DTT will be discussed.

Jan 1, 1994

By W. B. Carter, A. T. Hunt, G. W. Book

"Combustion Chemical Vapor Deposition (CCVDSM ), an open air, flame assisted CVD process, is under development. The CCVD process produces non-line-of-sight, epitaxial deposition. Materials deposited include YBa2Cu3Ox' Y2BaCuOx, BaTiO3, Y2FesOI2, ZrO2, yttria stabilized ZrO2 (YSZ), partially (yttria) stabilized ZrO2 (PSZ), and amorphous silica. Two modifications of the CCVD process are being studied. Liquid fuel CCVD deposition, involves the combustion of an organic solvent that contains dissolved reagents carrying the desired coating cations. Gaseous fuel CCVD deposition uses a flammable gas as fuel. A non-flammable solution containing dissolved reagents is either aspirated into the flame or mixed with the fuel gas as an aerosol prior to its combustion. Substrates to be coated are held near the flames' ends.IntroductionThin films and coatings can be deposited using a wide variety of techniques including chemical vapor deposition (CVD). CVD is ""a materials synthesis process whereby constituents of the vapor phase react chemically near or on a substrate surface to form a solid product.""lIn conventional CVD processing, gases carrying coating constituents flow into a reaction vessel where deposition occurs onto a heated substrate. The deposition process is often conducted at reduced pressure. Both cold and hot wall reaction chambers are used. Heat can be provided by a resistance furnace, rf induction, or high-intensity radiation lamps. Plasma, microwave, photo, laser, RF, and electron-enhanced CVD processes have been developed. The necessity of using a reaction vessel limits the substrate size and affects coating economics. Although most CVD depositions are performed as batch processes, continuous deposition can be accomplished with the use of appropriate hardware.The chemical vapor deposition of thin, dense oxide films has been accomplished in the open atmosphere with a flame assisted process. The process is called combustion chemical vapor deposition (CCVDSM).2 Two modifications of the CCVD process have been developed. The liquid fuel CCVD process involves the combustion of an organic solvent in which reagents (containing the coating cations) are dissolved. The gaseous fuel CCVD process uses a flammable gas as fuel. In this modification, a non-flammable solution containing dissolved reagents is either aspirated into the flame or mixed with the fuel gas as an aerosol of small droplets prior to its combustion. Substrates to be coated are held near the flames' ends."

Jan 1, 1994

By Lloyd R. Nelson

The feasibility of producing low carbon (LC) ferromanganese (FeMn) by lime-'ore' melt refining of high-grade ferromanganese silicon (FeMnSi) was investigated. Thermodynamic simulations demonstrated significant benefits in moving from a single-stage ladle operation to a two-stage counter-current reladling operation (to emulate the commercial Penin Process). The theoretical alloy silicon content was predicted to be refined from 1.57 to 0.005 per cent silicon, at a 6.2 per cent higher manganese yield (yield predicted to increase from 82.3 to 88.5 per cent). Extension of this counter-current refining principle, to a multistage Counter-Current Reaction Launder (CCRL) was investigated using the Slag Metal And Gas Klnetics (SMAK) software to model the mass transfer kinetics of the multicomponent coupled reaction system. Simulation results suggested that commercial production of 50 000 tonnes per annum (tpa) of refined LC FeMn, containing less than 0.5 per cent silicon, at manganese yields of up to 90 per cent, should be feasible in a compact CCRL (7 m long by 0.7 m wide).

Jan 1, 1994

By M. H. Lin, S. Kou

"Czochralski pulling has been a very widely used process for growing single crystals for electronic and optical applications. Dopant segregation can significantly degrade the quality and yield of single crystals. We have used the floating-crucible technique for segregation control in Czochralski pulling, our floating crucibles being unique in that the melt passageway is very long. As such, dopant back diffusion is suppressed, even when the cross-section of the melt passageway has to be relatively large to help the melt go through or when the pulling rate is very low. Single crystals of model materials K-doped NaN03 and Pb-doped Sn have been grown with very uniform dopant concentrations. IntroductionSingle crystals of electronic and optical materials are often doped with a small amount of impurities to develop required physical properties, e.g., P and B in Si for n-type and p-type semiconductors, respectively, and Nd in YAG lasers. Dopant segregation can result in nonuniform physical properties, thus degrading the quality and yield of the resultant crystals.Figure 1 is an illustration of the conventional Czochralski process for crystal growth. Several techniques have been developed to control dopant segregation in Czochralski pulling, including the push-pull technique (1,2), the drop-pull technique (3-7) and the floating-crucible technique (8-13). The first two techniques require precise sensing devices and feedback control systems to keep the feeding rate equal to the pulling rate. The last technique is simple since the feeding rate is automatically equal to the pulling rate."

Jan 1, 1994

By H. Kamarudin

The behaviour of cassiterite-sulphosuccinamate flotation system was examined in the light of zeta potentials measured by micro-electrophoresis method. It was observed that sulphosuccinamate substantially affects the zeta potentials of cassiterite, lowering its i.e.p. to pH 2.5 and indicating a specific adsorption and/or chemical interaction. The optimum concentration for flotation, as seen in micro-flotation tests, was found to be associated with the most effective lowering of the zeta potentials, the optimum pH being 3.0. The effect of cations in the pulp was examined for the presence of ferrous, ferric, aluminium and lead ions. The ions ferric and aluminium were observed to create an intense effect of increasing the potentials to positive side, possibly due to adsorption of cation hydroxy complexes, as indicated by their respective species distribution diagrams.

Jan 1, 1994

By Patrick R. Taylor

Sub-micron sized boron carbide powders have been synthesized in a non-transferred arc thermal plasma reactor. Precursors for this synthesis are boric acid or boron oxide powders and methane. The powders produced were characterized in terms of size, shape and purity. Methods to increase the purity of the product were evaluated and included hot water leaching to remove unreacted oxides and controlled temperature, air roasting to remove excess carbon. Theoretical results are also presented on the thermodynamics and mechanisms of the synthesis reactions.

Jan 1, 1994

By A. P. Paiva

Studies focused on the recovery of precious metals by solvent extraction have recently increased. either to devise suitable solvents or to clarify the involved extraction mechanisms and kinetics. In this work, a comparison of the performance exhibited by triphenylphosphine (TPP), bis-(penty1thio)-ethane (BPTE) and triisobutylphosphine sulfide CI"I'BPS) in the extraction of silver from acidic chloride media is carried out. Extraction and stripping isotherms involving the three extractants are presented together with the results obtained on the selectivity of silver extraction against high contents of iron, copper and lead. Attempts to clarify the mechanism of silver extraction by TIBPS were performed by studying the distribution coefficient dependence on ligand and chloride concentrations. The effect of temperature on extraction and stripping is also considered. The interfacial tension for the system, measured with different concentrations of extractant in the organic phase, is analysed.

Jan 1, 1994

By Jim Sundal

Primary steel manufacturers using electric arc furnaces generate one of the largest hazardous waste streams nationwide. The waste stream, known as electric arc furnace dust, is a listed hazardous waste with the designation K061. Oregon Steel Mills, Inc., (OSM) of Portland, Oregon, has implemented a process known as Glassificationn, which uses KO61 as an ingredient in an onsite recycling process. Because OSM was able to demonstrate that the Glassificationm recycling process beneficially uses all toxic constituents in the electric arc furnace dust and that the recycling process produces marketable products, the process is not subject to Resource Conservation and Recovery Act (RCRA) permit requirements. The marketable products manufactured using Glassificationn include roofing granules, ceramic glazes and colorants, abrasive blasting media and, more recently, synthetic slag fluidizers. The purpose of this paper is to identify the regulatory issues for recycling hazardous waste and demonstrate that OSM glass frit is effective as a slag fluidizer in primary steel manufacturing.

Jan 1, 1994

By Nathaniel R. Quick

"Nd: YAG, KrF excimer, and Cu-vapor lasers are used in air to synthesize conductors and semiconductors as a second phase in silicon carbide and aluminum nitride. Conductor resistivities as low as 104 O-cm are formed in these substrates; the resistivities for the untreated substrates range from 10 11to 1014 O-cm. The silicon carbide conversion is relatively independent of wavelength while the aluminum nitride conversion shows a dependence on wavelength over the range 248 nm to 1064 nm. Silicon carbide conductors, evaluated over the range 15 K to greater than 300 K, exhibit metal like conductivity; resistivity increases with temperature. Silicon, carbon, and oxygen are identified as the principal chemical species associated with the conductor in SiC substrates while aluminum, nitrogen, and oxygen are identified as the principal chemical species associated with the conductor in aluminum nitride substrates. The silicon carbide system, which has the less complex phase diagram, is evaluated in more depth to explain the synthesis mechanism. Oxygen was principally on the surface and increasing SiC conductivity is associated with decreasing spacing between 5 µm, or less, diameter carbon globules. This technology is proposed as a replacement for metallization in electronic packages, sensors and devices. INTRODUCTIONCeramics are commonly used for multichip module, hybrid and multilayer electronic packaging; semiconductor device and sensor applications because of the insulating, conducting, semiconducting, or superconducting properties that these materials possess (1,2) The majority of ceramics, however, have not been known to exhibit conductive or semi conductive properties when exposed to rapid thermal heat processing. A ceramic and process which through selective conversion can combine two or more of these electrical properties to eliminate the need for metallization is of interest to both the commercial and military sectors."

Jan 1, 1994

By Elliot Schwartz, Julian Szekely

"In this paper we describe an experiment that was recently performed on the IML-2 Space Shuttle mission in which the thermophysical properties of molten metals were measured using electromagnetic levitation. In the planning of these experiments calculations had to be performed to predict the levitation and stirring forces, heating rates, sample deformation, and internal flows within the sample. These predictive calculations were essential for both the planning of the experiments and for the re-planning of experimental runs during the actual Space Shuttle mission.Introduction""Materials Processing in the Computer Age"" involves the use of mathematical modeling to obtain a quantitative understanding of the phenomena that govern materials processing operations. Microgravity, or space shuttle experimentation represents a specific case in point here; the very high cost of the space shuttle flights, the very limited flight opportunities that are available, and the tight resources aboard a shuttle clearly mandate that these experiments be very precisely planned and that all possible opportunities for mathematical modeling be fully exploited.The purpose of this paper is to present the results of calculations performed for the planning of a space shuttle experiment involving electromagnetic levitation and wherever possible present a comparison of the computational predictions with both experimental measurements and asymptotic analyses. Finally we shall seek to discuss the practical implications of both the computational methodologies and the potential experimental findings."

Jan 1, 1994

By R. J. Batterham

This paper sets the scene for the Australian-Asian Pacific Course and Conference on Pyrometallurgy for complex materials and wastes. The relentless presence of competitiveness is rehearsed as the source of the current trends towards continuous improvement and benchmarking. While this might be expected to lead to more spending on pyrometallurgy, the opposite appears to be the case. The paper examines the reasons and suggests that we face an increasing challenge for selective developments that can lead to sustainable competitive advantage - both in mineral and in waste processing.

Jan 1, 1994

By X. K. Lan

The greater demand for high-quality large-diameter crystals has led to the robust idea of a free- flying solar-powered furnace satellite, whereby the buoyancy-driven convection effects are almost nonexistent, and diffusion-controlled crystal growth with minimal radial segregation is promoted. In the proposed solar furnace, a paraboloid of revolution imaging concentrator is used to focus the sun's radiation onto an-ampoule which holds the solid charge to be processed. The charge will start melting in the vicinity of the focal point, after which it is translated in order for the melt to resolidify as a single crystal. A ray-trace method has been developed to determine the incident concentrated solar heat flux on the ampoule surface for a perfectly-aligned configuration with an incoming columnated beam. A transient 2- dimensional conduction problem with phase change is formulated, which is solved using the commercial code FIDAP. Results highlighting the feasibility of growing GaAs, Ge and Si crystals with diameters of the order of 20 cm using the solar furnace satellite concept are presented. The transient temperature fields within various charge materials are quantified.

Jan 1, 1994

By P. Myllykoski, J. Nylander, A. S. Korhonen, J. Larkiola

The coefficient of friction and the deformation resistance have been determined from the measured rolling parameters by applying the Bland-Ford-Ellis rolling force model and the artificial neural network model (ANN). The dependence of friction on the parameters such as reduction, rolling speed, front and back tensions, contact pressure and deformation resistance have been studied by the ANN model. Measured data of over 10 000 coils have been used in the training stage. Various dependencies have been examined and the results show that the friction coefficient does not depend much on the rolling speed. The reduction and deformation resistance seem to have the strongest effect on the friction coefficient. A friction model based on neural computing has been included into the existing rolling force model.

Jan 1, 1994

By Norman L. Kotraba

Zia Metallurgical Processes, Inc. has developed and patented a steelmaking process capable of converting iron bearing metallurgical wastes into high quality steel products. The process utilizes a proprietary design rotary hearth furnace to convert iron bearing wastes, pelletized with coal, or other forms of carbon, into direct reduced iron (DRI). This DRI is fed, hot, from the rotary hearth furnace into a Zia All Purpose Vessel (ZAV) where it is smelted and refined into high quality steel. A specially designed turret with three independent arms, each supporting a separate ZAV, comprises the heart of the meltshop. No overhead cranes are required to transport molten metal from the smelting/refining operation to the ladle metallurgy station to the caster to an inspection station and back to the smelting/refining point. The molten steel is contained in the ZAV throughout the operations eliminating the possibility of steel con¬tamination by non-metallic inclusions occasioned by the exposure to ambient air during metal transfer into ladles. The result is the creation of very clean steel that can be alloyed to produce virtually any desired grade from stainless steel to common structural steel.

Jan 1, 1994

By R. G. Hilton

This paper deals with application of Super Detox? stabilization technology to the treatment of electric arc furnace dust (US-EPA listed hazardous waste KO61 ). The process has been used on approximately 170,000 tons of electric arc furnace dust. In addition to the nearly four years of commercial experience at Sterling, Illinois, the process is now being permitted for application at two other locations. The process was originally developed by the Bethlehem Steel Corporation and then further improved by Conversion Systems, Inc. (Bethlehem Steel's Licensee). The treatment process offers many unique bases for its selection, including: A) Low cost compared to the treatment alternatives; B) Lowest available TCLP leachate levels for any process treating K061. Many other processes leave some residue that represents a disposal requirement, although often not addressed; C) Produces minimized final waste disposed, including the fact that the total volume of dust generated and less than the volume occupied by the residue slag from HTMR; and, D) Opportunities for the beneficial utilization of part or all of the waste stream through the development of chemical and physical characteristics. Each of these aspects will be specifically discussed in the paper, including that status of the operations now under permit.

Jan 1, 1994

By Benoit DeBecker

Laboratory-scale experiments have shown that chromium metal could be recovered from chromate wastes by modifying slightly the chromium electrowinning flow-sheet. After reduction by sulhr dioxide and precipitation of chromic hydroxide, the solid residue is dissolved in the chrome alum solution and the metallic impurities are removed by cementation on manganese. The presence of dissolved manganese in the electrolyte does not affect the cathodic deposition of chromium and it eliminates the anodic production of Cr(V1).

Jan 1, 1994

By J. B. Cocanour

Pioneering work at the U.S. Bureau of Mines (USBM) has produced a personal computer (PC)-based, software-driven video photometric color sensor for real time process control of metallurgical streams. The video photometer is an inexpensive optical sensor which operates in the visual area of the electromagnetic spectrum and collects color information through plastic optical fiber. The red, green, and blue (R/G/B) voltage components of the color video signal are digitized and characterized through software and then presented as the control variable for software-based proportional-integral-differential (PID) control. This sensor has been successfully employed in the control of a laboratory copper electrolytic circuit. With this sensor, copper solutions were analyzed on-line without the need for sample removal, dilution, mixing or reagent addition, thereby allowing for the real time control of the circuit.

Jan 1, 1994