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By A. W. Bryson, S. P. Fox, S. A. Godorr

"This work is an extension of a previous investigation on the development of surface roughness during electrodeposition of copper. A comprehensive model based on diffusion and migration in a force field together with surface diffusion and sticking probabilities is used to generate profiles which are compared to those produced experimentally. The roughness is characterized by using the technique of fractal geometry which is shown to describe both qualitatively and 9uantitatively the development of surface morphology during electrodeposition.The work is extended to the deposition of copper in the presence of various concentrations of thiourea. The development of roughness is observed experimentally on the edge of a thin copper disc mounted between two glass plates. This enables photographs to be taken at various stages during growth. The surface outline is digitized using an image analyzer which enables the fractal dimension to be determined as growth proceeds. As expected, the presence of thiourea at low concentrations produces a fractal dimension which is closer to unity (i.e. the surface becomes smoother).IntroductionThe development of surface morphology during electrodeposition has far-reaching implications for copper plating in the electrowinning and electrorefining processes. Short circuits as the cathode surface grows unevenly require operator intervention in a dangerous environment and imply processing delays, and the inclusion of electrolyte in small gaps in the plated cathode have implications in downstream processing of the cathode. Higher current densities are obviously desirable, as they result in greater production rates, but as shown by Ettel et. al.(l), Harvey et. al.(2), Cook (3), and Harvey et. al.(4), it is not possible to operate near the projected economically optimum conditions because the electrodeposition of copper from sulphate and acid solutions is a mass transfer controlled process. It has been shown (Ettel et. al.(l), Harvey et. al.(2)) that the closer a system operates to mass transfer limiting conditions, the poorer the resulting cathode quality. One solution is to use agitation techniques to increase the limiting current density. Another is to add surface active additives to the electrolyte which has been shown by Ettel et. al.(l), Harveyet. al.(2) and Afifi et. a1.(5) to allow higher rates of production without decreasing cathode quality. The second proposed solution is of interest in this work, since there is very little knowledge of the conditions under which these additives operate effectively, and little fundamental understanding of the mechanism by which they operate. The current work seeks to contribute to this field by correlating a simulation model with experimental results to describe the development of surface morphology in the electrodeposition process."

Jan 1, 1997

By R. E. Aune

In the present work, a critical assessment of the thermodynamic information available for the ternary system Ni-W-0 has been carried out; This was complemented by experimental measurements of the standard Gibbs energy of formation of the ternary compound NiWO, by solid state galvanic studies involving Zr02-CaO solid electrolyte. The assessed thermodynamic data, together with the phase diagram information available in literature, were employed to generate the ternary phase diagram for the system Ni-W-0 in the temperature range 1073-1273 K. The calculation of the phase diagram was carried out by computer optimization according to the "CALPHAD" method. The computed phase diagram has been confirmed at isothermal sections by identification of the phases present in samples equilibrated at defined temperatures.

Jan 1, 1994

By Q. G. Liu

New solid-state electrochemical sensors 1;.1sing Li2SO4-Ag2SO4 electrolytes have been developed to measure SO2 and/or SO3 in gas mixtures. Silver embedded in part of the electrolyte is used as the reference electrode. Although single-phase electrolyte sensors yield accurate results for one to two days, a two-phase electrolyte cell exhibits excellent long-term chemical stability. For example, stable and accurate potent iometric responses have been obtained over a six mo.nth period. The. advantages of the two-phase electrolyte ( 23 mol% Ay 2SO4 ) cell include excellent mechanical strength on temperature cycling and an insensitivity to compositional variations in the electrolyte and to temperature fluctuations. Experimental tests have shown excell.ent results in SO2-air. mixtures with the SO2 concentration ranging from 3 to 10,000 ppm (vol). However, the SO2 concentration range was limited by a lack of standard gas mixtures, and our sensor cells can be used to measure S02 concentrations significantly less than or larger than our experimental range. Results also indicate that the presence of significant concentrations of CO2 and H2O in the gas mixture has no effect on the sensor response. Thus the two-phase electrolyte ( 23 mol% Ag2S04) sensor has exceptional selectivity, reliability and long-term chemical and mechanical stability.

Jan 1, 1985

By John J. Mazza

Treatability studies were performed to determine the effectiveness of two commercially available treatment methods (solvent extraction and thermal desorption) for the removal of PCBs and PAHs from contaminated dredged riverbed sediments. The solvent extraction method evaluated was the B.E.S.T. process which extracts the contaminants with triethylamine. The thermal desorption method utilized was the ATP process which desorbs the contaminants at elevated temperature in an anaerobic atmosphere. A description of both methods and. an evaluation of the treatability study results is provided. Each treatment method was used to treat two separate samples (high and low concentration) from the site. Overall, both methods proved to be very effective with solvent extraction achieving 98% removal of both PCBs and PAHs and thermal desorption achieving better than 99% removal of both the PCBs and PAHs from the high concentration sample. Both solvent extraction and thermal desorption achieved greater than 99% removals of PCBs and PAHs from the low concentration sample. Vendor cost estimates for full scale treatment were roughly equivalent. The primary differences between the two methods lies in the realm of permitting, operational requirements, and emission concerns.

Jan 1, 1994

By L. Petitnicolas

The experimental study of nitrogen absorption and its removal from a liquid Ni-20%Cr alloy at 1873 K has been undertaken, using an experimental, apparatus based on the Sieverts technique in order to determine the solubility of nitrogen in the alloy. as well as the kinetics of nitrogen transfer across the gas/melt interface. Experiments show that nitrogen solute equilibrium content can be calculated using the Sievens law. Measurements point out the nitrogen absorption reaction rate to be well described by first order kinetics, whereas experiments on nitrogen removal reveal that the rate is better expressed using a second order equation.

Jan 1, 1996

By Peijia Lin

Wheat straw was chemically modified by alkaline treatment followed by succinylation and sodium carbonate treatment for the use of cadmium and nickel adsorbent. The adsorption efficiency was calculated in different conditions. The experimental parameters were solution pH, adsorbent dosage, contact time and initial metal concentrations. The biosorbent was analysed by FTIR (Fourier- Transform Infrared Spectroscopy) to investigate the changes of surface functional group. The maximum adsorption percentages of cadmium (>99%) and nickel (>98%) were achieved using 5 g/L adsorbent with 50 mg/L initial metal concentrations. The adsorption kinetic study showed that the reaction was pseudo-second order kinetics and the adsorption isotherm was well fit by the Langmuir adsorption model. The dynamic column study indicates that modified adsorbent has a better adsorption capacity towards cadmium than nickel.

By Roger L. Williams

The Zinc Corporation of America Monaca smelter continues to use the St. Joe-developed electrothermic process for producing zinc metal and zinc oxide. As we enter the 1990s, the electrothermic process flexibility permits treatment of larger quantities? and lower-grade zinc-bearing recycle materials. A new sinter plant having one large sinter machine will increase sinter feed production required to meet our capacity target of 150,000 tons per year.

Jan 1, 1990

By E. Kuzeci, R. Kammel

"Lately various voltametric methods have gained increased attention as an analytic tool in hydrometallurgy. Voltammograms with mercury drop electrodes or glassy carbon electrodes provide information about the electrocrystallization of cathodic deposits and allow calculation of kinetic data by means of characteristic parameters like the peak potential and peak current and their variation with the voltage scanning rate.Cyclic voltammograms are also suitable for identification of reaction sequences. Voltammograms with carbon paste electroactive electrodes containing metal sulphide additions reveal information about the dissolution behavior. The stripping voltammetry can be applied to analyze metal ions and organic additives (e. g., thiourea) in extreme low concentration. Typical application of the various methods studied with microcomputer controlled measurement system are explained by examples selected from copper hydrometallurgy.IntroductionThe use of electroanalytical methods in metallurgical process control can be dated back to the starting period of industrial copper refining, when the deposition of the metal ions was followed electro-gravimetrically by weighing the electrode with deposits (1). The principles of metal deposition and dissolution have not changed but the methods to follow these phenomena were subjected to noticeable developments and especially the introduction of polarographic investigations by Heyrowsky (2) has greatly contributed to the progress in electro-analysis. A review about the fundamental work on the electrochemical kinetics in earlier time is compiled in a monograph of Vetter (2). With the steady improvements in the instrumental techniques, it is nowadays possible to apply several current and potential modulations for measurements with improved selectivity and sensibility. There is however, still a lack in theoretical interpretation of the data obtained. More theoretical information are already available for linear voltametric methods for systems where reduced as well as oxidized species are dissolved in the electrolyte (4, 5). Some recent investigations have also shown the reliability of these techniques to study electro-crystallization (6, 7). Main fields of the application in the hydro - and electro-metallurgy are:"

Jan 1, 1989

By K. Prashant Sarswat

Isotopes are critical to a variety of applications including physical science analyses, biology, medicine, pharmaceuticals, and national security. In most cases isotopes must be relatively pure or highly enriched before they become useful. Current isotope separation technologies are relatively inefficient, capital and labor intensive, and often produced by a limited number of suppliers. In the category of isotopes, lithium is among other important candidates. Lithium is found naturally in two isotopes, 6Li which accounts for 7.5% of all lithium, and 7Li which makes up the balance of 92.5%. Each of these isotopes is important to the nuclear industry. 7Li is often used in the form of lithium hydroxide which is used to control pH in pressurized water reactors. The current supply of 7Li is based mostly outside of the United States, and its long-term supply is uncertain. Apart from supply issues, the use of mercury for 7Li separation is also a concern in commercial processing using the most common and efficient approach [1–3]. Hence, a reliable, environmentally friendly, and efficient technique is needed to produce 7Li. In this line of investigations, the authors used a two-compartment system and significant separation was achieved. In this piece of research, some preliminary results are presented including cell design and actual isotope ratio after enrichment. Applying an electro-potential across two electrodes can be used to drive electromigration of Li isotopes. The electromigration is in addition to normal diffusion. Note that 6Li diffuses faster and hence there will be a lowering of the 6Li concentration near the positively charged electrode and an enhancement in 6Li near the negative electrode during the separation process. Similarly, 7Li will be more prevalent near the positive electrode and less prevalent near the negative electrode during the initial separation stage [1].

By Jennifer Murphy, Brad S. Schake, Karol Holmes, John R. FitzPatrick, Mike H. West

"The separation and purification of uranium from either nitric acid or hydrochloric acid media can be accomplished by using either solvent extraction or ion-exchange. Over the past two years at Los Alamos, emerging programs are focused on recapturing the expertise required to do limited, small-quantity processing of enriched uranium. During this period of time, we have been investigating ion-exchange as a method for extraction/purification of uranium from acidic media. In addition, waste stream polishing is associated with this effort in order to achieve more complete removal of the uranium prior to recycle of the acid. Extraction chromatography has been demonstrated to further polish the uranium from both nitric and hydrochloric acid media thus allowing for a more complete recovery of the actinide material and creation of less waste during the processing steps.We will discuss contact experiments for evaluation of eleven different resins for uranium removal from nitric acid, the evaluation (again by contact experiments) of uranium elution from the ion-exchange media by various chemicals, and small-scale experiments for the removal of 235U from nitric acid. Larger-scale (1 DO-gram) flow experiments, using depleted uranium, were done after the small-scale evaluation of the selected resin. A discussion is also included concerning the shortcomings of the contact experiments and how the flow experiments were modified in order to overcome these problems. We will also discuss the application of ion-exchange for some specific process needs at Los Alamos.Contact experiments were used to evaluate some commercially available solvent-impregnated resins in addition to evaluation of several resins of this type synthesized in our laboratory. These experiments involved both nitric and hydrochloric acid media. The data from these experiments will be used to determine the column size and amount of resin required to polish the waste stream produced by the ion-exchange process described above. Small-scale flow experiments will be described and data given on the mass balances achieved using this two step process.Future work for evaluation of new ion-exchange and solvent-impregnated resins as well as the search for new eluants will be discussed. Other future experiments for both processes, including large-scale experiments, will be discussed in detail."

Jan 1, 1996

By R. C. Hubli

A chemical model has been developed to investigate the dissolution of sulphide minerals in brine solutions containing copper and iron chlorides. The model has been employed to study the dissolution .of synthetic NiS using different initial concentrations of Cu(II), Cu(I), Fe(III) and temperature. The speciation of copper with particular reference to the formation of hydroxy-chlorides as a function of total chloride and H+ has been computed. The model predictions are in agreement with experimental results. It has been found that addition of Fe(III) results in the maintenance of a high Cu(II)/Cu(I) ratio leading to enhanced rates of dissolution and suppresses the loss of Cu(II) due to the formation of hydroxyl-complexes.

Jan 1, 1997

By Yanhui Sun, Yanan Zeng, Kaike Cai

"Hot ductility of Nb-V-containing steel has been studied by theoretical calculation and thermal simulation experiment. Meanwhile, microsegregation and precipitates were analyzed. The results showed that segregation degree of elements S, P, 0 is greater in mushy zone, while, the hot ductility was deteriorated by inclusions of Fe(S,O), (Fe,Mn,Si,Al)(S,O) in the interdendritic region. At the temperature 1100°C, a few NbN particles, 60-70nm, have little effect on mechanical property. In the temperature range 1000°C to 975°C, R.A declined rapidly from 82.36% to 69.61% with the diameters decreasing from 20 to 10nm and quantity of particles increased 23 to 45inds/µm2, respectively. In the temperature range from 900°C to 850°C, R.A reduced unobviously from 34.27 % to 30.01 % with ferric films thickening gradually. The critical stress, 52.38MPa, was equal to tensile strength at 975°C. Intergranular fracture was easy to occur with higher critical stress below 975° C.IntroductionProductivity and product quality of slab are seriously affected by cracks during continuous casting and the influencing factors of cracks are various[l]. From microcosmic angle, resisting deformation ability of initial solidification shell decreases obviously with solute elements segregation which can urge the low melting point ofliquid film to form at grain boundaries[2, 3]. Meanwhile, with temperature decreasing, particles would precipitate as the practical solubility product is greater than equilibrium solubility product. The carbonitrides would lead to stress concentration at austenite grain boundaries. Therefore, the transverse cracks of microalloyed steel would form during the straightening operation in the continuous casting process. The hot ductility of steels in the temperature of mushy zone was characterized by microalloy elements segregation, zero strength temperature (ZST) and zero ductility temperature (ZDT). The nature, shape, and size of precipitates have been investigated by TEM (JEM2100). Hot tensile test with low strain rate was simulated by Gleeble-1500. The objective of present study is to provide reference for zero defect of microalloyed steel during continuous casting process."

Jan 1, 2013

By Fuming Wang, Lifu Hu, Changrong Li, Ruipeng Pang

The solidification structure of 430 ferritic stainless steel has been calculated in the solidification process by using 3D-CAFE model under the condition of water cooling. The calculated results consistent with those obtained from experiment. Under watercooling condition, the solidification structure consists of chilled layer, columnar grain zone, transition zone and equiaxed grain zone

Jan 1, 2015

By R. D. Pehlke

The history and present status of continuous casting of steel are reviewed, including a genera 1 description of current processes. Plant layout, process development and elements of machine component design are outlined, and key steps in integration into a stee-1 production system are detailed. Recent productivity advances and improvements in quality are described. Process developments are reviewed, and some future avenues for this technology are considered.

Jan 1, 1985

By Jr. Napolitano, Jr. Sanders

"Morphological evolution of a dendritic growth front in a binary alloy is simulated using a cellular automaton approach to establish the feasibility of modeling such growth with a local rule-based scheme. The motivation for this work is derived from the need to predict the development of solidification structures within real components of complex geometry, where significant constraint of the thermal and solutal fields may exist. Such cases present complex boundaries and large domain sizes, which may preclude the effective use of more conventional methods. In this work, a model is presented which couples a two-dimensional alternate-direction-implicit finite-difference diffusion solution with a cellular automaton growth algorithm to simulate morphological evolution in alloys solidifying under directional growth conditions. Temperature, composition, and interface curvature are incorporated into a local growth potential which is used by the automaton, allowing the interface to evolve. Alloy solidification is simulated over a range of experimental conditions, producing various structures. Issues addressed include morphological instability, primary spacing selection, interface curvature, microsegregation, and tip conditions.IntroductionThe development of dendritic structure plays an essential role in alloy solidification. Virtually every microstructural feature, within a cast alloy component, is related to the interface morphology present during solidification. Conventional solidification theory, describing dendrite tip kinetics and mushy zone phenomena, provides a means for estimating overall microstructural parameters for an alloy solidified under steady-state conditions. Microstructural prediction for actual components, which are finite in size and complex in geometry, requires a description of the evolution of the interface morphology under transient conditions and geometrical constraint and an understanding of how the structure propagates through the mold. Any useful simulation tool must be equipped to handle these circumstances within the limits of computational feasibility."

Jan 1, 1998

By R. Kramer

During foundry sand reclamation process development, molds formed from reclaimed chromite sand showed a rapid decline in tensile strength during thermal cycling tests. Because this characteristic could limit reuse of chromite sand in the. foundry, the sand was examined in detail Scanning electron microscopy, x-ray mapping, magnetic susceptibility, and x-ray diffraction were utilized to evaluate processed chromite sand. It was found that process variables such as binder composition, reclamation temperature, and processing method had a significant effect on the chromite sand particle surface. X-ray diffraction indicated a crystallographic change in the processed sands. Magnetic susceptibility also increased after processing. Diffusion of iron to the particle surface and increased surface roughness were identified as potential causes of the decreased tensile strength in the molds.

Jan 1, 1991

By Takayuki Ichikawa

Hydrogen storage properties of ballmilled mixtures composed of the hydrogenated nano-structured carbon (CnanoHx) and lithium hydride (LiH) were examined by thermal and optical spectroscopic analyses. LiH needs higher temperature than 600°C for hydrogen desorption even under vacuum condition, while CnanoHx, which was mechanochemically synthesized from graphite powder by ballmilling under hydrogen atmosphere, reveals hydrogen and hydrocarbons desorption in wide temperature range from 300 to 800°C. Nevertheless, the composite of CnanoHxand LiH prepared by ballmilling desorbs hydrogen in relatively lower temperature range from 150 to 450°C. These phenomena indicate that the thermally liberated hydrocarbon radicals immediately react with LiH and release hydrogen instead of hydrocarbons emission, because CnanoHx contains hydrocarbon groups at the edge of nano-meter sized graphenes, which are recognized as IR active C-H stretching mode, and LiH is well-known as an ionic crystal. Furthermore, it is of interest that a nanostructural feature persists in this composite even after annealing at 350°C, which shows excellent cycle properties as hydrogen storage media.

Jan 1, 2006

By R. J. McClincy

The potential techniques for the direct smelting of copper sulfide concentrates to blister copper were evaluated from the standpoint of commercial application. Many existing smelters are adaptable to direct smelting practice but only with improved control of metallurgical performance. Modified and innovative procedures for slag cleaning and metal refining, prerequisites to direct smelting, are presented and discussed. The ability to smelt directly to blister copper using existing equipment and eliminating the need to convert matte offers ,significant advantages to traditional smelting practice from the viewpoint of cost, 'S02 control, and process simplicity.

Jan 1, 1983

By Yun Soon Han, Joo Hyun Park

Indium (In) solubility in the FeO-SiO2-Al2O3-5%CaO slag was measured under p(O2)=10¯¹¹ atm at 1573 K to clarify the dissolution mechanism of In in FeO-bearing metallurgical slag. The In solubility increased with increasing oxygen partial pressure, whereas it decreased by increasing the activity of basic oxide, viz. FeO. Thus, a dissolution mechanism of In in the FeO-SiO2- Al2O3-5%CaO slag was described by the following equation. In(s)+1/4O2(g)=(In+)+1/2(o2-) The enthalpy change of the In dissolution reaction was negative, indicating that the dissolution reaction was an exothermic reaction. This is consistent with the above reaction mechanism.

Jan 1, 2014

By H. Y. Sohn, Haitao Wang, Moo Eob Choi

"A novel ironmaking technology is under development at the University of Utah. This technology produces iron directly from iron ore concentrate by gas-solid suspension reduction. Hydrogen is the main reducing agent for high reactivity and for the elimination of carbon dioxide release in this ironmaking process. The direct use of concentrates allows bypassing the problematic pelletization/sintering and cokemaking steps in the steel industry.Intrinsic kinetics of the suspension reduction of magnetite concentrate particles by hydrogen has been measured. Experiments were carried out in the temperature range of 1423-1673 K, other experimental variable being hydrogen partial pressure, the amount of excess hydrogen and particle size. Under most experimental conditions, 95% reduction was attained within several seconds, which presents sufficiently rapid kinetics for a suspension reduction process. The reaction kinetics followed the nucleation-and-growth equation, and a rate equation that contains all the effects of the experimental parameters has been obtained.IntroductionWith the rapid increase in steel production, it is critical to control CO2 emissions which is the main greenhouse gas. It is inevitable to release a huge amount of CO2 when coke and/or coal are used as the main reducing agent in producing iron. As one of the methods to reduce the CO2 emission from ironmaking, the utilization of the gaseous reducing agents and fuels, including hydrogen, has been investigated [1-6]. The use of such gases forms the basis for a new ironmaking technology under development for producing iron directly from fine concentrates by a gas-solid suspension technology. This technology would reduce energy consumption by about 40% of the amount required by the blast furnace and drastically lower environmental pollution, especially CO2 emission, from the steel industry [4]. This is accomplished by adopting H2-based reductant and bypassing pelletization/sintering and cokemaking steps. Unlike other gas-based alternative ironmaking processes using shaft furnaces or fluidized-bed reactors, the suspension reduction technology is a high-intensity process because it will not suffer from the problems that other processes do when operated at high temperatures mainly from the sticking and fusion of particles."

Jan 1, 2011