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By Filiz Sahin

This paper presents a synthesis of TiB2 via carbothermal reduction method using a mixture of TiO2, B4C and C prepared in molar ratio of 2:1:3. Reduction experiments were carried out in a high temperature graphite furnace in a graphite crucible under argon atmosphere at different time (0, 15, 30 and 60 min.) and temperatures (1400, 1500 and 1600 °C). The products obtained were investigated using XRD technique.

Jan 1, 2008

By Masanori Abe, Yoshitaka Kitamoto, Kazuhiro Nishimura

"Ferrite plating is a chemical processing which utilizes Fe2+ - Fe3+ oxidation to synthesizing polycrystalline films of ferromagnetic spinels (MFe20 4, M = Fe, Co, Ni, Zn, Al, Cr, TI, etc:) directly from an aqueous solution at 24 - 100°C. This low temperature process allows us to fabricate new ferrite film devices on · substrates of such non-heat-resistant materials as plastics, GaAs integrated circuits, and biomaterials. Synthesized from an aqueous solution the ferrite plated ·films are highly biocompatible. Thus various magnetic device and biomedical applications have been proposed and realized using ferrite-plated films. Ferrite-encapsulated polymer microspheres are applied to antibody carries for enzyme immunoassay, and also to toners/carriers for photocopying. Perpendicular magnetic recording media utilizing plated CoNi ferrite films are proposed. The low-temperature synthesized films of NiZn and Co ferrites are potentially used as soft-magnetic and/or insulating layers, respectively at high/microwave frequencies.IntroductionFerrite plating is a processing which facilitates the formation of crystalline spinel ferrite films with various compositions, (Fe, M)30 4 (M = Fe, Co, Ni, Zn, Al, Cr, TI, etc.), directly from an aqueous solution at 60 - 100°C [1]. This opened the door to fabricating novel ferrite-film devices using substrates of such non-heat-resistant materials as plastics and GaAs integrated circuits [2-4]; conventional ferrite film preparation techniques such as sputtering, vacuum evaporation, MBE, LPE, etc., require high temperatures(> -600°C) for crystallization of ferrites, which deteriorates the non-heat-resistant substrates. Recently we extended ferrite plating to be preformed at room temperature [5, 6]. This enables us to use as substrates such organic materials as biomaterials (e.g. enzymes) having very low heat-resistance."

Jan 1, 2000

By K. S. Han, M. Yoshimuura, H. Fujita, Y. Sato, S. W. Song

"Film of LlCoO2 as cathode material for rechargeable lithium microbatteries has been fabricated on the platinum metal substrate by electrochemical-hydrothermal method in concentrated LiOH solution at 200 °C as Soft Solution-Processing. The film fabrication has been understood in terms of dissolution of cobalt metal powders and subsequent oxidative deposition on the substrate. The film structure was characterized using scanning electron microscope, X-ray diffraction analysis; X-ray photoelectron spectroscopy and micro-Raman spectroscopy.IntroductionRapid growth of wireless communications and emerging integrated optoelectronic circuits caused the miniaturization· cif electronic devices, thus the demand for high energy density microbatteries as a power source for the microelectronics increases. In this regard, all solid-state lithium microbatteries including LiCoO2 and LlMn2O 4 [l-4], the most promising intercalation cathode material, have been developed. However, major difficulty of .fabrication of a lithium microbattery arose from the preparation of cathode film, according to a· recent report on Rare Metal News [5]. Although many attempts have been made to deposit the cathode films, all those methods are mostly chemical vapor deposiiton (CVD), various evaporation, sputtering techniques and spray pyrolysis. These methods require preparation of bulk cathode materials cir its precursor, then deposition with complicated instruments including high· vacuum system, and even postsynthesis annealing to obtain desire electrochemical 'properties. It is clear that all of these techniques are neither economic nor environmentally friendly. Compared to those methods, film form.ation from an aqueous solution is thought to be simpler and more economical, and requires much· less energy consumption. Our .group has demonstrated the utility of Soft SolutionProcessing [6,7], which is defined as environmentally friendly processing using (aqueous) solutions, to produce films of a variety of functional solid materials. According to the Pourvaix's diagram [8], some metal can be dissolved in an alkaline solution and consequently combined with hydroxyl group or oxygen anion forming metalate or metalite. Cobalt also seemed to form cobaltite, HCoOi in strong alkaline solution in the Pourvaix's pH-potential diagram. Based on this information, it was expected that LiCoO2 could be prepared using the cobalt metal in Li OH solution by Soft Solution-Processing. Recently, we reported the successful single step fabrication of electrochemically active LlCoO2 films on the cobalt metal substrate by hydrothermal methods without any post-synthesis annealing as Soft SolutionProcessing [9,10]. Film formation mechanism could be elucidated by the following evidences. . As expected from Pourvaix's diagram, cobalt metal was dissolved in concentrated LiOH solution forming dissolved cobalt species which was detected by an observation of absorption band in UV-VIS absorption spectrum [10]. Thus the reaction was assumed to be started from dissolution. Time dependent potential of Co electrode exhibited only one-step evolution with 0.6 eV from Co metal to LiCoO2 [10]. Another strong evidence was the finding of LiCoO2 powder precipitates at the bottom of tetlon beaker after the reaction [11]. Based on those experimental findings, it was understood that film is formed by dissolution-precipitation mechanism [9-11]."

Jan 1, 2000

In low carbon TRIP steels, the formation of carbide-free bainitic ferrite is crucial for the stabilization of austenite. Based on experimental investigations modeling the bainite reaction is examined adopting diffusional and displacive mechanisms, as well as the semi-empirical JMAK approach. Transformation tests were carried out to study the isothermal austenite decomposition into bainitic ferrite for a model steel containing 0.6wt%C, 1.5wt%Mm and 1.5wt%Si which replicates the composition of remaining austenite at the start of the bainite reaction in a classical C-Mn-Si TRIP steel. In the diffusional approach, classical nucleation theory is employed and subsequent growth of bainite plates is modeled using the Zener-Hillert theory. In the displacive approach, the autocatalytic nucleation of bairtite plates is assumed to be rate controlling. The predictive capability of all models is evaluated for temperature ranges where different morphologies of bainitic ferrite have been detected, The shortcomings and inherent challenges associated with either of these modeling approaches will be delineated.

Jan 1, 2003

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 I. Perus, M. Fazarinc, G. Kugler, M. Tercelj

"Ledeburitic tool steels are highly alloyed steels used for specific highly loaded applications but are characterized by low and variable hot workability. In this contribution the importance of selecting the right choice of some essential process parameters, i.e. casting temperature, solidification rate and soaking temperature, needed for improving the intrinsic hot deformability of ledeburitic tool steels, is studied. An inappropriate selection of casting temperature and cooling rate results in precipitation of unusual eutectic carbides that decreases the hot workability, whereas with the selection of appropriate soaking temperature the temperature range of safe hot working can be broadened. For each initial as-cast microstructure individually determined soaking temperature should be selected.IntroductionThe surface cracking during hot deformation of ledeburitic tool steels reduces mechanical properties and their industrial yield. These tool steels have high hardness, wear resistance and high tempering resistance on one hand, and high flow stresses and low hot deformability on the other. Decreased hot deformability of the tool steels is attributed to the type, size, shape, distribution, fraction of eutectic carbides and/or other phases, grain growth, etc. at upper limit while precipitation of secondary carbides and decreased recrystallization rate at lower limit of the safe hot deformation temperature range, [1-6].The occurrence of cracks on most exposed areas of workpiece are related to the areas where similar conditions related to upper and/or lower limit of temperature working range prevail, i.e. areas with accelerated cooling, areas with higher value of accumulated strains where also decreased recrystallization rate with simultaneously presence of higher tensile stresses takes place, furthermore areas of workpiece which are due to combustion conditions in furnace heated to higher temperatures, etc. Thus the areas, where combination of previously mentioned conditions prevails, are more exposed to cracking. This additionally requires that hot deformability of ledeburitic tool steel should be considered as a complex problem. Publications in the literature with regards to hot deformability of tool steels are predominately of a partial nature thus all reasons for unexpected occurrence of cracks are not sufficiently explained in available literature so far. Furthermore modern practice proves that previous processing parameters significantly influence the hot deformability and thus this cannot be considered as a constant value. During heating, soaking and hot deformation various processes take place: decay (decomposition) of carbides, formation of new carbides, dissolution of carbides and of alloying elements, etc. Thus depending on variation of process parameters and chemical composition, that consequently influences the processes related to carbides, shifting of decreased deformability at both limits of temperature working range to higher and/or to lower temperatures can occur, [1-14]."

Jan 1, 2012

By W. K. Collins

Engineered Scavenger Compounds (ESCs), developed by the U.S. Bureau of Mines, are a novel class of compounds that can selectively recover a desired element from a solid or molten alloy. Lithium titanate (Li2Ti3O7 or L'20-3T'02) is being used as an ESC to recover lithium (Li) from Aluminum-Lithium (Al-Li) alloys. X-ray diffraction measurements have shown that lithium titanate undergoes a phase change from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of Li in the matrix of the material and the effect of temperature. Although both are metastable, the hexagonal phase that forms during the scavenging of Li from Al-Li alloys appears to be the more stable phase. Recovering Li from the ESC by electrodeposition does not cause the structure to revert to the orthorhombic phase. Both the orthorhombic and the hexagonal structures of Li2Ti3O7 have similar scavenging capacities for Li. This paper proposes a new mechanism for the phase transformation.

Jan 1, 1993

By D. J. Murdock

Cominco Ltd. has developed a number of innovative technologies for electrowinning. The paper discusses the application of these technologies to the copper industry. Tankhouse and cell design will be discussed in addition to anode cleaning and cathode handling. Specific examples of the application of this technology to the copper industry are cited.

Jan 1, 1987

By M. M. Monte

A method for removing metallic mercury from contaminated tailing, using the flotation process, is described. In order to define some relevant parameters for the mercury flotation system, microflotation and electrophoretic mobility tests were carried out on (pure) metallic mercury in the presence of several surfactants. Based on the results obtained from fundamental studies a series of bench scale flotation experiments with mercury containing tailings from two wetland sites in Brasil were done. The results of microflotation tests with mercury showed that by using cetyl trimethyl ammonium bromide, an increase in mercury flotability is observed in the acid pH range, whereas in the presence of potassium oleate the highest mercury flotability was found in the alkaline pH region. The mercury flotability using potassium amyl xanthate was improved by the addition at sodium dithionate as an activator. The bench scale flotation tests with contaminated tailings from Poconé (brazilian wetland site) showed a recovery of 70% when sodium dithionate was used as activator and potassium amyl xanthate as collector. The resulting coefficient of separation is around 60%. However, the results of the flotation experiments with fine fractions from amalgamation tailings from Peixoto de Azevedo (brazilian wetland site) showed a low mercury recovery (32%).The results from this work suggest that since in the Poconé site tailings, the metallic mercury is not completely associated to the finer particles, the flotation process to recover the metallic mercury seems very promisor.

Jan 1, 1996

By W. D. Riley

Engineered Scavenger Compounds (ESCs), developed by the U. S. Bureau of Mines I are a novel class of compounds that can selectively recover a desired element from 'a solid or molten alloy. Lithium titanate (Li2Tip7 or Li20' 3TiO.) is being used as an ESC to recover lithium (Li) from Aluminum-Lithium (AI-Li) alloys. X-ray diffraction measurements have shown that lithium titanate undergoes a phase change from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of Li in the matrix of the material and the effect of temperature. Although both of the structures are metastable, the hexagonal phase that forms during the scavenging of Li from AI-Li alloys appears to be the more stable phase. Recovering Li from the ESC by electtodeposition does not cause the structure to revert to the orthorhombic phase. Both the orthorhombic and the hexagonal structures of Li.Til07 have similar scavenging capacities for Li. This paper proposes a new mechanism for the phase transformation.

Jan 1, 1991

By L. A. Harris

The formation of coke during coal liquefaction can eventually result in catastrophic failure of the conversion system. Coking typically proceeds by the formation of liquid crystals (mesophase) and the subsequent separation of these crystals from the plastic phase formed during heating of coal. The anisotropy of the mesophase makes it readily detectable in the optical microscope under polarized light. This study examines the solids formed during coal liquefaction processing by optical and electron microscopy. Observations on the relationships between the coke morphology, minerals and inert macerals are presented.

Jan 1, 1982

By B. Wasmund, K. Adham, K. O'Keefe, C. Lee

"Metal chlorides (e.g. iron and nickel) can be pyrohydrolysed at elevated temperatures to yield an HCl rich off-gas and a metal oxide product. Typically, the high energy requirement for pyrohydrolysis is provided by the combustion of a hydrocarbon fuel with air. Here, it is demonstrated that the use of oxygen-enriched combustion can result in lower fuel requirements and higher HCl concentrations. In addition, the oxygen enrichment can result in a smaller volume of off-gas and thus, smaller and less expensive process equipment. This new concept can be applied to both the spray roaster (SR) and the fluidized bed reactor (FBR). Similar to the aircombustion case, the oxygen-enriched process can use a direct contact venturi scrubber, to recover energy from the roaster off gas, but at a higher efficiency. The new process also uses an absorption tower for capturing HCl from the roaster off-gas, but generates a stronger HCl solution than is possible with pyrohydrolysis in air.BackgroundIn recent years, the metallurgical industry has become increasingly involved with developing methods for extracting metals, upgrading products or cleaning metallic products by using hydrochloric acid. These applications of chloride metallurgy often result in metal chloride solutions, which should be processed to regenerate HCl for reuse, and to recover the metal value as a product or by-product oxide [2, 3, 4].The pyrohydrolysis of metal chloride solutions has been done in two types of air roasters: spray and fluidized bed. The existing roasters burn a hydrocarbon fuel in air, to provide the required energy for evaporating the feed solution and to provide an elevated temperature for the chloride pyrohydrolysis to occur, according to the following reactions:"

Jan 1, 2011

By J. F. White

An experimental study was undertaken to evaluate the feasibility of a selective chloridizing roasting pre?treatment process for the elimination of impurities from zinc feed?stocks prior to recovering zinc by conventional unit operations. In this investigation, a number of chemistries that might serve as a basis for such a pre? treatment process were examined. A variety of chloridizing agents were admixed with EAF dust to promote the selective removal of lead and cadmium by the formation of volatile metal chlorides, he results of the experimentation firmly establish that selective chloridizing roasting is a technically feasible means of eliminating lead and cadmium from EAF dust. Excellent extraction efficiencies were accomplished with a number of chloride additives; as high as 98 percent lead extraction and 88 percent cadmium extraction were attained with minimal zinc losses, Continuous pilot?scale tests reinforced the trends established by laboratory?scale experimentation, Attempts of chlorine elimination using pyrohydrolysis were less successful. The extent of chlorine elimination was found to be highly dependent upon EAF dust sample type and treatment temperature.

Jan 1, 1996

By Dong Joon Min, Joo Hyun Park, Mi Sun Choi, Jae Hong Shin

Sublimation of ZrCl4 is important for the production of nuclear grade metallic Zr in Kroll’s process. The sublimation kinetics of ZrCl4 was investigated by TGA under both isothermal and non-isothermal conditions. The sublimation rate of ZrCl4 increased with increasing temperature under isothermal conditions. ZrCl4 sublimation was confirmed to be a zero-order process under isothermal conditions, whereas it was first-order kinetics under non-isothermal conditions. The activation energy of ZrCl4 sublimation under isothermal conditions was 21.7 kJ/mol. The activation energy for non-isothermal sublimation was 101.4 kJ/mol and 108.1 kJ/mol with the Kissinger method and Flynn- Wall-Ozawa method, respectively. These non-isothermal activation energies were very close to the heat of sublimation (103.3 kJ/mol). Sublimation occurs by two elementary steps: surface reaction and desorption. Therefore, the overall activation energy of ZrCl4 sublimation is 104.8(±3.4) kJ/mol. The activation energy of the surface reaction and desorption steps are proposed to be 83.1 kJ/mol and 21.7 kJ/mol, respectively.

Jan 1, 2014

By Shilai Yuan, Huimin Lu, Zhijiang Gao, Panpan Wang

"Solvent refining of silicon through using Si-Al melts is a valid method to remove the impurities from metallurgical grade silicon (MG-Si) melt. The thermodynamic behavior of impurities Fe, Al, Ca, Ti, Cu, C, B and P in MG-Si during the solidification of MG-Si was studied based on the available thermodynamic parameters and experimental data. The morphology of inclusions was investigated by Scanning Electron Microscope (SEM). The chemical composition of inclusions in MG-Si and Al-Si melt was analyzed by EPMA. It is found that the amount of white inclusion reduces and most impurities are solved into the Al-Si melts. After solidification of Si–Al alloy using induction heating and acid leaching, impurities can be effectively removed. The solidification of silicon from the Si–Al melt is found to be more effective for purification than general silicon solidification.IntroductionPhotovoltaic energy is one of promising energy resources in a sustainable society because of its inexhaustibility and cleanliness. Although the production and installation of solar cells have increased significantly during the last decade, the cost of solar cell installation is still high. Multicrystalline silicon has now become the main material in the photovoltaic market because of its low production cost and because of the relative high conversion efficiency of solar cells made from this material, which has been studied for a long time [1-3].Electronic grade (EG) silicon (99.9999999% Si) is commonly used as the raw material to produce SOG-Si (99.9999% Si). Silicon produced from the chemical routes restricts the development of solar cells due to environment threaten, high energy consumption and low productivity. Purification of metallurgical grade silicon (MG-Si) is a low cost, environment friendly method. Although several metallurgical processes such as directional solidification, vacuum refining and electron beam melting [4], have been developed, the cost reduction and refining efficiencies for manufacturing silicon is still have to be further optimized.In the purification process, it is difficult to remove boron and phosphorus by the conventional metal refining method. The refining efficiency depends on the segregation behavior of different elements in solid silicon and the liquid phase. The segregation ratios of all investigated impurities were found to be much smaller than the segregation coefficients between solid and liquid Al-Si melts [5]. For instance, the segregation coefficient of B in Si is 0.8 at the silicon melting point (1687K), whereas it is around 0.2 when silicon is solidified from Si-Al melt at 1273K. For phosphorus the segregation coefficient is 0.06 when silicon is solidified from Si-Al melt at 973K°C, which is much less than 0.35 for recrystallization from liquid silicon. Since the segregation coefficient of boron in silicon is 0.8, it cannot be removed by directional solidification."

Jan 1, 2014

By Kun Wang, Xinhui Li, Huaqing Xie, Qingbo Yu, Qin Qin

"Three typical model compounds of bio-oil (ethanol, acetone and phenol) were studied in the steam reforming process for hydrogen production. In the thermodynamic analysis, the three componds showed the similar trends. The hydrogen yields increased with the increase of steam/carbon (S/C) ratios, and the temperatures of the maximum hydrogen yields moved afterward to low temperature zone. However, the hydrogen contents were just about 70%. For improving hydrogen yield, a new system for steam reforming of bio-oil with site CO2 capture was put forward. This system required the catalst with the larger granularity having greater mechanical strength and higher abrasion resistance. So, six Ni-base catalysts loaded on Al2O3 particles prepared were used and among them, Mg-Ni/Co catalyst showed the best catalytic performance. For the simulated bio-oil (the mixture of the compounds), the hydrogen yield can attain 63% with Mg-Ni/Co catalyst with the good stability and regeneration ability.IntroductionCurrently the interest in the use of hydrogen as a clean energy carrier is increasing, and the main way for producing hydrogen is steam reforming of fossil fuels, containing steam reforming of nature gas, naphtha and coal. But this way caused substantial amounts of CO2 emitted, and these sources of hydrogen which are non-renewable energy will eventually be used up [1, 2]. As a kind of renewable energy, biomass is recognized as an attractive alternative to fossil fuels, because of its neutral CO2 emissions [3]. There are mainly two thermochemical processes using biomass to produce hydrogen, gasification and flash pyrolysis followed by steam reforming (SR) of the biooil produced in the flash pryolysis process [4]. The latter was known as one of the most promising and economically viable methods for hydrogen production [5]. In the last decades, the biomass flash pyrolysis technology was adequately developed and fairly mature [6]. But the steam reforming of bio-oil is still at the research stage and yet has been leading to more and more concerns by the researchers. In their research, the catalysts were widely studied and yet mainly were powdery[7-10], and the reactors manily were fixed bed reactors[11-13], readly causing the carbon deposition and the catalyst deactivation, against the continuous running. In this paper, a new systerm was put forward and could realize continuous production of hydrogen, yet needed catalysts with the larger granularity having greater mechanical strength and higher abrasion resistance, as well as powdery CO2 sorbents which mainly calcium oxide based ones.In this paper, the thermodynamic analysis of the steam reforming processes of three typical bio-oil model compounds (ethanol, acetone, phenol) was performed, and the effect of S/C ratio and temperature on the hydrogen yield and the compositions of gaseous products were investigated. Then, a new systerm for steam reforming of bio-oil with site CO2 capture was put forward, and the catalysts with a certain granularity were prepared and studied."

Jan 1, 2014

By Benjamin P. Hay

Complexation of a metal ion to a ligand often results in structural changes that introduce steric strain within the ligand. A design criterior:1 for ligands that will complex metal ions more strongly is to choose Iigar:1d architecture, that minimizes this strain. This paper describes how molecular mechanics models can be used to define the degree of ligand binding site organization in terms of' ,strain energies associated with conformational reorganization and distortion of the binding conformer. This approach yields a method to predict how modifications to ligand structure will affect metal binding affinity.

Jan 1, 1999

By A. E. Isaacson

Bureau of Mines researchers developed and tested equipment to measure corrosion rates on a commercial-scale mill as an aid in predicting the effect of corrosion on minerals and how this effect relates to downstream processing. Bench-scale experiments were designed for duplicating ore grinding conditions closely enough that realistic rate determinations can be made in laboratory tests. Rates measured in a laboratory system compared favorably with those measured in the field. Cast steel was found to have corrosion rates in a copper mill and laboratory test cell of 22 and 21 mpy, respectively. Corrosion was found to account for less than 5% of the total grinding media wear in the operations studied.

Jan 1, 1987

By Jack S. McPartland

The recent developments on the concentration and recovery of gold from leached gold thiosulfate solutions by solvent extraction, reduction-precipitation, and electrochemical deposition are reviewed in this paper. Alkyl phosphorus esters have been found to extract gold only in alkaline thiosulfate solutions, The recovery of gold increases with thiosulfate concentration in the aqueous phase and with alkyl phosphorus esters concentration in the organic phase with aliphatic hydrocarbon diluents. The addition of ammonia improves the extraction. The extraction of gold with amines in either aliphatic or aromatic diluent decreased in the following order: primary>secondary>tertiary amines. Increase in the extractant concentration at high pH increased the extraction of gold. At pH < 9, the primary amine, RR&apos;CHNH2 with 1&apos;9-23 carbon atoms is the main extractant with TBP as the synergistic reagent and at pH >9, the primary amine shows a synergistic effect on the extraction of gold&apos; with TBP. TheAu(I) ions in thiosulfate solution are reduced by sodium borohydride (SBH) to metallic gold, with particles in the sub micron range, At an SBH/ Au ratio of 6.25, pH = 6, and at room temperature, the I e ppm Au(I) in a solution of ] 0 gil thiosulfate was completely reduced to metallic gold in about 60 minutes.

Jan 1, 1999

By Bora Derin

This work deals with the recovery of valuable metals from the ancient copper smelting slags located in Küre-Turkey. In this process, copper and cobalt were recovered in metallic form and/or as their compounds, whereas iron was recovered as magnetic oxide or pigment. Abrasive grit material was produced using reduced final slag. The process stages involved carbothermal reduction in a DC arc furnace, granulation, leaching, chemical precipitation, selective sulfidizing roasting and product preparations. In this paper, the process stages were described as theoretically and experimentally whereas slag and products were characterized in detail.

Jan 1, 2003