Search Documents

By Sven Eck, Andreas Ludwig, Menghuai Wu

"Phase separation is a frequently occurring phenomenon during solidification accompanied by melt convection, sedimentation or, in the case of two unmixable liquids, a Marangoni driven motion. In order to describe these phase separation phenomena a two-phase volume-averaging model was employed for globular equiaxed solidification of binary alloys and decomposition and solidification of hypermonotectic alloys. The model considers nucleation and growth of equiaxed grains or second phase droplets, motion and sedimentation of grains or droplets, feeding flow and solute transport by diffusion and convection. It allows the prediction of macro segregations and the distributions of grain size or droplet size. Evaluations were made by comparing the numerical predictions with experimental results. For example it is shown that the numerically predicted grain size distribution in a plate casting (Al-4wt%Cu) agrees reasonably well with the experimental analyses.IntroductionModeling of metallurgical processes is a rapidly expanding field and the research activities in the last decades cover a wide range of areas including melt pre-treatment, solidification and subsequent manufacturing routes. Among those activities solidification stands in the central position, because the primary structure of the materials, and even many defects such as porosity, (macro or micro) segregation and inclusions form during solidification. Those primarily formed structures or defects once existing are difficult to be removed or modified by the subsequent material processing.Solidification is a multi-disciplinary field involving thermodynamics, fluid dynamics and solid mechanics, heat and mass transfer, and other disciplinesr1 -31• One of the most challenging problems in solidification modeling is the complex interactions between physical phenomena occurring on different length scales ranging from atomic rearrangement over single crystal-melt interactions to heat extraction, momentum and species transport at the system level. Modeling an industry process on atomic scale is umealistic, even on grain scale (e.g. phase field method) it would need another 40 years to be able to model the exact grain morphology in a casting space envelope of 10x10x10 cm3 [ 4]. Therefore, the realistic models for industry process are based on the solution of the macro transport equations (mass, momentum, enthalpy and species) on system scale. The microscopic phenomena such as thermodynamics, nucleation law, crystal growth kinetics and interactions at the liquid-solid interface are considered with simplified models, which are coupled with the macroscopic transport equations."

Jan 1, 2004

By K. Osseo-Asare

Third phase formation, the separation of a solvent extraction organic phase into two liquids, is generally attributed to the limited solubility of the extracted complexes in the hydrocarbon diluents. Much of the research on third phase fomiation, therefore, emphasizes experiments designed to establish the stoichiometry of the species responsible for the limited solubility. This work offers a different approach, based on the recognition that the solvent extraction third phase, in fact, corresponds to the middle phase in a microemulsion fluid system. Using the tri-n-butylphosphate (TBP)-diluent-water-electrolyte system as a model system, current concepts of microemulsion phase behavior are utilized to develop a general framework for interpreting and predicting the patterns of phase behavior in solvent extraction systems.

Jan 1, 1999

By Dean Ilievski

Mathematical modelling of the precipitation process requires that the kinetics of crystal growth, nucleation and agglomeration be known: This paper reviews the current state of knowledge on these precipitation sub-processes (ie. growth, nucleation and agglomeration) and describes a number of experimental techniques for estimating their kinetics. The experimental methods used to generate the precipitation data and the data analysis techniques used to extract the kinetics information from the data are discussed separately. There is no universal "best" technique for determining the kinetics. However, studies on multi-crystal systems are more reliable for modelling purposes than are single crystal studies. The selection of a technique will depend on which sub-processes are present. A problem with all kinetics studies is that there is generally a large uncertainty in the estimated kinetic parameters. This stems from the scatter in the experimental data being further propagated by the mathematical techniques used to extract the kinetic parameters.

Jan 1, 1996

By N. L. Piret

Reprocessing of low zinc-bearing residuals with a zinc content of less than 10%, originating from the iron and steel industry, has been given more and more attention in the last few years, due to the potential landfill liability and the increasing cost of disposal by dumping. Whereas, recycling of hazardous electric arc furnace dust is already being performed commercially on a large scale in the U.S., Japan and Western Europe, almost no reprocessing takes place in the case of these low grade zinc-bearing materials. In blast furnaces and basic oxygen furnaces dusts and / or sludges are generated at a rate of 1 to 2 % of the respective production. The technologies for the retreatment of these types of materials, either commercially available or still being developed are briefly described hereafter. They involve internal recycling, upgrading by physical separation methods, separate hydrometallurgical processing and pyrometallurgical treatment. Their scope and limitations are critically assessed in terms of technological applicability, economic feasibility and environmental compatibility. Since, the possibtlity of achieving economic profitability is unlikely with this type of material, the main criteria for acceptability of the treatment process are: generation of a iron-rich material, suitable for treatment by the iron/steel industry, acceptance of the non--ferrous metal-bearing sub-product by zinc smelters, generation of non-hazardous waste materials.

Jan 1, 1992

By Xin Wang, Hongmin Zhu, Shuqiang Jiao

"The behavior of electrochemically depositing silicon in a molten high-melting-point fluoride electrolyte was studied at 1300 °C. The cathodic product was characterized by XRD, SEM and EDS. Though the analysis of structure and composition of deposition, it could certify that silicon deposited on the Mo rod and alloyed with molybdenum. A series of tests had been performed on the cathodic behavior of Si4+ ions in BaF 2-CaF 2-Na2S iF 6 molten salt. The influence of electrochemical parameters on the cathodic deposition of silicon was also investigated. The electrochemical behavior of Si4+ ions in applied fluoride melts was observed to proceed according to one-step reaction.IntroductionGreenhouse warming has been a serious global issue. lt is increasingly urgent for clean and renewable energy. Effective utilization of clean and inexhaustible solar energy has become very important. Solar cell (especially poly-Si solar cell) production has significantly increased this decade, as there is a growing demand for clean energy. Since the early 1980s, the annual growth of the photovoltaic (PY) solar cell industry is more than 30%. More than 90% of the annual solar cell production is based on crystalline silicon wafers. This rapid growth leads to a shortage of silicon of the adequate quality and price for the continued growth of this industry [I , 2J. The most conunonly used technology to produce silicon is the so-called Siemens process. This technology, involves the forming of gaseous Si compounds such as trichlorosilane (SiHCli) or silane (SiH4) with subsequent thermal decomposition of these back to Si. This technology is associated with transformations from solid to gas, and then back to solid phase, which lead to high irreversible thermodynamic losses and subsequent high energy consumption, the energy cost being around 200kWh/kg Si [3l_ The purity of the material from this process is very high (9 to 11 N). In general, what is needed for solar cell purposes are reported to require 4 to 6 N quality. To promote continued growth of the silicon-based PY industry, there is need for a low-energy silicon production process which can produce large amounts of silicon with an acceptable quality and a lower price particularly."

Jan 1, 2012

By Kimio Itagaki

Thermodynamics and rate process fundamentals are two of the important principles involved in nonferrous production processes. The process configuration establishes whether thermodynamics or rate process behavior is most relevant in a particular application. In this paper, thermodynamic theory and rate process fundamentals are used to analyze the main characteristics of smelting and converting processes. The effect of increased oxygen potential .is examined with emphasis in view of the increased use of highly oxygen-enriched gas in modem smelting processes. Phase equilibrium and the distribution of minor elements between copper or nickel matte and FeOx-SO2- or FeOx-CaO-based slag are reviewed. The use of oxygen-rich gas has no serious effects on 'the recovery of valuable copper and silver in the matte phase, while the recovery of nickel and cobalt is adversely affected. The oxygen content in the gas also strongly affects the distribution behavior of arsenic, antimony and bismuth. Analysis of the rate processes occurring in the shaft of flash smelting, and converting furnaces by a 3-D computational fluid-dynamics model is also discussed. After being validated with experimental data collected in a large laboratory furnace, the computer model has been used to simulate the main features of an industrial flash converting operation. The results present quantitative features of the improved mixing of the particle-gas suspension and increased oxygen efficiency obtained with a distributor-cone burner compared with those with a single axial entry burner. The role of basic principles in the engineering analysis of high-intensity matte smelting processes is also discussed.

Jan 1, 2002

Cospidie (3CaO*2SiO2*CaFe2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel, The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiO2-CaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been deterimed by an electromotive force methods using CaF2 as solid electrolyte and a transpiration method as follows: ^fG° (cuspidine) /kjmol-1 = 5198 + 0.825T (+12) (1313<T/K<1329): EMF method ^fG° (cuspidine) /kjmol-1 = 5178 + 0.813T (+8) (1221<T/K<1469): Transpiration method The chemical potential diagram and constituent activities for the CaO-SiO2-CaF2 System have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

By E. Maziar Sauber

In order to prepare a more desirable feedstock for a rare earth elements separation refinery, cerium, a penalty element in the refinery feedstock, should be removed from the mixed rare earth elements oxide or carbonate feedstock. In this study, cerium (III) to cerium (IV) oxidation by calcium hypochlorite and subsequent precipitation was used to remove cerium from a mixed rare earth elements chloride solution. A factorial design of experiments was used to determine the effect of process variables such as temperature, pH, and oxidizer addition on the oxidation of cerium (III) using synthetic solutions. Under certain test conditions, all of the cerium was successfully removed from the chloride solution, and some REE accompanied cerium and reported to the precipitate. This proposed technology can allow for low cost removal of cerium from mixed rare earth elements chlorides.

By Riyad N. Ahmad-Bitar, Shadia J. Ikhmayies

"CdS/CdTe solar cells were built by depositing a 200 nm layer of Sn02:F on glass substrates by the spray pyrolysis (SP) technique, a 500 nm CdS:In layer by the same technique and a 1-1.5 µm CdTe layer by vacuum evaporation. The cells were CdCh heat-treated in nitrogen atmosphere for 30 minutes at 350 -.C. The photoluminescence (PL) spectra were measured at the CdS/CdTe interface for two cells with different values of the CdTe layer's thickness at temperature T = 60 K. A deconvolution peak fit was performed from which it is found that the peaks are characteristic of the solid solution CdSxTei-x· The parabolic relation that relates the bandgap energy with the composition was used to estimate x, where xis [S]/([Te]+[S]) and [Te], [S] are the concentrations of Te and S atoms respectively. The results show that the interface is smooth and the change of the bandgap occurs gradually.IntroductionCdS/CdTe heterojunctions represent a combination of materials promising various applications, and for solar energy conversion in the first place [1]. In photovoltaic cells the CdS material acts as a wide bandgap window. Direct bandgap CdTe with high optical absorption coefficient is used as an absorber [1]. Solar cells with efficiencies of 10 to 16% have been obtained with CdTe grown by close space sublimation, electrodeposition, vacuum evaporation and rf sputtering methods [2]. In this work the CdTe layer was prepared by vacuum evaporation because it results with films of minimum impurities, while the Sn02:F and CdS:In layers were deposited by the spray pyrolysis technique because it is a low cost method which enables intentional doping and large area thin films."

Jan 1, 2011

By Giuseppe Bonifazi

Minerographic and petrochemical research was carried out on crude ore samples from the complex polymetallic Zn-Cu-Pb sulfide ores of , Sotiel in Huelva province west of Seville, Spain. A computerized image analysis system was used to define the structural and textural characteristics of the ore to obtain information on the degree of liberation of the different minerals (i.e. pyrite, sphalerite, galena, chalcopyrite). Techniques of digital multispectral image processing of reflected light microscopy images were used. Particular structures were identified by means of mineral associations and numerically quantified to obtain useful information for designing beneficiation processes.

Jan 1, 1991

By P. Umadevi

In the light of the discovery of the new super-conducting YBa2Cu3O7-x (YBCO), reactions in the Y2O3¬CuO-BaO system at 1300°C was investigated. The search was for any new phase that may be formed in the system at 1300°C (only 950°C reactions are known so far). 35 mixtures of different compositions were prepared and heated at 1300°C. No new phase was obtained. It was found that YBCO is decomposed at this temperature and Y2O3 and BaCO3 are the major components in the solid obtained after firing in air. However, on cooling the melt slowly and annealing at 950°C YBCO reforms. Such reactions on cooling might have implications on processing of the superconductor YBCO for practical applications as well as on its crystal growth by flux method.

Jan 1, 1989

By Bradley C. Bockrath

Some thirty coals were evaluated for liquefaction activity under a mixture of CO and H2 at 425° C. The viscosity of the liquid products was taken as an indicator of the degree of liquefaction. It was found that the direct liquefaction of a particular coal may be beneficially influenced by the presence of pyrite. Active pyrites are often found in the native mineral matter of the coal itself. For example, subbituminous and bituminous coals and lignites of relatively high pyrite content were found to liquefy more readily than similar coals or lignites which were poor in pyrite. The reactivity of inactive coals could be improved by using blends with active, pyrite-rich coals. In addition, pyrite was effective when added separately as pyrite concentrates obtained from coal beneficiation operations. Various other iron- and sulfur-bearing additives were also effective when used in combination as added slurry-phase catalysts, including iron oxides and mineral residues derived from liquefaction of active coals. Under liquefaction conditions, pyrrhotite ( Fe I- x5) is formed from pyrite or from the iron oxides and many sulfur containing species. Pyrrhotite was shown to be a hydrogenation/dehydrogenation catalyst for tetralin but is not active for initiating a variety of free radical reactions that do occur when pyrite is heated with tetralin. The role of pyrite in coal liquefaction is complex and still not well understood.

Jan 1, 1981

By K. A. Elbarawy

Processing of Egyptian barite ore with a composition of 85.5% BaSO4; 2.75%SiO2;1.56%Fe2O3 and 5.1% Al2O3 was performed with the aim to prepare pure barium salts. The process took place through pelletization-solid state reduction and leaching steps. Each of these steps was optimized. Pure barium sulphate (99% < 0.82µm) and carbonate (99%<0.75µm )were the final products. This article deals with the reduction process that occur whn coal was added to the ore during pelletization in the ratio of 5:1 stoichiometry. Optimum reduction of pellets of 8-12mm in diameter was achieved after 60 minutes at 1050oC and under a rate of 5 lmin-1 of nitrogen atmosphere, where 87.79% of the ore was reduced. The kinetic studies showed that the reduction process could be modeled according to the core mechanism of diffusion control in which the effective diffusivity is based on the surface area of unreacted ore. The activation energy calculated was 92.7 kJmol-1.

Jan 1, 2006

By F. Patisson

During exothermic gas-solid reactions, heat generation makes temperature rise and modifies the rate of the various mass transfer processes, namely the chemical reaction itself, the pore diffusion and the external transfer. We have investigated this thermal effect during the oxidation of zinc sulfide porous pellets in a thermo balance furnace, between 550 and 900°C-and under O2-N2 atmosphere. The results have been&apos; analyzed by using, firstly, the law of additive reaction times derived from the isothermal Grainy Pellet Model, and, secondly, a new numerical model taking into account non-isothermal conditions. Both the models can satisfactorily simulate conversion versus time, but the numerical model also depicts the temperature evolution within the pellet. Finally it is shown that owing to the heat generation the zinc sulfide oxidation takes place under diffusion control (3/4 internal, 114 external) in all the cases studied. During the course of reaction, the. pellet undergoes strong temperature variations, with thermal gradients confined to a shell oxide layer.

Jan 1, 1996

By F. -Z. Ji

Carbon injection into metallurgical slag is important in electric arc furnace (EAF) steelmaking for foamy slag practices and in nonferrous slag cleaning operations. The current publication presents kinetic data for coal injection into EAF slag to understand the interaction between injected carbon and metallurgical slag. Coal particles were injected into EAF slag and the kinetics were followed by gas and slag analysis. The results were analyzed, in terms of fundamental rate equations for each possible reaction step, as a function of temperature and slag composition.

Jan 1, 2003

By A. Cullaj

Several industrial sites suffer from the contamination of soils from heavy metals, which are emitted among others by anthropogenic mining and metallurgical activities. Effective and economic physicochemical technologies for remediation of these sites remain complicated and costly. A new alternative remediation technique is the so-called phytoremediation. This is based on the ability of some plants to accumulate very high concentrations of metals from soils and thus providing the basis for a remediation of the contaminated sites. This technique as an emerging branch of natural biotechnology, has several advantages compared to the sophisticated physicochemical techniques of soil remediation. It is not only environmentally friendly but also its costs are quite low since it is solar driven. Furthermore plants can accumulate metals to such levels that the mineral recovery maybe feasible even in conventional Ni refinery or smelting operations. In this work, thc potential of many plants to accumulate nickel has been investigated in order to identify the species which offer the best phytoremedial potential for nickel contaminated soils in Albania. Field surveys have been made in five nickel-containing sites in order to identify the nickel tolerant species that have spontaneously grown in contaminated soils. Atomic Absorption Spectrometry measurements were carried out on 145 different plants collected. 16 of them were identified as having an hyper ability to accumulate nickel since they contained more than 10 000 mg Ni per kg (DW). Seven taxa are of Alyssum genus and one of Bornmuellera genus of Cruciferae. The highest accumulation of nickel was present in aerial parts of Alyssum murale var. chlorocarpum Hausskn (25 500 mglkg or 2.5%) and Alyssum markgrafli O.E. Schulz (23 700 mg/kg or 2.37%). The seeds germinated are more evidenced at A.m.var. chlorocarpum, about 63%. These plants are suggested as the most promising species to be used for phytoremediation purposes in nickel contaminated soils and phytoextraction of nickel.

Jan 1, 2003

By A. Dadgar

Extraction of gold and silver from two refractory concentrates using cyanide and bromine reagents was reported at the 12th International Precious Metal Conference (1). The objective of this paper is to present the gold extraction, recovery, and economics for two refractory concentrates using cyanide and bromine reagents. Gold extractions for cyanide leaching (24- 48 hours) and bromine leaching (6 hours) were the same and ranged from 94% to 96%. Gold recoveries from bromine pregnant solutions using carbon adsorption, ion exchange, solvent extraction, and zinc and aluminum precipitation methods, were better than 99.9%. A preliminary economic analysis indicates that chemical costs? for cyanidation and bromine process are $9.50 and $10.50, respectively per ton of calcine processed.

Jan 1, 1989

By Eltefat Ahmadi

Iron-free titanium oxycarbonitride (TiOxCyNz) is a promising feedstock for production of titanium tetrachloride (TiCl4) at low temperatures. In this study, the effects of leaching variables such as temperature, time, particle size of staring material and concentration of the leaching solutions were evaluated on iron removal from nitrided Malaysian ilmenite by Becher process. The nitrided ilmenite was prepared by isothermal reduction with graphite at 1200 °C for 3 h in H2-N2 atmosphere. The aerated leaching experiments were conducted at 50–90 °C with addition of 0.3–2.0 wt% of NH4Cl catalyst. The highest extent of iron removal (XFe) was obtained at about 96.2% for the sample leached at 90 °C for 7 h with 2.0 wt% NH4Cl. The iron concentrate and titanium oxycarbonitride product were characterized by ICP-OES, XRD, XRF and SEM-EDX analyses. The results indicated that the aeration leaching process was a successful route to prepare low-iron titanium oxycarbonitride.

By Bing Li, Miao Shen, Qiang Wang, Yuqi Chen

Electrochemical methods including cyclic voltammograms, square wave voltammograms, chronopotentiometry are applied to characterize the reduction potentials of Na+ and Li+ ions in LiCl-KCl melts. According to theoretical calculation, the reduction potential for Na+ is slightly more negative than Li+ in NaCl-LiCl-KCl melts at 450℃. However, by electrochemical measurements, the reduction potential of Na+ is slightly more positive than Li+ in the above melt and the potential difference between Na+ and Li+ reaches 0.16-0.2V on an inert W electrode in 1.0-2.0 wt% NaCl-LiCl-KCl melts. An active Pb electrode is used to improve the removal rate of Na+ from LiCl-KCl melts. The reduction potentials for both Na+ ions and Li+ ions on a Pb electrode shift to more positive values and the reduction currents become larger. After 6h electrolysis on a Pb electrode at -3.0V, the practical removal efficiency of Na+ ions reaches 90.12% and the reduced products contain metallic Na and Li with a Na/Li mass ratio of 4.25/1.

Jan 1, 2015

By Sergio N. Monteiro

From the leaves of the sisal plant (Agave sisilana) a relatively strong fiber can be extracted and is nowadays being investigated as a possible reinforcement for polymeric matrix composites. For this purpose, it is important to determine the critical length of the fiber with respect to the matrix to be reinforced. This has never been properly done for sisal fibers in polyester matrix. Therefore, this work characterized the critical length of sisal fibers, with different sizes, embedded in polyester capsules by means of pullout tests. The critical length obtained allowed the sisal fiber/polyester matrix interface shear stress to be calculated. The relevance of these values for polyester composites reinforcement with sisal fibers is discussed.

Jan 1, 2009