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By S. C. Flood, J. D. Hunt

"The columnar-equiaxed transition (CET) has been studied numerically under unsteady-state conditions using mathematical models that: (i) include a non-equilibrium undercooling at the columnar front;and(ii) describe the simultaneous evolution of the columnar and equiaxed zones.The results are discussed and compared with those produced by a steady-state analysis.IntroductionThe majority of the previous work on the columnar-equiaxed transition (CET) has concentrated on the production of equiaxed nuclei, regarding this as being the critical step in the formation of an equiaxed zone. Recently, the growth of equiaxed grains has been considered and this is not unreasonable because, for an equiaxed zone to be present, the grains must grow as well as nucleate. Since the growth rate of the grains will be determined by the thermal environment at and ahead of the columnar tips, it was decided to model the liberation and flow of heat during solidification to discover whether the various trends in the columnar range might be explained by their effect on the temperature profile throughout the casting. The models presented here for the solidification of a casting are the first to include the latent heat liberated ahead of the columnar front. Burden and Hunt (1) consider its effect only qualitatively, and although Lipton et al (2) adopt a criterion for the CET which is based on the thermal interaction of the columnar and equiaxed grains, they do not actually include the latent heat in their calculations.It can be argued that the latent heat liberated by the equiaxed grains in the bulk will retard the columnar dendrites in a casting: once the equiaxed grains are sufficiently well-established, the latent heat that they evolve could slow down the columnar growth to such an extent that the equi axed would dominate. Alternatively, the latent heat produced by the equiaxed grains might suppress further equiaxed solidification by raising the bulk temperature. The nature of the thermal interaction between columnar and equiaxed growth is not obvious, and because it is dependent on the material parameters and the dimensions of the system, it cannot be considered effectively in a qualitative way but has to be studied quantitatively: hence the need for the mathematical models discussed in the following pages. The results of the models are discussed in the light of a steady state analysis."

Jan 1, 1986

By Dinesh Agrawal

Microwave energy has been in use for variety of applications for over 50 years. These applications include communication, food processing, wood drying, rubber vulcanization, medical therapy, polymers, etc. In the last two decades microwave heating has been also applied very effectively and efficiently to heat and sinter ceramic materials. Microwave heating is recognized for its various advantages, such as: time and energy saving, very rapid heating rates, considerably reduced processing cycle time and temperature, fine microstructures and improved mechanical properties, better product performance, etc. The most recent application of microwaves has been in the field of metallic materials for sintering, brazing/joining and melting. Several common steel compositions, pure metals and refractory metals have been sintered in microwaves to nearly full density with improved mechanical properties. Many commercial powder-metal components of various alloy compositions including iron and steel, copper, aluminum, nickel, Mo, Co, Ti, W, Sn, etc., and their alloys have also been sintered in microwaves producing better properties than their conventional counterparts by using a 2.45 GHz multimode microwave system. This work has been further extended to join and braze bulk metal pieces, especially super alloy based turbine blades. Further, in a specially designed microwave cavity, even the bulk metals can be made to couple with the microwave field and melted. The implications of these findings are obvious in the field of powder metal technology.

Jan 1, 2006

By Bora Derin

Optimization of slag composition has great importance on effective and clean metal production technologies. Reddy-Blander (RB) model, a priori, is very useful tool for prediction of impurity capacities of industrial slags. In this study, sulfide capacities (Cs) of 19 lead smelter slags indicated in the literature were calculated and effects of Cs values on sulfur content of lead bullions were discussed.

Jan 1, 2006

By K. Osseo-Asare

Aqueous stability diagrams (25°C) are presented for the systems M-H2O and M-Oxalate-H2O where M=Sm, Nd, Co, and Fe. With the aid of these diagrams (i.e., Eh-pH and log[Metal]- log[Oxalate]), the solution-chemical constraints on metal dissolution and precipitation are identified. By comparing the corresponding stability diagrams, conceptual flowsheets are developed for metal recovery from Sm-Co and Nd-Fe-B magnet scrap.

Jan 1, 1997

By Ronald L. Bruening

IBC Advanced Technologies, Inc. (IBC) has developed and commercialized SuperLig® materials based on Molecular Recognition Technology (MRT), which have proven to be very effective for the removal of bismuth from hydrometallurgical sulfuric acid process streams. The most common application is its removal from copper refinery electrolytes, where bismuth control is extremely critical. IBC has also developed an MRT system for extraction, recovery and refining of palladium from a copper refinery by-product stream originating from the treatment of copper tankhouse slimes. A high purity palladium salt is produced which meets market specifications. Results are reviewed and discussed.

Jan 1, 2003

By S. Kurama

Incorporation of de-watering sieve waste of borax (TSW) from Etibor Kirka Borax Company (Turkey) on the mechanical and physical properties of a commercial floor tile composition was investigated. In order to achieve this aim, TSW was partially employed in place of feldspar in the standard composition up to 20 wt %. The formulated compositions were wet milled, dried, shaped and then fired at 1190C for a total firing time of 38 minutes (from cold to cold) under industrial conditions. It was found that using of TSW up to 15 wt % improved the physical and mechanical properties of final product. The results indicated a good prospect for TSW as a co-flux in floor tile formulations.

Jan 1, 2006

By E. Gervais

Modern life in inconceivable without zinc. Zinc provides the most cost-effective and environmentally efficient method of protecting steel from corrosion. Zinc is also used to power electric vehicles and computers, to make brass, automotive equipment, household appliances, fittings, tools and toys, and to support the building and construction industries. It is also used in pharmaceuticals and cosmetics, in rubber, in fertilisers and in animal feeds. The links between properties, applications and performance, as well as zinc demand and market dynamics, will be reviewed along with market development opportunities and successes. The presentation will also include a progress report on the five-year plan of the International Zinc Association to increase the global market for zinc, over and above the natural growth, by 500,000 tonnes/year by 2002.

Jan 1, 2000

By Elizabeth M. Ho

Oxidants are added in uranium leaching in acid media to convert iron(II) in solution to iron(III). Iron(III) has an important role in the leaching of uranium by acting as an electron transfer agent for the oxidation of uranium(IV) to uranium(VI). The oxidation of iron(II) to iron(III) in sulfate solutions using sulfur dioxide/oxygen (SO2/O2) was carried out under typical uranium leaching conditions (pH 1-2, 20-50°C) to confirm literature trends and this work was then extended to the use of SO2/O2 in the leaching of uranium ore. The oxidation rate was found to be dependent on the initial SO2/O2 volumetric ratio and the oxygen mass transfer rate, but was independent of the initial iron(III) concentration above about 200 ppm at pH 2. The presence of 55 ppm organic extractant (Alamine 336) decreased the reaction rate. The oxygen mass transfer coefficient (kLa) for the mixing tank system was measured and was found to decrease with increasing solids density in a 1 g L-1 MgSO4.7H2O solution.

Jan 1, 2003

By Morimasa Ichida

One of the key factors of stabilized blast furnace operation under the conditions of high productivity and high pulverized coal rate is to enlarge the raceway to reduce the dead man area. With a reduced dead man area, the descent area is enlarged and the central gas flow is maintained at the same time. In this study, raceway furnace experiments were conducted with tuyere velocity and coke strength changed both in hot and cold conditions to measure the coke degradation rate. Using the coke degradation rate measurements, we examined the equivalent relation between the coke strength and tuyere velocity for coke degradation in the raceway. In addition, in this paper, we discuss the increase in tuyere velocity in relation to an increase in coke strength.

Jan 1, 2006

By Nobuaki Sato

For decontamination of SO2 containing waste gases from industries such as ferrous and non-ferrous metal companies, desulfurization with hydrogen production by the reaction of Br2 and SO2 was proposed as bromine-sulfur (BS) process. In this process, SO2 is fixed as H2SO4 in the presence of Br2 and H2O forming H2SO4 and HBr. Then hydrogen is produced by the decomposition of HBr and Br2 as byproduct is recycled. The reaction of Br2, SO2 and H2O was found not to occur in liquid phase but to occur in vapor one. The production ratios of H2SO4 and HBr showed a maximum at temperatures around 60 oC. The highest production ratio was obtained at 70 oC with a mixing ratio of Br2:SO2:H2O=1:1:10. The experimental results were discussed with thermodynamic consideration.

Jan 1, 2006

By Cyro Takano

This paper is a contribution to fundamentals data on the equilibrium metal/slag for refining silicon in relation to Ca and Al as impurities. Silicon containing 0.1% Al and no Ca was placed in contact with a slag of various contents of CaO, SiO2 and Al2O3. Slag Al2O3 contents were 11.4%, 25.1% and 29.6%, keeping the ratio %CaO/%SiO2 constant and equal to ~0.53. The experiments were conducted at 1550oC, in a graphite crucible with argon atmosphere. The equilibrium was observed with low and medium content of Al2O3. The derived activities coefficients of Ca and Al in dilute solution of Si presented good correlation with those of the literature. Parallel reactions with formations of SiO(g) and CO (g) were also observed.

Jan 1, 2006

By Fiseha Tesfaye, Pekka Taskinen

"A thermodynamic study of the equilibrium phase assemblage AgBi3S5-Bi2S3-S was made by an EMF-technique, using the RbAg4l5 solid electrolyte. The ternary phase was synthesized from the pure Ag2S and Bi2S3 in an evacuated silica ampoule and grinded into powder and mixed with appropriate compositions of B12S3 and S, in a series of experiments, for pressing in to pellets. The pellets were assembled to form the galvanic cells Pt (-) | Ag ] RbAg4ls | AgBi3S5+ Bi2S3 + S + (C) I Pt (+). The EMF-measurements were made in the temperature range 299 - 460 K.In this paper, thermodynamic functions of the ternary phase AgBi3S5 (pavonite) have been determined. The agreement between the obtained results and the literature values were established.IntroductionThe complex group of ore minerals constitutes from trace amounts to a major proportions of sulfosalts. Although the sulfosalts rarely form massive ore bodies, they are commonly associated with rich sulfide ore minerals for the base and precious metals and widely distributed in a metal poor sulfide minerals [1]. For instance, Ag-bearing sulfosalts are encountered in ore minerals for the production of the base metals and are common sources of silver. Nevertheless, thermodynamic properties of the sulfosalts are poorly known.Reliable thermochemical data are essential for quantitative modeling of the chemical behavior of the sulfosalts in equilibrium with sulfides, which in turn would promote the optimization of complex minerals treatment and extractive metallurgy of the valuable metals."

Jan 1, 2012

By C. Flores

The direct cementation of copper from a loaded D2EHPA 20 % vol. in kerosene using zinc, zinc-lead alloy and iron metallic powders was studied. Copper was loaded into the organic solvent from an aqueous copper sulfate solution. Results indicated that copper is reduced spontaneously with relatively fast reaction rates. The effects of several operating parameters such as water content in the organic system, initial copper concentration, reductant surface area, oxygen and nitrogen atmosphere, intensity of the agitation and temperature on the galvanic stripping of copper were studied. For a better understanding of the electrochemical reactions involved in the galvanic stripping, the dissolution of metallic copper in the organic solvent was also studied. Copper did not dissolve unless a small amount of water was present in the organic system. The results and possible reaction mechanisms are discussed.

Jan 1, 1999

By T. T. Chen

Secondary copper anodes are generally rich in Sn, Pb, Ni and Sb, but are notably deficient in Se, Te and Ag. In the secondary copper anodes, most of the Ni, virtually all of the Ag, slightly more than one-fifth of the Pb, about one-third of the As and Sb, and approximately one-tenth of the Sn are in solid solution in the copper. The remaining impurity contents occur as 1-5 µm grain-boundary inclusions in the anodes, and these are mainly Cu2O, SnO2, Cu-Pb-As-Sb-Bi oxide, Pb-Sb oxide, Sn-Ni-Zn oxide, Cu-Sn-Ni oxide, Cu-Sb-Ni oxide (Kupferglimmer) and trace Cu2(Se,Te). Barium sulphate, which originates from the mold wash used in casting, is also present in the anodes. During electrorefining, the BaSO4, SnO2, Pb-Sb oxide, Sn-Ni-Zn oxide, Cu-Sn-Ni oxide and Cu- Sb-Ni oxide inclusions are liberated and accumulate in the slimes layer. Solid solution Ni dissolves and the Ni accumulates in the electrolyte. Solid solution Sn and Pb dissolve, but partly reprecipitate as Sn arsenate and PbSO4, respectively. Solid solution Ag dissolves but rapidly reacts to form Ag2(Se,Te), Ag powder, Ag-bearing Cu2O, (Cu,Ag)SO4 or a complex oxidate phase. Partial dissolution of the Cu-Pb-As-Sb-Bi oxide particles takes place; the Pb component is converted to PbSO4, whereas Cu, As, Sb and Bi dissolve. The reacted particles retain the morphology of the original Cu-Pb-As- Sb-Bi oxide phase. Some of the solubilized As, Sb and Bi remains in solution, but much reprecipitates as SbAsO4, As-Sb-Bi oxide, and as a poorly defined oxidate phase which consists mostly of Cu-Ag-Pb arsenate-sulphate. The high Sn contents of secondary copper anodes do not seem to affect the behaviour of the anodes during electrorefining.

Jan 1, 1999

By Kalathur S. Narasimhan

Powder metallurgy is a net shape process competing favorably with machining, stamping, forging and castings. The growth of ferrous powder metallurgy over the past four decades reflect the advancements in materials technology, compaction technology, sintering technologies and other related fields. This presentation gives a brief background on how materials technology evolved.

Jan 1, 2006

By Yoshio Waseda

A laser flash method has been applied to obtain the thermal diffusivity values of Zr55Al10Ni5Cu30 alloy in the liquid, glassy, crystallized and supercooled liquid states. The electrical resistivity of this particular alloy was measured in the glassy, and crystallized states by a direct current four probe technique. A specific heat of Zr55Al10Ni5Cu30 alloy was also determined by a differential scanning calorimeter in the glassy state. On the other hand, thermal diffusivity values for two alloys of Zr60Al15Ni25 and Zr65Al7.5Cu27.5 were measured in the crystallized and liquid states. The thermal diffusivity values of three Zr-based alloys in the liquid state are summarized in the linear equations with positive temperature dependency and it is noted that the lower the thermal diffusivity values of Zr-based alloys at liquidus temperature, the lower the critical cooling rate to obtain metallic glass phase becomes. The thermal diffusivity values of Zr-based alloys were compared with those of Pd-based alloy case. These results suggest that thermal diffusivity of alloy liquids might be an indicator of the glass-forming ability of Zr-based and Pd-based alloys.

Jan 1, 2006

By Ray Y. Lin

This study explores the formation of sodium pyrosulfate in molten sodium sulfate resulting from dissolution of SO3 at temperatures between 1160 and 1250 K. Solubility of SO3 in Na2SO4 melts at temperatures between 1160 and 1250 K under gas mixtures of SO2, O2 and argon was investigated applying a thermogravemetric analysis (TGA) technique. The activity of Na2O in the melt was determined with a high temperature electrochemical cell (ECC). Results showed that the SO3 solubility in molten Na2SO4 increases with decreasing temperatures and increasing SO3 partial pressures. Enthalpy of SO3 dissolution in molten Na2SO4 was calculated to be -119 kJ/mol for infinite dilute solutions. Thermochemistry of Na2SO4-Na2S2O7 melts was analyzed based on information obtained from both TGA and ECC techniques. Detailed examinations of the earlier low temperature measurements in the Na2SO4-Na2S2O7 system along with data from this study reveal that the solution behavior between Na2SO4 and Na2S2O7 can be satisfactorily treated as regular with the interaction parameter, , being 2.7 kJ/mol. The phase diagram and the field of SO3 partial pressure has been generated with the thermodynamic calculation using a regular solution approach.

Jan 1, 2006

By Yongxiang Yang

High temperature processing of raw materials in metals production and recycling often involves complex multi-phase fluid flow and heterogeneous chemical reactions at various scales. Good understanding of the process physics and chemistry is crucial for process operation and process development. The traditional scale-up process through laboratory scale ? pilot scale ? commercial scale route has been more and more complemented and partially replaced by full-scale process simulation. Computational fluid dynamics (CFD) has become a very useful simulation tool in process research and development. At the same time industrial applications challenge the CFD development with its complex transport phenomena, often in large-scale reactors with small-scale physics and chemistry. The current paper discusses the applications of CFD to a number of high temperature metallurgical and materials processing applications. The research was carried out by using commercial CFD codes as the framework, and the emphasis was given to the special efforts for the development and implementations of sub-models with process-dependent physical and chemical characteristics. To illustrate the application of CFD simulation to high temperature metallurgical processes and coupling of sub-models to the general-purpose CFD codes, five examples are given: (1) melting of aluminium scrap in a rotary furnace for recycling, (2) molten hot metal flow in a heterogeneous coke-bed of a blast furnace hearth, (3) gas flow heat and mass transfer in a submerge electric arc furnace for phosphorus production, (4) high temperature incineration of hazardous waste in a rotary kiln, and (5) transient heating of metals in heat treatment furnaces.

Jan 1, 2006

By M. H. Ghandehari

Sintered (Pr,Sm)Co5 displays a multi-phase microstructure in which closely related intermetallic compounds are formed during the process of fabricating useful magnets from over-stoichiornetric compositions. These compounds have much lower magnetic crystalline anisotropies compared to those of SmCo5 and PrCo5. Despite a careful control of the microstructure in producing "single phase" PrCo5 base magnets, sufficient concentrations of the lower anisotropy phases are formed which act as nucleation centers for domain reversal, resulting in a drop in coercivity. This article describes the use of sintering additives, primarily oxides, to prevent the formation of the magnetically soft phases in the final microstructure.

Jan 1, 1989

By Pascal Gardin

The purpose of the paper is the mathematical modelling of flows inside steel continuous casting mould. For CFD validation of flow oscillation prediction, unsteady calculations with a realizable k- model were performed in a billet caster with rectangular section. Self sustained and regular oscillations were obtained. Calculated flapping frequency is very close to what is mentioned in literature. For slab caster configuration, flow oscillation is influenced both by lower roll, which creates very small frequency oscillation (0.012 Hz for our water model), and upper roll, which creates slightly higher frequency oscillation (0.05 Hz). The two rolls interact and it is possible to detect both frequencies in the nozzle jet region. Numerical results are in good agreement with measurements for fluctuating velocity spectra and provide explanation for interaction of rolls. To improve flow stability inside the mould, it is established that gas injection in the nozzle has a very positive effect.

Jan 1, 2006