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By Takeshi Nagano

Copper pyrometallurgy in Japan has experienced quite fundamental changes in last fifteen years. The severe environmental restriction coupled with increase of energy costs accelerated the development work of the new continuous process in Mitsubishi Metal Corporation. After several years of pilot plant test work the commercial plant was put into operation at Naoshima Smelter in 1974, the design capacity of which was 4,000 tonnes of copper per month. Many modifications and improvements have been incorporated into the process and 7,200 tonnes per month of copper production was achieved in 1983, proving that continuous process was much more economical than conventional process. It is now possible to design and operate the continuous process in wide range of capacity. This paper will review the process and describe the progress of the process in these 10 years. 311

Jan 1, 1985

By Shoukun Wei, Cong Wang, Lin Cheng, Zhiyu Qiao, Jingkui Liang, Weidong Zhuang

"The subsolidus phase relations in the Sm2O3-CeO2-CuO ternary system sintered at 1000°C in air have been investigated by X-ray powder diffraction. The system can be divided into two ternary phase regions and three binary phase regions. Solid solution Sm2-xCexCuO4-y is the only ternary phase in the system. The maximum solid solubility was confirmed to be x = 0.2. The crystal structure, oxygen content and superconductivity of the solid solution Sm2-xCexCuO4-y have been investigated.I. INTRODUCTIONAfter the first discovery of the superconducting ceramic system La-Ba -Cu-O[l] with Tc = 30 to 40K, other families of cuprate-based ceramics have been synthesized with higher critical temperature. These oxides include the R-Ba-Cu-O (R: rare earth) systems (Tc=90K or so)[2,3], the Pb-Sr-(R,Ca)-Cu-O systems (T c = 50 to 100K), the Bi-Sr-Ca-Cu-O systems (Tc=80 to 105K)[4], the T1-Ba-Ca-Cu-O systems (Tc=85 to 125K)[5], the Hg-Ba-Ca-Cu-O systems (Tc=90 to 150K)[6,7], and some others. The improvement of Tc is very rapid. The measurement of the Hall and Seebeck coefficients shows that they all are p-type superconductors. In 1989, Tokura et al.[8] discovered the superconductors R2_XCexCU04_y(R = Nd, Pr, Sm) with Tc=20 to 24K (onset) and found that the charge carrier is electron in contrast to their hole doped counterparts. This discovery increases the fundamental understanding of the cuprate-based superconductors by comparing their characteristics and mechanisms to those of the p-type superconductors.One of the outstanding features of these n-type superconductors is the difficulty in obtaining samples in good charactors, such as the difficulty in obtaining zero resistivity state in single crystal or bulk samples; the semi-conductivity of bulk samples in ordinary state (opposite to the superconducting state) and a reducing reaction involved before the superconductivity has been found[9]. Therefore, it is necessary to optimize the sample preparation of the n-type superconductors. All the n-type superconductors have been found· considerable solid solubility. The compositional variations play a governing role in the carrier doping of the superconducting phases. Also, it is vital to the ceramic processing of superconductors to identify the compatible phases in the phase diagram. Finally, there is always the possibility of finding additional compounds, both superconducting and non-superconducting, in an unexplored system."

Jan 1, 1996

By Akira Yazawa

Experimental results for the distribution ratios of various elements between the slag, matte and/or copper in the silica-saturated copper smelting system were summarized. The experiments were carried out under an oxidative smelting condition with S02 gas flow, and also a reductive smelting condition equilibrating with metallic copper or iron. To evaluate the results thermodynamically, the availability of one atom cation base expression for the constituent compounds is emphasized from both of theoretical and practical standpoints. Both of oxidic and sulfidic dissolutions in slag are postulated for some elements such as copper, nickel and lead., and the experimental results are reasonably explained thermo-dynamically. The results for the mutual solubility between matte and ferrite slag and the distribution of minor elements between liquid copper and ferrite slag are also discussed.

Jan 1, 1983

By P. N. Anyalebechi

The effects of a cross-hatched grooved mold surface topography, casting speed, and superheat on the morphology of solidifying shells of aluminum alloy 3003 have been characterized by a series of immersion tests. The cross-hatched grooves were 0.232 mm deep with wavelength or spacing between 1 mm and 15 mm. The shells solidified at casting speed of less than 10 mm/s on the 1 mm spaced cross-hatched grooved mold surface were fairly uniform with little or no localized variations in thickness. However, the propensity for non-uniform shell growth morphology was exacerbated by an increase in casting speed, melt superheat, and the wavelength of the cross-hatched grooves. This is provisionally attributed to their effects on interfacial heat transfer and wetting of the mold surface by the molten metal.

Jan 1, 2008

By Hector Henao

To provide thermodynamic data for converting the nickel matte to liquid nickel, an experimental study was conducted in the phase equilibrium between the Ni-S alloy and the CaO-Ah03 based slag melted in a MgO crucible at 1873 K under controlled Pso2 of 10.1 kPa and pO;, in a range between 2.5x,IO,2 and 10.1 Pa by using CO-C02-S0Z gas mixtures. The content of nickel in the slag at POz of 10.1 Pa, above which solid NiO is expected to precipitate in the equilibrium state, was found to be 4.1 mass% and the contents of sulfur and oxygen in the nickel melt were 0.4 and 0.2 mass%, respectively. It was clarified that increase in the temperature reduces the solubility of nickel in the slag and the contents of sulfur and oxygen in the alloy. The distribution of minor elements such as gold, silver, copper, cobalt, iron, arsenic and antimony between the Ni-S alloy and the CaO-AI20) based slag was also studied. The distribution ratios of iron and cobalt, defined by (%X in slag)/[%X in alloy] where X is the minor element, are larger values than that of nickel, while those of copper, silver and antimony are similar to that of nickel. The distribution ratios of arsenic and gold are lower than that of nickel in the higher range of oxygen partial' pressure.

Jan 1, 2003

By Haotian Xue

A new process to extracted antimony directly from stibnite concentrate by reductive sulfur-fixation smelting in sodium molten salt has been presented. The influences of sodium salt content and composition, ferric oxide addition, temperature and time was investigated, respectively. The optimum conditions was determined as follows: W????: ??concentrate=40%, W??alt: ????concentrate =88.75%, WFe2O3 :Wconcentrate =55.13%, W??aCl: ????alt=40%, 1123K, 1h. Under above-mentioned optimum conditions, the average direct recovery ratio of antimony can reach 91.48%, and the main chemical composition of obtained crude antimony is Sb 94.31%, Fe 4.436%, Pb 0.502%, Au 0.0236%. In comparison to traditional antimony pyrometallurgical process, the smelting temperature of present process is reduced from 1423~1473K to 1123~1173K. During the smelting operation, SO2 emision can be avoided completely due to sulfur-fixation as FeS. Furthermore , S0 can be obtained when the molten slag is handled by water leaching with conditions of 323K, L/S=5/1, 2h.

Jan 1, 2014

By Yuan She, Qihang Liu, Keng Wu, Hailiang Ren

By observing different coal char’s microstructures and microscopic morphologies during the coking process, the characteristics of COREX coal char’s microstructure and properties were analyzed. MCRI and MCSR were used to respectively describe the reactivity and the strength after reaction of coal char, with those of BF’s coke for reference, and then the physical meaning of MCRI and MCSR were given. MCRI and MCSR were determined by the composition of coal char. For the two kinds of COREX coal, the formula to forecast the hot performance of coal char was set up by making a multiple linear regression between the hot performance and microstructure of the coal char at 1100℃, and the predictive values of coal char’s hot performance at 600℃, 800℃ and 1000℃ coincided well with the measured values.

Jan 1, 2015

By Katsumi Ogi, Hiroto Uchida, Masamitsu Sato, Atsushi Itsuki

"(BTMSE)Ag(hfac) (BTMSE = trans-bis(trimethylsilyl)ethene) was chosen as a suitable precursor for the XeCl laser (308nm) MOCVD of Ag. Iso-propanol solution of (BTMSE)Ag(hfac) was used as a liquid source for the liquid delivery method, high deposition rate 9nm/min at substrate temperatures of 100°C and 120°C were obtained at the vaporizer temperature of 90°C. This deposition rate is three times faster than by conventional bubbling method and life of the source and reproducibility of the deposition were also improved. Electric resistivities of the laser deposited film shows significantly low resistivity of 10-6Q-cm compared to 1 o-3Q-cm of thermal MOCVD film. These results indicates that the laser MOCVD is one of the effective method for the preparation of the high quality silver film.IntroductionSilver films are a potentially important metallization material in electronic and photonic devises due to their lowest resistivity (1.6µ0-cm) among the metals, high optical reflectance and chemical stability. The MOCVD technique has advantages to sputtering or evaporation in the point of conformal growth and better coverage on sharp steps and narrow gaps[l-2]. For MOCVD application, silver precursors must have sufficient vapor pressure without decomposition at their evaporation temperature. To achieve stable precursor gas supply, liquid delivery of precursor material is promising[3-4] especially for materials that have not enough heat stability and high vapor pressure like silver complexes[S-10]. Several new silver complexes for MOCVD and UV irradiation effect to their MOCVD silver film quality were reported by same authors[5]. In this paper new solvent system for liquid delivery system of silver MOCVD were investigated to suite XeCl(308nm) laser MOCVD application."

Jan 1, 1998

By H. Dong, J. J. Valencia, L. Nastac

"A comprehensive computer model was developed to understand and optimize the centrifugal casting process for manufacturing TiC/Al-bronze friction drums. Performance of these components requires proper distribution of TiC particles, which is shown by dimensional analysis to be dominated by centrifugal buoyancy effects and solidification kinetics.The model addresses the following: (1) a rheology-viscosity model of the interference between moving particles, (2) engulfment (entrapment) or pushing of particles in the mushy region by the advancing solid/liquid interface, (3) nucleation and growth of equiaxed and eutectic phases, (4) effects of particle size, particle concentration, and cooling rate on the final grain size, and (5) the impingement effect of particles on the nucleation and growth kinetics of solidifying microstructure.Parametric studies were conducted using the computer model to investigate the effects of various process and material parameters on the distribution of TiC particles. The effects of the volume fraction, size, and morphology of the particles (including clusters and agglomerates) on the particle distribution were evaluated in detail. The complex interaction between the solidifying structure and insoluble ceramic particles in centrifugally-cast metal-matrix-composites was also investigated.The model predictions of particle distribution and microstructure were validated with experimental data for centrifugally-cast A356/SiC and TiC/Al-bronze alloys.This work was conducted by the National Center for Excellence in Metalworking Technology, operated by Concurrent Technologies Corporation under contract No. N00140-92- C-BC49 to the U.S. Navy as part of the U.S. Navy Manufacturing Technology Program."

Jan 1, 2000

By Chuanfu Zhang, Jinliang Wang

"Brickless reaction shaft is the latest progress for flash smelting furnace. However, there are many factors influence the melting point of the freeze slag inside brickless reaction shaft, and their variational regularities are not obvious, thus, it is difficult for conventional methods to analyze accurately the complex data. In this research, the experiment data of slag melting point were processed based on optimal discrimination plane. For this method, two orthogonal vectors were firstly built up based on the Fisher's criterion, and then the experiment data were projected onto the two vectors, thus, two-dimensional feature vectors were extracted as criteria to determine the factors effect degree on the slag melting point. Results show that the CaO content is the greatest factor to the melting point of the freeze slag inside brickless reaction shaft, the content of Fe3O4, SiO2, Cu2 O and MgO is the second, and the FeO content is the last.IntroductionBrickless reaction shaft is the latest progress of flash smelting furnace reaction shaft. To research the influence factors on the slag melting point inside the brickless reaction shaft is significant to form freeze slag with compact structure, good heat insulation, certain intensity, appropriate thickness and reasonable distribution, to extend furnace life, to reduce energy consumption, and to promote safe production.However, due to the complex components, there are many factors influence the melting points of the freeze slag inside brickless reaction shaft, and their variational regularities are not obvious. Therefore, it is difficult for conventional methods, such as variance analysis, data fitting, etc., to analyze accurately the complex experiment data.Pattern recognition can easily classify information, even if there are many influencing factors. For pattern recognition, there are some sub-disciplines such as discriminant analysis, feature extraction, error estimation, cluster analysis (together sometimes called statistical pattern recognition), grammatical inference, parsing and matching (sometimes called syntactical and structural pattern recognition) [1, 2]."

Jan 1, 2012

By A. J. Paul, K. O. Yu

"Today, foundries are moving towards the use of models and design tools to gain a competitive advantage in producing castings of high desired quality. This leads to a growing alliance between foundries, software developers and researchers seeking to model, visualize and understand the phenomena taking place during the casting process. In addition, there is a need to develop affordable techniques to produce parts in small lot sizes. This leads to the development of a Flexible Manufacturing System consisting of: (1) up-front computer-aided engineering; (2) computer integrated proto typing with solid freeform fabrication; and (3) fabrication of the actual mold and related equipment to cast the part.This paper discusses some of the developments that are taking place today in the areas of modeling the physical phenomena during the casting process as well as towards developing a Flexible Manufacturing System for producing cast parts. Areas that require most work involve prediction of defects and mechanical properties using simplified analyses. In addition, electronic data sharing for collaborative engineering between geographically dispersed team members is also discussed. Case studies are presented showing successes as well as failures.IntroductionCasting, one of the oldest forms of metalworking, has recently seen a flurry of developments in the area of solidification modeling. These developments have come about after the realization that, in order to stay competitive, foundries need to reduce their scrap rate and production costs, and increase casting quality. Even though this is not new knowledge for foundry engineers, the tools to help them achieve this goal are just being developed and put in place for use by foundries. Several state-of-the-art software packages are currently available to analyze the solidification behavior in complex shaped castings. These packages make use of several different approaches for solving the various problems associated with casting processes. The overall architecture of a comprehensive solidification modeling system is shown in Figure 1."

Jan 1, 1994

By Bhagyadhar Bhoi, Chitta Ranjan Mishra, Pravas Ranjan Behera

Red mud of Indian origin contains around 55% plus of Fe2O3 and is considered as a hazardous waste for the alumina industry. For production of one tone of alumina employing the Bayer’s Process, around two tones of red mud is generated from three tones of Bauxite. Conventional process of steel making is not devoid of environmental pollution. In the present investigation, efforts have been made to produce steel from red mud by adopting reduction roasting, magnetic separation and hydrogen plasma smelting route. Magnetic fraction, containing enriched iron oxide and minimal content of alumina, is produced following the first two stages which is then subjected to hydrogen plasma smelting process for production of steel. This novel concept follows a green path way for production of steel free from pollution and is termed as green steel. Further, the only by-product that is produced in the process, is water, which is eco-friendly and recyclable.

Jan 1, 2015

By T. R. A. Davey

A simple model for metal solution behaviour may be derived, on the basis of dilute solution solubilities (where? log concentration of solute varies linearly with reciprocal temperature) and not-so-dilute region solubilities (where the log of the alpha-function at saturation frequently varies linearly with reciprocal temperature) and assuming activity to vary according to the quadratic formalism in between. Matte binary systems usually exhibit regular .solution behaviour when the constituent species are chosen appropriately. In many recent papers, metal solubilities in .slags are expressed as the sum of several different and supposedly independant molecular species (e.g. oxides, sulfides, chlorides), Such a view is untenable because of the now proven ionic nature of slags. Some possible reasons for the great effect of sulfur on copper solubilities in slags are discussed.

Jan 1, 1985

By Atul Kurnar

In the present research a two-cell polymer electrolyte membrane fuel cell stack (PEMFCS) with SS-316 bipolar plates has been tested. Different flow field designs were studied and a modified multi-parallel channel design is proposed. The stack is stable within ±3 mV even after 1000 hours of continuous operation, indicating efficient water management and effective removal of any metal ions from the stack. Also no iron is detected in membrane electrode assembly (MEA) by EDAX analysis after 1000 hours of cell operation. Results indicate that high operating pressures beyond 138 kPa didn't significantly increase the performance of cell, however added much to the pressurization cost of the system. Tests at different temperatures showed that at temperatures below 80°C, external humidification could be completely removed. The prototype stack is also tested under variable load conditions simulating highway-driving schedule. The experimental efficiency of PEMFCS is 48%, which is in good agreement with the model predicted efficiency of 53.8 %. Results show that 59% of the total losses are due to ohmic polarization in the cell. Further analysis on applications of the stack in automotive transportation system is in progress.

Jan 1, 2002

By H. Kaffash

Ferromanganese is a ferroalloy with high manganese content which finds many uses for example as deoxidizer in steelmaking industry. However, there is very little data on the dissolution rate of carbonaceous materials in Mn containing metals. In this paper, the kinetic analysis of carburization reactions is investigated for Mn–Fe alloys. Dissolution rate of graphite in pure iron and four different alloys with 10 wt%, 40 wt%, 60 wt% and 85 wt% manganese at 1823 K was studied. Results showed that the dissolution rate of carbon from graphite increased with increasing time for all alloys. The dissolution rate constant increased with the increasing manganese content from 6.5 × 10−3 cm/s for 0%Mn to 23.6 × 10−3 cm/s for 85%Mn.

By V. I. Lakshmanan

Crown ethers are gaining importance in separation technology specifically for rare earth elements (REE, La to Lu plus Y) and precious metals (Au, Ag, Pt, Pd, Rh and Ir) due to their specific binding ability, metal complex stability and high extraction efficiency. The selectivity of crown ethers in extraction of these metals depends on different factors, including the cavity diameter and nature of a donor atom of the crown ether, size and charge of the metal ion, diluents and counter ion. Demand for strategic REE and precious metals are consistently increasing in the world while the separation of these metals is most challenging tasks. In this paper, the use of crown ethers in separation of REE and precious metals, reaction mechanisms and simplified process flowsheets will be elucidated. New reagents with high selectivity for the separation of these metals are further expected to produce high purity metals.

By Helena Byrdziak

Polish Copper Industry, located in the Lepica-Glogów region and operated since the 1970's, includes four mines and two smelters, "Legnica" and "Glogów", the latter consisting of "Glogów" I" and "Glogów II" both having different technologies. The "Legnica" and the "Glogów I" smelters using shaft furnaces, so sulfur elimination largely takes place during batchwise converting, resulting in fluctuation SO2-concentration between less than 1% up to 10% in the converter pas W the sulfuric acid plants. The ensuing difficulties of the past have now largely been overcome. Introduction of flash smelting at "Glogów II" with subsequent acid making by double SO2-conversion from the stable process gas, contributed significantly to further reduction Of SO2-emission. In 1994 a new double conversion sulfuric acid plant was installed at "Glogów l" as well as a "Solinox" desulfurisation plant at "Legnica", further reducing SO2 emission considerably, The next step towards this goal under consideration is a semi-dry desulfurization system for the "Glogów I" power station, SO2- abatement measures by KGHM and the results thereby achieved are presented.

Jan 1, 1996

By J. Leon-Torres, D. M. Stefanescu, P. A. Curreri, S. Sen

"Experiments were performed under terrestrial gravity (lg) and during parabolic flights (10·2 g) to study the solidification and macrosegregation patterns of Al-Cu alloys. Alloys having 2% and 5% Cu were solidified against a chill at two different cooling rates. Microscopic and Electron Microprobe characterization was used to produce rnicrostructural and macrosegregation maps.In all cases positive segregation occurred next to the chill because of the shrinkage flow, as expected. This positive segregation was higher in the low-g samples, apparently because of the higher heat transfer coefficient.A 2-D computational model was used to explain the experimental results. The continuum formulation was employed to describe the macroscopic transports of mass, energy, and momentum, associated with the solidification phenomena, for a two-phase system. The model considers that liquid flow is driven by thermal and solutal buoyancy, and by solidification shrinkage. The solidification event was divided into two stages. In the first one, the liquid containing freely moving equiaxed grains was described through the relative viscosity concept. In the second stage, when a fixed dendritic network was formed after dendritic coherency, the mushy zone was treated as a porous medium.The macrosegregation maps and the cooling curves obtained during experiments were used for validation of the solidification and segregation model. The model can explain the solidification and macrosegregation patterns and the differences between low- and high-gravity results."

Jan 1, 1999

By Kazuyuki Kakegawa

The sintering characteristics and the change in the compositional distribution in the PbTiO3 PbZrO3-Pb(Mgl/3Nb2/3)O3 system during the sintering process by spark plasma sintering (SPS) method were examined. They were compared with those by a normal sintering method. The densification by the normal sintering was slow even at high temperatures, When SPS method was employed, much lower temperature and shorter period resulted in sintered bodies having almost the theoretical density. As expected in normal sintering, the compositional distribution decreased as the sintered density increased. On the contrary, the change in the compositional distribution by SPS was much smaller than that in the normal sintering. This sintering characteristic of SPS suggested a possibility of fabrication of sintered material having a desired compositional distribution.-

Jan 1, 2003

By Kazuyuki Kakegawa

The sintering characteristics and the change in the compositional distribution in the PbTiO3-PbZrO3-Pb(Mg1/3Nb2/3)O3) system during the sintering process by spark plasma sintering (SPS) method were examined. They were compared with those by a normal sintering method. The densifieation by the normal sintering was slow even at high temperatures. When SPS method was employed, much lower temperature and shorter period resulted in sintered bodies having almost the theoretical density. As expected in normal sintering, the compositional distribution decreased as the sintered density increased. On the contrary, the change in the compositional distribution by SPS was much smaller than that in the normal sintering. This sintering characteristic of SPS suggested a possibility of fabrication of sintered material having a desired compositional distribution.

Jan 1, 2003