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By Robert P. Stevens

It is important for a refractory supplier to make systematic petro-graphic examinations of products which have been in service in the furnaces and kilns of customers. The petrographic examination of refractory service samples involves the microscopic study of polished and/or thin sections, supplemented by electron probe microanalysis, as well as the bulk chemical and XRD analysis of zones in the samples. The evolution of the A. P. Green Refractories Company petrographic laboratory is described, and the application of petrographic methods is illustrated in the examination of service refractories from a Portland cement rotary kiln and an AOD stainless steel vessel. The objectives of such studies are to assist the customer in the solution of his refractory problems, and to accumulate data which are of use in the design of improved refractory products.

Jan 1, 1981

By R. H. Crist

Reactive components of algal cell walls include uronic and alginic acids: In addition, many marine species have half ester sulfate groups which function as fixed anions. Associated metals vary with the media, eg., Ca and Mg in fresh water (FV) and Na, Ca, Mg in seawater. . These metals readily exchange with aqueous phase protons or metal cations. A plot of the total amount of metal cations displaced by protons vs .. pH shows one inflection at pH 4 for FV algae and' in addition a second inflection at pH 2, 3 for marine algae. The first inflection is interpreted as. Indicating the cations associated with carboxyl groups ,and the ,second with half ester ?Sulfate groups. The exchange capacities of various aigal ,species vary widely. When FV algae is placed in a Pb2+ solution,- the amount of Pb2"' deposited on the algae is. Equivalent to the. Total Ca2?, Mg2, and H+ displaced? thereby confirming the ion exchange mechanism. Ion exchange equilibrium constants are reported for the displacement of ca2+ from Vaucheria. With Mg2+, sr2+, Cd2+, Pb2+_ and Na+ as well as the reverse reactions. Cd2+ can .be removed partially from algae by precipitating it as CdS or Cd(OH) 2 Pb2+ and Cu2+ are also partially removed as the hydroxides. Rates of reaction for various alkali hydroxides decrease with increasing .unhydrated cation radius. It is concluded that theory is useful in predicting viable applications for algae in pollution abatement.

Jan 1, 1991

By Chuanfu Zhang, Liwei Liang, Yanxin Wu, Jinliang Wang

"According to the reaction shaft operation characteristics during the flash smelting process, 15 groups of slag samples containing high Fe3O4 were prepared by some chemical reagents, and then the slag viscosities were measured using a RTW-10 type synthetic test instrument for melt physical property by the rotating cylinder method. The effects of Fe/SiO2 ratio (mFe/mSiO2), Fe3O4 content (wFe3O4), Cu2o), MgO content (WMgO) and Cao content (wCaO) on the slag viscosity were also studied. Results show that slag viscosity is decreased with the increase of temperature, mFe/mSiO2, wCu2o, wMgO and wCao, and with the decrease of wFe3O4, under the range of slag contents: mFe/mSiO2 1.36~1.78, wFe3O4 17.83%~21.18%, wCu2o 3.51%~8.34%m wNgI 2.21%~6.57%m w/caI 6.22%~9.387% and temperature range if 1250 o/c~1450 oC. Only wFe3O4m and w/caO have great influence on the slag viscosity when temperatures as high as 1400 oC. Only wFe3O4 and wCaO have great influence on the slag viscosity when temperatures as high as 1400 oC or so. To form a freeze slag with higher viscosity inside the reaction shaft, wFe3O4 should be more than 20% and wCaO should be less then 6%.IntroductionSince its appearance in 1949, Outokumpu flash smelting technology has making continuous innovation and has become the most competitive intensified smelting technology [1], widely considered to be the standard clean smelting process [2]. At present, flash smelting technology is adopted to newly build or reconstruct most of the world's copper or nickel smelting enterprise [3]. Reaction shaft is the most important part of the flash smelting furnace. During the flash smelting process, reaction shaft must be able to withstand the following harsh conditions at the same time: 1) high temperature varying from 1400 °C to 1500 °C. 2) strong oxidative atmosphere containing 50% - 80% oxygen. 3) solid particles and melt with speed up to l00 m/s. 4) high acidic or basic slag with strong chemical corrosiveness. 5) smelting gas containing 50% - 80% SO2. 6) matte with strong dissolution."

Jan 1, 2012

By David J. Howard, Christine Broadbridge, David C. Paine

"High pressure vapor/solid reactions offer an opportunity for novel synthesis and processing of thin film materials and structures for electronic, optical, and magnetic applications. In this paper we review the use of two high pressure techniques that operate from 25 to 1000 atm (2.5 to 100 MPa) to fabricate thin film oxide structures from Si1-xGex deposited on Si wafers. High pressure synthesis enables temperature-independent control of reaction rates in the oxidation of this multicomponent semiconductor system and hence offers the opportunity to form thennodynamically metastable Si1-xGex<h from the alloy. The thermodynamics of the Si-Ge-0 system are reviewed and a method is described that utilizes selective chemical reduction (via H2 gas) of Si1-xGcx<h to form Ge precipitates in an SiO2 matrix. IntroductionAlloys of Si1-xGex grown epitaxially on Si substrates by chemical vapor deposition (CYD) and molecular beam epitaxy (MBE) have been used to create high performance microelectronic devices1. These devices show improved performance over conventional Si technology because they exploit the Si/Si 1-xGex band-gap discontinuity and take advantage of higher hole mobilities in the Ge containing alloys. While a range of devices based on heteroepitaxial systems have been demonstrated, the Si1_xGex alloys are of particular interest because they are most closely compatable with standard Si device processing. One disadvantage of Si-based materials systems is that they are not typically useful emitters of light. This is important since the use of light (rather than electrons) for transmitting and processing signals into, out of, and within Si-based microelectronics would represent a major technological advance in microelectronics-based communication and computer technologies. Nevertheless, through the use of innovative processing techniques it may be possible to use the Si1_xGex/Si heteroepitaxial system in integrated microelectronic/light-wave technologies."

Jan 1, 1994

By Toshio Suzuki, Machiko Ode, Won Tae Kim, Seong Gyoon Kim

"The Ostwald ripening and growth and coarsening of the secondary dendrite arm are studied using a phase-field model. The phase-field parameters are obtained at a thin interface limit proposed by Kim et al. In Ostwald ripening analysis, the difference of the concentration due ·to· the curvature effect is shown. The third power of the average particle radius Rav is proportional to time and the ripening constant shows a good agreement with the value by Deppers et al. The particle radii distribution shows the transition behavior to attain a self-similar stationary shape. The growth and coarsening behavior of the secondary dendrite arm is also analyzed using a phase-field model. The estimated arm spacing and its dependence on time are in good agreements with experimental data.IntroductionThe ripening or coarsening process controls the microstructure during the late stage of solidification. The ripening phenomena are recognized firstly by the Ostwald [1]. The first quantitative analysis for the Ostwald ripening in the limit of vanishing solid fraction was provided by Lifshitz, Slyozov and Wagner (LSW) [2,3]. In their study, that the mean radius grows proportional to the cubic root of time and the size distribution of precipitations shows a ""self-similar"" shape are shown. Most of the studies for the Ostwald ripening confirm or predict these two general rules above. In case of finite solid fraction, the general rules are observed but the ripening constant is larger and the self-similar shape is wider than the LSW prediction respectively [4-6]. To analyze· the high solid fraction system, the theories that consider the solute field correlation are proposed [4,7-8]. In the theory, however, since the particle is treated as the point, the effect of the concentration field deviation from the monopole field should be taken into account. Recently the numerical simulation, in which not only diffusive transportation of solute but also convection effect is considered, has been done using a phase-field model [9]."

Jan 1, 2000

By Eren Hüseyin Obuz

In this study, the leaching kinetics of rare-earth elements were investigated using HCl and HNO3 solutions. A standard crushed complex ore was utilized as raw material. The complex ore (particle size of under 54 μm) contains REE (Ce, La, Nd, Pr, etc.). Different leaching durations were selected for the kinetic studies. The highest leaching efficiency was obtained in HCl solution, and the leaching mechanism was identified to diffusion through a product layer. The rate constants of Ce, La, Nd, and Pr were calculated as 1.08 × 10−2, 0.86 × 10−2, 1.87 × 10−2, and 1.34 × 10−2 h−1, respectively.

By D. Mukerjee, Ramen Datta, Sanak Mishra, R. Veeraraghavan, K. L. Rohira

"Recent efforts at Steel Authority of India Limited (SAIL) has led to the successful development of atmospheric and marine corrosion resistant high tensile Thermo Mechanically Treated (TMT) bars with minimum specified yield strength of 50 kg.mm-2. These rebars are increasingly being used for a wide range of end-applications, namely, concrete reinforcement structures, bridges, flyovers, dams etc. Welding is an important processing tool for each of the above applications. In view of the importance of welding, a comprehensive evaluation of the weldability properties has been carried for the two grades of steels using Submerged Metal Arc Welding (SMAW) process; the most popularly used technique of welding of reinforcement bars (re bars).Implant tests were conducted to assess the cold cracking susceptibility of the steels. The static fatigue limit (SFL) value, determined for the atmospheric corrosion resistant (Cu-TMT) rebars under no preheat and no rebalcing conditions was found to be 63.8 kg mm-2, which was significantly higher than the Minimum Specified Yield Strength (MSYS) (50 kg.mm-2). This indicates adequate resistance to hydrogen induced cracking (HIC). On the other hand, the SFL value obtained for the marine corrosion resistant rebars (Cu-Cr TMT) under no preheat, no rebaking conditions was found to be inconsistent. Repeat of the test with fully rebaked electrodes (350°C-2h) resulted in a high SFL value (60.3 kg mm-2)_The rigidity of the structure or restraint influences the susceptibility of the weld joint to cracking. The cracking tendency increases with restraint intensity (K) of an assembly. The critical restraint intensities determined for the two steels were found to be· in excess of 1680 kg/mm.mm, indicating good welding behaviour with the following welding conditions : for Cu-TMT rebars with no preheat and no rebaking and for Cu-Cr TMT rebars with no preheat and fully baked electrodes; that is under low hydrogen levels."

Jan 1, 1998

The effect of rare earth element Y (0-2.0at.%) on the microstructure of TiAl alloys at the as cast and rapidly solidified conditions has been investigated. The results show that the addition of Y greatly refined the microstructure of TiAl alloys at both conditions. The refinement is more significantly with higher Y content. The refinement of Y in the cast alloys is attributed to that the strip-shaped Y-rich phase locating on the grain boundaries impedes the grain growth during solidification. In the rapidly solidified alloys, Y-rich phase dispersing uniformly as spherical particles in the matrix acts as heterogeneous nucleation sites which increases the nucleation rate of ??phase during the ????phase transformation, and produces a refined initial microstructure during solidification. Higher cooling rate restricts the grain growth during subsequent cooling.

Jan 1, 2010

By Sang Han Son

The vapor pressures of FeCI2 and ZnC12 in the FeCl2-ZnCl2 system were measured by the transpiration method at 873K and 917K. The vapor pressure data were interpreted to indicate the formation of complex ions in the FeCl2-ZnCl2 melts. It is presumed that the complex molecule FeZnCl4 as well as FeCI2 and ZnCI2 exists in the vapors in equilibrium with molten FeCl2-ZnCl2 mixtures. The activities in the FeCl2-ZnCI2 system are shown a negative deviation from Raoult&apos;s law. These results suggest the formation of complex ions such as ZnCl42- in molten FeCI2-ZnCI2 mixtures.

Jan 1, 2003

By H. Kohno

The Onahama No.3 tankhouse started commercial operation in early 1973, with the capacity of 8,500 metric tons per month. When the No.3 tankhouse was constructed, the starter sheet stripping section was rebuilt at the No.2 tankhouse and electrolyte purification section was expanded. The previous AIME paper in 1976 described the design principles of the No.3 tankhouse and its layout, This paper describes the starter sheet stripping machine in the No.2 tankhouse and the electrodes handling system in the No.3 tankhouse and all these equipments were developed for the operation of the No.3 tankhouse. A Hazelette continuous casting machine was also introduced in order to cast thin anodes with accurate shape. Owing to the adoption of thin anodes, gold, silver and copper inventory is reduced by 40%. Jumbo tanks and newly developed mechanical equipments were adopted and no work on cells during pulling up operation was achieved. Using thin anodes with accurate shape, inspection work was completely abolished while maintaining high current efficiency and high cathode quality. Labor cost was reduced by 70% and only six operaters can produce? 8,500 metric tons of cathodes per month. The same new electrolysis process is appreciated and has been used as a newly built independent tankhouse by Kidd Creek Mines Ltd., in Canada in 1981 with excellent results

Jan 1, 1987

By Florian Kongoli

While calcium ferrite slags have been successfully used in continuous copper converting for the last 30 years, ferrous calcium silicate slag was proposed about 8 years ago as an additional alternative for copper smelting. Although both slags are normal extensions of each other their phase relations have not been completely clarified. In this paper the liquidus relations of both slags have been quantified at various areas that cover both of them. The existing experimental data have been first reviewed and discussed in relation to the solidification procedure. An original physical model is then used to predict various diagrams of the liquidus surface of both slags. It is shown that the ternary liquidus diagrams normally used for FeOx-SiO2-CaO system are not suitable for industrial slags. The new model diagrams of Fe/CaO versus SiO2 and Fe/SiO2 versus CaO as well as Fe/CaO versus Temperature and Fe/SiO2 versus temperature are proven to be much more convenient for ferrite and ferrous calcium silicate slags. Based on these diagrams the effect of SiO2 and CaO on the melting temperature is quantified. The effect of Cu2O is also quantified through the model. Some Fe/CaO versus Cu2O and Fe/SiO2 versus CaO at various copper contents are predicted and the results show good agreement with the experimental data. It is also shown that in the presence of liquid copper, Cu2O is dissolved in the slag depending on the oxidation degree of the system and might lower the liquidus temperature. Some discussions are also presented taking into account plant observations and important conclusions are drawn for copper smelting and converting

Jan 1, 2006

By N. J. Tannyan

Laboratory bath smelting tests were conducted to determine the feasibility of smelting nickel- copper concentrate directly to a low iron matte in one step. Concentrate, air/oxygen and a silica flux were fed to a matte-slag bath kept in MgO crucibles at I 300°C. Various oxygen enrichments and smelting rates were used to maintain 0.5 to 2 wt% iron in the product matte. The slag losses are comparable to those obtained under similar industrial conditions. Due to the highly oxidizing conditions required to produce mattes with low iron contents, it is not recommended to target iron contents below about 2% in the matte. The specific bath smelting rates were equal to or higher than those in various industrial bath smelting processes.

Jan 1, 2003

By Yu. A. Grinin, Yu. A. Sannikov, M. A. Lyamina, V. A. Shumskij, L. V. Slobodkin, N. N. Ushakov

This manuscript describes the Kivcet treatment of lead-bearing materials having high contents of copper and zinc. The tests were carried out on bulk concentrates from the Zyrianovsk Mining and Concentrating complex, "Kazzinc" JSC (Kazakhstan) with the following composition: Pb 37.6%, Cu 10.4% and Zn 6.8%. Two properties of the concentrate were under investigation: their calorific value and their desulphurization rate. By adding flux, the charge properties were brought close to the properties of high-grade lead sulphide concentrate. The charge was melted with high productivity. To ensure high copper recovery, Waelz residue was added to the charge. The residue contained more than 20% carbon and about 30% iron metal. The residue was partially replaced by coke that facilitates high copper recovery into the matte. The smelting achieved a production rate of 20 t/h with one burner. Lead recovery into the lead bullion was 88.8%; copper recovery into matte was 92.3%; zinc recovery into slag was 75.5%; and zinc recovery into the fume was 5.1%.

Jan 1, 2000

By Aïda Espinola

Decontamination of synthetic solutions containing cadmium ions using coconut fibers in natura was investigated in laboratory scale. Cadmium ions, a serious pollutant of water ways, where it is detrimental to the environment, may be absorbed by fish and mollusk used as food, which will, eventually, poison humans; these ions are usually present in minero-metallurgical and electroplating industrial effluents. Usually employed for the aqueous effluents treatment are chemical precipitation, adsorption and electrolytic processes. Precipitation is not effective for cadmium removal, because of the high KpS of the cadmium hydroxide, which requires high pH; only sulfide would be efficient in cases of very small amounts. Some vegetal refuses have shown to be practical for absorption processes of several metallic ions. We have applied coconut (Cocos nucifera) shells, which are extremely abundant over most of the extensive Brazilian coast, in the removal of cadmium: it has been verified, in our laboratory, that the surface of the fiber of this coconut is rich in chemical compounds which are active scavengers for Cd2+. For the optimization of the process, hydrosoluble components existing on the surface of the fiber, which may be deleterious, were previously washed out by water, and variables, such as the pH and the proportion of mass of fiber to volume of solution, were adjusted. As much as 99% of the initial contaminant metallic ion has been eliminated, resulting a solution to be discarded which contains ca. 0.1 ppm; this attends to the maximum impurity legally admitted by the environmental control agency of Rio de Janeiro, FEEMA, for cadmium ions in aqueous effluents to be disposed in rivers and in the Guanabara Bay area.

Jan 1, 1998

By Mahmoud A. Rabah

"In this work, metal values were prepared from used beverage cans. The cans are made of aluminum and minor alloying metals and printed with a multi-color printing ink. A method has been investigated to remove the printed coating using organic solvents or by sand blasting technique in a rotating drum. Metal values of the cleaned cans are prepared applying combined hydro and pyrometallurgical treatments. Factors affecting the efficiency of the suggested method have been studied.The results show that the extent of removal of the printing coating is successfully performed with recyclable methyl ethyl ketone I dimethyl formarnide mixture. With sand blasting, it proceeds regularly with the inner diameter, the rotation speed of the drum, the size of the sand grains and temperature. The removed coating is stripped with the same solvent. Metal alloy(s) are prepared in two ways. In the first way, the cans are pressed into solid blocks using hydraulic press before melting at temperatures up to 1000°C using borax-sodium chloride salt mixture as a flux. The quality of the metal obtained is a function of the salt and temperature. The slag so formed was leached with mineral acid solutions. In the second way, the used beverage cans are directly dissolved in mineral acids whereby different metal values are selectively precipitated. The undissolved part is fused with sodium carbonate at 800°C and processed in the same manner. Results were explained in the light of the thermodynamic properties of the species involved."

Jan 1, 2000

By Chen-Ming Kuo, Esher Hsu

"The importers and manufacturers who import or produce products with packaging containers are charged a recycling fee in Taiwan. The amount of waste packaging containers used for calculating the recycling charge is based upon the amount declared by importers and manufacturers which might be underestimated. This study aims to estimate the amount of waste packaging containers generated by households in Taiwan and also explores its distribution. The sampling survey and ratio estimation are conducted for estimating the recycled amount; while the refuse sampling method for municipal solid waste composition is employed to estimate the un-recycled waste packaging containers. The estimated total amount of waste packaging containers in 2011 generated by households in Taiwan is 696,511 m.t., of which, 79.49% of the waste packaging containers were recycled and 20.51 % were landfilled or incinerated. This study shows that the amount of waste packaging containers declared by importers and producers is underestimated around 20%.IntroductionWaste packaging containers including iron cans, aluminum cans, glass bottles, plastic containers, paper containers, aluminum foiled paper packs are officially announced to be recycled in Taiwan. In order to create the economic incentive for raising recycling performance, associated manufacturers and importers are charged a recycling fee to subsidize recyclers. The amount of packaging containers declared by importers and manufacturers is used for calculating the recycling charge and recycling rate. The importers and manufacturers might underreport their producing (importing) amount to pay less recycling fees. Therefore, the estimated waste packaging containers based upon the amount declared by importers and manufacturers is usually underestimated. Related previous studies about waste packaging containers recycling in Taiwan are done by Hsu and co-workers [1-4]. Hsu and Kuo [1] estimated total production values of recycling and evaluated the performance of recycling performance based upon the estimated production values. Hsu and Liu [5] provided a cost analysis of recycling for waste packaging containers in Taiwan. Bor, Chien, and Hsu [2] presented a market-incentive recycling system for waste packaging containers in Taiwan. Hsu and Kuo [4] provided an amending mechanism for product charge and recycling subsidy in response to the social economic changes for waste packaging containers recycling. Lee and Hsu [ 6, 7] explored the distribution, fee rates, and collection rate of waste containers. This study aims to estimate the amount of waste packaging containers generated by households in Taiwan and also explore its distribution."

Jan 1, 2014

By Albert F. S. Seboukens

A 5;6 MVA pyrometallurgical demonstration-scale pilot plant was commissioned at Mintek, South Africa, in 1994, using lead blast-furnace slag and coke as raw materials. The plant included a.d.c. power. supply, two plasma-arc furnaces&apos; and an ISP lead-splash condenser. Slags containing typically 12 per cent zinc oxide and 3 per cent lead oxide are produced as a waste during the smelting of lead in a blast furnace. These slags are a potential: resource for the recovery of lead and zinc. During 1994, about 600 t of lead blast-furnace, slag was proceced through the pilot plant using the Enviroplas process. Zinc and lead oxides were reduced to their respective metals, volatilized, and collected in an. ISP lead splash condenser. Prime Western grade zinc and slags disposable in accordance with current US legislation, were produced. Zinc condensation efficiencies of about 80 per cent were achieved.

Jan 1, 1995

By R. A. Masumura, C. S. Pande, D. Agassi

"Grain size has a different effects on the critical current density (Jc) of high and low transition temperature (Tc) superconductors. In high Tc superconductors, the critical current density Jc across grain boundaries depends sensitively on the misorientation 8. It was pointed out by Pande that this dependence is directly related to dislocation structure of the grain boundaries i.e., it is due to dislocation cores and stresses. These ideas are developed further in this paper leading to a relation between Jc and 8. The analytical result is compared with the experimental results on bicrystals and used to explain the difference in behavior between high and low Tc superconductors.IntroductionThe grain size distribution and its evolution with time and temperature is important in determining the properties of high and low transition temperature (T c) superconductors. The distribution is a convenient function to characterize the processing of a high Tc material during sintering. For example, it is known that the maximum density of ceramic materials is obtained when the grain growth is reduced but grain boundaries are still mobile. For practical superconductors, the processing parameters are selected to achieve optimum properties: highest possible T c and maximum critical current (Jc). In terms of an average grain size, the requirements for optimum T c and Jc are sometime in conflict. In A15 type superconductors and even in NbTi, larger Jc have been measured in smaller rather than larger grain sized material. Conversely, in a high Tc materials like YBa2Cu307, higher Jc have been found in larger grain sized or single crystal specimens.Extended defects such as grain boundaries in low T c superconductors can be effective pinning agents for magnetic flux lines, thereby increasing the transport critical current density of these materials [1]. On the other hand, the transport critical currents in polycrystals of high Tc superconductors such as YBa2Cu307 is found to be relatively small (much smaller than those in single crystals of the same material) [2]. It is now known that grain boundaries in high Tc polycrystals can in many cases form ""weak links"" reducing the critical current density across them. This phenomenon can be studied more precisely by experiments on bicrystals, where there is only one grain boundary. It is found that the critical current density is quite sensitive to the misorientation angle of the bicrystal [3,4]. Although the original experiments were conducted on YBa2Cu307, other Tc superconductors have been shown to give the same result [5]."

Jan 1, 1994

By Dinesh P. Amalnerkar, Nagegownivari Munirathnam, Tirthalli Prakash, Katia Vutova, Vania Vassileva, Veliko Donchev

"A time-dependent model for electron beam melting and refining (EBMR) of different metals and alloys is developed. The model is 3D axi-symmetrical and an adapted numerical scheme of Pismen-Rekftord type is applied. The developed computer program computes the thermal fields in the metal ingots during EBMR process as well as the dynamics of the thermal streams and the geometry of the molten metal pools. Calculated results for different regimes of EBMR of titanium are obtained and discussed in the paper. Experiments are performed and impurities' concentration data are presented. Simulation results are compared with experimental data and are used for optimization of the EBMR process in the case of Ti.IntroductionElectron beam melting and refining (EBMR) has an important role in the special electrometallurgy[ 1-6] and it is approved for obtaining of pure titanium [7]. EBMR of metals and alloys is being recognized as a competitive and even the single method for obtaining new materials for all areas of human activity.The principal scheme of the EBMR drip process is shown in Fig.1. A thin layer of molten metal is formed on the front part of the feeding rod during the e-beam processing and generated droplets fall into the molten pool in the crucible where the ingot is formed. The refining is mainly realized at the boundary liquid metal - vacuum. There are three zones in EBMR (Fig.1) - on the front part of the feeding rod (zone I in Fig.1 ), on the surface of the generated droplets (zone II in Fig.1) and the surface of the molten pool in the water-cooled copper crucible (zone III in Fig.1)."

Jan 1, 2013

By R. Boom, Y. V. Meteleva-Fischer, B. Kraaijveld, H. Kuntzel

"Segregation of impurities during refining of metallurgical grade silicon (MG-Si) is an option to produce solar grade silicon (SG-Si). Directional solidification is a last step in production of SG-Si effective for removal of metallic impurities. The possibility is investigated to use metallic impurities originally present in MG-Si for removing boron and phosphorus. MG-Si has been treated using two methods: 1) alloying with calcium and 2) refining with Na2O-CaO-SiO2 slag, both by controlled cooling. The microstructure of silicon and the impurities distribution have been studied before and after the treatments. Using EPMA phosphorus and boron have been detected in 1-2 wt% concentration range in several intermetallic compounds in grain boundaries after both treatments. This observation points to a different possible mechanism of silicon refining from boron and phosphorus. Controlled cooling improves migration of phosphorus and boron to the silicide phases in grain boundaries, which can be removed by acid leaching treatment.2. IntroductionStandards for silicon solar cells and growing demand on “green” energy require economical and efficient route to the production of solar grade silicon. Refining of cheap metallurgical grade silicon is one of the promising options, where application of existing metallurgical approaches can result in cost-efficient production on industrial scale. Focus in refining is on impurities, which are most difficult to remove: B, P, Al, Ti, due to their large segregation coefficient in silicon and low vapour pressure [1]. Moreover, more environmentally friendly technology in comparison to the traditional Siemens process [2] will be in accordance with societal needs. Based on properties of common impurities in metallurgical grade silicon, alloying refining and slag refining are suggested as competitive techniques having potential effect on removal of impurities harmful for conversion of solar energy [3, 4]. Alloying with Ca followed by acid leaching was found to be effective for removal of Fe and Ti from silicon [5] and to enhance also removal of boron [6] and phosphorus [7, 8]. In the work of Inoue et al. [8] drastically increasing removal of phosphorus from silicon has been observed with an increase of Ca content and a thermodynamics-based explanation was provided. Since phosphorus has been found to condense in the secondary precipitate mainly composed of CaSi2, it can be removed together with iron and titanium by consecutive acid leaching treatment. Slag refining is one of the metallurgical methods proposed to be effective for refining of metallurgical grade silicon from boron [9, 10]. Slags with additions of the following oxides to silica have shown positive effect on removal of boron: CaO [11-13], Na2O [11,14]. Mechanism of slag refining from boron is based on oxidation of boron followed by its incorporation in the slag network [9,11]; the same mechanism is suggested for refining from phosphorus taking into account that oxides of boron and phosphorus are known as network-formers [15]."

Jan 1, 2012