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By Bart Blanpain, Muxing Guo, Zhuangzhuang Liu

In order to stabilize free lime in the basic oxygen furnace (BOF) slag to achieve high value products, quartz sand and other additives are injected into slag. However, the current hot stage slag stabilization does not work in case of slag (before treatment) with a liquid fraction lower than 90%, where the slag containing solid particles is too viscous. Therefore, it is essential to understand how solid phases affect the viscosity of the slag system. In this study, the industrial BOF slags were investigated with respect to the correlation between volume fraction of solid phases and its viscosity. Slag viscosity was measured with a rotating type viscometer at temperatures below the liquidus. The volume fraction of solid phases was quantitatively calculated with FactSage. The Einstein-Roscoe equation was employed to predict the viscosity of BOF slag.

Jan 1, 2016

By Jie Li, Shu Yang, Zhongliang Tian, Xun Hu, Yanqing Lai

The purity of the electrolyte has an important influence on the content of the impurities in electrodeposited silicon. In this paper, effects of electrolysis temperature, current density and the time on the concentrations of two important impurities: phosphorus and iron in the electrolyte were investigated during the purification of Na3AlF6-10%K2SiF6-AlF3 melt. It was observed that the concentrations of P and Fe in the electrolyte decreased with the electrolysis temperature, current density and the electrolysis time increasing. X-ray fluorescence (XRF) of the electrolyte shows that the concentrations of P and Fe decrease from 4.2ppmw to 1.3ppmw and 204.0ppmw to 42.6ppmw, respectively. The removal rates of P and Fe are 69.08% and 79.12% when the electrolysis was performed for the duration of 3 hours and at a current density of 20mA·cm-2 while the operating temperature was 1225K.

Jan 1, 2015

By Sun Ying, Zhang Jing, Li Qiuju

A new process of enrichment Cu in molten copper slag under electric field is presented in this article. The experiments were carried out in the laboratory on a kilogram scale. The mobility of copper slag was improved by the technique of carbon reduction. The effects of temperature, electric field strength and intermittent feeding speed were investigated on Cu migration. The results showed that the best experimental conditions were the temperature at 1523K, electric field strength was 1.5V•cm-1 and feeding rates was 15 g•(10min)-1. The copper content of the slag decreased below 0.6wt%. The process was compared to the traditional electric furnace process of slag cleaning, there was reduced the energy consumption and heat loss, and also harmful gas emissions such as SO2 and CO2, accompanied by improved the efficiency of slag cleaning.

Jan 1, 2016

By Xuefeng She, Qingguo Xue, Jingsong Wang, Guang Wang

Iron nugget could be got at high temperature using carbon composite pellet, which were made by the mixture of ludwigite and reducing agent. In order to reduce sulfur content in the nugget, effects of additives on the desulfurization was investigated. The sulfur content could be dramatically reduced if the CaO was introduced into the pellet and the sulfur content was as low as 0.046wt.% when the addition amount of CaO was 5wt.%. However, the melting separation of pellet became increasingly difficult and the yield of iron decreased when CaO content in the pellet gradually increased. Na2CO3 could also reduce the sulfur content in the iron nugget and made the iron and slag separate difficultly as well. When 6wt.% Na2CO3 was added into the pellet, the pellet was too difficult to melt separation and the sulfur content in the nugget was 0.084wt.%, which didn’t meet the need of steel making.

Jan 1, 2015

By Xue Sun, Dengfu Chen, Yuting Chen, Mujun Long, Song Xu, Helin Fan

In order to seek an effective extraction process for vanadium, the recovery of vanadium from a high Ca/V ratio vanadium slag was studied by sodium roasting and ammonia leaching. In the present paper, the oxidation and leaching process of vanadium slag was investigated by X-ray diffraction (XRD), scanning electron microscopy and energy dispersive X-ray spectrometry (SEM/EDS) techniques. The effects of ammonium carbonate concentration, leaching temperature and leaching time on the leaching ratio of vanadium were discussed. As indicated in the experimental result, the optimal (NH4)2CO3 concentration was 120g/L, leaching temperature was 60°C and leaching time was 20 min. Approximately 92% of the vanadium was recovered under the optimal conditions. Furthermore, by means of X-ray diffraction analysis, the phase transformations of the vanadium slag during roasting and leaching processes were analyzed and discussed.

Jan 1, 2014

By Rolando Campos

The CODELCO-CHILE Teniente Converter Technology, is presently being applied in four Chilean smelters (Caletones, Chuquicamata, Potrerillos and ENAMI-Ventanas). A Teniente Converter is due to be used at ENAMI-Hernan Videla Lira (Paipote) smelter in the near future. Also, a Teniente Converter is to be installed as part of a retrofit project for Nkana smelter of Zambia Consolidated Copper Mines Ltd. (ZCCM). The charge to be treated through this smelter will consist of a blend of concentrate arisings from the various concentrators within the ZCCM group. The present status on the application of the Teniente Converter Technology at Caletones smelter as well as its projected performance when used at Nkana smelter, are presented in this paper. The design operational basis, autogenous smelting throughputs, concentrate to matte ratios and benefits due to the use of technical oxygen, are presented and analysed.

Jan 1, 1992

By D. Majuste

This paper describes an experimental approach to evaluate the effect of organic impurities or even additives on metal electrowinning and product quality. In addition to electrowinning tests and electrochemical measurements, the approach includes organic analysis by Fourier Transform Infrared spectroscopy and gas chromatography; video monitoring of the reaction interface; and product characterization by using scanning electron microscopy, crystallographic texture and bending tests. The mechanical behavior of metal cathodes was assessed with a customized bending device that is able to bend the cathodes up to angles similar to that of the stripping machine. In this work, the effect of a potential organic impurity, lubricating oil, on the production of electrolytic zinc is taken as a case study. The findings of the investigation allowed a better understanding on the role of this organic on energy consumption and product quality and a qualitative prediction for the behavior of Zn cathodes during the stripping operation. Simple control and optimization procedures resulted in significant energy savings.

By Francois Barthelat, Sam Goroshin, David Frost, Alexander Cappozi, Atefeh Nabavi

"In this study, a novel chromium–chromium sulfide cermet was produced by self-propagating high-temperature synthesis (SHS). Conventional techniques for manufacturing metal sulfides are complex, environmentally harmful, and not suitable for producing complex-shape articles. To overcome these disadvantages, a new method for the preparation of the metal-sulfur precursor charge is proposed, which can be described as reactive casting. The first cermet samples produced with the SHS process were found to be very porous, brittle, and have low mechanical strength. The possible sources for the generation of porosity were identified and analyzed and the process for manufacturing the cermet was modified. By improving the manufacturing process, the porosity inside the produced cermets was reduced from 70% to 12%.IntroductionMetal sulfide composites are in high demand in the chemical, metallurgical, and electrical industries because of their valuable characteristics such as hardness, semi-conductivity, electroluminescence, infrared transparency and catalytic properties. Current manufacturing methods for metal sulfides usually involve one of two different principal methods, including a complex multistage wet chemical process involving the precipitation of the corresponding salts from an aqueous solution with hydrogen sulfide, or hot sintering of the respective elemental reactant powders in a resistive furnace in a high-pressure inert or hydrogen-sulfide atmosphere [1, 2]. These conventional methods for synthesizing ceramic metal composites are complex, extremely time and energy consuming, environmentally harmful, and rarely able to manufacture articles with complex shapes. Therefore, in order to overcome these disadvantages, self-propagating high-temperature synthesis (SHS) was considered as an alternative method that offers significant improvements over the traditional cermet manufacturing methods [3]. SHS, which is a relatively new and attractive method for producing a wide range of advanced materials, is based on the self-sustaining feature of the highly exothermic reactions of the reactants. The SHS process results in high product purity, since the high temperatures generatedin the reaction cause any impurities to volatilize [4, 5]. SHS has low energy consumption and doesn’t require an external energy source and complex equipment, and it is self-contained [1, 5]. Since combustion synthesis has low power requirements, it is one of the few methods of materials synthesis that is feasible in outer space. Also, the process has a low cost and is capable of directly synthesizing articles with the desired shape, size and structure [5, 6]. The chemical reactions associated with SHS are typically completed in a few seconds leading to the formation of the condensed product. The high reaction rates and relatively rapid cooling in SHS reactions can avoid undesirable grain growth in products which often occurs with the conventional sintering method [3, 5, 7]. The traditional method for sample preparation in the SHS technique is to compact the reactant mixture powders in a steel die by a press to a typical density of about 80% of the theoretical maximum value, before igniting the mixture [8]. This method requires a large compression force to increase the green density and to minimize any pores in the green compact. To overcome these disadvantages, a new method for the preparation of the precursor charge in metal-sulfur by SHS is proposed which can be described as melt casting of a reactive mixture, or reactive casting in short."

Jan 1, 2012

By Wiraseranee. Chompunoot, Kazuki Morita, Toru H. Okabe

"Aiming at the development of more effective recycling processes, dissolution behavior of rhodium into molten slag was investigated. Using a pure rhodium crucible and Na2O-SiO2 slag system, equilibration experiments were carried out for 18 h at 1423-1623 K under various oxygen partial pressures of 0.005-1 atm with varied slag basicity. Rhodium solubility increased with increasing oxygen potential, slag basicity, and temperature. Rhodium dissolved into slag as rhodate ion ([RhO2]-) by the endothermic reaction: Rh(s) + 3/4O2(g) + 1/2O2-(in slag) = [RhO2]-(in slag). In the dissolution reaction, the “rhodate capacity” of slag is newly-defined. The correlation between rhodate capacity and optical basicity is reported.IntroductionDue to its high chemical resistance and outstanding catalytic properties, rhodium (Rh), one of the platinum group metals (PGMs), is utilized in various applications such as catalysts, molten glass vessels and containers, and electronic devices. Owing to the rarity of Rh resources in nature, recycled Rh from scraps such as spent automobile catalytic converters is currently considered as an important source of Rh supply [1]. According to the recycling practices, Rh is currently mainly recovered from scraps along with other PGMs such as platinum (Pt) and palladium (Pd) by a dry process (e.g., smelting), a wet process (e.g., leaching and subsequent separation of PGMs from aqueous solution), or a combination of both processes [2]-[4]. Among these processes, smelting is commonly applied because PGMs can be effectively separated from a relatively large amount of various impurities coexisting in scraps. In the smelting process, Rh and other PGMs are collected in the collector metal (e.g., iron and copper), and impurities in scraps are removed into slag [4]-[6]. The process may be carried out at a temperature range of 1573-1973 K, in either an oxidizing or reducing atmosphere. Due to the high oxidation resistance at high temperatures, Rh is expected to be collected efficiently in the metal collector rather than being oxidized and forming RhOx in a molten slag. However, Rh loss into slag does occur in this process [7]."

Jan 1, 2011

By Donald P. Ziegler, James F. Klausner, Srinivas S. Garimella

"By 2015, nearly half the world's population will live in ""water stressed"" areas. Production of fresh water utilizing waste heat from industrial processes has been identified globally as a research priority.About 15% of the electricity required to produce aluminum is lost as waste heat in the off-gas. However, the low temperature (low grade) of the heat limits reuse. The off-gases contain 50-150 ppm SO2 ; tightening regulations coupled with increasing coke sulfur levels are motivating SO2 control, for which seawater scrubbing is attractive for smelters with suitable access.We describe a process that produces fresh water, utilizing the waste heat while scrubbing SO2 . It uses direct contact between seawater and off-gas to humidify the off-gas. The vapor is subsequently condensed. In smelter trials, a unit treating a slip stream produced high quality water in the anticipated quantity, attaining over 95% SO2 scrubbing. Future work involves scaling the process to be economically attractive.BackgroundPopulation growth, coupled with industrialization and urbanization, are increasing demand for water. Water scarcity already affects every continent. Around 1.2 billion people, or almost one-fifth of the world's population, live in areas of water scarcity, and 500 million people are approaching this situation. By 2025, 1.8 billion people will be living in countries or regions with absolute water scarcity, and two-thirds of the world's population could be living under water stressed conditions (< 1,700 m3 per person annually) [1]. An assessment by the U.S. General Accounting Office revealed that under normal conditions, by 2013, water managers in 36 states in the USA anticipate water shortages, and that the number might grow to 46 states under drought conditions [2].The obvious choice to alleviate water scarcity is the 97% of available water in the oceans, which is saline and requires desalination for use in biological, agricultural and industrial applications. Technologies developed for desalination include Thermal Distillation, Reverse Osmosis (RO), Electro-Dialysis, and Vacuum Freezing. Distillation and RO are the most commercially prominent. Thermal distillation technologies include Multiple Effect Distillation (MED) and Multi-Stage Flashing (MSF). The report commissioned by the World Bank [3] is one of the many excellent references on desalination technologies. According to the International Desalination Association working paper [4], there were more than 17,348 industrial scale desalination plants installed or contracted by 2004. The total production from these plants is on the order of 8.3 billion imperial gallons per day. RO provides 47.2% of the total capacity. The leading thermal process, MSF, provides 36.5% of the total capacity. Although MSF and RO technologies currently provide the most cost effective means for desalination, their drawback is that they are very energy intensive, and whether or not they remain cost effective strongly depends on energy prices and energy supply."

Jan 1, 2012

By L. Katgerman, H. J. Brinkman, J. Duszczyk

"The phase formation sequence in the in-situ synthesis ofTiB2 in A1 from elemental A1, Ti and B powders is identified with a combination of DSC and XRD. After the melting of A1, A1B2 and A13 Ti are formed at the contact areas between A1-B and A1-Ti. The influence of variations in starting composition on the reaction kinetics is explained in terms of there effect on the different processes in the formation sequence. Parameters in the starting composition that were investigated are; fraction ofTiB2 forming reactants, non stoichiometric Ti:2B ratio's, and addition of alloying element Cu.It was found that a liquid Al phase is necessary for the in-situ TiB2 forming reaction from the intermediate A1B2 and A13 Ti phases. If all Al is consumed by the formation of A1B2 and A13 Ti the TiB2 formation is halted until the decomposition of A1B2 and A13 Ti .Overstoichiometric amounts of B are needed for complete conversion of the Ti, present in A13Ti, into TiB2 This is explained by the fact that some of the stable A1B12 phase is formed after the decomposition of A1B2•The addition of Cu leads to an increasing reaction rate in the A1-Ti reaction. A possible explanation for this is that the A1-Cu liquid penetrates more easily between the Ti and its surface oxide than the unalloyed A1 liquid."

Jan 1, 1998

By R. C. Hubli

A panial equilibrium model? to simulate the dissolution of millerite (NiS) in aqueous solutions containing copper(II) chloride as the oxidizing species has been developed. The predominant copper(I) and copper(II) species are CuQ3 and CUO2 respectively. The model computes the initial concentrations of the species present in the aqueous phase under the specified input conditions, prior to the simulation of dissolution. During the dissolution of millerite, nickel enters the leach liquor as NiH and it has been found that the H+ decreases as a function of NiS dissolution. The simulation has been accomplished under conditions prevailing during actual dissolution, with only one mineral undergoing dissolution. The model can be applied for the simulation of co-dissolution of two or more sulfides. Under the given conditions, the precipitation of Cu1(OH»)O is negligible but loss of Cu(1l) could be significant if the initial H+ is lower than 0.03 M. The results of the simulation compare favorably with experimental observations.

Jan 1, 1996

By Robert G. Telewiak

During the past few years, the international nickel industry has taken some important steps to respond to conditions of global production overcapacity, relatively flat demand and low prices. These include the implementation of major cost reduction programs by most producers, closure of some high cost operations and the establishment of the Nickel Development Institute. Consumption in the western world increased by about 7 per cent in 1987 compared to 1986, supplies were less than demand, inventories were low, and late in the year prices increased dramatically. By year-end 1987, most producers were operating at, or close to, their effective capacities. Nickel demand is expected to increase to the year 2000 at an annual rate of about 1.7 per cent, led by increasing usage in the stainless steel sector. If this rate of growth is realized, then there will be need for the effective capacity of the nickel industry to be increased. Producers in Canada have put considerable effort in the past few years into reducing costs - with impressive results. Mining costs, in particular, have been reduced dramatically. While production is still less than the peak years of the yearly 1970&apos;s, it has increased substantially from levels of the early 1980&apos;s. Over the next few years, production is expected to increase slowly. A key determinant of the level of production in the 1990&apos;s could be the effect that regulations on sulphur dioxide emissions have on limiting production.

Jan 1, 1988

By Chao Du, Xiaohui Ning, Hongmin Zhu, Qiuyu Wang, Shuqiang Jiao

"TiCxOl-x solid solutions were synthesized by sintering a mixture of titanium carbide and titanium monoxide at 1600 °C. The corresponding structures and morphologies of the TiCxOl-x solid solutions were characterized by XRD and SEM. A series of tests has been performed on the electrochemical dissolution behavior of TiCxOl-x solid solutions in NaCl-KCl molten salt. The influences of synthesis time and electrokinetic parameters on the anodic dissolution behavior were also investigated. The results showed that TiCxOl-x solid solutions can dissolve as Tin+ into alkali chloride melt. Titanium ion species dissolved from TiCxOl-x solid solutions changes between Ti2+ and Ti3+ depending on the applied potential. The tail gas on the anode was monitored by a mass spectrometer. It was found the synthesis time significantly affects the components of the anodic gas.IntroductionTitanium and titanium alloys have been desired greatly because of their many uses. The critical factor that restricts the range of uses for Ti is its high cost of extraction. The primary titanium metal, sponge titanium, is still produced industrially worldwide by a process invented by Dr. Kroll in the 1940s[1] •Since the early 1970s, the research focus of the titanium industry has been directed towards developing a continuous process to produce high purity titanium at low cost. [2-10] Of the many alternative methods that have previously been investigated, the electrolytic process has been considered a promising method for titanium metallurgy [4-10]. Recently, several electrolysis and related methods such as the PFC-Cambridge process[11-15], calciothermic reduction[16-18], USTB [19,20] and MER[21] process were extensively investigated.The USTB process is a new approach where the pure titanium can be directly obtained by the electrolysis with an anode of titanium oxycarbide in molten salts[19, 20]. The titanium oxycarbide was produced by carbothermal reduction of titanium dioxide under vacuum at a temperature"

Jan 1, 2011

By R. Stefaniuk, T. Le, J-Y Huôt, H. Henein

"One of the most important process variables in gas atomization is the gas to metal (G/M) mass ratio as it has a direct effect on the mean particle size of the atomized powder. If this ratio can be controlled during the atomization process, the powder produced would be more uniform and the d50 more predictable. Thus, atomization using a tundish or gravity feed from a crucible would be more stable. In gas atomization, the gas flow rate can be easily monitored; while it is very difficult to determine the molten metal flow rate. This research paper presents a new method of recording the molten metal height with time using a conducting metal height detector. The metal height recorded in real time during atomization was used to characterize using a model the friction losses in the metal delivery system. It is found that the integrity of the metal delivery tube and the cleanliness of the melt play a key role in the maintaining a stable metal feed.IntroductionIn the gas atomization process, molten metal is normally fed to the system either continuously using a tundish or in most cases a certain amount of metal is melted in a crucible and flows into the atomizing chamber under gravity. In the first case, the metal flow rate is believed to be constant during the atomization process despite the presence of slag or dross on the molten metal surface. In the second case, the amount of molten metal is depleted with time and the rate at which the metal flow decreases with time varies from test to test in a seemingly unpredictable fashion.' Furthermore, most atomization systems are confined units and the metal level in the crucible cannot be detected by a visualization method. In industry as well as in laboratories, the metal flow rate is normally calculated on either the mass of input material or the mass of total production divided by the duration of the test. This figure is not accurate enough and obviously cannot be used as a control parameter for the gas to metal ratio as it is only determined after the completion of an atomization run. The need exists for a metal flow rate measurement and control methodology; thereby the d50 of the powder produced may be estimated and controlled in real time. Clearly, the smaller the variation of the G/M ratio during the atomization process the more uniform the powder produced and hence the size of the particles can be predicted."

Jan 1, 1994

By Hiromichi Ohla

Precise thermal properties of molten materials are essentially required for analyzing the metal production process. These properties are also important as a clue to consider the dynamic structure of liquid materials. However, it is difficult to obtain the precise thermal diffusivity values of molten oxides at high temperature because of the experimental uncertainties arising from the bubble formation or the severe separation of radiative and conductive heat components. Recently a novel laser flash method has also developed for measuring thernnal diffusivity of molten oxides at high temperature. In this new technique, the sample is melted in a metal crucible and heated to the desired temperature. A single laser pulse is flashed on the bottom of the metal crucible and the infrared ray irradiated from the same bottom surface is measured for obtaining the temperature decay, from which the thennal diffusivity of the liquid sample can be estimated. The usefulness and validity of this new laser flash technique have been confirmed by obtaining the thermal diffusivity values of silicate melts in the wide temperature range between 773 and 1673 K.

Jan 1, 2003

By Matthias Merzkirch, Volker Schulze, Kay Andre Weidenmann

"Unidirectionally reinforced light weight compounds based on light metals such as the aluminium alloy EN A W-6082 are adequate materials for the future use in transportation means like automobiles and airplanes. Due to the occurring cyclic loads knowledge about the crack growth behaviour of such composites is needed. The investigations at a load ratio of R = 0.18 show that the crack growth rate of the aluminium matrix is reduced if reinforced by spring steel wire with a reinforcing ratio of only about 1 Vol.-%. Additionally, the acoustic emission analysis allows detecting crack growth within the matrix material, crack propagation along the interface wire/matrix and crack closure which could also be determined with the help of a self designed capacitive displacement measuring gauge. The damage behaviour could be verified by metallographic and SEM investigations.IntroductionIn the field of lightweight structures for transportation means the need for light, strong and stiff materials, in particular composite materials, is increasing in order to save resources and costs. Lightweight materials such as aluminium and magnesium alloys are highly efficient candidates to be used in the composite extrusion process [1] which allows for a simple production of unidirectionally reinforced profiles with a large diversity of geometries at low costs. Figure 1 depicts the principle of the composite extrusion process; within the first part of the tool the billet material is split into several strands whereas the middle part of the tool allows the supply of the reinforcing elements. The third part of the tool rejoins the matrix material and the reinforcing elements and defines the final shape of the profile."

Jan 1, 2011

By Junzo Hino

Most of the waste that contains a small portion of copper is landfilled. The recycling process of copper from the waste, such as shredder residue, should be developed in order to save mineral resources and prevent environmental pollution. Shredder residue, generated from disposed automobiles and electric appliances, consists of many types of plastics, glasses and metals. The combustion heat of plastics is efficiently used for smelting in the recycling process that consists of melting and reduction. Because the waste contains numerous components the knowledge of the distribution behaviors of the main components is necessary to develop the recycling process. The distribution behaviors in the recycling process are evaluated by using the thermodynamic calculation program, HSC Chemistry. The calculation results are compared with the practical operation data of the recycling process and discussed.

Jan 1, 2003

By Andriy Burbelko, Daniel Gurgul, Wojciech Kapturkiewicz, Marcin Gómy

"The mathematical model of the globular eutectic solidification in 2D was designed. The proposed model is based on the Cellular Automaton Finite Differences (CA-FD) calculation method. The model has been used for studies of the primary austenite and of globular eutectic grains growth during the ductile iron solidification in the thin wall casting. The model mentioned above takes into account, among other things, non-uniform temperature distribution in the casting wall cross-section, kinetics of the austenite and graphite grains nucleation, solute diffusion and non-equilibrium nature of the interphase boundary migration.Some aspects of stochastic nature of the solidification processes are taken into account. The results of the CA solidification modeling have been shown, that differences between cooling curves obtained in the same conditions of the casting solidification may be a result of the stochastic nature of the grain nucleation.The results of modeling were compared with the experimental microstructure. The model is well worked for thin walled ductile iron casting, for fast solidification process.IntroductionNodular graphite cast iron, also known as ductile iron (DI), has major applications in critical engineering parts due to its mechanical properties and castability. The mechanical and physical properties of this material depend on the shape and number of the graphite grains andmicrostructure of the metallic matrix.Solidification of DI was a subject of many computer modeling programs described in literature [ 1-5], in which the stationary conditions of carbon diffusion in austenite is pre-assumed. Recently, a tendency for production of thin-walled castings has been observed [ 6-8]. In this technology, the process of the fast solidification may be very far from equilibrium and steadystate conditions [9].The purpose of the present work is a two-dimension model development for simulation of the DI structure formation during the solidification in the condition of non steady-state temperature and diffusion fields in the thin-wall casting.Model of process The CA-FD is one of the known methods of the simulation ofmicrostructure formation during the solidification [ 10, 11]. In the CA microstructure modeling the outer grain shape is the result of the simulation and does not superimposed beforehand. The model development for a onephase microstructure evolution is a subject of the numerous researches [12 -23]. Model of the eutectic solidification of DI in the uniform temperature field and superimposed cooling rate is known [24]."

Jan 1, 2013

By K. Yamaguchi, Y. Takeda

"Partial pressure - temperature - composition correlation diagrams of the Ga-As, In-As, Ga-P and In-P systems were contracted based on the obtained experimental data of the phase diagram and thermodynamic properties for the III-V systems. The total vapor pressures of arsenic or phosphorus at melting point of GaAs, InAs, GaP and InP were determined as 101, 10.1, 1510 and 253 kPa, respectively, at the corresponding melting points of 1509, 1211, 1739 and. 1336K , These diagrams are applied to the analysis of the horizontal Bridgman method and the liquid phase epitaxial growth technique. On the other hand, the analysis of the equilibrium state of the. chloride-CVD process was carried out using the data of the Gibbs energy of the compounds obtained by· authors.IntroductionThe group III-V compound semiconductors ate important materials used in optoelectronic liquid high speed electronic device. The crystal growth of the III-V compounds can involve processes that require contact between the solid, liquid and vapour phases at near equilibrium condition. Examples of processes that involve contact between the solid, liquid and vapour phases include bulk crystal growth such as the horizontal Bridgman and the liquid encapsulated Czochralski method and liquid epitaxy, and between the solid and vapor include chemical vapour deposition and molecular beam epitaxy. Therefore, the knowledge of the phase diagram and thermodynamic properties for the III-V binary alloys is essential for the analyses of crystal growth techniques of III-V compounds.For these reasons, a series of different · types calorimetric measurements had been carried out: (1) The heat contents of alloys for the Ga-As, In-As, Ga-P and In-P systems by a drop calorimeter [1;2,3]; (2) the heats of formation of the GaAs, InAs, GaP and InP compounds by a twin solution calorimeter [4]; and (3) the standard entropy of these compounds by an adiabatic calorimeter [5]. Based on the third law method, the Gibbs energies of these compounds were derived from the heat capacity, standard heat of formation and standard entropy data obtained by authors. Integral molar thermodynamic quantities of the liquid III-V .alloys were also determined from combining the heat contents of alloys with standard heat of formation and standard entropy data of the compounds· by applying the thermodynamic analysis method developed by Oelsen [6]. In the present study, the thermodynamic calculations for the crystal growth processes of the III-V compound were carried out using newly experimental data of the phase diagram and thermodynamic .properties measured by authors"

Jan 1, 2000