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By H. J. Roorda

With an increasing need to obtain metals by processing complex fine intergrown ores, the use of electron-optical techniques will become more important as a tool for mineralogical studies. Electron images enable a higher spacial resolution than can be obtained by optical microscopy and thus provide a powerful and necessary aid for the examination of small grains and finely locked particles. In this paper the mineralogy of Meggen ore was investigated. Both light-optical and electron-optical techniques were used to evaluate the mill feed and products of the concentrator. Detailed examination by reflected-light microscopy to assess the comportment of galena in the complex pyritic ore was inconclusive in establishing the cause for low lead recovery of only forty percent of the ore's lead content. Electron microprobe analyses indicated that the majority of the lead lost to the tailings was accounted for by extreme fine (often smaller than one micron) and complex intergrowths of galena in pyrite. The remainder was lost as fine free galena grains.

Jan 1, 1987

By Anja Pfennig, Axel Kranzmann, Phillip Zastrow

"Properties of pipe steels for CCS technology require resistance against the geothermal corrosive environment (heat, pressure, salinity of the aquifer, CO2-partial pressure). To predict the reliability of two different injection pipe steels with 13% chromium and 0.46% carbon (1.4034, X46Cr13) as well as 0.20% carbon (1.4021, X20Cr13) steel coupons were heat treated by comparable routines prior to long term corrosion experiment (60°C, 100 bar, artificial brine close to a CCS-site in the Northern German Basin, Germany). In general higher carbon content exhibits better corrosion resistance with respect to corrosion rate, amount of pits and maximum intrusion depth in the case of local corrosion. At 100 bar hardened steels with martensitic microstructure have the lowest corrosion rates with an average of 0.003 mm/a after 2000 h exposure time. At ambient pressure normalized steels show the lowest corrosion rates, indicating that the corrosion is driven by grain boundaries.IntroductionEngineering a geological on-shore saline aquifer CCS-site (CCS Carbon Capture and Storage [1-3]) corrosion of injection pipe steels may become an issue when emission gasses, e.g. from combustion processes of power plants, are compressed into deep geological layers [4-8]. Typically 42CrMo4 (1.7225, AISI 4140) is used for casing, and for injection pipe the steel X46Cr13 (1.4034, AISI 420 C) or X20Cr13 (1.4021, AISI 420 J) is used. Saline formations are the most favorable storage sites in Germany [9], because of their large potential storage volume and their common occurrence. Leakage of CO2 back into the atmosphere may be a problem in saline aquifer storage, especially around the water level within the borehole. Carbon dioxide corrosion may cause failure of pipelines and wells as known from the oil and gas industry [4,6,10,11, 12].From thermal energy production it is known, that the CO2-corrosion is sensitively dependent on alloy composition, contamination of alloy and media, environmental conditions like temperature, CO2 partial pressure, flow conditions and protective corrosion scales [6-8,13- 20]. Considering different environments, aquifer waters and pressures, the analyzed temperature regime between 40 °C to 60 °C is a critical temperature region well known for corrosion processes as shown by Pfennig et al. [21-23] and various other authors [10,24-28] (figure 1). Here a maximum around 4.7 mm/year was found for the pit intrusion depth of 13% Cr steel X46Cr13. Still this may be predicted by the rather conservative Norsok-Model used in the oil and gas industry to calculate surface corrosion rates of carbon steels [29]."

Jan 1, 2014

By KNona C. Liddell

The ion interaction model Pitzer proposed twenty years ago is today the most widely used method for calculation of osmotic coefficients and electrolyte and single ion activity coefficients in aqueous solutions. This is due in part to the accuracy of the results that have been obtained for many concentrated electrolytes. An additional factor is that, compared to alternative activity coefficient models, there are many more parameter values available for the Pitzer equations. The important features of this model are reviewed. Published parameter values for Co, Ni, Cu, Zn and Fe are tabulated, and applications of interest in the aqueous processing of these metals are described.

Jan 1, 1993

By Shantaliu S. Shevade, Muhammad M. Rahman

"This paper presents a systematic analysis of fluid flow and heat transfer processes during the magnetic heating of the substrate material. Heat is generated in the substrate material when a magnetic field is imposed due to change in orientation of the molecules. As a result, the substrate temperature rises. The i;tudy considered microchannels with rectangular and square cross section with heat generation in the substrate due to imposed magnetic field. The results computed were for Gadolinium substrate and water as the working fluid. The purpose of this study is to explore the transient heat transfer coefficient when the fluid is circulated through the substrate via microchannels. Equations governing the conservation of mass, momentum, and energy were solved in the fluid region. In the solid region, heat conduction was solved. From the simulation results, plots of Nusselt number and heat transfer coefficient were obtained over the length of the channel. A thorough investigation for velocity and temperature distributions was performed by varying channel aspect ratio, Reynolds number, and heat generation rate in the channel. It was found that the peripheral average heat transfer coefficient and Nusselt number is larger near the entrance and decreases downstream because of the development of the thermal boundary layer. With the increase in Reynolds number, the outlet temperature decreased and the average heat transfer coefficient increased.IntroductionMagnetocaloric effect (MCE) is the heating or cooling of the magnetic materials due to varying magnetic field. The effect was originally discovered by Warburg. Magnetocaloric materials store heat energy in the way the atoms vibrate and in the way electrons spin within each atom. More heat energy increases the vibrations and also makes the spins more random. When a strong magnetic field is applied to a magnetic material, the magnetic moments of its atoms become aligned making the system more ordered. The more ordered material has lower entropy and compensates for the loss by heating up. When the magnetic field is removed, the magnetic moments return to their random directions, entropy increases and the material cools. Gadolinium is a magnetic material that exhibits high temperature rise during adiabatic magnetization around its transition temperature of 295 K. It has been experimentally observed that adiabatic temperature rise increases with magnetic field strength and can be as high 20 K when a magnetic field of IO T is applied. Thus magnetic field, when applied to a microchannel heat exchanger, causes temperature change in the magnetic material. The fluid flowing through the channel gets cooled or heated due to this adiabatic temperature change."

Jan 1, 2004

By M. R. Baren

Unpublished results obtained by Baren on thermodynamic properties of sulfur in liquid Fe. Co. Ni. Fe-Co. Fe-Ni. and Co-Ni are reevaluated. correlated. and interpreted on the basis of recent developments in thermodynamics of alloys:. Existing reliable data are reviewed and compared with the? present results. Sulfur obeys Henry's law up to 0.04 mol fraction. and in this range the standard Gibbs energy of solution of sulfur is expressed as a linear function of temperature for each pure metal. The activity coefficient of sulfur in each binary metal solvent 1s correlated with the composition of alloy.

Jan 1, 1983

By Geoffrey Brooks, Ben M. Ekman, M. Akbar Rhamdhani

"Concentrated solar collectors including solar simulators have been studied to concentrate solar radiation to flux levels capable of reaching temperatures of 3000K. Currently, there are no industrial scale solar reactors used for material processing and only small research units have been tried. Various laboratory scale solar reactor designs are reviewed including their operating temperature and heat transfer efficiency. Solar reactor designs can be classed into directly or indirectly irradiated and single or double cavity construction. Thermal efficiencies of up to 40% have been achieved in experimental units while operating at 1500K. Problems are encountered that relate to the transfer of high heat flux. Hybrid reactor system should be considered in the future to overcome some of the practical issues associated with solar thermal reactors.I. INTRODUCTIONIn the high temperature processing of materials, such as the production of metals, cement, refractory or glass, the reactions are typically performed in the range of 500° to 2000°C. Metals are produced from minerals, which maybe oxides, sulphides, chlorides or silicates, and to recover the metals, these compounds have to undergo chemical reaction to liberate the metal. The thermodynamic stability of these compounds found in minerals necessitates the use of high temperatures to break down the bonds between the metals and other elements. Normally, the raw metals produced from smelting require refining, which is often carried out in the molten state. As new energy sources have been established, new furnace designs have evolved to incorporate the latest technology. Although solar energy has existed longer than all the current energy sources, it has not yet been incorporated into any industrial smelting; refining or melting processes. The solar radiation reaching the earth’s atmosphere, called the “Solar Constant” (SC), is defined as the rate at which solar energy is incident on a surface normal to the sun’s rays at the outer edge of the atmosphere when the earth is at its mean distance from the sun. The currently accepted value is 1367 W/m2 [1]. The earth intercepts only a small amount of this and 30% is reflected back into space, 47% is converted to low-temperature heat and reradiated into space and 23% powers the evaporative and precipitation cycle of the biosphere [2]. As a result, the solar energy reaching the earth’s surface is weakened considerably to about 1000 W/m2 or one sun, on a clear day and much lower on cloudy or smoggy days [3]. The thermodynamic limit for solar concentration is determined from the inverse square law [4] by the factor sin2? = 46,764 sun’s [5] where ? is the angular size of the sun and equals 0.0093 radians [7]. This would produce a steady state temperature equal to that of the sun’s surface of approximately 5800oC. In practice however much lower concentrations are achieved due to geometrical and optical imperfections, shading effects and tracking inaccuracies. Optical configurations based on parabolic-shaped mirrors are commercially available for large-scale collection and concentration of solar energy for the generation of electrical power. The most common configurations used for concentration of the sun’s energy in solar thermal applications are parabolic troughs, solar towers and parabolic dishes [8,9]."

Jan 1, 2014

By Lucas Nana Wiredu Damoah, Lifeng Zhang

"Increasing demand for Solar Grade Silicon (SoG-Si) due to rising interest in renewable energy has lead to increased SoG-Si Top – cut scraps generated from the multi-crystalline silicon making process. Due to the high cost of SoG-Si and the potential to use the top-cut scraps as feedstock material, there has been increased effort to develop cost effective and efficient technologies. As a result, several methods to recycle the top-cut scraps are currently been applied, and researched. These include settling under gravitation field, which is a slow process to be industrially applicable. Natural settling of inclusions by gravitational force is a slow process and not attractive to the industry. Recent experiments on Top-cut SoG-Si scrap under high frequency, high voltage, electromagnetic field showed that SiC inclusions settled within a short time to the bottom of the crucible and the characteristic rod-like morphologies of Si3N4 inclusions in SoG-Si were not detected. This study investigates the enhanced settling of SiC inclusions and the behavior of Si3N4 particles under the influence of high frequency, high voltage, electromagnetic field in Top-cut SoG-Si.IntroductionThe photovoltaic industry depends on silicon based PV materials either as single-crystalline silicon, or multi-crystalline Si (MC-Si), or amorphous Si [1] for over 90 % of its market share. [2] MC-Si produced by directional solidification of solar grade silicon melt dominates the silicon PV market. During the directional solidification process, SiC and Si3N4 particles within the melt are pushed by the solidification front to the top of the ingot which is the last to solidify. Therefore the top of the ingot is cut generating what is known as top-cut solar silicon scraps. The Si3N4 particles are mainly from the coating material at the inside surface of the silica crucible and from air absorption during the solidification process. The SiC particles mainly stem from the carbon reduction process of the primary production of silicon [3]. Due to the growth of the PV industry as a result of global demand for clean, reliable, and affordable energy [4], there is the need to develop new methods to compliment exiting ones to recycle SoG-Si waste (e.g. top-cut) for sustainability."

Jan 1, 2012

By Steven M. Puricelli

Sulfuric acid plants associated with smelters, have historically been an overworked and often neglected pollution control device. They could do little more than manage the wide fluctuations in gas flow and SO2 strength from the smelter. With the introduction of flash smelting, the picture began to change, but the fluctuating batch converters continued to dictate acid plant design. More recently, the commercial use of continuous converting processes utilizing high levels of oxygen enrichment has dramatically upgraded the SO2 strength and stabilized the gas flow to the acid plant. The SO2 gas now issues continuously and at concentrations that allow for compact and, cost effective acid plants. Relieved of the burden of excessive dilution air, the heats of reaction can also be recovered as medium pressure steam and used to drive a generator, making the acid plant a net producer of power and a valuable asset to balance sheets. This concept was put into practice at the Kennecott Utah Copper Corporation smelter modernization project, located in Salt Lake City, Utah. The new acid plant, which was commissioned in June of 1995, is a sophisticated, low environmental impact, energy producing plant, worthy of review. This paper examines the key features of this acid plant, such as controlling its tail gas, by catalysis alone, to an environmentally friendly, 100 ppm of SO2, while feeding the acid plant converter with an efficient 14% SO2. The acid plant is also a prudent steward of energy resources, recovering 220,000 lb/hr of 140 psig steam from process heat which is used to generate a substantial 20 MW of gross power. Also discussed will be some of the ongoing issues, such as handling of selenium and fluorine in the gas cleaning sections, as well as a review of some. of the problems that were identified and resolved. Today's modem acid plants, by necessity, are becoming a producer of quality, valuable products, making the acid plant an asset and not a liability. Plants like Kennecott are already gaining wider acceptance and are expected to be the vision of the future.

Jan 1, 1998

By Won C. Park

Experiments showed changes in the mineral content of dolomitic oil shale at temperatures and exposure times which bracket conditions encountered during in situ retorting. Laboratory results correlate with cores from a spent in situ retort at Occidental's Logan Wash test site at Garfield County, Colorado. Dolomite, CaMg(CO3)2, decomposes rapidly to form periclase, MgO, calcite, CaCO3, and CO . Both calcite and periclase are intermediate products that can be stabilized by CO atmosphere at lower temperatures, while steam accelerates the formation 2 of silicates. The decarbonation of calcite appears to involve a direct reaction with both quartz and periclase in forming these silicates. Decarbonation preceeds the formation of akermanite, Ca2 MgSi 207, and diopside, CaMgSi 206, within several hours of heating and is followed by the nucleation of forsterite Mg2SiO4, and monticellite, CaMgSiO4. Under in situ retorting conditions, akermanite and diposide are the major minerals above 800°C. Equilibrium is not attained within 200-300 hours. In situ retorting temperatures above 800°C for extended periods of time should reduce potential ground water leaching by the formation of silicate minerals. These silicates are less soluble than free lime, magnesium or alkali oxides. There is a corresponding decrease in the natural pH of these silicates from approximately 12 down to 7.5 to 9:

Jan 1, 1981

By Rollie E. Dutton, David A. Stubbs

"A sensor has been developed and tested that is capable of emitting and receiving ultrasonic energy at temperatures exceeding 900°C and pressures above 150 MPa. The sensor works with standard ultrasonic pulser-receivers and has demonstrated the capability of measuring workpiece deformation during hot isostatic pressing (HIP). Details of the sensor design, performance, and coupling of the ultrasound to the workpiece are described. Ultrasonic data acquired by the sensor, in situ, during HIP runs and at elevated temperatures in air are presented.INTRODUCTIONHigh temperature structural components, such as structural castings for jet engines, nickel-base superalloy turbine blades, and ceramic and metal matrix composites made from powders are often densified by hot isostatic pressing (HIP). For powder consolidification, the HIP process involves sealing the powder (and reinforcing fibers for composites) within an evacuated ""Can"" made of a material that softens at high temperatures. A hydrostatic pressure is then applied by pressurizing the inside of the HIP vessel with argon gas (up to 140 MPa). The hydrostatic pressure densities the powder through the elimination of the porosity between the powder particles.This paper presents details of the development and preliminary testing of an ultrasonic displacement sensor that can be used to monitor materials processing, in situ, at temperatures and pressures significantly higher than current ultrasonic displacement sensors. The target processing environment for this sensor is that typically found in a hot isostatic pressure (HIP) vessel, i.e., temperatures exceeding 1000°C and pressures above 138 MP a."

Jan 1, 1997

By S. S. Chabot, S. E. James

A recent survey of CEOs from major steel companies worldwide revealed the importance of recycling zinc units from EAF dust, mill scale, blast furnace dust, and other zinc containing streams in their plants. Many processes were developed and installed in response to this challenge. The most successful approach involves the production of a crude zinc oxide and selling it to primary zinc producers to recover the metal value. The problem with this process is the high concentration of halides in the crude oxide. This type of material cannot be processed directly in an electrolytic zinc plant because of corrosion problems it will cause in electrolysis. In 1999, BRZ installed a zinc oxide receiving and washing plant to minimize the impact of halides to its circuit. A description of the washing plant and initial operating results are included.

Jan 1, 2000

By S. L. Kher

The Singhbhum Copper Belt located in the state of Bihar in Eastern India bears evidence of ancient workings and indicates the existence of a civilized habitation in this region in the past. It was in 1833. how- ever, that the first official announcement of the occurrence of copper in the district was made. Although the occurrence was confirmed in 1847, it was not until 1857 that the first company was formed to exploit the deposits. This Company was dissolved in 1859 and from then until 1920, there were many unsuccessful attempts to develop and exploit the copper deposits in the Singhbhum area. In 1920. the Cordoba Copper Co. took an option on the Mosaboni area, which is nearly 10 km away from the present works located at Moubhandar, Ghatsila and exercising the option in 1924, purchased the mining rights from the Cape Copper Company. The Cordoba Copper Co. was then converted into Indian Copper Corporation Ltd. This was subsequently taken over by the Government of India in March 1972 and is now known as Indian Copper Complex (ICC), forming one of the two smelting units of Hindustan Copper Ltd.

Jan 1, 1976

By N. Ono, H. Fujiwara, S. Otsuka-Yao-Matsuo, T. Omata

"The electrical conductivity and the oxygen release and uptake of sintered indium tin oxide (ITO) upon heating and cooling under the condition that P(O2)/P*=4.9X10-4 (P* = atmospheric pressure), :when P(O2) was approximately 50Pa, were simultaneously measured by using a closed-system oxygen-gas analyzer. A large increasing in -the electrical conductivity - upon the· oxygen release detected in 1130<T<1273K was observed. Quantitative relationship between the number of oxygen atom released from ITO and the conduction electron density in ITO was studied. The release of one oxygen atom agreed with the generation of two conduction electrons, i.e., the efficiency-carrier-generation for the oxygen release from the ITO was almost one. The oxygen atom released must be originally at the quasi-anion site in the C-type rare-earth lattice, i.e., the 16c site in the space group of Ia3, as an interstitial excess oxygen, Oi"". It was concluded that the mechanism of conduction carrier generation and compensation upon SnO2 doping into In2O3 can be expressed by the defect equation, 2SnO2-2Sn1n +2(1-z)e'+zOi""+3O0 x+(l-z)/2O2, and that the oxygen release bringing the increase in the electrical · conductivity can be expressed by the equation, Oi""-1/2O2+2e'.IntroductionThin films of SnO2-doped In2O 3 (generally designated as ITO, for indium tin oxide), which have high optical transparency for visible light and high electrical conductivity, have been used as transparent electrodes for liquid crystal and electrochromic displays. It is well known that the electrical conductivity of ITO depends on the content of SnOi-dopant and oxygen. However, a reliable relationship between electrical conductivity and the absolute oxygen content in ITO has yet to be reported. The elucidation of such a relationship is one of the important clues for realizing extremely highly conductive ITO electrodes."

Jan 1, 2000

By Takahiko Okura

Most non-ferrous raw materials are associated with sulphur. To extract the metals, the sulphur is recovered typically as Sulphuric acid or liquid S02. On the other hand, natural gas may contain over 20% of hydrogen sulphide (H2S) and a huge quantity of elemental sulphur is produced through oil and gas refining processes in the world. A large fraction of the sulphur mined from natural sources is eventually returned to the earth as fertilizers, by-products of desulphurisation and neutralisation processes, or as fugitives to the atmosphere. However, the supply and demand for sulphur are in imbalance. Such situation urges to develop a new smelting process without sulphuric acid production. This paper briefly reviews the global sulphur balance and the technologies for recovering elemental sulphur. The core of this paper is a proposal to convert S02 gas to elemental sulphur by using organic materials. Some results of thermodynamic calculations and experiments are presented.

Jan 1, 2003

By Takahiko Okura

Most non-ferrous raw materials are associated with sulphur. To extract the metals, the sulphur is recovered typically as sulphuric acid or liquid SOz, On the other hand, natural gas may contain over 20% of hydrogen sulphide (HzS) and a huge quantity of elemental sulphur is produced through oil and gas refining processes in the world. A large fraction of the sulphur mined from natural sources is eventually returned to the earth as fertilizers, by-products of desulphurisation and neutralisation processes, or as fugitives to the atmosphere. However, the supply and demand for sulphur are in imbalance. Such situation urges to develop a new smelting process without sulphuric acid production. This paper briefly reviews the global sulphur balance and the technologies for recovering elemental sulphur. The core of this paper is a proposal to convert SO2 gas to elemental sulphur by using organic materials. Some results of thermodynamic calculations and experiments are presented.

Jan 1, 2003

By T. Ahokainen, J. Pitkälä, J. L. Xia, A. Jokilaakso, J. Vaamo

"The aim of the present paper is to use the two CFD codes to model the two phase flow in a water model ladle with central gas injection. The codes examined are CFX and Phoenics. An Eulerian two phase model is used and predictions are compared against the experimental data available. The results show that the codes can reasonably well predict the gas-liquid plume in the ladle, and predictions are generally in a good agreement with experimental data. However, differences do exist in predicting the gas volume fraction and velocity profiles. The results should be interpreted most carefully and cautiously, because they are very sensitive to the boundary conditions and dependent on the models for the physical phenomena involved. IntroductionSubmerged gas injection has widely been used in the metallurgical industry for more than a century. At the present, the use of gas is most effective in steelmaking industry where the advantages of the gas injection have already been long well understood. Effective mixing, large contact area between reactants, easy modifications and flexibility of the processes are the most important advantages. Disadvantages include refractory wear, blocking in the tuyeres, and splashing. These disadvantages can be reduced and advantages further improved by studying the flow phenomenon in process vessels. However, it is difficult to study flow in a real vessel because of the high temperatures and physical and mathematical modelling is therefore increasingly used in the process development work."

Jan 1, 1999

By Chao Li, Qian Li, Yong-bin Yang, Kai Li, Qiang Xie, Yuan-yuan Zhu, Dong-ye Li, Qi-bing Tan

"The permeability of sintering mix is a vital technological property in sintering process. However, it can only be measured by off-line method on samples picked from the production. In order to acquire the properties of sintering mix accurately, on-line measuring of permeability is urgently required. Based on the reflection characteristics of bed permeability on pipe flowing parameters, a new method is presented in this paper for on-line measuring of sintering mix permeability. The measurement can be performed by blowing gas flow in the bed with the measuring pipe. Measuring results are obtained by picking the data on flowing rate and pressure in the pipe. The function of flowing rate to pressure may be certain for samples with the same permeability. Thus, the permeability was determined by contrasting this function to the result of off-line measuring, and the relative coefficient or R2 value was more than 99%.IntroductionThe permeability of sintering mix is a vital technological property in sintering process, which directly determines production and quality of sinter, or even determines whether the sinter production is carried out smoothly [1,3].The permeability have more obvious influence on vertical sintering speed, which is mainly related to air quantity passing through material bed. Under certain inducing capacity and negative pressure, the vertical sintering speed mainly depends on the permeability of sintering mix. Low permeability may make burning through point of sintering move back, and the sinter mix cannot be burnt through. High permeability may make burning through point of sintering move forward, improving production efficiency by increasing the speed of sintering machine [4] Good permeability means a small resistance of fan ,reduction of negative pressure of sintering machine, and full contact between air and sulfide, which can strengthen physical-chemical reaction during sintering process and increase desulphurization rate. In gas well through material layer process, gas-solid desulfurization reaction and gas-solid-liquid heat exchange are completed and hot gas through the combustion zone supplies the sintering process with heat. Finally uniform sintering of the material layer in height and width direction is achieved [5] While high permeability index leads to weak sinter strength, fast sintering speed, short residence time of high temperature region and little liquid phase. Moreover, liquid phase in the fast cooling process is too late to fully crystallize but forming glass phase which is harmful to sinter strength as well. Bad permeability means a big fan resistance and increase of negative pressure of sintering machine, which make the air pass through material layer difficultly. When air and mix contact difficultly, removal of sulfide reduces so that desulfurization is incomplete. Meanwhile, low caking efficiency, slow sintering speed and easily burnt sinter , reduce sinter output. Therefore appropriate permeability of sintering mix is the premise of stable burning through point and satisfactory sinter output and quality."

Jan 1, 2013

By E. Oshima

The only one reverberatory furnace smelting in Japan has been alive in Onahama Smelter, Onahama Smelting and Refining Company. The fuel for the reverberatory furnaces had been changed from bunker C-oil to mainly coal and partially waste tires to reduce the energy cost. The steam, recovered by the waste heat boilers of the reverberatory furnaces, has been utilized fully for the power generation to save the purchase power. Copper concentrate has been smelted also by injection through tuyeres in the P.S. converters since 1983. The amount of concentrate, treated in the converters, was increased by the construction of small oxygen plant in December, 1990. In the paper, the current practice and improvements in the reverberatory and converter operations are described.

Jan 1, 1993

By Toru H. Okabe

As part of a systematic study on the thermodynamic properties of complex nitrides, phase equilibria of the system Li-M-N (M Mg, AI, Ga) at 900 K were investigated. An attempt to determine the thermodynamic properties of complex nitrides was made by using the galvanic cell method, which utilizes LiMgN as an electrolyte under nitrogen atmosphere. The electromotive force (Emf) of the cell at temperatures between 800 and 1100 K was measured. While the Emf of the cell at 900 K was measured to be 0.137 V, data discrepancies of ±0.03 V were found. It was difficult to determine temperature dependence of the Emf. The Gibbs energy change for the reaction, 113 Li3N (s) + 1/3 Mg3N2 (s) = LiMgN (s), at 900 K was determined to be !&apos;J.Go, (LiMgN) = -13.2 (±2.9) kJ/mol. Using thermodynamic information on the binary nitride from literature, the standard Gibbs energy of LiMgN was derived to be !&apos;J.Go f (LiMgN)= - 121 kJ at 900 K. The thermodynamic stability range of nitride was discussed by constructing isothermal chemical potential diagrams that provide a better understanding of the stability region of the LiMgN phase. The diagram was found to be in good agreement with the isothermal phase diagram determined by the alloy equilibration method. Although the obtained data includes large uncertainties, the results provide a better understanding of the thermodynamic stability of nitrides. The potential application of this complex nitride to nitrogen chemical sensors or a medium for controlling nitrogen potential is also shown.

Jan 1, 2003

By Wilson Pascheto

This paper presents results of investigations performed as part of a Root-Cause-Failure-Analysis (RCFA) of a DC smelting furnace that was brick lined with MgO-based refractories. An unusual continuous contraction of the furnace hearth was identified during operation. Cracks in the refractories were envisaged after a major shutdown of the furnace. To determine the mechanism and causes of the unusual contraction behaviour of the furnace hearth, refractory samples were taken from the furnace at different locations and subjected to different analysis including Scanning Electron Microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDX), QEMSCAN and Electron Probe Micro Analysis (EPMA). Creep testing of refractories under different loads (ASTM C832) was also employed to evaluate the mechanical integrity of the used bricks in comparison with the new ones. Results of the various characterisation analyses revealed that there was an interaction between refractory bricks and molten material during furnace operation, which resulted in reduced creep resistance of the MgO-based refractories. This was verified by comparing creep performance of the used brick samples and new brick samples at different temperatures and applied stresses.