Search Documents

By Tadafumi Adschiri

"Supercritical water can provide an unique reaction atmosphere for synthesizing metal oxide nanoparticles. Due to the drastic change of properties of water around the critical point, including density, dielectric constant and ionic product, the reaction phase with O 2 or H2 gas and the reaction rate and equilibrium can be varied to synthesize new materials or define particle morphologies. In this work, hydrothermal crystallization experiments are performed with several types of flow apparatus that allow convenient manipulation of variables such as temperature, pressure, and residence time. Key features in the flow modes and material preparation are discussed. The proposed supercritical hydrothermal synthesis method has the following desirable features: i) nanoparticles can be produced, ii) morphology of the produced particles can be controlled with small changes in pressure or temperature, and iii) a reducing or oxidizing atmosphere can be applied by introducing oxygen or hydrogen or other gases. An overview of this method is given for functional material synthesis of significant industrial interest including barium hexaferrite magnetic particles, YAO/Tb phosphor fine particles and lithium cobalt fine crystals.IntroductionHydrothermal crystallization, a method of metal oxide formation from metal salt solutions, is typically used at temperatures ranging from 373 K to 473 K. We are developing a new process for hydrothermal crystallizations that uses temperatures in the range of 673 K to 723 K, which is just above the critical temperature of water1 • 8 • In this work, we refer to this process as supercritical hydrothermal synthesis. The supercritical state of water allows one to vary reaction rate and reaction equilibrium by shifting the dielectric constant and solvent density with pressure and temperature. From of our research on material production in supercritical water, we have identified the following specific features of the supercritical hydrothermal synthesis method: (i) ultrafine particles can be produced, (ii) morphology of the produced particles can be controlled to some extent with pressure and/or temperature, and (iii) a homogeneous reducing or oxidizing atmospheres can be provided by introducing gases, such as O 2, H2, H2O 2• and so on.1"

Jan 1, 2000

By M. Rockandel

"Universal Dynamics Ltd. of Vancouver, Canada has developed, patented and commercialized the ""REMERC"" process for the treatment of mercury contaminated sludges and soils. Mercury is extracted into an acidified and oxidizing, sodium chloride brine solution. REMERC was initially developed to treat mercury contaminated EPA listed wastes (K106) generated by the chlor-alkali industry. More recent work has expanded the capability;' of REMERC to include remediation of mercury contaminated sites, equipment and building materials.In the process mercury is currently recovered from solution by cementation on iron powder in an agitated reactor. The process recovers high purity elemental mercury (99.9% purity). Cementation typically recovers about 90-95% of the mercury in 30 minutes. Higher recovery is not necessary because of the recirculation of the leach solution. When treating highly contaminated chloralkali wastes (5-13% mercury content), REMERC will reduce the mercury laden solutions from 400-1,000 mg/L mercury to 50-100 mg/L. In the treatment of less concentrated wastes «1,000 mg/kg mercury) such as those encountered in site remediation, the treated solutions will generally contain 10-20 mg/L mercury. Cementation while being simple and able to achieve the required recovery has the. undesirable properties of; requiring a solid-liquid separation and adding iron to solution which must be precipitated, ultimately increasing the weight of residue to landfill. .The potential advantages of electrolysis were recognized early in the development of REMERC. Mercury electrolysis is well known in gold and chloralkali processing. Initial testwork utilized a liquid mercury cathode and a coated titanium anode both common to chloralkali producers. The mercury cathode appeared susceptible to polarization and solution impurities significantly affected performance. Agitation of the mercury pool improved performance but it was still not possible to achieve the reduction objectives. Current efficiencies were low, near 10%, and it was apparent that a relatively large cathode pool would be required to limit the current density. A number of electrode combinations with and without a membrane were then tested in a vertical electrode' configuration but the desired performance was not obtained."

Jan 1, 1997

By Shaik Jeelani, Mahesh Hosur, Esperidiana A. B. Moura, Rejane D. Campos, Emilia S. M. Seo, Kerry Kirwan, Francisco R. V. Díaz, Maria Sotenko

The use of natural fibers with polymeric resins has spread rapidly. In order to improve the mechanical properties of material, in this work, two variables were used: mercerization and electron beam irradiation. This paper describes the preparation and characterization of biocomposites that were prepared in two different routes using green high density polyethylene (HDPE) and Brazil nut pod fiber (BNPF): the first was to irradiate the composite with 150 kGy and the second was to irradiate the matrix with 15 kGy followed by composite preparation. In both cases mercerized and non-mercerized fibers were used. The irradiation process was carried out using a 1.5 MeV electron beam accelerator, at room temperature and in the presence of air. The material was characterized to evaluate the effect of treatment on mechanical properties of material.

Jan 1, 2015

By Omid Marzoughi

In this research, both the kinetics and the mechanisms of the roasting of a sphalerite concentrate from the Bafgh mining complex in Iran were investigated. The oxidation process was performed in a muffle furnace in air and the effects of time and temperature on the degree of oxidation of the zinc sulfide sample were quantitatively studied. The experimental data were fitted to the shrinking core model. In the temperature range of 650–800 °C, the rate-controlling step was the chemical reaction between the zinc sulfide and oxygen with an activation energy of 103 kJ mol−1. On the other hand, in the temperature range of 850–950 °C, the rate-controlling step was oxygen diffusion with an activation energy of 50 kJ mol−1. Also, the roasting process was studied using thermogravimetric (TGA) and derivative thermogravimetric (DTGA) techniques.

By Takahiro Miki

In order to use metallurgical grade silicon (MG-Si) as a starting material for solar cell, phosphorus has to be removed from silicon because phosphorus is a n-type dopant. On the other hand, silicon, ferrosilicon, and silicomanganese are widely used as deoxidizers in steel refining processes. Since most of the phosphorus introduced during the deoxidation process is brought into final products, it is important -to lower the phosphorus content of these alloys. Hence, thermodynamics of phosphorus in such metals is important for the evaluation of dephosphorization processes. In the present study, thermodynamic properties of phosphorus in molten Si-P alloys at 1723- 1848K and those of Si-Fe-P and Si-Mn-P alloys at 1723K have been determined by equilibrating respective metals in a controlled phosphorus partial pressure. The results are expressed as follows.

Jan 1, 1998

By Ximeng Zhu

In the transpassive region, about 0.4 to 0.8 V (SCE), aggressive oxidation of pyrite occurred. The reaction products in this region were Fe(III) oxide, sulfate ion and partially oxidized sulfur intermediates. The growth kinetics of the reaction product film, resulting from transpassive oxidation of pyrite were studied using chronoamperometry measurement with both stationary and rotating disk electrodes. The effect of electrode rotation speed, solution pH and temperature were examined. Potentiostatic measurements were well correlated by a paralinear rate equation, suggesting the formation of an intermediate passive film, associated with the simultaneous dissolution of the outer layer of the film. Activation energies of 66.17 kJ/mole (15.83 kcal/mole) and 38.67 kJ/mole (9.25 kcal/mole) were obtained for associated parabolic and linear rate constants respectively, at an applied potential of 0.6 V.

Jan 1, 1993

By Hiroyuki. Fukuyama

The pseudo-binary phase diagram of the cuspidine (3CaO2?SiO2?CaF2) - CaF2 system has been studied by electron probe microanalysis (EPMA) and X-ray diffractometry (XRD). To prevent fluorine loss in the form of a HF gas by a reaction of CaF2 with water vapor at elevated temperatures, the equilibrium experiments were conducted with the sample hermetically sealed in a platinum tube. By employing this technique, it was successfully revealed that cuspidine exists as a stable phase and congruently melts at 1684 ± 1 K, and the cuspidine - CaF2 system presents a simple eutectic type of phase diagram, of which eutectic temperature has been estimated to be around 1540 K, corresponding to the composition of 40 mass% 3CaO?2SiO2 - 60 mass% CaF2?

Jan 1, 1999

By Xiaojie Gao, Jingshe Li, Chengsong Liu, Haiyan Tang

In order to clarify the reaction between MnO-SiO2 oxides with low FeO content and Fe-Mn-Si alloy, two diffusion couples were produced by the new method using confocal scanning laser microscopy (CSLM). The interface of the alloy and oxide, content of Mn and Si in the alloy near the interface, size distribution and composition of the particles which precipitated in the alloy were observed and analyzed using the electron probe microanalysis (EPMA). Results show that though the FeO content in the oxides decrease to 1% which is lower than the equilibrium with the molten steel at 1873K, the diffusion of oxygen from oxide to alloy still exists during the heat treatment at 1473K and causes shorter Particle Precipitated Zone (PPZ) and Manganese Depleted Zone (MDZ) normally for the reduction of diffusion flux of oxygen.

Jan 1, 2015

By T. Iriyama, Y. Fujita, R. Omatsuzawa, T. Nishio, N. Okochi

Sm-Fe-N hard magnetic materials are good candidates for high performance bonded magnets. Rapid-quenching method should be highly favorable for the fabrication of isotropic magnet powder with high coercivity. We report here the magnetic properties of Sm-Fe-N powders produced by a few kinds of rapid-quenching processes. Sm2Fe17 powders were prepared by gas-atomization (GA), rotating-disk atomization (RDA), or melt-spinning (MS) method. The Sm2Fe17 GA powder had dendritic solidification structure, while the RDA powder had micro crystalline structure with size of 3-5 µm. Coercivities (HcI) of their nitrides were 56 (for GA) and 217 ka/m (for RDA). The H cI of nitrided Sm2Fe17 MS powder with wheel velocity (V5) of 5-20 m/s, which had also microcrystalline structure, was 53 to 509 Wm. These coercivity values are not sufficient for bonded magnet applications. From the study of additive effects, it was found that C, C-Si, C-Ga, or C-Al addition decreased the crystal size of quenched Sm2Fe17 powder. Consequently, high coercivity was obtained; the HcI of nitrided Sm2Fe1C1Si1 MS powder with V5 of 10 m/s was 898 kA/m, and 708 kA/m for the nitrided Sm2Fe15C1Si1 RDA powder. The compression-molded bonded magnet made from Sm2Fe18Si0.1Nx MS powder showed a high (BH)max of 82.7 kJ/m3.

Jan 1, 2000

By Do-Hyeong Kim, Jong-Jin Pak, Jung-Mock Jang, Min-Kyu Paek

"Thermodynamic relations among Mn, Al and N in liquid iron were studied by measuring the effect of Mn on the solubility product of AlN in liquid Fe-Mn-Al-N alloys in the temperature range from 1773 to 1873 K. The critical Al and N contents for AlN formation were determined by the metal-nitride-gas equilibration technique over wide ranges of melt composition and temperature. The effects of Mn on N solubility in Fe-Mn and Fe-Mn-Al melts containing Mn up to 26 mass% were separately determined in the same temperature range. The experimental results were thermodynamically analyzed using the Wagner's formalism to estimate the critical Al and N contents for the onset of A1N formation. The validity was checked by the observation of inclusion evolution in Fe-20%Mn-1.5%Al-0.6%C-0.3%Si-0.012%N melt during cooling and solidification.IntroductionRecently, high manganese steels such as Twinning Induced Plasticity (TWIP) steels have been developed as next generation steels because of their high formability as well as excellent strength and ductility.[1•2l In these steel grades, a large amount of Mn (15-20 mass%) and Al (1-2 mass%) are added to liquid steels, and such high Mn and Al concentration bring the great challenges to the steelmaking and casting processes. Mn significantly increases the N solubility in liquid iron and the AlN inclusions can be easily formed at such high Al concentrations due to high affinity of Al and Mn with N in liquid steels. Although the AlN inclusion is known to be a dominating and considered as a detrimental phase for the hot ductility of steels,l3l thermodynamics of AlN formation in high Mn-Al alloyed liquid steels was not well known.Moreover, the melting point of these steels decreases down to near 1623 K as increasing Mn content up to 20 mass%. However, most of thermodynamic data has been measured at the steelmaking temperature around 1873 K. Even at steelmaking temperature, there are huge scatters in thermodynamic interactions of Mn and Al on N in liquid iron. The nitrogen solubility in Fe-Mn alloy melts has been measured using the Sieverts' method[4l and the samplinij method[5-7J in the temperature range of 1813 to 1973 K. In the authors' recent study,[8•9 the N solubility in Fe-Al alloy melts was measured using the sampling method in the temperature range of 1823 to 1973 K. However, the simultaneous effect of Mn and Al at high concentrations on Nin liquid Fe-Mn-Al-N alloys is still not known. Also, there remains uncertainty about the temperature dependence of the interaction parameter of Mn on N in liquid Fe-Mn alloys. Therefore, it is worthwhile to check the temperature dependence of this parameter at a low temperature near the melting point of Fe-Mn alloys. There have been few studies on the characterization of non-metallic"

Jan 1, 2014

By A. A. Hejja

The effect of composition on electrical conductivity, viscosity and liquidus temperature of the slags was investigated in the temperature range of 1300" to 1450°C. The synthetic slags containing CaO, MgO, SiO,, A1,0, and FeO were similar to those employed in the electric furnace smelting of sulphide Cu-Ni concentrates containing PGM (Platinum Group Metals) from the Merensky Reef of South Africa. FeO and SiO, were found to affect the viscosity and conductivity the most while liquidus temperature depended on MgO content in addition to these. The activation energy for electrical conduction was found to vary from 67 to 159 kJ/mol and that for viscosity from 125 to 209 kJ/mol. Optimization of the slag composition was attempted on the basis of opposite trend of the viscosity-electrical conductivity relationship with slag composition.

Jan 1, 1994

By D. Y. Wang, G. Y. Sha, X. L. Shen, D. R. Gu

The study of the volatilization kinetics of zinc and lead in pellets made of zinc-leadbearing dust mixed with coal powder, in a nitrogen atmosphere and at a temperature range between 1100 °C and 1300 °C, shows that the reduction temperature has a significant effect on the volatilization rates of zinc and lead, and that both the particle size of the coal powder and the extra carbon content has no effect on the volatilization rates. The obtained activation energies for the volatilization of zinc and lead are 79.42kJ/mol and 88.74kJ/mol respectively. The volatilization rate of zinc is controlled by the reaction between the zinc oxide and carbon monoxide while that of lead is controlled by the lead evaporation reaction, and the diffusion of gaseous lead through the gas boundary layer covering the surface of the reduced liquid lead.

Jan 1, 2000

By J. S. Kirkaldy

A theoretical procedure is demonstrated for calculating two-dimensional binary cellular single-valued interfaces and extended to triple-valued (remelt) shapes. The numerical calculations for the single-valued local equilibrium problem which yield unique shapes as functions of the supersaturation parameter a and the partition coefficient k are reviewed. The cell amplitude L and wavelength A scale identically as the inverse velocity to the 112 power and the aspect ratio r is a constant equal to 312, independently of a and k for a < 0.5.. For 0.5 < a < m, L, A and r decrease asymptotically to zero indicating the finite amplitude nature of the instability at a = 1 and the existence of sub-marginal states which converge to a flat interface at a- m (Glv- m). Scaling comparisons between equilibrium single-valued and triple-valued and deep-rooted non- equilibrium cells are made.

Jan 1, 1992

By Byung-Su Kim

Most electric arc furnace dust (EAFD) treatment processes employ carbon as a reducing agent for the zinc oxide in the EAFD. In the present work, the reduction reaction of zinc oxide with carbon in the present of various additives was studied. The effects of temperature and the additives of calcium carbonate, magnetite, and mill scale on the kinetics of the reduction reaction were measured in the temperature range of 1173 K - 1373 K under nitrogen atmosphere using a weight-loss technique. The mill scale is one of byproducts generated from the steel rolling process. From the experimental results, it was concluded that all three additives accelerates the reaction rate of zinc oxide with carbon, but the effect of addition of calcium carbonate is the highest. It was also found that magnetite, mill scale, and calcium carbonate in the reduction reaction of zinc oxide with carbon promotes the carbon gasification reaction.

Jan 1, 2006

Convential smelting of copper - cobalt - iron sulphide concentrates result in th eoxidation of cobalt and iron, which are subsequently lost into the slag. The emission of SO2 bearing gas from smelting causes serious health and environmentsl problems. In this investigation, three different types of copper - cobalt - iron sulphide concentrates, derived from froth flotation, were investigated, the concentrates, each containing more than 40 wt % percent gangue material, were directly reduced in the presence of lime and corbonin the temperature rnage of 1073 K - 1573 K, fo rthe production of an alloy containing copper, cobalt and iron. We demonstrate the basic principles of process physical chemistry for the recovery of alloy by carrying out a detailed process analysis utilising the predictions from thermodynamic equilibrium and results from the kinetics of reduction reaction. The effect of temperature on the reduction kinetics and alloy formation were determinedand analyzed in detail.

Jan 1, 2012

By Murray Johnston

New measurements have been made on the equilibrium distribution of selenium and tellurium between molten slag and metal phases. Distribution coefficients of Se and Te between magnesia-saturated calcium ferrite slag and copper or silver alloys were measured over the temperature range 1473 and 1673 K under controlled oxygen patrial pressures of 10-11 to 10-0.68atm. The results demonstrate that the minor elements are present in the calcium ferrite slag as the selenide (Se2-) and telluride (Te2-) respectively, up to a PO2 of 10-6 atm. As conditions become more oxidising, Te undergoes a transition to the divalent oxide whereas Se does not. Increasing the temperature was found to enhance partitioning of the minor elements to the slag. In terms of activities, at 1573 K, Se showed strong negative deviation from the ideal behaviour in the slag, while Te showed only slight positive deviation.

Jan 1, 2006

By Donald L. Stewart, Ken Overfield, Edward M. Williams

"Recent increases in energy cost have lead to a renewed focus on energy efficiency during aluminum melting operations to reduce fuel usage. The goals of a batch melting operation are to melt the charge using the minimum required energy, to melt the metal to the required temperature within the required timeframe, and to avoid generating unwanted contaminants by overheating the charge.The heat transfer efficiency of a conventional hydrocarbon fired aluminum melting furnace varies over the course of the melt cycle, depending on the conditions in the furnace. The purpose of this work was to develop a method of determining the transient heat transfer efficiency throughout the furnace cycle and to take advantage of this knowledge to optimize the melting process through furnace controls and proper production operations. This furnace survey methodology has been developed and used to evaluate a number of furnaces.Description of a Typical Batch Melting Furnace CycleA typical batch melting furnace cycle will consist of three stages:1. Charging – Solid metal charged through an open roof, solid or molten charged through an open door, and/or molten poured through a furnace blister2. Melting – From the time the door or roof is closed and the burners are turned to high fire until the charge is all liquid and has reached a temperature suitable for alloying (typically ~1350 °F / 730 °C)3. Holding – From the end of the melting stage until transfer or casting is completeIn some cases, further charging can take place after the melting cycle has started. This can happen when the entire solid charge will not fit in the furnace in one load, or if additional molten metal is added while the charge is melting. The bulk of the energy used in the melter is consumed during the melting cycle. The thermodynamic minimum energy requirements for melting pure aluminum are:• Energy required to heat pure aluminum from room temperature to the melting point at 1220°F (660°C) is 288 BTU/lb (670 kJ/kg)• Energy required to change state of pure aluminum from solid to liquid (heat of fusion) is 171 BTU/lb (397 kJ/kg)• Energy required to heat molten from melting point at 1220°F (660°C) to 1350°F (730°C) is 36 BTU/lb (83 kJ/kg)• Total energy required to melt a solid charge from room temperature to 1350°F (730°C ) is 495 BTU/lb (1151 kJ/kg)"

Jan 1, 2009

By Yoshisada Michiura, Junko Umeda, Katsuyoshi Kondoh

Rice husks or straws, one of the main agricultural wastes in South-east Asia, have a large possibility to be employed as usefully renewable resources to produce energy and high-purity silica (SiO2), because they consist of about 70% organics such as cellulose or hemi-cellulose, and 20% amorphous SiO2. The former is utilized as bio-mass energy; for example, thermal or electric energy, and bio-mass ethanol. High-purity silica can be used as raw materials in the industrial uses. It would be possible to extract silica elements from rice husks and straws by burning them in air because their main contents are organics. In the previous studies, a strong acid leaching treatment on rice husks before burning was carried out by using H2SO4, HCl and HNO3 to prepare high-purity silica materials. This was available to accelerate the hydrolysis of celluloses and hemicelluloses contained in rice husks, and remove the above metallic impurities. A strong acid leaching treatment, however, is significantly hazardous to environment and human life, and causes an increase of the process cost. In this study, the environmentally benign, harmless to human and economically effective process to produce high-purity amorphous SiO2 materials from rice husks has been established without using strong acids. From a viewpoint of the harmless influence on human body, the carboxylic acids were used in the leaching treatment on rice husks. TG-DTA measurement and GCMS analysis indicated that the leaching was effective for the hydrolysis of celluloses and hemicelluloses contained in rice husks at 473K~873K, which produced the same results in using the conventional sulfuric acid. The metallic impurities could be also removed from the husks via a chelate reaction between carboxyl groups (-COOH) and the metal elements. In particular, it was clarified that cadmium (Cd) were completely removed from rice straws by this reaction. Concerning the burning conditions of rice husks after the acid leaching, it was necessary to supply a suitable amount of air to completely combust organics; for example it required air supplement of 50 ml/min. or more. The burning temperature should be less than 1273K to obtain amorphous structured silica. High-purity amorphous silica materials with 99% or more were prepared from rich husks by applying the citric acid leaching treatment and burning process at 1073K in air.

Jan 1, 2008

By Norihiro Murayama

Syntheses of zeolitic materials were carried out from coal fly ash by alkali hydrothermal treatment as part of the reuse and recycle technologies of coal ash, For the obtained zeolites, the cation exchange capacity and acid resistance, which are very important in the practical use of cation exchanger in aqueous solution, are investigated during this stufY, The cation exchange amounts of the NaP, CaP and K-CHA zeolites are measured for various cations such as K+, Na +, NH4+ Ca2+, Mg2+, Pb2+, Cd2+ and so on. The change in crystallization degree are researched as a function of pH. The simultaneous removal ability of NH4+ and PO43- in solution is examined for an example of the water purification with CaP zeolite. From these results, the characteristic and its mechanism of cation exchange are clarified for the various zeolitic materials obtained from coal fly ash.

Jan 1, 2003

By Shigeatsu Nakazawa

Activities of Bi and In in the Bi-In liquid alloy were measured over the whole range of composition at the temperatures from 850K to 1050K. An alloy was vacuum-sealed in a quartz cell and heated at the temperature of interest. The absorption for 307nm radiation from Bi lamp was measured for Bi atom vapor in the cell. By heating a pure metal as a standard and measuring the absorbance as a function of the temperature, an analytical curve for Bi atom vapor was constructed and used for conversion of the absorbance to the vapor density. Bi activity was determined as the ratio of the Bi atom vapor density over the alloy to that over a pure metal. The same procedure was applied to the In 304nm radiation from In lamp and In activity was determined independently of Bi. Results showed that the liquid Bi-In system behaves like a regular solution.

Jan 1, 2003