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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)  

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Authorship：Corresponding author   Language：Japanese   Publishing type：Research paper (scientific journal)  

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Authorship：Corresponding author   Language：Japanese   Publishing type：Research paper (scientific journal)  

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)  

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Japan Petroleum Institute  

A Belousov-Zhabotinsky reaction in a liquid-liquid system was observed under non-stirring conditions to evaluate control of the non-equilibrium reaction by microwave irradiation through color changes of the solution. Irradiation power and time, and droplet size were important factors to control the oscillatory reaction in the droplet. During irradiation, the oscillatory period of any droplet sizes became shorter because the reaction rate became faster. In smaller droplets (2 mm), this behavior can be explained by the non-thermal effect because the temperature was equal to the temperature of the surrounding oil. Moreover, the oscillatory behaviors of the reaction in smaller droplets did not change after the irradiation even under higher power and longer irradiation time. On the other hand, shorter oscillatory period was observed in larger droplets (7 mm) after the irradiation, and the special microwave effect persisted. Overall, microwave irradiation was useful for controlling the non-linear reaction in a liquid-liquid system because of activation of the interface through the oil phase.

DOI： 10.1627/jpi.61.150

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Thermal radiation in a packed bed is controlled by temperature, emissivity, particle size, and bed structure, including void fraction, particle configuration, and the number of contact points. Thus, thermal radiation plays an important role in higher temperature operation of bed reactors. In this study, effect of the radiation/conduction ratio, namely, the Biot number with a thermal radiation coefficient, on effective thermal conductivity was investigated to clarify heat transfer in a packed bed. The Biot number for thermal radiation was defined as a function of temperature, particle size, emissivity, and configuration factor. The results obtained by the homogenization method showed that effective thermal conductivity with thermal radiation is simplified by the Biot number. Finally, the behavior of thermal radiation in the packed bed can be expressed by a sigmoidal function with the Biot number, even though the bed structure is complex. (C) 2017 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.ijheatmasstransfer.2017.06.083

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

In this study, bubble formation phenomena in the dispersion medium of magnetite nanoparticle in water during microwave irradiation were investigated. From the experimental results, it was found that under microwave treatment, the maximum bubble size was greatly influenced by the suspension density at a given temperature due to the distribution of microwave energy to the particles itself or the liquid-air interface of bubbles around the particle. Nanoparticles in the dispersion medium were also found to play a key role in achieving stable nucleation of bubbles on particles surface. Smaller bubble sizes were produced at higher suspension density. Microwave power also has a positive impact on the maximum bubble size especially at low suspension density. Moreover, particle material having dielectric constant property was also found to be an important factor for bubble size during microwave irradiation. From these results and findings, it is envisaged that bubble size can be controlled by the presence of nanoparticle and microwave irradiation.

DOI： 10.1016/j.cep.2017.06.005

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

Microwave technology has emerged as one of the useful methods for nanoparticle synthesis. Despite many studies on this area, its underlying mechanism has not been clearly understood. In this study, in-situ observation of nanoparticle growth was carried out and the profiles and behaviors of produced bubbles and particles under microwave effect were reported. Sizes of bubble and nanoparticle particle were measured during and after microwave irradiation using a DLS apparatus and behavior of particle growth and superheating effect were observed. From the experimental data, it is apparent that the maximum bubble sizes were greatly influenced by the irradiation power and solute concentration. Particle number density, which is related to the initial solute concentration, is also an important factor for the bubble size produced during the irradiation. Finally, through in-situ observation of superheating effect, the behavior was frequently caused by the irradiation at higher power. To prevent superheating effect, influencing factors such as the irradiation power and number density should be controlled to ensure a stable operation of particle formation process.

DOI： 10.1002/crat.201700108

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

The present work investigates the influence of heating methods on the interfacial tension of the decane-water interface in the presence of the common industrial surfactant, Triton X-100. The work considers heating by conventional methods, such as a waterbath, in contrast to microwave irradiation. Use of the holm interface allowed the measurement of interfacial tension even during irradiation. The interfacial tension was found to increase as the samples were heated from 25 to 65 degrees C by the two methods. However, microwaves were found to elicit changes to the response of interfacial tension to changing temperature, resulting in a much more dramatic increase in interfacial tension. The impact of microwaves can be attributed to different networks of hydrogen bonding between surfactant and water at the interface and in the bulk.

DOI： 10.1016/j.colsurfa.2017.04.044

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：IOP PUBLISHING LTD  

Microwave has been widely used for nano-particle synthesis because rapid growth and mono-dispersed particle size can be obtained. In our previous work, it was found that bubble formation during the irradiation is greatly affected by particle size and suspension density. Nevertheless, the underlying mechanism has not been clearly understood, especially pertinent to superheat behavior caused by the higher power when colloidal particle of ferric hydroxide was produced by heating ferric chloride solution under the irradiation. In this study, to prevent superheat behavior, two-stage irradiation was proposed in nano-particle formation process. Based on in-situ measurement data, such as the profiles of bubble size, final particle size and brightness of scattering light of suspension, it is evident that nucleation of nano-particle is promoted by higher power of the first irradiation. As a result, particle number density became higher, and then microwave absorbance energy was evenly distributed to each particle. Due to suppression of heat generation in a particle, bubble size became smaller. Two-stage irradiation became more advantageous in obtaining smaller particle than continuous irradiation because lower power of the second irradiation prevents superheat behavior.

DOI： 10.1088/1757-899X/206/1/012055

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：IOP PUBLISHING LTD  

Manipulation of the surface tension is useful in improving heat and mass transfer performances of nanofluids in thermal systems. In our previous study, the effect of microwave irradiation on the reduction of surface tension of nanofluids (Fe2O3) was found even after it was turned off. In this study, a synergistic effect of microwave irradiation and surfactant addition (SDS) was investigated to obtain further surface tension reduction of nanofluid. Experimental results indicate that surfactant addition is effective for wider particle number density in reducing surface tension, and the reduction level strongly depends on the surfactant concentration. On the other hand, effect of the number density on the surface tension reduction is less significant for the same concentration of surfactant. From the obtained data, a combination of microwave irradiation and surfactant addition shows potential to be used as a promising method to manipulate surface tension of nanofluids.

DOI： 10.1088/1757-899X/206/1/012011

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Water behavior during and after microwave irradiation is important phenomena for industrial applications. Recently, we reported a non-thermal effect of microwave on water surface tension. The bubble formation during microwave irradiation was suggested as one of the underpinning causes. This study examined the possibility by monitoring bubble formation during and after microwave irradiation. Moreover, the influence of NaCl on surface tension and bubble formation were also investigated. It was found that the presence of NaCl strongly increased both bubble formation and surface tension effect. The results indicated that bubble formation played an important role in surface tension reduction. The phenomena can provide useful pathways to improve the efficiency of chemical processes with microwave. (C) 2016 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.ijheatmasstransfer.2016.07.086

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SPRINGER  

Effective thermal conductivity including radiation is analyzed using a homogenization method. This method can precisely represent the microstructure of a porous medium with ellipsoidal pores. Here, the effects of parameters such as porosity, pore shape, pore distribution, and temperature of the porous medium on the conductivity are estimated to clarify the mechanisms in complex pore structures. For example, heat transfer by radiation does not dominate if the medium has pores of less than 1 mm in size. Moreover, the anisotropy of the effective thermal conductivity is found to depend on temperature, pore shape, pore size, and pore distribution.

DOI： 10.1007/s00231-015-1726-9

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SPRINGER  

A microwave reactor was designed for in situ observation of nano- and micro-bubbles, and size profiles during and after irradiation were measured with respect to irradiation power and time. Bubble formation in water during irradiation was observed even at temperatures below the boiling point of water. The maximum size strongly depended on radiation power and time, even at a given temperature. Nano-particles in the dispersion medium were found to play an important role in achieving more stable nucleation of bubbles around particles, and stable size distributions were obtained from clear autocorrelation by a dynamic light scattering system. Moreover, a combination of microwave induction heating and the addition of nano-particles to the dispersion medium can prevent heterogeneous nucleation of bubbles on the cell wall. Quantitative nano-bubble size profiles obtained by in situ observation provide useful information regarding microwave-based industrial processes for nano-particle production.

DOI： 10.1007/s00231-015-1703-3

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SPRINGER  

The effective thermal conductivity of composites with ellipsoidal fillers is analyzed by using a homogenization method that is able to represent the microstructure precisely. In this study, various parameters such as the volume fraction, shape, and distribution of the filler are quantitatively estimated to understand the mechanisms of heat transfer in the composite. First, thermal boundary resistance between resin and filler is important for obtaining composites with higher thermal conductivity. Second, the anisotropy of the effective thermal conductivity arises from contact between filler in the case of ellipsoidal filler and produces lower thermal resistance. Finally, the filler network and thermal resistance are essential for the heat transfer in composites because the path of thermal conduction is improved by contact between neighboring filler particles.

DOI： 10.1007/s11630-016-0880-9

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE INC  

Manipulation of the surface tension is one of the key pathways to enhance heat and mass transfer performances of nanofluids in thermal systems. Current practices and existing literature on the surface tension reduction indicate that surfactant is usually employed as a chemical-additive to manipulate surface tension. This study, on the other hand, aims to explore a physical method to manipulate the surface tension of nanofluids based on microwave irradiation. This paper, therefore, is the first publication to report surface tension behaviors of nanofluids during and after microwave irradiation. Experimental results show that after microwave treatment, lower surface tensions were observed for both TiO2 and Fe2O3 based nanofluids for an extended period of time, even though the temperature has returned to its initial condition. These preliminary findings suggest that microwave irradiation treatment has the potential to be a non-chemical method to manipulate surface tension of nanofluids. (C) 2015 Elsevier Inc. All rights reserved.

DOI： 10.1016/j.expthermflusci.2015.11.015

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Effective thermal conductivity with contact resistance is analyzed by a homogenization method that can precisely represent the microstructure of a packed bed. The homogenization used in this study explains the heat transfer due to conduction through the solid, the fluid phase, and the contact area between particles, and radiation between solid surfaces. In particular, the effects of parameters, such as the hardness, contact pressure, roughness, temperature, and particle size of the packed bed, on conductivity are estimated in order to clarify the thermal conduction mechanism for the complex packed structure. Heat transfer with thermal contact resistance does not dominate if the Biot number is near 100. In case of larger particle size and no convective heat transfer, the micro-hardness, contact pressure, surface roughness are important factor for effective thermal conductivity. Moreover, thermal radiation in the bed becomes more important for larger particles (>1 mm) and contact resistance can be neglected. However, effective thermal conductivity of pebble bed is dependent on the void fraction. (C) 2015 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.powtec.2015.12.006

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：ELSEVIER SCIENCE BV  

In this study, mechanism of microwave heating on water was investigated through a combination of the experimental and simulation works on bubble formation. Fine bubbles were firstly observed and confirmed at the temperature below the boiling temperature of water using a reactor equipped with DLS system. It was hypothesized that thermal non-equilibrium condition such as a hot spot was formed under microwave irradiation. Secondly, the initial stage potential of bubble nucleation (clathrate), which consists of water molecules, was calculated through a molecular orbital method. From the experimental and simulation results, it was found that high energy was generated by the bubble collapse, reconstruction of water molecule clathrate, and repetition of clathrate formation and collapsing cause higher heating efficiency of microwave. Thus, it can be deduced that microwave heating is greatly influenced by clathrate formation and the collapse. (C) 2016 The Authors. Published by Elsevier Ltd.

DOI： 10.1016/j.proeng.2016.08.332

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：IEEE  

In previous study, it was found that bubble sizes in dispersion medium were controlled by two-stage microwave irradiation. These results indicated that particle number density was the most important factor for the maximum bubble size when PSL particle, which is not active for microwave, was used. In this study, to understand the mechanism of controlling bubble size and to find optimum operation of microwave, the effect of the particle number density and surfactant addition on bubble profiles was investigated under microwave. For example, in the case of lower particle number density of magnetic particle, bubble size obtained by twostage irradiation became larger than that of continuous mode. Power of first irradiation of two-stage irradiation was higher because bubble nucleation was caused by the quick thermal response of microwave. Accordingly, because heat generation of magnetic particle became larger, the much energy of microwave absorbance was used for the evaporation. However, as the particle number density was higher, two-stage irradiation became more influential for getting fine bubbles. Finally, two-stage irradiation should be a useful tool for nano-particle formation process because fine bubble was obtained in suspension with magnetic particle.

DOI： 10.1109/PIERS.2016.7735587

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：IEEE  

Microwave has been often used for nano-particle synthesis because rapid growth and mono-dispersed particle size are obtained. However, superheat behavior causes larger bubble and disorders temperature distribution when higher power of microwave is irradiated. Accordingly, superheat must be prevented for stable operation of nano-particle process. In previous study [1], we found that bubble formation happened during particle formation at the same time when FeCl3 aqueous solution is heated by microwave. According to the results through in-situ particle size measurement during the irradiation, superheat behavior occurred at the condition of the higher power and lower suspension density. In this study, ethylene glycol with lower electric constant was added to promote particle nucleation and to enlarge particle number density. Moreover, the solute is not dissolved in ethylene glycol as anti-solvent although ethylene glycol is dissolved in water. The results showed that bubble size during the irradiation and particle size after the irradiation became smaller by the ethylene glycol addition. As a result, operation by higher power became possible, and higher particle number density was obtained as synergy effect of anti-solvent effect and quick thermal response by microwave. Finally, addition of alcohol became a good method for nano-particle formation process to prevent superheat behavior during higher power microwave irradiation.

DOI： 10.1109/PIERS.2016.7735180

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

In this study, to investigate the effect of combustion enhancement by irradiating microwave power, NO concentrations have been measured in the combustion experiments using premixed CH4/air flame with and without microwave irradiation. Analyses of NO formation using numerical simulation with a detailed kinetic model have been performed to investigate thermal effect and non-thermal effect of microwave for the combustion enhancement by irradiating microwave power. The experimental result shows that NO concentration in case of combustion with microwave superposition is higher than that in case of normal combustion. In particular, when equivalence ratio is less than 1.0 and Zeldovich NO is a dominant formation mechanism, there has a high increasing rate of NO concentration. The simulation result indicates that NO concentration tends to decrease, when the reaction rate is increased as non-thermal effect of microwave. On the other hand, NO concentration tends to increase, when the combustion temperature is increased as thermal effect of microwave. As a consequence, it is suggested that non-thermal effect of microwave is a small and thermal effect of microwave becomes a dominant factor for the combustion enhancement on premixed CH4/air flame with irradiating microwave power.

DOI： 10.1252/kakoronbunshu.42.155

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

A Belousov-Zhabotinsky reaction in a pendant drop under microwave radiation was observed under nonstirring conditions. The period decreased as the irradiation power and time were increased because the droplet temperature increased. Moreover, the color change of the solution during the oscillatory reaction depended on the irradiation power and time although the droplet temperature returned to room temperature quickly. Irradiation at higher powers or longer times suspended the oscillatory reaction. However, for moderate irradiation powers or times, the oscillatory reaction stopped after irradiation because the concentration distribution of the reagents became homogeneous. After a time, the oscillatory reaction restarted because a concentration gradient developed again. Accordingly, the effect of the microwave irradiation history continued because the oscillatory reaction stopped even after the irradiation was stopped. This is because the rotation of the polar molecule caused by the irradiation produced a flat concentration distribution for the reagents through increased molecular diffusion. (C) 2015 Wiley Periodicals, Inc.

DOI： 10.1002/kin.20964

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

DOI： 10.1021/acs.langmuir.5b02378

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：INST CHEMICAL ENGINEERS  

Surface tension of fluids is an important factor controlling multiphase systems and is often manipulated by surfactants during industrial processes. Previously, we have found that water surface tension was reduced under continuous microwave irradiation. The reduction was not explainable by thermal effects. The new insights can lead to important application of microwaves in multiple-phase systems. In this study, effect of various microwave irradiation modes on surface tension of water was investigated. The surface tension reduction was confirmed for pulsed microwave irradiation. The reduction varied with the applied power as well as interval between irradiations. The droplet oscillation and internal convection were also investigated during and after microwave irradiation to clarify the mechanism. It was found that the convection within the water droplet was proportional to the microwave power. In contrast, the frequency of oscillation was independent on the microwave power. These results on surface tension, oscillation and convection will provide important insights for designing microwave applications. (C) 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

DOI： 10.1016/j.cherd.2015.05.019

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

In this study, the combustion experiments using premixed CH4/air flame with and without the irradiation of a microwave have been carried out to investigate the effect of combustion enhancement by irradiating microwave power under equivalence ratios between 0.7 and 1.1. When the flame is radiated by a continuous wave microwave field of approximately 100 W, the consumption rates of CH4 and O-2 increase and the generation rate of CO2 increases at all equivalence ratio conditions. The generation rates of H-2 and CO increase at equivalence ratio 1.1. As a result, it is shown that the combustion flame is enhanced by irradiating microwave power. The optical emission intensities of OH radical and CH radical, which play an important role on combustion process, increase at 10 mm from the nozzle and they decrease at 25 mm from the nozzle, when the flame is radiated by a microwave. As a consequence, it is indicated that the combustion reaction is enhanced and the flame length is shortened by irradiating microwave power.

DOI： 10.1252/kakoronbunshu.41.167

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

The effect of microwave radiation on anti-solvent crystallization was investigated by in situ observation of nanoparticle size in a reactor. The precipitation of sodium chloride by the addition of ethanol was accelerated by the increase in molecular diffusion caused by microwave radiation. The microwave power controlled the particle size because increasing the power increases the temperature, which leads to the dissolution of the precipitate. The salt concentration in the solution, and the anti-solvent concentration and volume were important factors in anti-solvent crystallization under microwave radiation. (C) 2014 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jcrysgro.2014.04.031

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

In this study, microwave irradiation was applied to hanging droplets of both water and ethylene glycol. Once the irradiation had ceased and the droplet was allowed to return to its original temperature, it was found that the surface tension of ethylene glycol returned to its original value. In contrast, the water surface tension remained well below its original value for an extended period of time. Similar observations have been reported for magnetically treated water, but this is the first time that such a lasting effect has been reported for microwave irradiation. The effect can be attributed to the unique hydrogen bonds of interfacial water molecules. While the irradiation intensities used in this study are well above those in household devices, there is certainly the potential to apply the methodology to industrial applications where the manipulation of surface tension is required without the use of chemical addition.

DOI： 10.1021/la5019218

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Effective thermal conductivity with radiation is analyzed by the homogenization method. This method can precisely represent the microstructure of a packed bed. In this study, the effects of parameters such as the radiation emissivity, temperature and particle size of the packed bed on the conductivity have been estimated to clarify the mechanism of complex packed structure. For example, heat transfer by radiation does not dominate if the material has voids of less than 1 mm in size. Moreover, by comparing a conventional model and the homogenization method, applicability of their models were shown for estimating the effective thermal conductivity. (C) 2014 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.ijheatmasstransfer.2014.01.065

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

The nucleation and crystal growth of sodium chloride in aqueous solution during crystallization by ethanol droplet feeding were investigated by determining the suspension density and crystal size distribution. Crystallization was conducted in a microwave reactor, and the effect of the power, stirring speed, and ethanol concentration were investigated to clarify the anti-solvent effect under microwave radiation. Molecular diffusion was accelerated by fine particle production due to microwave radiation when the stirring speed was low and ethanol concentration was high. However, moderate microwave power and stirring speed were required for efficient molecular diffusion.

DOI： 10.1002/crat.201300327

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：Aabo Akademi University  

Surface tension of fluid is crucial for multiphase systems and is often manipulated during industrial processes by introducing surfactants. In this study, effect of microwave radiation on surface tension of ethylene glycol was investigated for new physical method to manipulate the surface tension without using chemicals. It has found that surface tension profiles of ethylene glycol during microwave are different with water. Moreover, convections in the water and ethylene glycol droplet during and after microwave radiation were compared to provide new understanding on the non-thermal effect of microwave.

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：SPIE-INT SOC OPTICAL ENGINEERING  

Surface tension of fluid is crucial for multiphase systems and is often manipulated during industrial processes by introducing surfactants. In this study, effect of microwave radiation on surface tension of aqueous solution was investigated for new physical method to manipulate the surface tension without using chemicals. It has found that surface tension profiles of aqueous solution during microwave are different with the salt concentration. Moreover, convections in the droplet during microwave radiation were compared to provide new understanding on the non-thermal effect of microwave.

DOI： 10.1117/12.2063433

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：SPIE-INT SOC OPTICAL ENGINEERING  

In this study, microwave irradiation is applied to a liquid droplet and the surface tension, the circulation flow and temperature of water droplet are measured dynamically under the irradiation. The droplet was allowed to return to its original temperature after the irradiation, it was found that water surface tension remained well below its original value for an extended period of time. Surface tension reduction shown similar effect of "impurity" at molecular level during the microwave, and some "memory" after microwave, which might be caused by nano-bubble. On the other hand, microwave can introduce the circulation flow of higher rotation speed and will be expected to be applied for non-contact stirring method.

DOI： 10.1117/12.2063436

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：The Heat Transfer Society of Japan  

The effective thermal conductivity with convection and radiation is analyzed by the homogenization method. This method can represent the microstructure in the packed bed precisely. In this study, Effect of parameters such as emissivity of radiation, temperature, contact area and particle size of the packed bed, on the conductivity has been estimated. For example, heat transfer by radiation is not dominant for the material with void less than 1 mm. Effect of contact area and pressure on effective thermal conductivity are negligible for thermal radiation. The homogenization method can become a powerful tool for the estimation of the effective thermal conductivity of the packed bed by considering the microscopic behavior.

DOI： 10.11368/tse.21.13

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Other Link： https://jlc.jst.go.jp/DN/JALC/10013630828?from=CiNii

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

The depolymerization reaction of poly(ethylene terephthalate) (PET) was analyzed on the basis of experimental and numerical data obtained from molecular orbital calculations. Various types of PETs polymerized by different methods and preheated by microwave irradiation were used to investigate the depolymerization mechanism. The activation energies obtained from the optimized structures of the ground state and the transition state were compared with the experimental data. On the basis of these comparisons, it was found that not only the crystallinity but also configuration changes caused by preheating were essential for realizing a high rate of transesterification reactions, such as depolymerization. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

DOI： 10.1002/app.34878

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

An improved reaction rate of biodiesel fuel formation was observed under microwave irradiation. Such irradiation is effective for not only heating during the reaction but also preheating. The advantages observed in this study suggest that a continuous process, that is, the introduction of reactant preheated by microwave irradiation into reactor will be feasible. The reasons for the improved reaction rate are explained through the use of optimized structures, dipole moments, IR spectra and activation energies obtained using molecular orbital calculations. Planar triolein formed by microwave irradiation has higher reactivity, a lower dipole moment, a lower activation energy and stronger vibration around the carboxyl carbon, and is more reactive than triolein with a higher dipole moment. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.

DOI： 10.1016/j.bej.2011.08.003

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The transesterification of triglycerides under various conditions was considered in terms of the activation energy obtained from molecular orbital calculations. The transesterification reaction proceeds via a cyclic transition state, consisting of the carboxyl carbon and the alcohol. Moreover, the reaction pathway was shown by an activation energy analysis and an electrostatic potential distribution. © 2011 International Journal of Thermodynamics.

DOI： 10.5541/ijot.301

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：INST CHEMICAL ENGINEERS  

Freeze-dried macroporous foams were prepared from an aqueous colloidal suspension of chitosan/xanthan gum/Na(+)-montmorillonite nanoclay (MMT). The suspension formed gel structure as a consequence of freezing, named cryogel. Cryogel is defined as a gel formed due to the concentration increase of the substrates caused by the ice formation during freezing. This obtained cryogel was subsequently dried under vacuum condition to produce porous foam materials. Two freezing methods were employed in the present work in order to investigate the influence of the processing on sample characteristics, namely; contact freezing with a heat exchanger and immersion freezing in a cryo-bath. Based on the SEM observation, in the case of contact freezing; rapid freezing (-2 degrees C/min) resulted in randomly aligned pores as compared to the pore alignment obtained in the case of slow freezing (-0.25 degrees C/min); the mean pore size for rapid freezing and slowing freezing were 40 mu m and 68 mu m, respectively. However, in immersion freezing samples, aligned and bamboo-like straight structures with pore layer spacing of 22 mu m were observed. The different microstructures significantly influenced the mechanical hardness of the prepared foams nanocomposites. The MMT dispersion within the bionanocomposites was found to be characteristically exfoliated from X-ray diffraction and electron microscopy analysis. Small angle X-ray diffraction data indicated that the polymeric networks were modified by the exfoliated MMT and the MMT also improved the hardness of the prepared foams. (C) 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

DOI： 10.1016/j.cherd.2011.02.023

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

Transesterification in a homogeneous mixture with the volatile co-solvent dimethyl ether (DME) has been proposed as a new fatty acid methyl ester (FAME) processing technique. Ternary feed mixtures of triolein, methanol and DME form a homogeneous solution, but the product mixtures of FAME, glycerin and DME form an emulsion after transesterification. In order to obtain FAME only, the glycerin phase mush be separated out from their mixtures by a centrifuge or settler. Therefore, we investigated the de-emulsification process at different methanol compositions in the feed mixtures, either with or without DME co-solvent. The rate of de-emulsification of the product mixture increased as the methanol content in the feed mixture increased: moreover, the rate of de-emulsification with DME co-solvent was 3-5 times faster than that without DME. The rate of de-emulsification was evaluated as a function of the molar ratio of dispersed glycerin phases in the product mixture. When the molar ratio of dispersed glycerin phases increased in the product mixture, the coagulation of the dispersed glycerin phases accelerated according to the Smoluchowski model. The de-emulsification was measured by UV spectroscopy as a function of time, and the relative transmissivity measured by UV spectroscopy was fit to the simple Smoluchowski equation, and the rate of de-emulsification was considered with respect to the molar ratio of dispersed glycerin phases, as calculated from the liquid-liquid equilibrium using the universal functional activity coefficient (UNIFAC) model. (C) 2011 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.cej.2011.03.017

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Used for biofuel production, fatty acids and their corresponding triglycerols are stored in most plants. At room temperature, saturated fatty acids and their triglycerols are solid, whereas unsaturated fatty acids and their triglycerols are liquid. Solid-liquid equilibrium data were measured for various binary systems of fatty acids and their triglycerols by differential scanning calorimetry. The freezing temperatures from liquidus curves for the binary systems containing tripalmitine were higher than those for systems containing palmitic acid. At the eutectic point, the melting temperatures for binary systems containing tripalmitine or palmitic acid were similar. The liquidus curves from the Solid-liquid equilibrium data were compared with the predicted values obtained by using the LLE-LTNIFAC model, and good agreement between the experimental and calculated results was found.

DOI： 10.1021/je101092j

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SPRINGER/PLENUM PUBLISHERS  

The depolymerization reaction of polyethylene terephthalate (PET) was analyzed on the basis of both experimental data and numerical data obtained from quantum chemistry calculations. Various alcohols were used as solvents in the search for the reaction mechanism. The activation energy obtained from the optimized structures of the ground state and the transitional state was compared with our experimental data. Based on these comparisons, it was found that the formation of rings from alkoxyl groups and carbonyl carbon atoms at the transitional state is highly important when the ester bonds of PET are broken. Moreover, the most appropriate alcohol was suggested for the depolymerization reaction.

DOI： 10.1007/s10924-010-0263-3

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

A seeded batch cooling crystalliser in a laboratory setup was utilised to produce mono-ammonium phosphate (NH(4)H(2)PO(4)) crystals. The effects of different initial saturation, seed size and seed loading ratio on crystal size distribution were thoroughly studied to gather more insight into mono-ammonium phosphate batch crystallization, its kinetics, and for model validation purposes. The seed loading ratio shows the most significant effect on the crystal size distribution profiles followed by the supersaturation factor and seed size. The supersaturation level not only influences the growth rate but the crystal shape as well. A simultaneous method has been applied in the procedure for the estimation of crystallisation kinetics. The nucleation constant (k(b)) was found to be in the range of 1.0-6.9 x 10(8) [no/kg s (kg/kg)(b+1)] and the growth constant (k(g)) measured was in the range of 3.0-9.4 x 10(-5) [m/s (kg/kg)(g)] with the nucleation (b) and growth (g) exponents determined as 2.2 and 1.4, respectively. Wavelet orthogonal collocation method was utilised to solve the seeded batch crystalliser model and the solution was compared with the experimental data. (C) 2010 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.

DOI： 10.1016/j.apt.2010.02.017

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

NH(4)H(2)PO(4), mono-ammonium phosphate (MAP) and (NH(4))(2)HPO(4), di-ammonium phosphate (DAP) have become leading phosphate fertiliser products worldwide. Ammonium phosphates are produced by reactions of ammonia and phosphoric acid resulting in the formation of the mono-basic, di-basic, or tri-basic salts. Inefficiencies in the MAP/DAP production process are due to the lack of a fundamental understanding of the crystallisation-reaction mechanisms. A semi-batch reactive crystalliser equipped with a cooling jacket, a dual feed system and a turbine type agitator has been used in this study. Effects of N/P ratio, seed crystals, feeding system, feed flow rate, initial supersaturation, feeding time and mixing intensity to the real-time supersaturation, crystal yield, crystal shape (aspect ratio) and final crystal size distribution (CSD) were studied in order to understand the kinetics. This study aims to provide new insights into the MAP/DAP reaction-crystallisation mechanisms. (C) 2009 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.cej.2009.04.055

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Language：Japanese   Publishing type：Research paper (scientific journal)  

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

To promote the biodiesel production, low-quality fats in addition to waste vegetable oils are still required. Low-quality waste vegetable oils and low-quality fats as feed mixtures contain free saturated fatty acids and/or commercial solidifiers in addition to triolein as a main component, and they are solid at room temperature. However, liquid feed is desired for biodiesel production processes. In this study, solidification properties of a system of commercial solidifier and commercial vegetable oil as low-quality fats and a binary system of palmitic acid and triolein as low-quality vegetable oils were investigated, and the melting temperature was calculated by a simple thermodynamics function of composition. The binary mixture of palmitic acid and triolein could be liquefied at above 65 degrees C regardless of the composition, and the melting temperature of the mixture could be represented by the simple thermodynamic function. On the other hand, the melting temperature of the mixture of the commercial solidifier and commercial vegetable oil increased sharply to 80 degrees C even at low solidifier concentration, and the melting temperature of waste fats could not be represented by the simple thermodynamic function.

DOI： 10.1252/kakoronbunshu.36.432

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：IOP PUBLISHING LTD  

The movement of particles with a size smaller than few microns is governed by random Brownian motion. This motion causes the fluid to flow around the particles. The force acting upon Brownian particles as well as their velocities are measured by using the dynamic light scattering (DLS) technique. It provides the relationship between fluid shear stress and shear rate over the Brownian particle and determines the viscosity properties of the fluid. In this study, we propose a new rheometer which is widely applicable to fluid viscosity measurements at both normal and high pressure levels for Newtonian and non-Newtonian fluids.

DOI： 10.1088/1742-6596/215/1/012073

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：IOP PUBLISHING LTD  

We demonstrate a new apparatus for optical observation under high pressure conditions with 4-way optical glasses. We use the proposed apparatus to study solubility of ammonium salts in aqueous solutions and to measure the nucleation pressure for different concentrations of salts in the solution. Despite the fact that the solubility of electrolytes usually increases as the pressure increases, it is found that the solubility of ammonium salts decreases as the pressure increases. In both cases, high pressure can be used towards a crystallization process. Finally, we observe high pressure induced nucleation of electrolytes in an aqueous solution.

DOI： 10.1088/1742-6596/215/1/012066

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2010f.0.387.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2010f.0.292.0

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Language：Japanese   Publisher：The Japan Institute of Energy  

Effect of microwave irradiation on BDF formation was considered by simulation and experiment. First, it was confirmed that reactivity of triolein is improved for preheating and keeping temperature by microwave irradiation. The reasons of the improvement effect for BDF formation were estimated by FT-IR measurement, simulated IR spectrum and activation energy obtained from molecular orbital method. Secondly, because flat triolein was formed by microwave irradiation and higher reactivity could be explained by lower dipole moment, lower activation energy and stronger vibration around carboxyl carbon. Finally, combination of experiment and simulation becomes good tool for mechanism of BDF formation.

DOI： 10.20550/jietaikaiyoushi.19.0_154

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

Spray evaporation of aqueous ethanol solution with dilute potassium chloride (KCl) was examined for the generation of extremely small electrolyte crystals in dry state. Ethanol content in the aqueous solution played an important role in decreasing the solubility of KCl. Evaporation of small liquid droplets of the aqueous ethanol solution produced a small amount of KCl crystals. The concentration of ethanol in the solution was the operative variable,and the ultrasonic spray nozzle and flow rate of the solution were fixed in this study. The crystals collected were observed by SEM, and crystal size distributions were obtained for different operative conditions. The average crystal size ranged from 100 to 800 run. When the ethanol content increased in the solution, the crystal size decreased. We consider the crystal size according to the slight solubility of KCl in liquid droplets of aqueous ethanol Solution. (C) 2009 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.cep.2009.06.003

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCI LTD  

The transesterification of various triglycerides was considered in terms of the activation energy obtained from quantum computational chemistry. According to these values, the effect upon the reactivity of the structure of the triglyceride is not particularly large. Moreover, the transesterification reaction is completed via a transition state, in which ring formation consisting of the carbon of the carboxyl and alkoxy groups appears, even if a long-chain alcohol is used as a reactant. Finally, an ideal reaction pathway, in which the ester bond at the center of the triglyceride is transesterified before peripheral ester bonds, was shown by an activation energy analysis and electrostatic potential (ESP) distribution. (c) 2008 Published by Elsevier Ltd.

DOI： 10.1016/j.fuel.2008.10.045

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

The solubilities of electrolyte salts, such as sodium chloride (NaCl) and potassium chloride (KCl), are small in alcohol solution. As an application of such dilute solubility, nucleation phenomena were investigated by the dynamic laser scattering (DLS) method at different supersaturation degrees, prepared by different solubilities of KCl in aqueous ethanol solutions. The supersaturated solution of KCl was very stable, and therefore ultrasonic irradiation was utilized as a trigger of nucleation. The time-change of the sizes of fine KCl crystals was measured, and the nucleus size was obtained by extrapolating the size of the fine crystals to zero-time. The nucleus size of KCl was correlated by the modified Gibbs-Thomson equation as a function of supersaturation. it was found that the nucleus size tended to increase when supersaturation decreased, but three different curves for three different temperatures could be obtained. The modified Gibbs-Thomson equation represented the nucleus size at three different temperatures. The correlated "minimum supersaturation energy" parameters were converged to zero at the saturated temperature. The parameter "minimum supersaturation energy" could be interpreted as "ultrasonic effective energy" that could be defined as the received energy in the solution from ultrasonic irradiation. (c) 2008 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.cep.2008.12.003

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：JOHN WILEY & SONS LTD  

BACKGROUND: The use of fatty acid mixtures, natural biochemical compounds, will be extended to various chemical industries for the production of a wide variety of products, and various mixtures of fatty acids are necessary for production. Separation of a binary fatty acid mixture of lauric acid and myristic acid using physical vapour deposition (PVD) on a cold quartz crystal resonator is examined. The extremely small amount of deposits can be measured with the quartz crystal resonator. The vapour phase is prepared by vaporizing a calculated composition of melt according to the vapour-liquid equilibrium (VILE).
RESULTS: The composition of lauric acid in the melt and the melt temperature were utilized as operating variables in the PVD. The growth rate of deposit increases when melt temperature and the composition of lauric acid in the melt are increased. The composition of lauric acid in the deposit is significantly lower than that of the melt of 19% lauric acid, but the composition of lauric acid in the deposit is much higher than that of the melts of 50% and 75% lauric acid.
CONCLUSION: The distribution coefficient of lauric acid between solid and vapour phases can be correlated as a function of the growth rate of deposit. The possibility of separation of fatty acid mixtures by PVD is suggested experimentally and theoretically. (C) 2008 Society of Chemical Industry

DOI： 10.1002/jctb.2039

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

The solubilities and complex phase equilibria for the system of MnSO4 center dot 4H(2)O+MgSO4 center dot 7H(2)O+H2O+CH3OH were determined at the temperatures 291.2 and 301.2 K over the methanol mole fraction range of 0.00-0.12. The solubility data were used for modelling with the modified extended electrolyte non-random two-liquid equation. The salting-out effect Of MgSO4 and methanol on the solubilities of two manganese salts (MnSO4 center dot H2O and MnSO4 center dot 4H(2)O) are represented in the several thermodynamic figures as a function of temperature. The solventing-out effect was stronger than the salting-out effect, which results in a decrease of the solubilities of manganese, salts even though the solubility of MnSO4 center dot H2O decreased and solubility Of MgSO4 center dot 4H(2)O increased as temperature increased. Crown Copyright (c) 2008 Published by Elsevier B.V. All rights reserved.

DOI： 10.1016/j.fluid.2008.11.010

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

The complex phase equilibria for the solubilities of MnSO4 center dot H2O and MgSO4 center dot 7H(2)O in three different organic solvents (methanol, ethanol, and 2-propanol) were predicted by the ion-specific electrolyte NRTL model. The salting-out effect of Mg2+, solventing-out effects of alcohols, and their combined effects on the solubility of MnSO4 center dot H2O were represented in several thermodynamic figures as a function of temperature. We found that the solventing-out effect was stronger than the salting-out effect for the solubility of MnSO4 center dot H2O even though the solubility of MnSO4 center dot H2O decreased as temperature increased.

DOI： 10.1021/je800457g

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCI LTD  

The depolymerization reaction of polyethylene terephthalate (PET) was analyzed using a computational chemistry approach. The reaction is a type of transesterification reaction using alkoxide. In this study we employed the calculated optimum structure, electrostatic potential distribution, activation energy, electric charges and pathway to investigate the mechanism. We found that the tetrahedral intermediate produced by ring formation with alkoxide is an essential feature of the depolymerization process. Moreover, there is a possibility that a PET molecule is depolymerized by multiple alkoxides at the same time. However, the effects of degree of polymerization and the position of attack by the alkoxides do not strongly influence the reactivity. (C) 2008 Published by Elsevier Ltd.

DOI： 10.1016/j.polymdegradstab.2008.10.029

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Metal ion adsorption in saturated aqueous potassium dihydrogen phosphate solution was analyzed using kinetic, equilibrium model and computational chemistry approaches. The isotherm constants (K(F) and n) in the Freundlich model and the first order Lagergren kinetic model parameter k assist with a general understanding of the fundamental adsorption behavior of trivalent and divalent metal ions. The electrostatic force based on electrostatic potential distribution was found to be an essential feature for metal ion adsorption via a correlation between the ESP values of each metal ion and these experimental parameters. (C) 2008 Published by Elsevier B. V.

DOI： 10.1016/j.apsusc.2008.10.112

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2009.0.259.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2009.0.590.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2009f.0.156.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2009f.0.890.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2009f.0.751.0

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Language：English   Publishing type：Research paper (scientific journal)  

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Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： 10.4164/sptj.46.750

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

The decomposition temperature and pressure (quadruple point) of chlorodifluoromethane (R22) gas hydrate in aqueous sodium chloride (NaCl) solution was measured at different NaCl concentrations in the Solution as a phase diagram. The operative concentration curve of NaCl was obtained as a function of temperature. The maximum decomposition temperature of R22 hydrate was about 290 K at 0.9 MPa pressure, and it decreased as the NaCl concentration increased in the solution. R22 hydrate caused supercooling, and the supercooling Occurrence temperature was much lower than the decomposition temperature. The ultrasonic charge reduced the supercooling of hydration effectively even though the ultrasonic charge did not change the decomposition temperature at all. The concentration experimental results from the several NaCl solutions having different NaCl concentrations were in good agreement with the theoretical operative concentration curve for NaCl. (C) 2008 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.cep.2008.01.002

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Impurity adsorption, crystal growth by adsorption of growth unit and step-pinning mechanism of metal ion adsorption were investigated for potassium dihydrogen phosphate (KDP; KH(2)PO(4)) and ammonium dihydrogen phosphate (ADP; NH(4)H(2)PO(4)) by quantum chemistry. In this study, the ideal crystal morphologies, the growth unit and the crystal surface with and without metal ions were calculated and analyzed by using electrostatic property. It is found that the computational results based on electrostatic potential distribution can account for the observed behaviours on KDP and ADP crystal growth. (c) 2008 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.apsusc.2008.01.058

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

In biodiesel production, transesterification in a homogeneous mixture is possible if a solution of triolein and methanol could be prepared with the use of a cosolvent. The volatile solvent dimethyl ether (DME) can make the immiscible mixture of triolein and methanol miscible; moreover, it can be easily recovered due to its high volatility after reaction. Therefore, the vapor-liquid-liquid equilibrium for the triolein + fatty acid-methanol + DME system was measured by determining the liquid composition, temperature, and pressure of the system. Results showed that DME and palmitic acid effectively promoted the mutual solubilities of triolein and methanol. In addition, the UNIFAC prediction was compared with experimental data, and it was found that the UNIFAC model could represent the complicated phase equilibrium of biodiesel compounds.

DOI： 10.1021/je700711n

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

In chemical engineering processes in which crystal is produced, the strength of the substances plays a key role. In this study, micro-level measurements of the fracture strength of aggregated crystal were performed under various operating conditions of an MSMPR crystallizer. The attrition and the fragmentation mechanisms were considered from the fracture strength, the fracture energy and impact velocity calculated from micro-hardness properties. The results showed that these properties had different values between aggregated and non-aggregated crystals. Inclusion of mother liquor caused by aggregation was accounted for the decline of the crystal strength. According to these parameters based on microhardness, there was a possibility that the collision between aggregated crystal and impeller caused not only attrition but also fragmentation. (c) 2007 Published by Elsevier B.V.

DOI： 10.1016/j.powtec.2007.05.010

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Many researchers have studied the impurity effect, which usually prevents step propagation of crystal surface. However, this effect has never been analyzed quantum-theoretically. Four aspects of impurity effect by metal ion for KDP crystal were investigated in this study by using Gaussian software and their tendencies were quantitatively considered through calculation results of quantum chemistry such as atomic charge and electrostatic potential of impurity. In particular, electrostatic distribution of impurity molecule is an important factor for impurity effect because the attractive force between (100) face and impurity can be predicted from these distributions. (C) 2007 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.theochem.2007.11.017

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER INST PHYSICS  

Directional crystallization from a binary mixture was performed by pseudo-NpT ensemble molecular dynamics. The initial crystal phase having a face-centered-cubic (fcc) structure grew toward the whole cell according to the temperature gradient in the universal cell. The growing crystal phase was not planar even though the solute molecules grew in two-dimensional coordinates because the solvent molecules disturbed the crystallization of the solute molecules at the diffusive crystal-solution interface. This represented the essential phenomenon of solute distribution during crystallization. Consequently, the growing crystal phase still contained solvent molecules having a liquid structure. The time change of the solute composition in the early phase of crystal growth showed an increase in solute composition as the time step proceeded. The resulting solute composition in this early phase was considered at different temperature gradients in the universal cell and it increased as the temperature of the initial crystal-solution interface increased. A new distribution coefficient model was proposed as a function of the difference between the local solute composition and bulk solute composition in the solution around the crystal-solution interface. The impurity-solvent distribution coefficient could be represented by the new model for faster growth of the lower temperature's initial interface. As regards a better distribution coefficient, there was found to be a very dilute solution phase over the crystal phase. The new variable "distribution rate" instead of the ambiguous variable "growth rate" was considered as a function of temperature gradient in the universal cell. (C) 2008 American Institute of Physics.

DOI： 10.1063/1.2825601

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：Society of Computer Chemistry, Japan  

Impurity effect of KDP(KH<SUB>2</SUB>PO<SUB>4</SUB> crystal growth by trivalent metal ion in solution is reasonably well documented. If the metal ion is adsorbed onto the crystal surface, it prevents the step propagation relevant to the crystal growth rate. Although a recovery effect of the metal ion adsorption was discovered in our recent work on the addition of chelate agents, the impurity effect and recovery mechanisms are not clearly understood both theoretically and phenomenally. Moreover, the dye compound in solution can colour the KDP crystal. However, dyes are segregated in specific growth sectors due to crystal anisotropy. The mechanism of the dye selectivity and the orientation of the adsorbed dye are also not clear. Accordingly, the impurity effect by metal ion, recovery effect by chelate and colouring mechanism by dye about the KDP crystal were investigated by computational chemistry in this study. It was found that these behaviors could be explained by electrostatic potential (ESP) distribution.

DOI： 10.2477/jccj.H1918

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Other Link： https://jlc.jst.go.jp/DN/JALC/00310711160?from=CiNii

Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

Ice was formed on it rotating cold cylinder, and the distribution of cations (i.e., K(+), Na(+), Mg(2+) and Ca(2+)) between ice and water as a function of the operating variables of ice crystallization was discussed. Ice growth rate was controlled by the rotation speed and temperature of the cold cylinder. The shape of the ice formed on the rotating cold cylinder depended on (lie flow structure of Taylor vortices in the water solution, The effective distribution coefficients of the cations were extremely, small compared with those in the fatty acid system. The effective distribution coefficients of the cations correlated well as it function of ice growth rate. According to the correlation model, pure ice can form if the ice growth rate is lower than the critical growth rate. The critical temperatures of the four cations showed no difference front each other. and increased with the supercooling temperature.

DOI： 10.1252/jcej.08we009

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Publisher：The Society of Chemical Engineers, Japan  

DOI： 10.11491/scej.2008f.0.568.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2008f.0.161.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2008f.0.153.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2008.0.694.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2008.0.693.0

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Publisher：The Society of Chemical Engineers, Japan  

DOI： 10.11491/scej.2008.0.695.0

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

A homogenization method is applied to the estimation of effective thermal conductivity of a hydrogen storage alloy bed. By including the contact conditions between the alloy particles, the effect of contact conditions on the thermal conductivity is investigated. When the pressure is lower than 1 bar, the effective thermal conductivity increases with an increase in the mean gap distance and the contact ratio of point contact. On the other hand, when the pressure is higher than 1 bar, the effective thermal conductivity increases with an increase in the contact ratio of plane contact and the Biot number. In addition, in the comparison of the parameters before and after charge and discharge cycles, it is shown that the mean gap, the contact ratio of plane contact and Biot number are involved in a decrease in effective thermal conductivity of the pulverized alloy particle bed. (C) 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.ijhydene.2007.06.003

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Data on the solubility of manganese sulphate monohydrate in water, and in aqueous alcohols is essential for salting-out crystallization studies. The solubilities of the quaternary system MnSO4 center dot H2O + MgSO4 center dot 7H(2)O + H2O + (CH3)(2)CHOH were determined in the temperature range 293.2-313.2 K over the 2-propanol mole fraction range of 0.00-0.07. The solubility data were used for modelling with the modified extended electrolyte non-random two-liquid (NRTL) equation. The present extension uses ion-specific parameters instead of the electrolyte-specific NRTL binary interaction parameters. This approach has feasibility for many electrolytes and mixed aqueous solution systems in principle. The model was found to correlate the solubility data satisfactorily. Crown Copyright (c) 2007 Published by Elsevier B.V. All rights reserved.

DOI： 10.1016/j.fluid.2007.08.007

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

A fatty acid mixture of lauric acid and myristic acid was deposited on a cold quartz crystal sensor from the binary vapor phase of the mixture by physical, vapor deposition (PVD). The cold quartz crystal sensor could detect a small amount of deposit in real time, and provided the growth rate of the thin solid deposit by the PVD. The composition of lauric acid in vapor phase was fixed at a mole fraction of about 0.5 by controlling the composition of lauric acid in melt phase computed from the vapor-liquid equilibrium (VLE). The growth rate of solid phase in the PVD increased with the elevation of the melt temperature, because the vapor pressure of the melt raised by the temperature elevation was the driving force of the PVD. The composition of lauric acid in the solid phase was considerably lower than that in the vapor, and it was increased as the growth rate in the solid phase rose. The distribution coefficient of lauric acid between solid and vapor phases was much less than that between solid and melt phases. We compared the separation capacity in melt crystallization with that in the PVD using the effective distribution coefficient, and found that the PVD had higher separation capacity. (c) 2006 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.cep.2006.07.007

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

The impurity effect by trivalent metal ion such as Al(3+), Fe(3+) and Cr(3+) during crystal growth of KDP is reasonably well documented. If a metal ion is adsorbed onto the crystal surface, it prevents the step propagation relevant to the crystal growth rate. However, this impurity adsorption mechanism is still not well understood. Recently, in our work on the addition of chelate agents, a recovery effect of the metal ion adsorption was discovered. However, its recovery mechanism is not clearly understood both theoretically and phenomenally. In this research, ethylene-diamine-tetra-acetic acid, EDTA, which is the most common chelate agent, was used as a recovery agent. The recovery mechanism was considered from the correlation of experimental data and the interfacial distribution model that we proposed in our former study. Furthermore, quantum calculation of EDTA metal complex can explain the relaxation of impurity adsorption by the addition of EDTA. (C) 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/crat.200610842

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Dye adsorption mechanism, in particular, colouring mechanism of KDP (KH2PO4) crystal was investigated by quantum chemistry in this study. Phenomena, such as different preferentially coloured faces of KDP when co-crystallised with different dyes, are explained by the minimum and maximum values of electrostatic potential (ESP). Furthermore, it is found that the ESP distribution of a dye molecule may not necessarily be the single mechanism affecting the dye adsorption in a crystal structure; and that the degree of protonation, crystal surface condition, steric exclusion of dye and the orientation of dye molecules situating on the crystal surface may as well be important factors for the dye adsorption. (c) 2007 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.theochem.2007.01.041

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

We measured the elastic modulus and fracture strength at the micro-level for various types of crystal generated by an MSMPR crystallizer. The attrition behavior was determined from the fracture energy and attrition coefficient, which were calculated from micro-hardness properties. The different values observed for each tested crystal size revealed that crystal size was an important factor in attrition behavior. Therefore, we could predict the amount of attrition through the fracture energy. Future work will involve applying the estimation method in a scaled-up suspension crystallizer. (c) 2006 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.powtec.2006.10.001

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

This paper describes the surface topography characteristics of the (100) and (101) faces of potassium dihydrogen phosphate (KDP) crystals by using atomic force microscopy (AFM) for nanoscale observation. Fractal dimensions of the surface pattern were measured, including step height and terrace distance of KDP crystals under different supersaturation levels and dye concentrations, and the relationship between dye concentration and surface structure was examined.

DOI： 10.1021/cg0602055

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2007.0.833.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2007f.0.774.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2007.0.100.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2007.0.92.0

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DOI： 10.11491/scej.2007.0.95.0

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Data on the solubility of manganese sulphate monohydrate in water, and in aqueous alcohols is essential for salting-out crystallisation studies. The solubilities of the quaternary system MnSO4 center dot H2O +MgSO4 center dot 7H(2)O + H2O + EtCH were determined in the temperature range 293.2-323.2 K over the ethanol mole fraction range of 0.00-0.12. The solubility data were used for modelling with the modified extended electrolyte non-random two-liquid (NRTL) equation. The present extension uses ion-specific parameters instead of the electrolyte-specific NRTL binary interaction parameters. This approach has feasibility for many electrolytes and mixed aqueous solution systems in principle. The model was found to correlate the solubility data satisfactorily. (c) 2006 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.fluid.2006.08.006

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

A solid phase of a fatty acid mixture (lauric acid + myristic acid) on a rotating cold cylinder from the binary melt was formed in an annular cylindrical vessel. The growth rate of the solid phase was kept constant by cooling the rotating cold cylinder. The shape of the solid phase formed on the rotating cold cylinder depended on the hydrodynamics of Taylor vortices in the melt phase. The solid phase consisted of a concave part and convex part. We observed the detail structures of the surface and the inside of the solid phase under a microscope, and analyzed the crystallinity of the solid phase by using X-ray diffraction. We measured the weight fraction of myristic acid from the thin slices of the solid phase by gas chromatography. The growth rate of the solid phase decreased as the rotation speed increased or as the temperature of the hot cylinder increased. When the growth rate decreased, the crystalline part of the solid phase obviously increased. The effective distribution coefficient of lauric acid between the solid phase and melt phase increased according to the crystalline of the solid phase. The effective distribution could be well correlated with the growth rate by using our interfacial distribution model.

DOI： 10.1252/jcej.39.1154

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

A single KDP (potassium dihydrogen phosphate) crystal was grown in a supersaturated solution containing a metallic ion (Al3+, Fe3+, or Cr3+). The growth rate, morphology, and distribution of the metallic ions into the KDP crystal were measured as the ionic concentration and supersaturation in the solution changed. It was found that in the KDP crystal, Al3+ and Fe3+ were greatly concentrated, but Cr3+ was diluted. Complete expressions for the effect of metallic ions on all aspects of the growth of KDP crystal were suggested. The growth rates of (100) and (101) faces were well correlated by the empirical equation and resulted in good estimation of morphology. The distribution of metallic ions into KDP crystal was also correlated by the distribution model. (C) 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/crat.200610704

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Language：English   Publishing type：Research paper (international conference proceedings)  

DOI： 10.11457/swsj1965.60.187

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2006f.0.100.0

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DOI： 10.11491/scej.2006f.0.294.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2006f.0.92.0

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Data on the solubility of manganese sulphate monohydrate in water, and in aqueous alcohols is essential for salting-out crystallization studies. The solubilities for the quaternary system (MnSO4H2O)-H-.+MgSO(4)(.)7H(2)O+H2O+MeOH solution were determined in the temperature ranges 293.2-308.2K over the mole fraction methanol ranges of 0.00-0.16. The solubility data were used for modelling with the modified extended electrolyte non-random two-liquid (NRTL) equation. The present extension uses ion-specific parameters instead of the electrolyte-specific NRTL binary interaction parameters. This approach has feasibility for many electrolytes and mixed aqueous solution systems principally. The model was found to correlate the solubility data satisfactory. (c) 2005 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.fluid.2005.09.028

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Crystallization of solute molecules from homogeneous binary Lennard-Jones solutions was simulated by molecular dynamics of an NPT ensemble. Isothermal (equilibrium) and cooling (non-equilibrium) conditions were examined to observe the configuration of solute molecules for the crystallization process. The isothermal simulations could clearly determine the temperature of crystallization or nucleation of solute molecules by the change of density. The cooling simulations could describe the effect of cooling rate on the temperature of crystallization or nucleation. The configurations of solute molecules in the solution during crystallization were discussed from the radial distribution function (RDF) and the local composition of solute (LC) in the solution. The nuclei that have a crystalline structure could be distinguished from clusters that have a liquid structure. It was found that the liquid clusters were not stable, but the crystal nuclei have very rigid structure and were stable. LC was used to image how many solute molecules gathered in the solution with relation to the clusters and nuclei. It was found that LC fluctuated dramatically when the solute molecules crystallized. The cooling simulations showed that the configuration of solute molecules obtained at a slower cooling rate showed the crystalline structure, but the faster cooling rate caused the liquid structure of clusters in the solutions even at low temperature. (c) 2005 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.molliq.2005.01.008

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

A hydrophobic compound dissolves very slightly in an aqueous solution. As an application of such dilute solubility, the concept for making nanometer-scale crystals of lauric acid from the aqueous ethanol solution was suggested. There are two different dilute solubilities in the aqueous phase. One thing is defined as the solubility of solid lauric acid; another is defined as the mutual solubility of liquid-liquid equilibrium between aqueous phase and oil phase. Two possible processes for crystallizing lauric acid were shown according to two different solubility curves. One process is direct crystallization of lauric acid; another process is indirect crystallization of lauric acid after emulsification. The crystals formed by two processes were experimentally observed, and then the size of crystals was analyzed by dynamic light scattering (DLS). The crystals formed through both emulsification and crystallization processes were 500 nm in size. The crystals formed through direct crystallization process ranged from 30 to 100 run in size. The size of the latter crystals was a function of ethanol mole fraction in aqueous phase and cooling temperature. The modified Gibbs-Thomson equation was examined to correlate the crystal-nuclei size of the wide range. (c) 2004 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.cep.2004.10.005

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

To develop an activity coefficient model for aqueous multielectrolyte systems, ion-specific NRTL parameters were applied to the electrolyte-NRTL model. In total, 132 ion-specific NRTL parameters for 21 ionic species (K+, Na+, Mg2+, H+, Ca2+, Zn2+, Al3+, NH4+, Cd2+, Co2+' Cu2+, Pb2+, Mn2+, Ni2+, Cr3+, Cl-, SO42-, NO3-, OH-, ClO4-, CrO42-) were determined from the binary activity coefficient data of aqueous electrolytes and used to predict the activity coefficients of electrolytes in aqueous multieletrolyte solutions without any additional parameters. Furthermore, solubilities of inorganic salts including heavy metals in aqueous mixed electrolyte systems and the distribution ratio of Cu in a solvent extraction process containing HCl and CuCl2 were predicted using the activity coefficients derived from our ion-specific electrolyte-NRTL model. The results showed that the NRTL parameters obtained in this study accurately predict phase equilibria of systems involving inorganic salts such that this model can be used in the design of recovery processes such as crystallization and solvent extraction.

DOI： 10.1021/ie049377u

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Colored potassium dihydrogen phosphate (KDP) crystals from a dye (sky blue) solution were produced in a mixed suspension mixed product removal (MSMPR) crystallizer. The crystal size distribution (CSD) of the KDP crystals was correlated by a size-dependent growth rate model. The growth rate increased with crystal size, but it decreased as the residence time increased. Two different concentrations of dye in the solution were examined for MSMPR crystallization of KDP crystals. The colored crystals from the solution with low dye-concentration generated regular-shaped KDP crystals. The dye distribution coefficient into the regular-shaped KDP crystals was less than unity. However, the colored crystals from the solution with high dye-concentration formed the special-shaped KDP crystals having no (10 0) sector. The dye distribution coefficient into the special-shaped KDP crystals from the dye solution was larger than unity. The dye distribution coefficient as a function of crystal size was presented, and then the relationship between the aspect ratio of the morphology of KDP crystals and dye distribution coefficient was discussed. As a result, a distribution model of dye impurity in KDP crystals for an MSMPR crystallizer could be first proposed in this work. (C) 2004 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.seppur.2004.10.006

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

The crystal size distribution (CSD) of potassium dihydrogen phosphate (KDP) and inclusion ratio of mother liquor have been measured in a mixed suspension mixed product removal (MSMPR) crystallizer. A small amount of sodium dihydrogen phosphate (SDP) was added as an impurity tracer in order to measure the inclusion ratio of mother liquor inside the KDP crystals. The effects of residence time on the CSD and inclusion of mother liquor were investigated. The crystal growth rate and nucleation rate were determined from the population density balance theory by assuming a size-dependent function of the growth rate, because the size-dependent growth rate of KDP crystals was observed under a microscope. MSMPR operation with a shorter residence time produced larger KDP crystals, and showed more size-dependency of the growth rate. The inclusion ratio was depicted as a function of crystal size, growth rate, and agglomeration. The degree of agglomeration was effectively correlated with the inclusion ratio of the KDP crystals that had a large hardness property. (C) 2004 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.seppur.2004.10.002

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2005.0.125.0

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DOI： 10.11491/scej.2005.0.127.0

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Language：Japanese   Publisher：公益社団法人 化学工学会  

DOI： 10.11491/scej.2005.0.126.0

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

Single potassium dihydrogen phosphate (KDP) crystals were grown in a supersaturated solution containing an organic dye (sunset yellow FCF, brilliant blue FCF, and sky blue). The growth rate, morphology, and impurity dye distribution of faces, (100) and (101) in a KDP crystal were measured as dye concentration and the supersatutation of KDP were changed. Complete expressions for the effect of dye on all aspects of the growth of KDP crystals were discussed. The growth rates of (100) and (101) faces were well correlated by the empirical equation, and resulted in good estimation of the morphology. The distribution of dye in a KDP crystal was represented by the distribution model containing the minimum growth rate for coloring. The growth rate equation and distribution equation were expressed by functions of the supersaturation and dye concentration, and they could effectively provide the operational conditions with coloring the KDP crystal. (C) 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/crat.200410285

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

The effective thermal conductivity of the metal hydride bed is analyzed by the homogenization method. This method can represent the microstructure in the bed precisely. The referenced material is LaNi4.7Al0.3, which is practically used. Temperature and pressure ranges investigated here are from -80degreesC to + 140degreesC and from 10(-6) to 100 bar, respectively. Hydrogen, helium, nitrogen and argon are chosen as the filling gas. The validity of the homogenization method as the multi-scale analysis is confirmed by a good correspondence with the experimental data that the effective thermal conductivity depends on the pressure of the filling gas under these various conditions (Int. J. Hydrogen Energy 23(2) (1998) 107).
The homogenization method can become a powerful tool for the estimation of the effective thermal conductivity of the metal hydride bed by considering the microscopic behavior such as the pulverization and the change of the contact area. (C) 2003 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

DOI： 10.1016/S0360-3199(03)00106-X

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Language：English   Publisher：The Society of Chemical Engineers, Japan  

KDP crystals in a dye solution were colored by using an MSMPR crystallizer. The CSD (crystal size distribution) of KDP crystals was correlated by the size-dependent growth rate model. Two different concentrations of dye in the solution were examined for the MSMPR crystallization of KDP crystals. The coloring crystals from the concentrated dye solution formed the special shape having no (100) sector of KDP crystal. The dye distribution into the special KDP crystals from the dye solution was larger than unity. However, the coloring crystals from the dilute dye solution generated the general shape of KDP crystal. The dye distribution into the general KDP crystals was less than unity. The dye distribution as a function of crystal size was discussed.

DOI： 10.11491/apcche.2004.0.177.0

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Storage capacity and fast reaction rate are the most important properties for hydrogen storage alloys. To clarify the mechanism of the rate-controlling step, we analyzed the hydrogen diffusion coefficients of the hydride by the homogenization method, which considers the microstructure of the alloy at the microscale (0.1-10 mum) precisely. By applying nucleation and growth model, we have discussed the absorbing and desorbing mechanism of the metal hydride. Our results and analysis show that it is important for the hydriding or dehydriding reaction to consider the number of nuclei and the transfer of hydrogen atom through the alpha-beta interface data. Estimation of the microstructure of the metal hydride by using the homogenization method is useful for the absorbing and desorbing mechanism. (C) 2002 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0360-3199(02)00136-2

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Iron and Steel Institute of Japan  

The homogenization method is proposed as new numerical approach to understand the fracture mechanism of the microscopic behavior in coke because the evaluations of the strength has been still difficult for the improvement of coke qualities in coke making process. The conditions for the stress concentration and relaxation effect are investigated by homogenization method. These results show that the distribution of micro cracks and pores in coke is important factor for the microscopic fracture. Also, the digital image technique is applied to the actual coke with the complicated microstructure and the improvement mechanism of coke strength by the carbon deposition is clarified by using homogenization method. The effect of carbon deposition on the coke strength is illustrated from the stress distribution while calculating the homogenized elastic modulus. Although the stress concentration between large pores is caused in the case of carbon deposited coke, the maximum stress becomes smaller than the tensile strength of coke because of large homogenized elastic modulus. As a result, the microscopic fracture does not easily occur for carbon deposited coke.

DOI： 10.2355/isijinternational.43.1151

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：IRON STEEL INST JAPAN KEIDANREN KAIKAN  

The homogenization method is proposed as new numerical approach to understand the fracture mechanism of the microscopic behavior in coke because the evaluations of the strength has been still difficult for the improvement of coke qualities in coke making process. The conditions for the stress concentration and relaxation effect are investigated by homogenization method. These results show that the distribution of micro cracks and pores in coke is important factor for the microscopic fracture. Also, the digital image technique is applied to the actual coke with the complicated microstructure and the improvement mechanism of coke strength by the carbon deposition is clarified by using homogenization method. The effect of carbon deposition on the coke strength is illustrated from the stress distribution while calculating the homogenized elastic modulus. Although the stress concentration between large pores is caused in the case of carbon deposited coke, the maximum stress becomes smaller than the tensile strength of coke because of large homogenized elastic modulus. As a result, the microscopic fracture does not easily occur for carbon deposited coke.

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：IRON STEEL INST JAPAN KEIDANREN KAIKAN  

Nano-indentation method is proposed to measure the elastic modulus of matrix of coke and to study the relativity of the elastic modulus to raw coal.
Coke strength is the most important qualities to retain the permeability in a blast furnace, Then coke strength must be clarified, Matrix of coke elastic modulus and its relation to raw coal are essential for theoretical approach based on Mechanics of Materials to reveal the fracture behavior of coke. Nano-indentation method, which couples the equation obtained by finite element analysis with the load-displacement curves in the microscopic region measured by ultra-micro-hardness tester, enables us to determine the elastic modulus of coke substrate except the effect of pores.
The matrix elastic modules of cokes made from four kinds of coal are measured for each coke texture. Elastic modules of flow texture, coarse mosaic texture and fine mosaic texture that axe the texture originated in reactives are 17-18 GPa for every raw coal, so they can be regarded as same strength. The elastic modulus of inerts is higher than that of the textures organized in reactives, and increases as coal rank increases,
As a result it follows that matrix of coke is simplified to a composite material composed of two kinds of materials, reactives and inerts.

DOI： 10.2355/tetsutohagane1955.88.4_188

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：IRON STEEL INST JAPAN KEIDANREN KAIKAN  

In order to clarify the bulk breakage mechanism of metallurgical coke in blast furnace, the overlaying mesh finite element analysis that can consider both macro and micro-structure simultaneously is applied for complex micro-structural geometry such as coke. We introduced the stress intensity factor, a criterion of stress concentration around the crack tip, which can get from displacements of singular points by the template mesh putting on the crack tip and evaluated characteristics of fracture for high-strength coke.
The numerical results show that the stress intensity factor (K-l*) is dependent on porosity (epsilon) linearly and then we proposed the following equation considering a shape parameter (C) and the stress intensity factor (B) at epsilon =0.
K-l*=B(1-C epsilon)
This equation shows that the stress intensity factor decreases with porosity because principal stress around pores in the neighborhood of the crack tip becomes larger and pores prevent stress around the crack tip from concentrating. This negative effect of relaxation becomes larger as porosity increases. Here the parameter C is a specific value, it depends on pore shape and does not depend on crack length.
We conclude that this numerical analysis is very useful for estimation of coke quality.

DOI： 10.2355/tetsutohagane1955.87.11_685

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：IRON STEEL INST JAPAN KEIDANREN KAIKAN  

Homogenization method and s-version FEM are proposed to estimate the strength of coke in the view of its microstructure.
It is important fbr improvement of permeability in a blast furnace to estimate the condition for making high-strength coke by evaluating its strength. To evaluate the strength of brittle materials with complex microstructural geometry such as coke, it is required to develop analytical procedures that can consider microscopic fractures. Stress intensity factor considering influence of microscopic cracks and inclusions can be estimated by using homogenization method and s-version FEM.
To evaluate the strength of macroscopic base, we use homogenization method and estimate the stress intensity factor. Then the influence of the crack distribution on the stress intensity factor is considered. The stress intensity factor is estimated in the case when inclusions exist.
On the other hand s-version FEM is used to estimate the stress intensity factor of macrocracks that are a principal factor of coke's brittle fracture considering the influence of microstructure.
Numerical results calculated by those two methods are in good agreement with analytical result, and the performances of these methods are verified.
When the Young's modulus of includes is higher than that of the matrix: the stress intensity factor of the microcrack decreases and increases in case inclusions locate ahead of the microcrack-tip and aback of the microcrack-tip, respectively.
Macrocrack will propagate easily when microcracks lay ahead of macrocrack, and it will be hard for macrocrack to propagate when microcrack lay aback of macrocrack.

DOI： 10.2355/tetsutohagane1955.87.5_245

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC CHEMICAL ENG JAPAN  

Nonlinear oscillations of molten silicon drops in an electromagnetic levitator under microgravity are numerically investigated. The electromagnetic field and the magnetic pressure on the drop surface are calculated by the surface integral method assuming that the skin depth is much smaller than the drop radius. The Galerkin finite element method in combination with the Lagrangian technique is used to analyze the moderate-amplitude axisymmetric oscillations of the silicon drops on which the magnetic pressure acts. The effect of the electric current ratio of the heating coils to the levitation coils on the frequency of the oscillations is evaluated for molten silicon drops released from either an initially prolate spheroid configuration or four-lobed spherical harmonic configuration. The numerical results show that, in the former case, the frequency decreases with the current ratio. Also, for the latter, the dynamics of the second mode becomes dominant as the current ratio increases, because the inward magnetic pressure from the heating coil increases.

DOI： 10.1252/jcej.33.861

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SPRINGER  

For the electromagnetic levitation of a molten silicon drop in a microgravity environment, the effect of the electric current ratio of the heating coils to the levitation coils on the equilibrium drop shape was numerically investigated, using the mathematical model based on the hybrid finite element and boundary element methods. As a result, it was found that the drop shape becomes more prolate as the current ratio increases, and the calculated results were in good agreement with the experimental ones obtained in a microgravity environment using a drop tower.

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE INC  

Experiments and numerical simulations were carried out to analyze the soot aggregation mechanism during benzene pyrolysis. Soot was formed by the pyrolysis of 1 mol% benzene (in 99 mol% nitrogen) in an alumina tube, which was kept at 1573K with variations of residence time (0.03 to 0.5 sec).
A new cluster-cluster aggregation model called the Aggregate Mean free Path (AMP) model was developed. This model simulated the cluster-cluster aggregation between soot particles and aggregates using the particles or aggregates mean free paths. The projected images of simulated soot were compared with the electron micrographs of experimental soot with the same magnification. Simulated shape, peripheral fractal dimension and size distributions of aggregates were in good agreement with experimental data. (C) 1999 by The Combustion Institute.

DOI： 10.1016/S0010-2180(98)00124-2

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Language：Japanese   Publishing type：Article, review, commentary, editorial, etc. (scientific journal)  

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It has been recognized that different crystal morphologies can be formed by adding impurities. However, a quantitative understanding is lacking on how the impurities change the crystal shape and/or size. KDP crystallisation is chosen in this study because of the almost- perfect shape and manageable size (̃ 1 cm) of KDP crystals. It is found that in forming KDP crystals, by adding trivalent metal ion groups, the crystal shape is elongated by about 80 % (but depending on concentration). Our previous study speculated that the trivalent metal ion groups were preferably adsorbed on the (100) face, subsequently the ion groups inhibited the crystal growth on these faces, and crystal growth were dominated by electrostatic potential of impurity and crystal faces. In this contribution, various chelate agents, which have different number of carbonic acid, are used for examining the effect of electrostatic potential of impurity on its adsorption onto crystal faces. Computational simulations employing Gaussian method are performed to provide insight on the impurity adsorption and the subsequent effect on crystal morphology formation. Simulation results are verified by our experimental results on KDP crystal growth.

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The ion-specific NRTL parameters were applied to correlate the binary activity coefficient data of aqueous electrolytes with the electrolyte-NRTL model for developing an activity coefficient model for aqueous mixed electrolyte and mixed solvent systems. The parameters were useful to predict the activity coefficients of electrolytes in aqueous mixed electrolyte and mixed solvent systems without using additional parameters. A variety of inorganic solubility in the aqueous mixed electrolyte and mixed solvent systems were correlated and predicted. The prediction showed that the resultant NRTL parameters suitably represented phase equilibria of inorganic salts required for the design of crystallization processes.

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Experiments have been performed on the impurity incorporation in the solid layer grown from a binary melt of myristic acid and lauric acid using an annular cylindrical vessel, the inner cylinder of which was cooled and rotating. The binary melt forms a simple eutectic diagram. The solid layer grew at constant growth rate by keeping the constant cooling rate of the inner cylinder. The purity of the crystal layer grown on the inner cylinder was correlated well with the growth rate by applying the solute-distribution theory proposed by the present authors [FUK98].

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Language：Japanese   Publisher：ソルト・サイエンス研究財団  

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Storage capacity and fast reaction rate are the most important properties for hydrogen storage alloys. To understand the mechanism of the rate-controlling step, we have analyzed the hydrogen diffusion coefficients of the hydride by the homogenization method, which considers the microstructure of the alloy at the micro scale (0.1-10μm) precisely. By applying nucleation and growth model, we have discussed the absorbing and desorbing mechanism of the metal hydride. Our results and analysis show that it is necessary for the hydriding or dehydriding reaction to consider the number of nuclei and the transfer of hydrogen atom through the α-β interface. Fig. A-1 shows the effect of H/M (atomic Hydrogen/Metal ratio) on the homogenized diffusion coefficients, D^H in the case of Sh=0.01. The homogenized diffusion coefficients decrease more quickly against the hydride ratio, H/M with the increase in the number of nuclei. The thickness of a completely closed hydride layer on the hydride particle is very important because hydrogen transport is faster in the α-phase than in the β-phase and hydrogen atoms hardly pass through the α-β interface in the case of Sh=0.01. Once the β-phase hydride layer is formed, the [figure] hydriding reaction is limited to the interface. This means that the homogenized diffusion coefficients become small value as shown in Fig. A-1 because of the closed layer. Therefore, the hydriding reaction nearly stops in the case of small Sh number and large nuclei number because the closed layer of the β-phase is formed faster. With regard to the deterioration by oxidation reaction, the effect of the thickness of oxide layer, w/l on the homogenized diffusion coefficients, D^H were investigated on condition that various hydrogen diffusion coefficients, D_o. Fig. A-2 shows that the homogenized diffusion coefficients are constant regardless of the thickness if the oxide layer exists on the surface. However, the diffusion coefficients are dependent on the diffusion coefficients of the oxide layer. Therefore, adsorption of oxygen on the hydride surface affects hydrogen diffusion into the particle. Estimation of the microstructure of the metal hydride by using the homogenization method is useful for the absorbing, desorbing and deteriorating mechanism. Actually, the compositions such as the α, β phase and the oxide layer in micro region of the metal hydride should be considered for the decision of the rate-controlling step.[figure]

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Event date： 2021.12

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Event date： 2021.12

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Event date： 2021.10

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Event date： 2021.10

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Event date： 2021.10

Language：English   Presentation type：Oral presentation (general)  

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Event date： 2021.10

Language：English   Presentation type：Oral presentation (general)  

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Event date： 2021.10

Language：English   Presentation type：Oral presentation (general)  

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Event date： 2021.10

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Event date： 2021.10

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Event date： 2021.10

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Event date： 2021.9

Language：English   Presentation type：Oral presentation (general)  

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Event date： 2021.9

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Event date： 2021.9

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Event date： 2021.9

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Event date： 2016

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Event date： 2016

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2014

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Event date： 2013

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Event date： 2013

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Event date： 2013

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Event date： 2012

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Event date： 2012

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Event date： 2011

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Event date： 2011

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Event date： 2011

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Event date： 2011

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Event date： 2010

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Event date： 2009

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Event date： 2009

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Event date： 2009

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Event date： 2009

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Event date： 2009

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Event date： 2009

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Event date： 2008

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Event date： 2005

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Event date： 2005

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Event date： 2004

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Event date： 2004

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Event date： 2004

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Event date： 2001

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Language：English   Presentation type：Oral presentation (general)  

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Language：Japanese   Presentation type：Oral presentation (invited, special)  

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Language：Japanese   Presentation type：Oral presentation (invited, special)  

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Language：English   Presentation type：Oral presentation (invited, special)  

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Language：Japanese   Presentation type：Oral presentation (invited, special)  

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Language：Japanese   Presentation type：Oral presentation (invited, special)  

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Language：English   Presentation type：Oral presentation (general)  

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Language：Japanese   Presentation type：Oral presentation (keynote)  

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Language：English   Presentation type：Oral presentation (general)  

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Language：Japanese   Presentation type：Public lecture, seminar, tutorial, course, or other speech  

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Language：Japanese   Presentation type：Oral presentation (invited, special)  

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Language：English   Presentation type：Oral presentation (general)  

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Language：English   Presentation type：Oral presentation (general)  

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Language：English   Presentation type：Oral presentation (general)  

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Language：English   Presentation type：Oral presentation (general)  

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Language：Japanese   Presentation type：Oral presentation (general)  

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Language：English   Presentation type：Oral presentation (general)  

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