• Title/Summary/Keyword: Activation energies

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Reactivity Study on the Kideco Coal Catalytic Coal Gasification under CO2 Atmosphere Using Gas-Solid Kinetic Models (기-고체 반응 모델을 이용한 Kideco탄의 이산화탄소 촉매 석탄가스화 반응 특성)

  • Lee, Do Kyun;Kim, Sang Kyum;Hwang, Soon Cheol;Lee, Si Hyun;Rhee, Young Woo
    • Clean Technology
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    • v.21 no.1
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    • pp.53-61
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    • 2015
  • In this study, we have investigated the kinetics on the char-CO2 catalytic gasification reaction. Thermogravimetric analysis (TGA) experiments were carried out for char-CO2 catalytic gasification of an Indonesian Kideco sub-bituminous. Na2CO3 and K2CO3 were selected as catalysts which were physically mixed with coal. The char-CO2 catalytic gasification reaction showed a rapid increase of carbon conversion rate at 850 ℃, 60 vol% CO2, and 7 wt% Na2CO3. At the isothermal conditions ranging from 750 ℃ to 900 ℃, the carbon conversion rates increased as the temperature increased. Four kinetic models for gas-solid reaction including the shrinking core model (SCM), random pore model (RPM), volumetric reaction model (VRM), and modified volumetric reaction model (MVRM) were applied to the experimental data against the measured kinetic data. The gasification kinetics were suitably described by the MVRM for the Kideco sub-bituminous. The activation energies for each char mixed with Na2CO3 and K2CO3 were found 55-71 kJ/mol and 69-87 kJ/mol.

The Potential Energy Recovery and Thermal Degradation of Used Tire Using TGA (열분석법을 이용한 사용후 타이어의 열적 특성과 포텐셜 에너지의 회수)

  • Kim, Won-Il;Kim, Hyung-Jin;Hong, In-Kwon
    • Elastomers and Composites
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    • v.34 no.2
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    • pp.135-146
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    • 1999
  • The thermal degradation kinetics of SBR and tire were studied using a conventional thermogravimetric analysis in the stream nitrogen at a heating rate of 5, 10, 15, $20^{\circ}C/min$, respectively. Thermogravimetric curves and their derivatives were analyzed using various analytical methods to determine the kinetic parameters. The degradation of the SBR and tire was found to be a complex process which has multi-stages. The Friedman method gave average activation energies for the SBR and tire of 247.53kJ/mol and 230.00kJ/mol, respectively. Mean-while, the Ozawa method Eave 254.80kJ/mol and 215.76kJ/mol. It would appear that either. Friedman's differential method or Ozawa's integral method provided satisfactory mathematical approaches to determine the kinetic parameters for the degradation of the SBR and tire. Approximately 86% and 55% of oil products were obtained at a final temperature of $700^{\circ}C$ and a heating rate of $20^{\circ}C/min$ for the SBR and tire respectively.

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Study on the Non-isothermal Crystallization Kinetics of Branched Polypropylene (분지형 폴리프로필렌의 비등온결정화 거동 연구)

  • Yoon, Kyung-Hwa;Shin, Dong-Yup;Kim, Youn-Cheol
    • Polymer(Korea)
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    • v.36 no.2
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    • pp.245-250
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    • 2012
  • Branched polypropylenes (PP) with long chain branch were prepared by solid state reaction with three different branching agent of 0.3 wt% content. The chemical structures, non-isothermal crystallization behavior and complex viscosity of the branched PP were investigated by FTIR, DSC, optical microscope, and dynamic rheological measurement. The chemical structure of the branched PP was confirmed by the existence of =C-H stretching peak of the branching agent at 3100 $cm^{-1}$. There was no distinct change in melting temperature in case of PP-D-0-3 and PP-F-0-3, but PP-H-0-3 indicated a decrease in melting temperature. The decrease in melting temperature was interpreted by the fact that the degradation reaction of PP was more dominant than branched reaction, and confirmed by a decrease in complex viscosity. The non-isothermal crystallization behavior of the branched PP was analyzed using by Avrami equation. The Avrami exponent of PP was 3, and the values of the branched PP with DVB and FS were below 3. The activation energy of PP calculated by Kissinger method was 25 kJ/mol, and there were no big difference in activation energies of the branched PPs compared to PP.

Kinetic Studies on Cooking of Rice of Various Polishing Degrees (도정도별 쌀의 취반에 대한 역학적 연구)

  • Cheigh, Hong-Sik;Kim, Sung-Kon;Pyun, Yu-Ryang;Kwon, Tai-Wan
    • Korean Journal of Food Science and Technology
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    • v.10 no.1
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    • pp.52-56
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    • 1978
  • The mechanism of cooking rice was investigated using a japonica type rice variety, Akibare, of 50%, 70% and 90% polishing degrees. The hardness of rice cooked at various cooking temperatures ($90^{\circ}-120^{\circ}C$) was measured with a Texturometer. The cooking rate followed the equation of a first-order reaction. The reaction rate constants were in the increasing order of 50%, 70% and 90% polished rice. The temperature coefficient of the reaction rate constant at cooking temperatures of ($90^{\circ}-100^{\circ}C$) was about 2 in all rice samples. The activation energies of cooking at temperatures below $100^{\circ}C$ and above $100^{\circ}C$ were about 17,000 and 9,000 cal/mole, respectively. The polishing degrees and water soaking time of rice did not affect the activation energy of cooking; however, the lower polishing degrees and shorter soaking increased the cooking time The experimental results suggested that the cooking process of rice comprises two mechanisms: At temperatures below $100^{\circ}C$ the cooking rate is controlled by the reaction rate of rice constituents with water, and at temperatures above $100^{\circ}C$, it is controlled by the rate of diffusion of water through the cooked portion (or layer) toward the interface of uncooked core in which the reaction is occurring.

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Thermal Stability of the Major Color Component, Cyanidin 3-glucoside, from a Korean Pigmented Rice Variety in Aqueous Solution (한국산 유색미의 주요성분인 Cyanidin 3-glucoside의 수용액에서의 열안정성)

  • Jo, Man-Ho;Yoon, Hye-Hyun;Hahn, Tae-Ryong
    • Applied Biological Chemistry
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    • v.39 no.3
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    • pp.245-248
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    • 1996
  • Thermal stability of the major color component, cyanidin 3-glucoside, isolated from Korean pigmented rice (Oryza sativa var. Suwon 415) were investigated to explore possible application of value-added natural colors as food additives. The anthocyanin showed red and blue color with maximum absorption peaks at 511 nm and 572 nm in acidic (pH 2.0) and alkaline (pH 9.0) buffer solutions, respectively, and the thermal degradation reactions were carried out with different temperature ranges at $50{\sim}95^{\circ}C$. Degree of degradation was determined with UV/Vis spectra which indicate characteristic absorption patterns with sharp isosbestic points at 350 nm (pH 2.0), and 275, 310, and 405 nm (pH 9.0). Thus the reaction follows simple first-order kinetics. The anthocyanin was very stable against heat at acidic pH and relatively stable at alkaline pH with half-life values of 50.3 hr and 0.6 hr at $70^{\circ}C$, respectively. The activation energies and Arrhenius frequency factors of the pigment were 26.9 kcal $mol^{-1}\;and\;6.0{\times}10^{11}\;s^{-1}$, at pH 2.0, and 15.2 kcal $mol^{-1}\;and\;1.4{\times}10^{6}\;s^{-1}$, pH 9.0, and respectively.

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Thermal Recovery Behaviors of Neutron Irradiated Mn-Mo-Ni Low Alloy Steel (중성자에 조사된 Mn-Mo-Ni 저합금강의 열처리 회복거동)

  • Jang, Gi-Ok;Ji, Se-Hwan;Sim, Cheol-Mu;Park, Seung-Sik;Kim, Jong-O
    • Korean Journal of Materials Research
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    • v.9 no.3
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    • pp.327-332
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    • 1999
  • The recovery activation energy, the order of reaction and the recovery rate constant were detemined by isochronal and isothermal annealing treatment to investigate the recovery behaviors of neutron irradiated Mn-Mo-Ni low alloy steels$(fluence: 2.3\times10^{19}ncm^{-2}, 553K, E\geq1.0 MeV)$. Vickers microhardness tests were conducted to trace the recovery behavior after heat treatments. The results were analyzed in terms of recovery stages, behavior of responsible defects and recovery kinetics. It was shown that recovery occurred through two annealing stages(stage I : 703-753K, stage n : 813-873K) with re$\infty$very activation energies of 2.5 eV and 2.93 eV for each stage I and n, respectively. From the comparison of unirradiated and irradiated isochronal anneal curves, a radiation anneal hardening(RAH) peak was identified at around 813K. Most of recovery have occurred during about 120 min irrespective of isothermal annealing temperatures of 743K and 833K. Recovery rate constants were determined to be $3.4\times10^{-4}min^{-1} and 7.1\times10^{-4}min^{-1}$ for stage I and II, respectively. The order of reaction was about 2 for both recovery stages. Comparing the obtained data with those of previously reported results on neutron irradiated Mn- Mo- Ni steels, the thermal recovery be­havior of the present material seems to occur by the dissociation of point defect clusters formed during irradiation, and by the recombination process of self-interstitials and vacancies from dissociated vacancy clusters.

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Thermal Inactivation Parameters of Peroxidase in Flammulina velutipes and Lyophyllum ulmarium (팽이 및 만가닥버섯에서 추출한 peroxidase의 열 불활성화 특성)

  • Lee, Kyun;Kim, Kong-Hwan;Kim, Hyun-Ku
    • Korean Journal of Food Science and Technology
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    • v.34 no.6
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    • pp.1067-1072
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    • 2002
  • Peroxidase was used as a standard enzyme to determine optimum blanching conditions of Flammulina velutipes and Lyophyllum ulmarium. Crude peroxidase extracted from raw mushrooms had maximum activity at $10{\sim}15^{\circ}C$ and pH 5.5 (50 mM, potassium phosphate buffer) using substrates of $H_2O_2$ and p-Phenylendiamine. Thermal inactivation of the crude peroxidase followed the first-order kinetics. The activation energy and z value of the crude peroxidase for F. velutipes were 59.58 kcal/mol and $9.0^{\circ}C$, whereas were 43.05 kcal/mol and $12.4^{\circ}C$ for L. ulmarium, respectively. On the basis of thermal kinetics parameters obtained, the optimum blanching conditions for F. velutipes and L. ulmarium were 1 min at $70^{\circ}C$ and 5 min at $80^{\circ}C$, respectively. Activation energies and z values of peroxidases extracted from heat-treated mushrooms were 7.97 and 6.55 kcal/mol, and $59.8^{\circ}C\;and\;74.1^{\circ}C$ for F. velutipes and L. ulmarium, respectively.

Adsorption Characteristic of Brownish Dark Colored Compounds from the Hot Water Extract of Auricularia auricula Fruit Body (흑목이 버섯 자실체의 열수추출물로부터 흑갈색 색소 성분의 흡착 특성)

  • Kim, Hyeon-Min;Hur, Won;Lim, Kun Bin;Lee, Shin-Young
    • Food Engineering Progress
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    • v.13 no.2
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    • pp.138-146
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    • 2009
  • The crude polysaccharide fraction from fruit body of Auricularia auricula were obtained by using hot water extraction and ethanol precipitation. As the crude polysaccharide fraction contained the brownish dark colored compounds, the adsorption study of pigments from the crude polysaccharide using activated carbon was carried out. The pigment compounds showed an absorption characteristic with $\lambda_{max}$ of 230 nm and the absorbance at 230 nm was taken as color intensity. Adsorption capacity of pigment depended on increase of the activated carbon to sample loading ratio. The adsorption capacity increased with increase of pH and temperature in the pH range of 3.0-7.0 and temperature range of 25-40$^{\circ}C$, but decreased in the temperature range of 40-70$^{\circ}C$. The optimum capacity was obtained at addition of 16.7 mg activated carbon per mL sample solution (concentration = 3 mg/mL) at pH of 7.0 and temperature of 40$^{\circ}C$. Treatment for 10 min was sufficient to achieve the 80% decolorization and 1.25 fold purification of polysaccharide. Langmuir isotherm and pseudo second-order kinetic model provided the best fitting for adsorption of the brownish dark colored compounds onto powdered active carbon. The activation energies of adsorption from the Langmuir isotherm parameter in the ranges of 25-40$^{\circ}C$ and 40-70$^{\circ}C$ was -2.54 and 4.38 kcal/g, respectively. The results of low activation energy also indicated that the adsorption process was a physical adsorption which was controlled by diffnsion.

Highly Doped Nano-crystal Embedded Polymorphous Silicon Thin Film Deposited by Using Neutral Beam Assisted CVD at Room Temperature

  • Jang, Jin-Nyeong;Lee, Dong-Hyeok;So, Hyeon-Uk;Hong, Mun-Pyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.08a
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    • pp.154-155
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    • 2012
  • The promise of nano-crystalites (nc) as a technological material, for applications including display backplane, and solar cells, may ultimately depend on tailoring their behavior through doping and crystallinity. Impurities can strongly modify electronic and optical properties of bulk and nc semiconductors. Highly doped dopant also effect structural properties (both grain size, crystal fraction) of nc-Si thin film. As discussed in several literatures, P atoms or radicals have the tendency to reside on the surface of nc. The P-radical segregation on the nano-grain surfaces that called self-purification may reduce the possibility of new nucleation because of the five-coordination of P. In addition, the P doping levels of ${\sim}2{\times}10^{21}\;at/cm^3$ is the solubility limitation of P in Si; the solubility of nc thin film should be smaller. Therefore, the non-activated P tends to segregate on the grain boundaries and the surface of nc. These mechanisms could prevent new nucleation on the existing grain surface. Therefore, most researches shown that highly doped nc-thin film by using conventional PECVD deposition system tended to have low crystallinity, where the formation energy of nucleation should be higher than the nc surface in the intrinsic materials. If the deposition technology that can make highly doped and simultaneously highly crystallized nc at low temperature, it can lead processes of next generation flexible devices. Recently, we are developing a novel CVD technology with a neutral particle beam (NPB) source, named as neutral beam assisted CVD (NBaCVD), which controls the energy of incident neutral particles in the range of 1~300eV in order to enhance the atomic activation and crystalline of thin films at low temperatures. During the formation of the nc-/pm-Si thin films by the NBaCVD with various process conditions, NPB energy directly controlled by the reflector bias and effectively increased crystal fraction (~80%) by uniformly distributed nc grains with 3~10 nm size. In the case of phosphorous doped Si thin films, the doping efficiency also increased as increasing the reflector bias (i.e. increasing NPB energy). At 330V of reflector bias, activation energy of the doped nc-Si thin film reduced as low as 0.001 eV. This means dopants are fully occupied as substitutional site, even though the Si thin film has nano-sized grain structure. And activated dopant concentration is recorded as high as up to 1020 #/$cm^3$ at very low process temperature (< $80^{\circ}C$) process without any post annealing. Theoretical solubility for the higher dopant concentration in Si thin film for order of 1020 #/$cm^3$ can be done only high temperature process or post annealing over $650^{\circ}C$. In general, as decreasing the grain size, the dopant binding energy increases as ratio of 1 of diameter of grain and the dopant hardly be activated. The highly doped nc-Si thin film by low-temperature NBaCVD process had smaller average grain size under 10 nm (measured by GIWAXS, GISAXS and TEM analysis), but achieved very higher activation of phosphorous dopant; NB energy sufficiently transports its energy to doping and crystallization even though without supplying additional thermal energy. TEM image shows that incubation layer does not formed between nc-Si film and SiO2 under later and highly crystallized nc-Si film is constructed with uniformly distributed nano-grains in polymorphous tissues. The nucleation should be start at the first layer on the SiO2 later, but it hardly growth to be cone-shaped micro-size grains. The nc-grain evenly embedded pm-Si thin film can be formatted by competition of the nucleation and the crystal growing, which depend on the NPB energies. In the evaluation of the light soaking degradation of photoconductivity, while conventional intrinsic and n-type doped a-Si thin films appeared typical degradation of photoconductivity, all of the nc-Si thin films processed by the NBaCVD show only a few % of degradation of it. From FTIR and RAMAN spectra, the energetic hydrogen NB atoms passivate nano-grain boundaries during the NBaCVD process because of the high diffusivity and chemical potential of hydrogen atoms.

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The Studies of the Water-Vapour Transmission Rate and It's Proofness on the Various Commercial Polymer Films (상업용 고분자 필름의 투습속도 및 방습도에 관한 연구)

  • Hwan Kyu Suh;Jung Keun Lee
    • Journal of the Korean Chemical Society
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    • v.23 no.5
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    • pp.329-337
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    • 1979
  • The water-vapour transmission ratios (WVTR) of the various commercial polymer films have been investigated at the constant pressure and relative humidity (RH). Water proofnesses, the reciprocals of WVTR for the various samples, were determined using a cup device and maintaining the sample films at a constant temperature ($40{\pm}1^{\circ}C$) and a constant R. H ($90{\pm}2%$) for 24 hours. The following order of the relative proofness was observed; oriented polypropyrene (O.PP) > high density polyethylene (HDPE, Inflation) > high density polyethylene (HDPE. T-die) > casted polypropylene (C. PP) > nonoriented polyester (N. PET) > low density polyethylene (LDPE) > oriented polyester (O. PET) > rigid polyvinyl chloride (Rigid PVC) > semirigid polyvinyl chloride (Semirigid PVC) > nonrigid polyvinyl chloride (Nonrigid PVC) > oriented nylon (O. Nylon) > nonoriented nylon (N. Nylon). And water proofness order was also observed to decrease with the temperature rising; HDPE (T-die) > C. PP > O. PET > LDPE > O. Nylon. The activation energies of LDPE, HDPE (T-die), C. PP, O. PET and O.Nylon films were 12.0, 11.1, 11.4, 11.7, 14.1 kcal/mole, respectively. The WVTR's of the films were increased with the polarity of polymer and the addition of plasticizer in PVC, decreased with the increase of the film thickness and mechanical orientation. The WVTR's of the laminated films O. PP/LDPE, N.Nylon/LDPE, C.PP/LDPE were also more dependent on the film thickness than the WVTR's of the single films.

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