• Title/Summary/Keyword: Activation energies

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Cure Behaviors and Fracture Toughness of PEl/Difunctional Epoxy Blends (PEI/DGEBA 블랜드계의 열적특성 및 파괴인성)

  • Park, Soo-Jin;Jin, Sung-Yeol;Kaang, Shinyoung
    • Journal of Adhesion and Interface
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    • v.4 no.3
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    • pp.33-40
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    • 2003
  • In this work, diglycidyl ether of bisphenol A (DGEBA)/polyetherimide (PEI) blends were cured using 4,4-diaminodiphenyl methane (DDM). And the effects of addition of different PEI contents to neat DGEBA were investigated in the thermal properties and fracture toughness of the blends. The contents of contents of containing PEI were varied in 0, 2.5, 5, 7.5, and 10 phr. The cure activation energies ($E_a$) of the cured specimens were determined by Kissinger equation and the mechanical interfacial properties of the specimens were performed by critical stress intensity factor ($K_{IC}$). Also their surfaces were examined by using a scanning electron microscope (SEM) and the surface energetics of blends was determined by contact angles. As a result, $E_a$ and $K_{IC}$ showed maximum values in the 7.5 phr PEI. This result was interpreted in the increment of the network structure of DGEBA/PEI blends. Also, the surface energetics of the DGEBA/PEI blends showed a similar behavior with the results of $K_{IC}$. This was probably due to the improving of specific or polor component of the surface free energy of DGEBA/PEI blends, resulting in increasing the hydrogen bonding of the hydroxyl and imide groups of the blends.

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Dosimetric Properties of LiF:Mg,Cu,Na,Si TL pellets (LiF:Mg,Cu,Na,Si TL 소자의 선량계적 특성)

  • Nam, Young-Mi;Kim, Jang-Lyul;Chang, Si-Young
    • Journal of Radiation Protection and Research
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    • v.26 no.1
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    • pp.7-12
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    • 2001
  • Sintered LiF:Mg,Cu,Na,Si thermoluminescence (TL) pellets were developed for application in radiation dosimetry. In the present study, the TL dosimetric properties of LiF:Mg,Cu,Na,Si TL pellets have been investigated for emission spectrum, dose response, energy response, and fading characteristics. LiF:Mg,Cu,Na,Si TL pellets were made by using a sintering process, that is, pressing and heat treatment from TL powders. Photon irradiations for the experiments were carried out using X-ray beams and a $^{137}Cs$ gamma source at the Korea Atomic Energy Research Institute (KAERI). The average energies and the dose were in the range of 20-662 keV and $10^{-6}-10^{-2}\;Gy$, respectively. The glow curves were measured with a manual type TLD reader(System 310, Teledyne) at a constant nitrogen flux and a linear heating rate. For a constant heating rate of $5^{\circ}C\;s^{-1}$, the main dosimetric peak of glow curve appeared at $234^{\circ}C$, the activation energy was 2.34 eV and frequency factor was $1.00{\times}10^{23}$. TL emission spectrum is appeared at the blue region centered at 410 nm. A linearity of photon dose response was maintained up to 100 Gy. The photon energy responses relative to $^{137}Cs$ response were within ${\pm}20%$ at overall photon energy region. The fading of TL sensitivity of the pellets stored at the room temperature was not found for one year.

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Fundamental Studies on the Equilibrium and Kinetics for the fractional Distillation Reaction of Waste Organic Solvent (폐용제 분별증류 회수 반응의 평형 및 속도론적 기초연구)

  • Noh Hyun-Sook;Kim Dong-Su
    • Resources Recycling
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    • v.11 no.6
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    • pp.38-46
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    • 2002
  • Fundamental investigations were conducted far the recovery process of waste organic solvent by fractional distillation in the aspects of equilibrium and kinetics. Mixture of toluene and xylene, which were both being used in the largest amount as industrial organic solvent, was taken as the artificial waste organic solvent and their distillation behaviors were studied. The purity of recovered solvent was investigated by Cir Chromatography and shown to be in the range of 94~98%. Based upon equilibrium calculations, the changes in the Gibbs free energy, standard enthalpy, and standard entropy for distillation reaction have been estimated. The standard enthalpy changes for toluene and xylene were shown to be 44.833 and 47.044 kJ $mol^{-1}$ respectively, which were similar to their molar heats of evaporation. The activation energies of distillation fur toluene and xylene obtained from kinetic studies were 3.281 and 2.699 kJ $mol^{-1}$ and they were about one tenths of the standard enthalpy changes of distillation reaction. The highness of the purity of recovered organic solvents suggested the possibility that the recovered waste organic sol-vent could partly replace the original solvent.

Oxidation of Ethanol in the Gas Phase with Alcohol Oxidase and Alcohol Dehydrogenase (Alcohol Oxidase와 Alcohol Dehydrogenase를 이용한 기상에서의 Ethanol의 산화반응)

  • 박현규;장호남김동옥
    • KSBB Journal
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    • v.9 no.3
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    • pp.239-245
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    • 1994
  • The effects of reaction temperature and the level of hydration(water activity) were studied for gas phase reactions of alcohol oxidase and alcohol dehydrogenase immobilized on DEAE-cellulose and controlled pore glass(CPG). Optimum reaction temperature zone of gas phase reaction was similar to that of aqueous phase reaction. The activity of alcohol oxidase increased dramatically and the stability decreased when the water activity was increased from 0.3 to 0.8. The apparent activation energies of the gas phase reaction decreased approaching the values obtained in the aqueous phase reaction as the water activity increased. In the both cases of alcohol oxidase and alcohol dehydrogenase, the rate constants of the gas phase reaction were lower than those of aqueous phase reaction by two orders of magnitude and these results could be correlated to the vapor-liquid equilibrium data of the substrate, ethanol.

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Rheological Properties of Gelatinized Model Foods (모형식품의 리올로지 특성)

  • Chun, Ki-Chul;Park, Young-Deok;Chang, Kyu-Seob
    • Korean Journal of Agricultural Science
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    • v.22 no.1
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    • pp.103-109
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    • 1995
  • The model foods were prepared by simulating mositure, protein and starch, and they were heated for 30 mins, at $80^{\circ}C$ and then cooled at $25^{\circ}C$ in water bath. Their rheological properties were investigated by the use of Brookfield wide-gap rotational viscometer at $30{\sim}60^{\circ}C$, and the rotation speed ranged from 0.6 to 6 rpm and solid content ranged from 8% to 11%, the results obtained were as follows. 1. All the model foods ($P_1S_3$, $P_2S_2$, $P_1S_1$, $P_2S_1$, $P_3S_1$, $P_4S_0$) exhibited pseudoplastic behaviors with yeild stress and were thixotropic foods which showed time - dependent structural decays, but the starch food of 8 ~ 11 % solid content did not show the flow behavior. 2. The correlation between the rheological parameters and the protein content of model foods in various moisture content did not appeared a constant relationship. 3. The change of shear stress against shear rate in high starch foods was larger than that in high protein foods and the structure at initial shear time was decayed with a quatic equation according to the Tiu's Model and structural decay was in parallel with the increase of shear rate. 4. The temperature dependency of the apparent viscosity of $P_1S_2$, and $P_2S_1$ was fully expressed by Arrhenius equation and activation energies of their food were 2.35 and $1.34Kcal/g{\cdot}mol$, respectively.

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Theoretical Studies of the Gas-Phase Identity Nucleophilic Substitution Reactions of Cyclopentadienyl Halides

  • Lee, Ik-Choon;Li, Hong-Guang;Kim, Chang-Kon;Lee, Bon-Su;Kim, Chan-Kyung;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.24 no.5
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    • pp.583-592
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    • 2003
  • The gas phase identity nucleophilic substitution reactions of halide anions (X = F, Cl, Br) with cyclopentadienyl halides (1) are investigated at the B3LYP/6-311+G**, MP2/6-311+G** and G2(+)MP2 levels involving five reaction pathways: σ-attack $S_N2$, β-$S_N$2'-syn, β-$S_N$2'-anti, γ-$S_N$2'-syn and γ-$S_N$2'-anti paths. In addition, the halide exchange reactions at the saturated analogue, cyclopentyl halides (2), and the monohapto circumambulatory halide rearrangements in 1 are also studied at the same three levels of theory. In the σ-attack $S_N2$ transition state for 1 weak positive charge develops in the ring with X = F while negative charge develops with X = Cl and Br leading to a higher energy barrier with X = F but to lower energy barriers with X = Cl and Br than for the corresponding reactions of 2. The π-attack β-$S_N$2' transition states are stabilized by the strong $n_C-{\pi}^{*}_{C=C}$ charge transfer interactions, whereas the π-attack γ-$S_N$2' transition states are stabilized by the strong $n_C-{\sigma}^{*}_{C-X}$ interactions. For all types of reaction paths, the energy barriers are lower with X = F than Cl and Br due to the greater bond energy gain in the partial C-X bond formation with X = F. The β-$S_N$2' paths are favored over the γ-$S_N$2' paths only with X = F and the reverse holds with X = Cl and Br. The σ-attack $S_N2$ reaction provides the lowest energy barrier with X = Cl and Br, but that with X = F is the highest energy barrier path. Activation energies for the circumambulatory rearrangement processes are much higher (by more than 18 kcal $mol^{-1}$) than those for the corresponding $S_N2$ reaction path. Overall the gas-phase halide exchanges are predicted to proceed by the σ-attack $S_N2$ path with X = Cl and Br but by the β-$S_N$2'-anti path with X = F. The barriers to the gas-phase halide exchanges increase in the order X = F < Br < Cl, which is the same as that found for the gas-phase identity methyl transfer reactions.

Electrical Properties and Defect States in ZnO Substrates Irradiated by MeV Electron-beam (고 에너지 전자빔 조사에 따른 ZnO 기판의 결함생성 및 전기적 특성 변화)

  • Lee, Dong-Uk;Song, Hoo-Young;Han, Dong-Seok;Kim, Seon-Pil;Kim, Eun-Kyu;Lee, Byung-Cheol
    • Journal of the Korean Vacuum Society
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    • v.19 no.3
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    • pp.199-205
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    • 2010
  • The electrical properties and defect states in ZnO substrates were studied during high-energy electron beam irradiations. 1 MeV and 2 MeV electron-beam with dose of $1{\times}10^{16}$ electrons/$cm^2$ were irradiated on Zn-surface of the sample. In the sample irradiated by 1 MeV, the leakage current was increased by electron-beam induced surface defects, while the enhancement of on/off property and the decrease of leakage current appeared in the 2 MeV irradiated sample. From the deep level transient spectroscopy measurements for these samples, it showed that the defect states with the activation energies of $E_c$-0.33 eV and $E_v$+0.8 eV are generated during the high energy electron-beam irradiation. Especially, it considered that the $E_c$-0.33 eV state related with O-vacancy affects to their electrical properties.

Compressive Creep Behavior of Rice Starch Gels (쌀 전분 젤의 creep 특성)

  • Hong, Seok-In;Kim, Young-Sug;Choi, Dong-Won;Pyun, Yu-Ryang
    • Korean Journal of Food Science and Technology
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    • v.24 no.2
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    • pp.165-170
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    • 1992
  • The creep behavior of gels made with $30{\sim}45%$ gelatinized rice starch was measured over a wide range of temperature. Compressive creep curves of rice starch gels conformed to a six element mechanical model consisting of one Hookean, two Voigt and one Newtonian component. The creep compliance of gels decreased with increasing starch concentrations. Among viscoelastic constants of the mechanical model, elastic modulus was mainly influenced by the change of starch concentrations. The concentration-invariant compliance curve was obtained by reduction to 38% using reduction parameter $a_{c}$. The creep compliance curves of 45% starch gels increased with temperature, which indicated that rice starch gels became softer and less rigid with increasing temperature. When the compliance at $20^{\circ}C$ was set as a reference curve, creep compliance data for 45% gels at various temperature could be superimposed as a continuous smooth curve. The apparent activation energies of 45% rice starch gels calculated by the modified WLF equation were not intrinsic, but decreased as temperature increased.

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Influence of Surfactants(Ag, Sn) in Si/Si(111) Homoepitaxial Growth (Si(111) Homoepitaxial성장에서 중간금속이 미치는 영향)

  • Gwak, Ho-Won;Lee, Ui-Wan;Park, Dong-Su;Gwak, Lee-Sang;Lee, Chung-Hwa;Kim, Hak-Bong;Lee, Un-Hwan
    • Korean Journal of Materials Research
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    • v.3 no.3
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    • pp.230-236
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    • 1993
  • We have the homoepitaxiallayers on the surfaces of Si(111) with and without the adsorbed surfactants, for example, Ag or Sn. In this paper, We have studied the difference of growth for these two cases by the observation of intensity oscillations of RHEED specular spots during the growing processes. In the case of growth without the adsorbed surfactants, the Si atoms fill first the stacking fault layer of Si(111) 7 ${\times}$7 structure. Therefore, the irregular oscillations are observed in the early stage of growing process. However, in the case of growth with the adsorbed surfactants, the surfactants already have the ${\sqrt}{3}$ ${\times}$ ${\sqrt}{3}$ structures on the surfaces of Si(111) at the adjucate temperatures of 300`$600^{\circ}C$ and 190~$860^{\circ}C$ for the surfactants of Ag and Sn, respectively. We also find that the number of oscillations is a little larger for the case of growth with the adsorbed surfactants. The reason for this is that for the case of growth with the adsorbed surfactants, the activation energies of Si atoms decrease due to the segregation of surfactants toward the growing surfaces.

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Metalorganic Chemical Vapor Deposition of Copper Films on TiN Substrates Using Direct Liquid Injection of (hfac)Cu(vtmos) Precursor ((hfac)Cu(vtmos)의 액체분사법에 의한 TiN 기판상 구리박막의 유기금속 화학증착 특성)

  • Jun, Chi-Hoon;Kim, Youn-Tae;Kim, Dai-Ryong
    • Korean Journal of Materials Research
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    • v.9 no.12
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    • pp.1196-1204
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    • 1999
  • We have carried out copper MOCVD(metalorganic chemical vapor deposition) onto the reactive sputtered PVD-TiN and rapid thermal converted RTP-TiN substrates using direct liquid injection for effective delivery of the (hfac)Cu(vtmos) [$C_{10}H_{13}O_{5}CuF_{6}$Si: 1,1,1,5,5,5-hexafluoro-2,4- pentadionato (vinyltrimethoxysilane) copper (I)] precursor. Especially, the influences of deposition conditions and the substrate type on growth rate, crystal structure, microstructure, and electrical resistivity of copper deposits have been discussed. It is found that the film growth with 0.2ccm precursor flow rate become mass-transfer controlled up to Ar flow rate of 200sccm and pick-up rate controlled at a vaporizer above 1.0Torr reactor pressure. The surface-reaction controlled region from 155 to 225$^{\circ}C$ at 0.6Torr reactor pressure results in the apparent activation energies of 12.7~14.1kcal/mol, and above 224$^{\circ}C$ the growth rate with $H_2$ addition could be improved compared to the pure Ar carrier. The Cu/RTP-TiN structures which have high copper nucleation density in initial stage of growth show more pronounced (111) preferred orientations and lower electrical resistivities than those on PVD-TiN. The variation of electrical resistivity with substrate temperature reflects the three types of film microstructure changes, showing the lowest value for the deposit at 165$^{\circ}C$ with small grains of good contacts.

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