• Title/Summary/Keyword: relaxation kinetics

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Theoretical and Experimental Studies on the Kinetics of Cation Redistribution Processes in Complex Oxides

  • Shi, Jianmin;Becker, Klaus-Dieter
    • Journal of the Korean Ceramic Society
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    • v.47 no.1
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    • pp.39-46
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    • 2010
  • The kinetics of cation reequilibration have been studied theoretically and experimentally in complex oxides after an external perturbation of equilibrium by temperature jumps. A general kinetic model for cation redistribution amongst non-equivalent sites in complex oxides is derived based on a local homogeneous point defect mechanism involving cation vacancies. Temperature-jump optical relaxation spectroscopy has been established to investigate cation kinetic processes in spinels and olivines. The kinetic model satisfactorily describes the experimental absorbance relaxation kinetics in cobalt containing olivines and in nickel containing spinels. It is found that the kinetics of cation redistribution in complex oxides shows a strong temperature- and composition-dependence. Activation energies for cation redistribution in Co-Mg olivines are found to range between 200 and 220 kJ/mol whereas an energy barrier of about 230 kJ/mol is observed in the case of nickel gallate spinel.

Ultrasonic Studies of Proton-Exchange Reaction Between Hydrogen Phosphate Ions and Imidazole

  • Choi, Chang-Ha;Chung, Myung-Kiu
    • The Journal of the Acoustical Society of Korea
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    • v.16 no.1E
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    • pp.24-28
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    • 1997
  • Ultrasonic relaxation measurements for imidazole and its derivative in phosphate buffer exhibit a high peak of absorption at neutral pH. Near neutral pH, protolysis and hydrosis may be neglected and the essential reaction only consists of a direct proton-exchange. The kinetics constants and the volume changes for the proton transfer reaction with the protonated imidazole and 2-methylimidazole have been determined at 25℃. The kinetics constants are 7.2×108s-1M-1for imidazole and 1.7×108s-1M-1 for 2-methylimidazole. The kinetics constants are used to estimate the spectrum of relaxation times and acoustic relaxation amplitude associated with intermolecular and intramolecular proton-exchange reactions in bilogical media. It is concluded that the magnitude of the acoustic absorption reasonalbly attributable to the perturbation of proton-transfer equilibria between imidazole and inorganic phosphate is comparable in magnitude with the acoustic absorption observed in some intact tissues.

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The Effect of the Collision Process Between Molecules on the Rates of Thermal Relaxation of the Translational-Rotational-Vibrational Energy Exchange (분자간 충돌과정에 따른 병진-회전-진동에너지의 이완율)

  • Heo, Joong-Sik
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.28 no.12
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    • pp.1494-1500
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    • 2004
  • A zero-dimensional direct simulation Monte Carlo(DSMC) model is developed for simulating diatomic gas including vibrational kinetics. The method is applied to the simulation of two systems: vibrational relaxation of a simple harmonic oscillator and translational-rotational-vibrational energy exchange process under heating and cooling. In the present DSMC method, the variable hard sphere molecular model and no time counter technique are used to simulate the molecular collision kinetics. For simulation of diatomic gas flows, the Borgnakke-Larsen phenomenological model is adopted to redistribute the translational and internal energies.

Defect Structure, Nonstoichiometry and Nonstoichiometry Relaxation of Complex Oxides

  • Yoo, Han-Ill
    • Journal of the Korean Ceramic Society
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    • v.44 no.12
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    • pp.660-682
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    • 2007
  • An SOFC consists of all ceramic complex oxides each with different electrochemical-property requirements. These requirements, in principle, can be made met to a great extent by controlling or tailoring the defect structure of the oxide. This paper reviews the defect structure, nonstoichiometry as a measure of the total defect concentration, and the defect relaxation kinetics of complex oxides that are currently involved in a variety of growing applications today.

The Relaxation and Elimination Characteristics of Polarization-Photoinduced Dichrosim in Obliquely Deposited Amorphous Chalcogenide Thin Films (경사 증착된 비정질 칼코게나이드 박막에 평광-광유기된 이색성의 이완 및 소거 특성)

  • Park, Soo-Ho;Chun, Jin-Young;Lee, Hyun-Yong;Chung, Hong-Bay
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.11 no.10
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    • pp.891-896
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    • 1998
  • The relaxation and elimination characteristics of polarization-photoinduced dichroism have been investigated in amorphous chalcogenide thin films deposited having normal(0。) and obique (80。) vapor incident angles. The dark relaxation kinetics of dichroism from a saturation point(D\ulcorner\ulcorner) to a certain relaxation point(D\ulcorner\ulcorner) grew to be longer on subsequent cycles of switching on and off of the inducing light, and these decays are changed from simple exponential decay to stretched exponential decay. The dichroism induced by a long time(~3.3 hrs) exposure exhibited the characteristics of longer time maintenance and smaller decreasing rate, in contrast with that by a short time (~min) exposure. In addition, the dichroism was eliminated by the exposure of non-polarized He-Ne laser.

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Implication of Dynamic Materials and Softening Models to the FEM Analysis of SAF2507 Hot Forging (동적재료모델 및 연화모델을 도입한 SAF 2507의 열간단조 유한요소해석)

  • 방원규;정재영;장영원
    • Proceedings of the Korean Society for Technology of Plasticity Conference
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    • 2003.05a
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    • pp.195-198
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    • 2003
  • High temperature deformation and softening behavior of SAF 2507 super duplex stainless steel (SDSS) has been investigated in connection with an FEM analysis of hot forging process. Flow curves at various strain rates and temperatures were determined first from compression tests, and the kinetics of dynamic recrystallization were also formulated through the analysis of load relaxation test results. Applying the dynamic materials and proposed by Prasad et al., it was possible to determine the characteristics of deformation behavior effectively at a given condition of deformation. Constitutive relations and recrystallization kinetics formulated from the test results were then implemented in a commercial FEM code. Flow stress compensation formulated upon the volume fraction of recrystallization and adiabatic heating was found to improve significantly the FEA solutions in predicting the forming load and the distribution of recrystallized volume fraction after forging.

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Application of Dynamic Materials and Softening Models to the FEM Analysis of Hot Forging in SAF2507 Steel (동적재료모델 및 연화모델을 응용한 SAF 2507 강의 열간단조 유한요소해석)

  • 방원규;정재영;장영원
    • Transactions of Materials Processing
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    • v.12 no.4
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    • pp.308-313
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    • 2003
  • High temperature deformation and softening behavior of SAF 2507 super duplex stainless steel (SDSS) has been investigated in connection with an FEM analysis of hot forging process. Flow curves at various strain rates and temperatures were determined first from compression tests, and the kinetics of dynamic recrystallization were also formulated through the analysis of load relaxation test results. Using the dynamic materials theory proposed by Prasad, the deformation behavior was effectively determined for various conditions. Constitutive relations and recrystallization kinetics formulated from the test results were then implemented in a commercial FEM code. The forming load as well as the distribution of recrystallized volume fraction after forging was successfully predicted by means of the flow stress compensation formulated upon the volume fraction of recrystallization and adiabatic heating.

Complex Formation of Adenosine 3',5'-Cyclic Monophosphate with β-Cyclodextrin: Kinetics and Mechanism by Ultrasonic Relaxation

  • Bae, Jong-Rim;Kim, Jeong-Koo;Lee, Chang-Woo
    • Bulletin of the Korean Chemical Society
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    • v.31 no.2
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    • pp.442-446
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    • 2010
  • Adenosine 3',5'-cyclic monophosphate (cAMP) is a second messenger responsible for a multitude of cellular responses. In this study, we utilized $\beta$-cyclodextrin ($\beta$-CD) as an artificial receptor with a hydrophobic cavity to elucidate the inclusion kinetics of cAMP in a hydrophobic environment using the ultrasonic relaxation method. The results revealed that the interaction of cAMP with $\beta$-CD followed a single relaxation curve as a result of host-guest interactions. The inclusion of cAMP into the $\beta$-CD cavity was found to be a diffusion-controlled reaction. The dissociation of cAMP from the $\beta$-CD cavity was slower than that of adenosine 5'-monophosphate (AMP). The syn and anti glycosyl conformations of adenine nucleotides are considered to play an important role in formation of the inclusion complex. Taken together, our findings indicate that hydrophobic interactions are involved in the inclusion complex formation of cAMP with $\beta$-CD and provide insight into the interactions of cAMP with cAMP-binding proteins.

The application of model equations to Non-Fickian diffusion observed in Fluoropolymers

  • Lee, Sangwha
    • Proceedings of the Membrane Society of Korea Conference
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    • 1996.04a
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    • pp.34-35
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    • 1996
  • The diffusional behavior of many non-solvents in glassy or semicrystalline polymers cannot be adequately described by a concentration-dependent form of Fick's law, especially when mass transfer is coupled with structural changes. Many mathematical models have been devised to interprete non-Fickian diffusion dominated by relaxation kinetics. In formulation of non-Fickian diffusion mathematics, therefore, the most important factor to consider is how relaxation effects can influence the governing constitutive equation and boundary conditions. That is, relaxation parameters can be accommodated by variable boundary conditions or a modified continuity equation, or both, depending on specific systems and conditions (Frish, 1980). Accoring to Astarita and Nicolais (1983), the model equations can be broadly categorized as continuous or discontinuous. Continuous model equations encompass phenomena where the structural change takes place gradually over the whole volume of the polymer sample (Crank, 1953; Long and Richman, 1961; Berens and Hopfenberg, 1978). On the other hand, discontinuous model equations deal with the phenomena where the morphological change appears to be abrupt (Li, 1984). Four mathematical models with different relaxation parameters were applied to fit the anomalous sorption data observed in fluoropolymers (PVDF, ECTFE). The fitted result for PVDF-benzene sorption data is shown in Fig. 1.

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Swelling Controlled Drug Release from Acrylamide-Styrene Copolymer Hydrogels (Acrylamide-Styrene Copolymer 하이드로겔로부터의 수팽윤 속도조절에 의한 약물 방출)

  • Kim, Min-Kyoung;Lee, Seung-Jin
    • Journal of Pharmaceutical Investigation
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    • v.19 no.4
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    • pp.173-178
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    • 1989
  • Drug release rates from copolymer hydrogels were controlled by their hydrophilic-hydrophobic balances. As a model copolymer hydrogel, poly(acrylamide-co-styrene) was synthesized at different monomer composition. Release mechanisms of propranolol-HCI from the copolymer matrices were investisated. Swelling rates of the copolymer hydrogels retarded as their hydrophobicity increased. Swelling kinetics of the copolymer hydrogels regulated drug release rates via polymer relaxation controlled release mechanisms. Zero order drug release could thus be achieved within certain periods.

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