• Title/Summary/Keyword: Phase Behavior

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Dependence of an Interfacial Diels-Alder Reaction Kinetics on the Density of the Immobilized Dienophile: An Example of Phase-Separation

  • Min, Kyoung-Mi;Jung, Deok-Ho;Chae, Su-In;Kwon, Young-Eun
    • Bulletin of the Korean Chemical Society
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    • v.32 no.5
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    • pp.1679-1684
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    • 2011
  • Interfacial reactions kinetics often differ from kinetics of bulk reactions. Here, we describe how the density change of an immobilized reactant influences the kinetics of interfacial reactions. Self-assembled monolayers (SAMs) of alkanethiolates on gold were used as a model interface and the Diels-Alder reaction between immobilized quinones and soluble cyclopentadiene was used as a model reaction. The kinetic behavior was studied using varying concentrations of quinones. An unusual threshold density of quinones (${\Gamma}_c$ = 5.2-7.2%), at which the pseudo-first order rate constant started to vary as the reaction progressed, was observed. This unexpected kinetic behavior was attributed to the phase-separation phenomena of multi-component SAMs. Additional experiments using more phase-separated two-component SAMs supported this explanation by revealing a significant decrease in ${\Gamma}_c$ values. When the background hydroxyl group was replaced with carboxylic or phosphoric acid groups, ${\Gamma}_c$ was observed at below 1%. Also, more phase-separated thermodynamically controlled SAMs produced a lower critical density (3% < ${\Gamma}_c$ < 4.9%) than that of the less phaseseparated kinetically controlled SAMs (6.5% < ${\Gamma}_c$ < 8.9%).

PRECIPITAlON BEHAVIOR OF 8090 ALUMINIUM ALLOY BY HERMOMECANICAL AND DUPLEX AGING TREAMENT (가공열처리 및 2단시효처리에 의한 8090알루미늄 합금의 석출거동)

  • Lee, Hag-Yong;Kim, Sug-Woo;Woo, Kee-Do
    • Journal of the Korean Society for Heat Treatment
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    • v.7 no.4
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    • pp.270-276
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    • 1994
  • The effects of thermomechanical and duplex aging treatment on precipitation behavior were investigated for the 8090 aluminium alloy by tensile test, hardness test, plane-strain fracture toughness test and electron microscope. Both pre-aging stretch and duplex aging with pre-aging stretch were effective to homogenize the distribution of S' phase in this alloys. The latter makes more homogeneous distribution of S' phase than that of the former, but the sizes of S' phase in both specimens are almost same. The size and distribution of 0' phase were not changed by thermomechanical or duplex aging treatment. The strength was increased by thermomechanical treatment, but the elongation was decreased. Duplex aging treatment couldn't change the strength and elongation. Pre-aging stretch and duplex aging with pre-aging stretch have same effect on the strength and elongation. The increase of strength by thermomechanical treatment in 8090 alumunium alloy was caused by homogeneously precipitated S' phase.

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Study on Initial Scattering State as a Function of Curing Temperature for Polymer Dispersed Liquid Crystal Cells with Different Mixing Ratio (고분자 분산형 액정 셀에서 혼합물의 비율에 따라 노광 온도가 초기 산란도에 미치는 영향)

  • 김미숙;서영현;이명훈;이종문;이택수;이승희
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.17 no.1
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    • pp.59-64
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    • 2004
  • We have fabricated the polymer dispersed liquid crystal (PDLC) cell where a control of phase separation is very important. The factors to influence the phase separation are mixing ratio of LC and polymer, curing temperature and UV intensity. In this paper, we inspected the change of a phase separation as a function of curing temperature for the mixture of E7 and. NOA65 with different ratios. When the LC concentration is less than polymer such as LC:NOA65 = 40:60wt%, the PDLC cell is influenced strongly by the curing temperature. However, when the LC concentration is much less than polymer such as LC:NOA65 = 80:20wt%, it is influenced slightly by the curing temperature. The reason is because the mixture shows upper critical solution temperature behavior and therefore it is important to know the behavior of phase separation as a function of curing temperature of the mixture.

A Study on Numerical Analysis Using the Two Phase Flow in Alkaline Water Electrolysis Stacks (알카리 수전해 스택에서 수소기포의 2상유동 수치해석에 관한 연구)

  • HAN, JINMOK;BAE, YOOGEUN;SEO, YOUNGJIN;KIM, SEWOONG;JUNG, YOUNGGUAN
    • Transactions of the Korean hydrogen and new energy society
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    • v.29 no.2
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    • pp.155-162
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    • 2018
  • In this paper, the reliability of the numerical analysis using the two phase flow on the behavior of the hydrogen bubbles in the alkali electrolysis stacks was investigated by comparing the results obtained from numerical analysis and flow visualization experiments. As the results, through comparison with results gotten to visualization experiments, it is possible to approximate analysis for the flow of hydrogen bubbles in the stacks by numerical analysis using the two-phase flow. Also, the flow of hydrogen bubbles around the electrodes could be similarly analyzed by numerical analysis using the two-phase flow.

Determination of the Frumkin and Temkin Adsorption Isotherms of Hydrogen at Nickel/Acidic and Alkaline Aqueous Solution Interfaces Using the Phase-Shift Method and Correlation Constants

  • Chun, Jang-H.
    • Journal of the Korean Electrochemical Society
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    • v.15 no.1
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    • pp.54-66
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    • 2012
  • The phase-shift method and correlation constants, which are unique electrochemical impedance spectroscopy techniques for studying the linear relationship between the phase shift ($90^{\circ}{\geq}-{\varphi}{\geq}0^{\circ}$) vs. potential (E) behavior for the optimum intermediate frequency ($f_o$) and the fractional surface coverage ($0{\leq}{\theta}{\leq}1$) vs. E behavior, are proposed and verified to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and the related electrode kinetic and thermodynamic parameters. At Ni/0.5 M $H_2SO_4$ and 0.1M LiOH aqueous solution interfaces, the Frumkin and Temkin adsorption isotherms (${\theta}$ vs. E) of H for the cathodic hydrogen ($H_2$) evolution, interaction parameters (g), equilibrium constants (K), standard Gibbs energies (${\Delta}G^0_{\theta}$) of H adsorption, and rates of change (r) of ${\Delta}G^0_{\theta}$ with ${\theta}$ have been determined using the phase-shift method and correlation constants. A lateral repulsive interaction (g>0) between the adsorbed H species appears. The value of K in the alkaline aqueous solution is much greater than that in the acidic aqueous solution.

Development Behavior of Vaporizing Sprays from a High-Pressure Swirl Injector Using Exciplex Fluorescence Method

  • Choi, Dong-Seok;Kim, Duck-Jool;Hwang, Soon-Chul
    • Journal of Mechanical Science and Technology
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    • v.14 no.10
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    • pp.1143-1150
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    • 2000
  • The effects of ambient conditions on vaporizing sprays from a high-pressure swirl injector were investigated by an exciplex fluorescence method. Dopants used were 2% fluorobenzene and 9% DEMA (diethyl-methyl-amine) in 89% solution of hexane by volume. In order to examine the behavior of liquid and vapor phases inside of vaporizing sprays, ambient temperatures and pressures similar to engine atmospheres were set. It was found that the ambient pressure had a significant effect on the axial growth of spray, while ambient temperature had a great influence on the radial growth. The spatial distribution of vapor phase at temperatures above 473K became wider than that of liquid phase after half of injection duration. From the analysis of the area ratio for each phase, the middle part (region II) in the divided region was the region which liquid and vapor phases intersect. For liquid phase, fluorescence-intensity ratio was greatly changed at lms after the start of injection. However, the ratio of vapor phase was nearly uniform in each divided region throughout the injection.

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The Study on the Cavitation Erosion Behavior of Hardfacing Alloys for Nuclear Power Plants (원전 밸브용 경면처리 합금의 캐비테이션 에로젼 (cavitation erosion) 거동에 관한 연구)

  • O, Yeong-Min;Kim, Yun-Gap;Kim, Seon-Jin
    • Korean Journal of Materials Research
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    • v.12 no.4
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    • pp.308-316
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    • 2002
  • The cavitation erosion behavior of wear-resistant hardfacing alloys such as Co-base Stellite 6, Fe-base Norem 02 and new Fe-base alloy were investigated up to 50 hours by using a 20kHz vibratory cavitation erosion test equipment. The crack, initiated easily at the interfaces between matrix and hard second phase, was repressed effectively in Stellite 6 because the matrix was hardened by phase transformation. For this reason, Stellite 6 showed an excellent cavitation erosion resistance compared to Norem 02. The phase transformation also occurred in Norem 02, but the increase of volume fraction of the interfaces caused the crack to be initiated frequently, thus resulting in a 1arge material loss. The matrix of NewAlloy was hardened effectively by vlongrightarrow$\alpha$' phase transformation and the volume fraction of the interfaces was very small compared to Norem 02. This caused the propagation of crack to the matrix to be repressed effectively. Therefore, NewAlloy showed a very excellent cavitation erosion resistance. It wasn't considered that the cavitation erosion resistance of NewAlloy was influenced the temperature of the bath filled with a distilled water up to $80^{\circ}C$.

Post Test Analysis to Natural Circulation Experiment on the BETHSY Facility Using the MARS 1.4 Code

  • Chung, Young-Jong;Kim, Hee-Cheol;Chang, Moon-Hee
    • Nuclear Engineering and Technology
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    • v.33 no.6
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    • pp.638-651
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    • 2001
  • The present study is to assess the applicability of the best-estimate thermal-hydraulic code, MARS 1.4, for the analysis of thermal-hydraulic behavior in PWRs during natural circulation conditions. The code simulates a natural circulation test, BETHSY test 4. la, which was conducted on the integral test facility of BETHSY. The test represented the cooling states of the primary cooling system under single-phase natural circulation, two-phase natural circulation and the reflux condensation mode with conditions corresponding to the residual power, 2% of the rated core power value and 6.8 MPa at the secondary system. Based on MARS 1.4 calculations, the major thermal-hydraulic behaviors during natural circulation are evaluated and the differences between the experimental data and calculated results are identified. The calculated results show generally good behavior with regard to the experimental results; the region of single-phase natural circulation is 100-92% of the initial mass inventory, two-phase natural circulation is 84-63 %, and the reflux condensation mode occurred below 58 %. U-tubes empty and the core uncovery are obtained at 39 % and 34 % of the initial mass inventory, respectively.

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In situ measurement-based partitioning behavior of perfluoroalkyl acids in the atmosphere

  • Kim, Seung-Kyu;Li, Donghao;Kannan, Kurunthachalam
    • Environmental Engineering Research
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    • v.25 no.3
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    • pp.281-289
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    • 2020
  • Environmental fate of ionizable organic pollutants such as perfluoroalkyl acids (PFAAs) are of increasing interest but has not been well understood because of uncertain values for parameters related with atmospheric interphase partitioning behavior. In the present study, not only the values for air-water partition coefficient (KAW) and dissociation constant (pKa) of PFAAs were induced by adjusting to in situ measurements of air-water distribution coefficient between vapor phase and rainwater but also gas-particle partition coefficients were also estimated using three-phase partitioning model of ionizable organic pollutants, in situ measurements of PFAAs in aerosol and air vapor phase, and obtained parameter values. The pKa values of PFAAs we obtained were close to the minimum values suggested in literature except for perfluorooctane sulfonic acids, and COSMOtherm-modeled KAW values were assessed to more appropriate among suggested values. When applying parameter values we obtained, it was predicted that air particle-associated fate and transport of PFAAs could be negligible and PFAAs could distribute ubiquitously along the transection from urban to rural region by pH-dependent phase transfer in air. Our study is expected to have some implications in prediction of the environmental redistribution of other ionizable organic compounds.

Fabrication of Stabilized Fine Leucite Powder and Its Thermal Expansion Properties (상안정화된 Leucite의 미세분말 합성과 열적 팽창 특성 연구)

  • Hong, Sung-Jin;Kim, Deug-Joong;Yoo, Young-Sung
    • Journal of the Korean Ceramic Society
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    • v.46 no.5
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    • pp.493-496
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    • 2009
  • Phase stabilized leucite, which has high coefficient of thermal expansion, was synthesized, and its thermal expansion behavior was investigated. The homogeneous leucite phase was synthesized by solid state reaction from the mixture of $K_2CO_3-Al_2O_3-SiO_2$. and its stabilization from tetragonal to cubic phase was attempted by adding $Cs_2CO_3$ into starting materials. And fine powder with an average particle size of a few hundreds ${\mu}m$ were fabricated by planetary milling. During milling, amorphization of leucite was observed and recrystallized after heat treatment. The thermal expansion behavior of tetragonal and cubic leucite has measured and discussed. The average coefficient of thermal expansion of tetragonal and cubic phase leucite from room temperature to $750^{\circ}C$ was $21.4{\times}10^{-6}/^{\circ}C$ and $14.5{\times}10^{-6}/^{\circ}C$, respectively.