• Title/Summary/Keyword: Interfacial reaction kinetics

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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%).

Kinetics of Lipase Reactions in Two Phase System (이상계내에서 리파제의 반응동력학)

  • Kwon, Dae Y.;Rhee, Joon S.
    • Microbiology and Biotechnology Letters
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    • v.15 no.2
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    • pp.98-103
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    • 1987
  • Two phase reaction system was used to hydrolyze the olive oil for fat splitting. Kinetics of lipases in two phase system were investigated by determining the hydrolysis rate of triglycerides at various olive oil concentrations in isooctane using the microbial lipases from Candida rugosa and Rhizopus arrhizus. The rate equation in lipid hydrolysis for various olive oil concentrations in two phase system was deviated from the Michaelis-Menten kinetics. The results suggested that the olive oil concentration in isooctane affects the interfacial area. The dependency of the interfacial area on olive oil concentration is greater at the lower olive oil concentration than at the higher substrate concentration. We modified the rate equation by considering the interfacial area between two phases depending on the olive oil concentration in solvent phase.

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On the Reaction Kinetics of GaN Particles Formation from GaOOH (GaOOH로부터 GaN 분말 형성의 반응역학에 관하여)

  • Lee Jaebum;Kim Seontai
    • Korean Journal of Materials Research
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    • v.15 no.5
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    • pp.348-352
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    • 2005
  • Gallium oxyhydroxide (GaOOH) powders were heat-treated in a flowing ammonia gas to form GaN, and the reaction kinetics of the oxide to nitride was quantitatively determined by X-ray diffraction analysis. GaOOH turned into intermediate mixed phases of $\alpha-\;and\;\beta-Ga_2O_3$, and then single phase of GaN. The reaction time for full conversion $(t_c)$ decreased as the temperature increased. There were two-types of rapid reaction processes with the reaction temperature in the initial stage of nitridation at below $t_c$, and a relatively slow processes followed over $t_c$ does not depends on temperatures. The nitridation process was found to be limited by the rate of an interfacial reaction with the reaction order n value of 1 at $800^{\circ}C$ and by the diffusion-limited reaction with the n of 2 at above $1000^{\circ}C$, respectively, at below $t_c$. The activation energy for the reaction was calculated to be 1.84 eV in the temperature of below $830^{\circ}C$, and decreased to 0.38 eV above $830^{\circ}C$. From the comparative analysis of data, it strongly suggest the rate-controlling step changed from chemical reaction to mass transport above $830^{\circ}C$.

Reaction Kinetics and Morphological Changes at Polymer-polymer Interface measured by Rheological Properties (유변학적 성질 측정으로 측정한 고분자 계면에서의 반응 kinetics와 morphology 변화)

  • Kim, Hwang-Yong;Unyong Jeong;Kim, Jin-Kon
    • Proceedings of the Korean Society of Rheology Conference
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    • 2002.05a
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    • pp.25-27
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    • 2002
  • In this study we investigated the reaction kinetics by a convenient but useful method-rheology to characterize the interface between two immiscible blends with a Reactive compatibilizer. Also, we made an attempt to correlate changes of interface roughness with rheological properties. The blend systems employed in this study was mono-carboxylated polystyrene (PS-mCOOH) and an poly(methyl methacrylate-ran-glycidylmethacrylate) (PMMA-GMA). PS-mCOOH was synthesized by an anionic polymerization and PMMA-GMA by a free radical polymerization. We prepared two plates of each polymer using compression molding with a smooth surface molder, then put one upon another. As soon as these two plates welds together inside a rheometer under nitrogen environment, the torque and moduli were obtained with reaction time at different temperatures. Through the analysis of this modulus change with reaction time, we estimated interfacial reaction and roughening. The increment of modulus in initial state can be correlated to the extent of reaction. We obtained the reaction kinetic constant by fitting appropriate kinetic equation into experimental data. We also showed that increment of modulus in later state was due to by roughened interface.

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Cure Kinetics and Mechanical Interfacial Characteristics of Zeolite/DGEBA Composites (제올라이트/DGEBA 복합재료의 경화 동력학과 기계적 계면특성)

  • Soo-Jin Park;Young-Mi Kim;Jae-Sup Shin
    • Journal of the Korean Chemical Society
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    • v.47 no.5
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    • pp.472-478
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    • 2003
  • In this work, the zeolite/diglycidylether of bisphenol A(DGEBA) systems were investigated in terms of the cure kinetics and mechanical interfacial properties of the composites. The 4, 4-diamino diphenyl methane(DDM) was used as a curing agent for epoxy. Two types of zeolite(PZ) were prepared with 15 and 35 wt% KOH treatments(15-BZ and 35-BZ, respectively) for 24 h, and their surface characteristics were studied by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction(XRD). Cure kinetics of the composites were examined in the context of differential scanning calorimetry(DSC), and mechanical interfacial properties were investigated in critical stress intensity factor($K_{IC}$) and critical strain energy release rate($G_{IC}$). In the results of XPS and XRD, sodium ion(Na) of zeolite was exchanged for potassium ion(K), resulting from the treatment of KOH. Also, $Si_{2p}/Al{2p}$ composition ratios of the treated zeolite were increased, which could be attributed to the weakening of Al-O bond in framework. Cure activation energy($E_a$) of 15-BZ composites was decreased, whereas KIC and $G_{IC}$ were increased, compared with those of the pure zeolite/DGEBA composites. It was probably accounted that the acidity of zeolite was increased by surface treatments and the cure reaction between zeolite and epoxy was influenced on the increased acidity of zeolite.

Kinetics in Phase Transfer Catalysis with Heterogeneous Liquid-Liquid System (액-액 불균일계에서 상이동촉매의 반응속도론 해석)

  • Park, Sang-Wook;Moon, Jin-Bok;Hwang, Kyong-Son
    • Applied Chemistry for Engineering
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    • v.5 no.2
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    • pp.230-237
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    • 1994
  • The reaction conversions of n-butyl acetate in the alkaline hydrolysis of n-butyl acetate by Aliquat 336 were measured in a flat agitator and a dispersion agitator. These measured data was used to analyze the complicated reaction mechanism of the liquid-liquid heterogeneous reaction by a phase transfer catalyst with a pseudo-first order reaction model, a interfacial reaction model and a bulk-body reaction model. The pseudo-firsts order reaction model and the interfacial reaction model could be explained by the experimental data from the dispersion agitator and the bulk-boby reaction model could be explained by those from the flat agitator and the reaction rate constants were $3.1{\times}10^{-4}$, $7.3{\times}10^{-4}$, $6.6m^3/kmol.s$ from these models at $25^{\circ}C$, respectively.

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Effect of Low Temperature Annealing on the Magnetoresistance in Co/Cu Artificial Superlattice (Co/Cu인공초격자에서 저온 열처리가 자기저항에 미치는 영향)

  • 민경익;송용진;이후산;주승기
    • Journal of the Korean Magnetics Society
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    • v.3 no.4
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    • pp.305-309
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    • 1993
  • Thermal stability of Co/Cu artificial superlattice (AS) prepared by RF-magnetron sputtering and the effect of low temperature annealing on the magnetoresistance of the AS have been investigated in this work. Dependence of annealing behavior on the Cu spacer thickness, Fe underlayer thickness, and kind of the underlayer was examined and the relationship between the interfacial reaction and magnetoresistance was studied. It turned out that when Co/Cu AS was annealed at low temperature ($<450^{\circ}C$), the magnetoresistance could increase in the case of AS with thick spacer Cu ($20~25\AA$) layer, whereas it decreased in the case of AS with thin spacer Cu ($7\AA$) layer, which of the former is in contrast with previous reports and the latter in consistent with them. The increase of magnetoresistance is due to increase of interfacial atomic sharpness, which is supported by low angle X-ray diffraction analysis. The thermal stability of Co/Cu AS was better in the case of thick Fe underlayered AS. Interfacial reaction (separation of intermixed Co and Cu) could be observed at lower temperature for (200)-textured samples than for (111)-textured samples, which can be interpreted in terms of interdiffusion kinetics depending on the crystallographic orientation.

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Growth Kinetics of Intermetallic Compound on Sn-3.5Ag/Cu, Ni Pad Solder Joint with Isothermal Aging (등온시효에 따른 Sn-3.5Ag 솔더 접합부의 금속간 화합물 성장에 관한 연구)

  • 이인영;이창배;정승부;서창제
    • Journal of Welding and Joining
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    • v.20 no.1
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    • pp.97-102
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    • 2002
  • The growth kinetics of intermetallic compound layers formed between the eutectic Sn-3.5Ag solder and the Cu and Ni/Cu pad by solid stateisothermal aging were examined. The interfacial reaction between the eutectic Sn-3.5Ag solder and the Cu and Ni/Cu pad was investigated at 70, 120, 150, $170^{\circ}C$ for various times. The intermetallic compound layer was composed of two phase: $Cu_6Sn_5$(${\varepsilon}-phase$) adjacent to the solder and $Cu_6Sn_5$(${\varepsilon}-phase$) adjacent to the copper and on solder/Ni pad the intermetallic compound layer was $Ni_3Sn_4$. Because the values of time exponent(n) have approximately 0.5, the layer growth of the intermetallic compound was mainly controlled by volume diffusion over the temperature range studied. The apparent activation energy for layer growth of total Cu-Sn($Cu_6Sn_5 + Cu_6Sn$), $Cu_6Sn_5$, $Cu_3Sn$ and $Ni_3Sn_4$ intermetallic compound were 64.82kJ/mol, 48.53kJ/mol, 89.06kJ/mol and 71.08kJ/mol, respectively.

Growth Behavior of Intermetallic Compounds in Sn-Ag-Bi/Cu Solder Joints during Aging (Sn-Ag-Bi/Cu 솔더 조인트의 aging시 금속간화합물 성장 거동)

  • Han Sang Uk;Park Chang Yong;Heo Ju Yeol
    • Proceedings of the International Microelectronics And Packaging Society Conference
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    • 2003.11a
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    • pp.133-137
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    • 2003
  • The effect of Bi additions to the eutectic Sn-3.5Ag solder alloy on the growth kinetics of the intermetallic compound (IMC) layers during solid-state aging of Sn-Ag-Bi/Cu solder joints has been Investigated. The Bi additions enhanced the growth rate of the total IMC layer comprising of $Cu_6Sn_5$ and $Cu_3Sn$ sublayers. This enhanced IMC growth rate was primarily due to the rapid increase In the growth rate of $Cu_6Sn_5$ sublayer. The growth rate of $Cu_3Sn$ sublayers was little influenced and appeared to be retarded by the Bi additions. The observed growth behavior of $Cu_6Sn_5$ and $Cu_3Sn$ sublayers could be understood if the interfacial reaction barrier at the $Cu_6Sn_5/solder$ interface were reduced by the segregation of Bi at the interface.

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Progress in the modification of reverse osmosis (RO) membranes for enhanced performance

  • Otitoju, T.A.;Saari, R.A.;Ahmada, A.L.
    • Journal of Industrial and Engineering Chemistry
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    • v.67
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    • pp.52-71
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    • 2018
  • RO membranes, the core elements for RO process formed using polyamide, have found prominent space in membrane technology. RO membranes with better application perspective could be achieved by precise controlling the kinetics of IP reaction and surface modification strategy. Despite huge progresses, great challenges still exist in trade-off between flux, rejections and fouling. More works are necessary to enhance the performance and stability of RO membranes via surface modification. Further insights into the use of natural monomers are necessary. It is anticipated that this article can provide clues for further in-depth evaluation and research in exploring more advanced RO membranes.