• Macromolecular Research
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• v.11 no.5
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• pp.311-316
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• 2003

The kinetics of photoinitiated polymerization of dimethacrylate macromonomers have been studied to determine the diffusion-controlled reaction parameters using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). A predicted kinetic rate expression with a diffusion control factor was employed to estimate an effective rate constant and to define the reaction-controlled and diffusion-controlled regimes in the photopolymerization. An effective rate constant, k$_{e}$, can be obtained from the predicted kinetic rate expression. At the earlier stages of polymerization, the average values of kinetic rate constants do not vary during the reaction time. As the reaction conversion, $\alpha$, reaches the critical conversion, $\alpha$$_{c}$, in the predicted kinetic expression, the reaction becomes to be controlled by diffusion due to the restricted mobility of dimethacrylate macromonomers. A drop in value of effective rate constant causes a drastic decrease of reaction rate at the later stages of polymerization. By determining the effective rate constants, the reaction-controlled and diffusion-controlled regimes were properly defined even in the photopolymerization reaction system.m.m.

• Bulletin of the Korean Chemical Society
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• v.27 no.8
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• pp.1181-1185
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• 2006

By using two different computer simulation methods, of which one produces exact results while the other is based on the Wilemski-Fixman closure approximation, we evaluate the utility of closure approximation in calculating the rates of diffusion-controlled reactions involving a reactant with multiple reaction sites. We find that errors in the estimates of steady-state rate constants due to closure approximation are not so large. We thus propose an approximate analytic expression for the rate constant based on the closure approximation.

• Polymer(Korea)
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• v.27 no.5
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• pp.421-428
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• 2003

The kinetics of photoinitiated polymerization of reactive oligomer methacrylates and oligomer methacrylate/SBS blends have been studied to characterize the diffusion-controlled reaction using Fourier Transform Infrared Spectroscopy-Attenuated Total Reflectance (ATR-FTIR). The polymerization rates of reactive oligomer methacrylates and oligomer methacrylate/SBS blends were autocatalytic in nature at the initial stage and then a retardation of the reaction conversion occurred gradually as the polymer matrix became vitrified, and finally the reaction became diffusion controlled. Photopolymerization behavior of methacrylate/SBS blends was well predicted using the diffusion-controlled reaction model. N-Vinyl-2-pyrrolidinone (NVP) as a reactive solvent was used to incorporate SBS into methacrylate to form semi-IPN via photopolymerization. Due to the high reactivity of NVP, polymerization rate increased with the increase of NVP content. As the content of NVP-SBS in the blends increased up to 10 phr, the reaction conversion maintained almost constant. But above 20 phr of NVP-SBS in the blends, the reaction conversion gradually decreased since the increase of viscosity affected on the photopolymerization rate. The semi-IPN films of methacrylate/SBS blends were transparent at room temperature as well as at increased temperature and were able to be applied to surface coating.

• Journal of the Korean Ceramic Society
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• v.33 no.6
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• pp.718-724
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• 1996

Deformation mechanism map of Langdon-Mohammed type for YBa2Cu3O7-x superconducting ceramic was constructed by considering mechanisms of Nabarro-Herring Coble and powder-law creep and grain boundary sliding (GBS) with an accommodation by grain boundary diffusion. The map was found consistent with experi-mental results not only of the creep the also of the superplastic deformation. It showed the transition from interface reaction-controlled to the grain boundary diffusion-controlled GBS mechanism at about 1 ${\mu}{\textrm}{m}$ grain size and 100 MPa flow stress in agreement with the experimental results.

• The Journal of Engineering Research
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• v.3 no.1
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• pp.223-233
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• 1998

The kinetic and mechanism of the hydrothermal reaction between lime and quartz used solid state reaction equations have been investigated. Hydrothermal reaction on the starting materials was carried out in an autoclave that quartz mixed with calcium hydroxide in CaO/$SiO_2$ ratio of 0.8-1.0 for 0.5-8 hour at saturated steam pressure of $180-200^{\circ}C$. The rate of reaction was given from the ratio of uncombined lime and quartz content to the total lime and quartz content. The rate of reaction was obtained the results by the Jander's equation $[1-(1-\alpha)^{1/3}]^N=Kt$. The reaction of lime is controlled mainly by the dissolution such as N=1, and the reaction of quartz is controlled mostly by the diffusion such as $N\risingdotseq2$. The rate of hydrothermal reaction in the calcium silicate hydrates system is suggested to be determined generally by the mass transfer through the product laver formed around the reactant particles. The rate equation for whole hydrothermal reaction is shown that it is converted into the rate determining step by the diffusion from the boundary reaction such as approximately $N=1-2$.

• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.2973-2977
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• 2011

It has been known that the inertial dynamics has a little effect on the reaction rate in solutions. In this work, however, we find that for diffusion-controlled reactions between a ligand and a receptor on the cell surface there is a noticeable inertial dynamic effect on the reaction rate. We estimate the magnitude of the inertial dynamic effect by comparing the approximate analytic results obtained with and without the inertial dynamic effect included. The magnitude of the inertial dynamic effect depends on the friction coefficient of the ligand as well as on the relative scale of the receptor size to the distance traveled by the ligand during its velocity relaxation time.

• Polymer(Korea)
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• v.24 no.1
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• pp.105-112
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• 2000

Using a commercial epoxy/carbon fiber composite prepreg (DMS 2224) as a model system, the cure kinetics of vitrifying thermoset system were analyzed by isothermal and dynamic-heating experiments. Focusing on the processing condition of high performance composite systems, a phenomenological kinetic model was developed by using differential scanning calorimetry (DSC) and reaction kinetics theories. The model system exhibited a limited degree of cure as a function of isothermal temperature seemingly due to the diffusion-controlled reaction rates. The diffusion-controlled cure reaction was incorporated in the development of the kinetic model, and the model parameters were determined from isothermal experiments. The first order reaction was confirmed from the characteristic shape of isothermal cure thermograms, and the activation energy wes 78.43 kJ/mol. Finally, the proposed model was used to predict a complex autoclave thermal condition, which was composed of several isothermal and dynamic-heating stages.

• Journal of Welding and Joining
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• v.15 no.3
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• pp.128-135
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• 1997

Reaction diffusion and formation of $Ni_3Al$phase with $L1_2$ structure have been studied in temperature range of 1432K to 1573K using the diffusion couple of (Ni-40, 5at%Al)/(Ni-14, 1at%Al) and (Ni-49, 2at%Al)/ (Nickel). The layer growth of Ni$_{3}$Al pyhase in the annealed diffusion couple was measured by optical microscope and electron probe microanalyzer (EPMA). The layer growth of $Ni_3Al$phase in diffusion zone obeyed the parabolic law without any indication of grain boundary effects. The layer growth of $Ni_3Al$phase in temperature range of 1423K to 1573K was mainly controlled by the volume diffusion mechanism. The rate of layer growth of $Ni_3Al$phase was found to be colsely related to the composition of intermetallic compound NiAl phase. The activation energy for layer growth of $Ni_3Al$phase was calculated to be 127kJ/mol.

• Macromolecular Research
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• v.10 no.5
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• pp.259-265
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• 2002

The cure kinetics of blends of epoxy (DGEBA, diglycidyl ether of bisphenol A)/anhydride resin with polyamide copolymer, poly(dimmer acid-co-alkyl polyamine), were studied using differential scanning calorimetry (DSC) under isothermal condition. On increasing the amount of polyamide copolymer in the blends, the reaction rate was increased and the final cure conversion was decreased. Lower values of final cure conversions in the epoxy/(polyamide copolymer) blends indicate that polyamide hinders the cure reaction between the epoxy and the curing agent. The value of the reaction order, m, for the initial autocatalytic reaction was not affected by blending polyamide copolymer with epoxy resin, and the value was approximately 1.3, whereas the reaction order, n, for the general n-th order of reaction was increased by increasing the amount of polyamide copolymer in the blends, and the value increased from 1.6 to 4.0. A diffusion-controlled reaction was observed as the cure conversion increased and the rate equation was successfully analyzed by incorporating the diffusion control term for the epoxy/anhydride/(polyamide copolymer) blends. Complete miscibility was observed in the uncured blends of epoxy/(polyamide copolymer) up to 120 $^{\circ}C$, but phase separations occurred in the early stages of the curing process at higher temperatures than 120 "C. During the curing process, the cure reaction involving the functional group in polyamide copolymer was detected on a DSC thermogram.gram.

• Proceedings of the International Microelectronics And Packaging Society Conference
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• 2001.11a
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• pp.134-137
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• 2001

The cure kinetics of a cycloalipatic epoxy / anhydride / Co(II) system for a no-flow underfill encapsulant, has been studied by using a differential scanning calorimetry(DSC) under isothermal and dynamic conditions over the temperature range of $160^{\circ}C ~220^{\circ}C$. The kinetic analysis was carried out by fitting dynamic/isothermal heating experimental data to the kinetic expressions to determine the reaction parameters, such as order of reaction and reaction constants. Diffusion-controlled reaction has been observed as the cure conversion increases and successfully analyzed by incorporating the diffusion control term into the rate equation. The prediction of reaction rates by the model equation corresponded well to experimental data at all temperature.