• Elastomers and Composites
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• 제50권2호
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• pp.92-97
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• 2015

A study on reaction kinetics for a PTMG/TDI prepolymer with 2,2'-dichloro-4,4'-methylenedianiline (MOCA), of which formulations may be generally used for fabricating high performance polyurethane elastomers, was peformed using non-isothermal differential scanning calorimetry (DSC). A number of thermograms were obtained at several constant heating rates, and analysed using Flynn-Wall-Ozawa (FWO) isoconversional method for activation energy, $E_a$ and extended-Avrami equation for reaction order, n. Urea formation reaction of the present system was observed to occur through the simple exothermic reaction process in the temperature range of $100{\sim}130^{\circ}C$ for the heating rate of $3{\sim}7^{\circ}C/min$. and could be well-fitted with generalized sigmoid function. Though activation energy was nearly constant as $53.0{\pm}0.5kJ/mol$, it tended to increase a little at initial stage, but it decreases at later stage by the transformation into diffusion-controlled reaction due to the increased viscosity. Reaction order was evaluated as about 2.8, which was somewhat higher than the generally well-known $2^{nd}$ order values for the various urea reactions. Both the reaction order and reaction rate explicitly increased with temperature, which was considered as the indication of occurring the side reactions such as allophanate or biuret formation.

• 한국환경과학회:학술대회논문집
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• 한국환경과학회 1998년도 봄 학술발표회 프로그램
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• pp.144-153
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• 1998

Sorbents of calcined limestone and oyster particles having a diameter of about 0.63mm were exposed to simulate fuel gases containing 5000ppmv H2S for temperatures ranging from 600 to 800C in a TGA. The reaction between CaO and H2S proceds via an unreacted shrinking core mechanism. The sulfidation rate is likely to be controlled primarily by countercurrent diffusion through the product layer of calcium sulfide(CaS) formed. The kinetics of the sorption of H2S by CaO is sensitive to the reaction temperature and particle size, and the reaction rate of oyster was faster than the calcined limestone.

• Nuclear Engineering and Technology
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• 제29권2호
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• pp.99-109
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• 1997

A dynamic model for hydrogen generation by Fuel-Coolant Interactions(FCI) is developed with separate models for each FCI stage, coarse mixing and stratification. The model includes the physical concept of FCI, semi-empirical heat and mass transfer correlation and the concentration diffusion equation with the general non-zero boundary condition. The calculated amount of hydrogen, which is mainly generated in stratification, is compared with the FITS experiments. The model developed in this study shows a good agreement within a range of 10 % fuel oxidation rate and predicts the controlled mechanism of the chemical reaction very well. And this model predicts more accurately than the previous works. It is shown from the sensitivity study that the higher initial temperature of fuel particle is, the larger the reaction rate is. Up to 2700 K of temperature of the particle, the reaction rate increases rapid, which can lead to metal ignition.

• 한국세라믹학회지
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• 제18권1호
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• pp.35-40
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• 1981

The kinetics of the dehydration of Ha-dong kaolin was studied isothermally at various temperatures. Dehydration rate was measured by thermogravimetry method in the temperature range of 440~50$0^{\circ}C$ and the particle size range of 170~325mesh. The general equation f($\alpha$)=kt, where $\alpha$ is the fraction reacted in the time and the function f($\alpha$) depends on the reaction mechanism, was applied to this reaction. The function, f($\alpha$) was obtained by application of reduced-time plot and plot of lnln (1-$\alpha$) vs. ln (time), and expressed as (1-$\alpha$) ln (1-$\alpha$)+$\alpha$=kt. The dehydration followed the diffusion-controlled reaction model and gave activation energy of 30Kcal/mole.

• 대한화학회지
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• 제14권2호
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• pp.141-145
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• 1970

The reduction of Mo-thiocyanate (V) complex on dropping mercury electrode has been studied at ionic strength 0.6 with pH less than 2.3. D-C polarogram obtained from acidic solutions are reversible, diffusion controlled current. The electrode reaction of Mo-thiocyanate(V) may be represented as follows. $MoO(SCN)_3\;+\;2H^+\;+\;2e\;{\to}\;Mo(SCN)_2{^+}\;+\;H_2O\;+\;SCN^-$From this reaction, the half wave potential assumed to be $E_{1/2}\;=\;E_0'\;-\;0.059\;pH\;-\;0.03\;log{\;frac{[Mo(SCN)_2{^+}][SCN^-]}{[MoO(SCN)_3]}}$Considering the dissociation of this complex, however, it was estimated that the electrode reaction may be written by. $MoO^{+3}\;+\;3SCN^-\;+\;2H^+\;+\;2e\;{\to}\;Mo(SCN)_2{^+}\;+\;SCN^-\;+\;H_2O$.

• 한국표면공학회지
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• 제21권4호
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• pp.160-167
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• 1988

Electrochemical behaviors od chromium electrodeposition from 0.05M chromium (III) sulface complexes in aqueous solutions using sodium formate-glycine mixtures as a complexing agent were studied. In the cathodic current-potential cures, it is found that the intial limiting current of Cr(III) is proportional to square root of scan rate and activiation energy from Arrhenius plot is s obtained 3.05Kcal/mol. From this results, the reaction is considered, Cr3++e longrightarrow Cr2+, which is controlled diffusion of Cr (III). It is also found that the chromium is deposited when the potential reaches to hydrogen evolution potential. Effects of NaSCN as a catalyser in the electrolyte were investigated NCS- anion seems to react strongly by specific absorption at the inner HelmholtZ layer, so that, it is considered to suppress the electrodeposition reaction reaction for chromjum, and also it is considered multipe-bridge such as Cr(III)-NCS---M(M;cathode).

• 한국표면공학회지
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• 제9권2호
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• pp.1-7
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• 1976

The dissolving and growth kinetics of intermetallic compounds for the reaction between solid iron and molten zinc were studied under nitorgen atmosphere over the temperature range between470$^{\circ}C$ and 680$^{\circ}C$. The rates of dissolution of solid iron into molten zinc were obtained under a static conditon, The amount of dissolution of sold iron and the growth of intermetalic compounds could be determined by means of microscopy. The thickness of intermetallic compound at a given temperature increases with increasing time, whereas for a given time decreases with increasing temperature . The rate of dissolution is controlled by the diffusion process of iron in the effective boundary layer of molten zinc over the temperature range 470$^{\circ}$-530$^{\circ}C$, 570$^{\circ}$-620$^{\circ}C$, and 650$^{\circ}$-665$^{\circ}C$, while by the surface reaction over the range 530$^{\circ}$-570$^{\circ}C$ and 620$^{\circ}$-650$^{\circ}C$.

• 한국환경과학회지
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• 제8권1호
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• pp.125-133
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• 1999

Sorbents of calcined limestone and oyster particles having a diameter of about 0.63mm were exposed to simulated fuel gases containing 5000ppm $H_2S$ for temperatures ranging from 600 to 80$0^{\circ}C$ in a TGA (Thermalgravimetric analyzer). The reaction between CaO and $H_2S$ proceeds via an unreacted shrinking core mechanism. The sulfidation rate is likely to be controlled primarily by countercurrent diffusion through the product layer of calcium sulfide(CaS) formed. The kinetics of the sorption of $H_2S$ by CaO is sensitive to the reaction temperature and particle size, and the reaction rate of oyster was faster than the calcined limestone.

• 한국세라믹학회지
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• 제31권11호
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• pp.1249-1258
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• 1994

Titanium carbide was synthesized by reacting the prepared titanium powder and carbon black using SHS method sustains the reaction spontaneously, utilizing heat generated by the exothermic reaction itself. In this process, the effect of the particle size of titanium powder on combustion temperature and combustion wave velocity was investigated. By controlling combustion temperature and combustion wave velocity via mixing Ti and C powder with TiC, the reaction kinetics of TiC formation by SHS method was considered. Without reference to the change of combustion temperature and combustion wave velocity, TiC was easily synthesized by combustion reaction. As the particle size of titanium powder was bigger, or, as the amount of added diluent(TiC) increased, combustion temperature and combustion wave velocity were found to be decreased. The formation of TiC by combustion reaction in the Ti-C system seems to occur via two different mechanisms. At the beginning of the reaction, when the combustion temperatures were higher than 2551 K, the reaction was considered to be controlled by the rate of dissolution of carbon into a titanium melt with an apparent activation energy of 148 kJ/mol. For combustion temperatures less than 2551 K, it was considered to be controlled by the atomic diffusion rate of carbon through a TiC layer with an apparent activation energy of 355 kJ/mol. The average particle size of the synthesized titanium carbide was smaller than that of the starting material(Ti).

• Bulletin of the Korean Chemical Society
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• 제18권8호
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• pp.850-856
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• 1997

A series of tetradentate Schiff-base ligands; 1,3-bis(salicylideneimino) propane, 1,4-bis(salicylideneimino)butane, and 1,5-bis(salicylideneimino)pentane, and their Cu(Ⅱ) and Ni(Ⅱ) complexes have been synthesized. The properties of ligands and complexes have been characterized by elemental analysis, IR, NMR, UV-Vis spectra, molar conductance, and thermogravimetric anaylsis. The mole ratio of Schiff base to metal at complexes was found to be 1 : 1. All complexes were four-coordinated configuration and non-ionic compound. The electrochemical redox processes of the ligands and their complexes in DMF solution containing 0.1 M TEAP as supporting electrolyte have been investigated by cyclic voltammetry, chronoamperometry, differential pulse voltammetry at glassy carbon electrode, and by controlled potential coulometry at platinum gauze electrode. The redox process of the ligands was highly irreversible, whereas redox process of Cu(Ⅱ) and Ni(Ⅱ) complexes was observed as one electron transfer process of quasi-reversible and diffusion-controlled reaction. Also the electrochemical redox potentials of complexes were affected by chelate ring size of ligands. The diffusion coefficients of Cu(Ⅱ) and Ni(Ⅱ) complexes in DMF solution were determined to be 4.2-6.6×10-6 cm2/sec. Also the exchange rate constants were determined to be 3.6-9.7×10-2 cm/sec.