• Current Research on Agriculture and Life Sciences
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• v.30 no.1
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• pp.41-50
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• 2012

As a part of abating formaldehyde emission of urea-formaldehyde resin, this study was conducted to investigate the rmalcure kinetics of both neat and modified urea-formaldehyde resins using differential scanning calorimetry. Neat urea-formaldehyde resins with three different formaldehyde/urea mol ratios (1.4, 1.2 and 1.0) were modified by adding three different additives (sodium bisulfite, sodium hydrosulfite and acrylamide) at two different levels (1 and 3wt%). An isoconversional method at four different heating rates was employed to characterize thermal cure kinetics of these urea-formaldehyde resins to obtain activation energy ($E{\alpha}$) dependent on the degree of conversion (${\alpha}$). The $E{\alpha}$ values of neat urea-formaldehyde resins (formaldehyde/urea = 1.4 and 1.2) consistently changed as the ${\alpha}$ increased. Neat and modified urea-formaldehyde resins of these two F/U mol ratios did show a decrease of the $E{\alpha}$ at the final stage of the conversion while the $E{\alpha}$ of neat urea-formaldehyde resin (formaldehyde/urea = 1.0) increased as the ${\alpha}$ increased, indicating the presence of incomplete cure. However, the change of the $E{\alpha}$ values of all urea-formaldehyde resins was consistent to that of the Ea values. The isoconversional method indicated that thermal cure kinetics of neat and modified urea-formaldehyde resins showed a strong dependence on the resin viscosity as well as diffusion control reaction at the final stage of the conversion.

• Elastomers and Composites
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• v.39 no.4
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• pp.281-285
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• 2004

In this paper, the simple way to evaluate the value of the activation energy for the overall rate of free radical polymerization by using DSC thermograms was studied using free radical polymerization or butylacrylate as a model. Activation ehergies were determined at heating rates of 1, 2, 5, and $10^{\circ}C/min$ by applying the multiple scanning-rate methods of Kissinger, Osawa, and half-width methods as well as the single rate method of Barrett. The value of the overall activation energy measured was closely matched with the values calculated from individual data. This work also demonstrated that the use of the isoconversional method was a simple and effective way to estimate the activation energy for the overall free radical polymerization.

• Elastomers and Composites
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• v.40 no.1
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• pp.3-11
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• 2005

The ruling kinetics of epoxy resins with 3 different kinds or alkenylsuccinic anhydride (ASA) having C-8, C-12, and C-16 pendant side chain length with two different catalysts was studied by using differential scanning calorimetry (DSC). Nonisothermal and isoconversional method has been used for characterizing the effect of the pendant side chain length in the curing process. Results or nonisothermal method showed that there was no significant difference in the effect of the pendant side chain length of ASA. But isoconversional analysis showed that the value of the activation energy for the initiation reaction or C-8, C-12, and C-16 were $61.7{\sim}57.7kJ/mol$, $63.0{\sim}57.3 kJ/mol$, and $130.4{\sim}94.2 kJ/mol$, respectively, depending on the catalyst used. The values of activation energy for the initiation is different as reported value of 20 kJ/mol which indicating the difference in the effect of the pendant side chain length of ASA in the initial stage of the reaction.

• 한국연소학회:학술대회논문집
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• 2015.12a
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• pp.219-222
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• 2015

The kinetic analysis of energetic materials using Differential Scanning Calorimetry (DSC) is proposed. Friedman Isoconversional method is applied to DSC experiment data and AKTS software is used for analysis. The frequency factor and activation energy are extracted as a function of product mass fraction. The extracted kinetic scheme does not assume multiple chemical steps to describe the response of energetic materials; instead, multiple set of Arrhenius factors are used in describing a single global step. The proposed kinetic scheme has considerable advantage over the standard method based on One-Dimenaionl Time to Explosion (ODTX). Reaction rate and product mass fraction simulation are conducted to validate extracted kinetic scheme. Also a slow cook-off simulation is implemented for validating the applicability of the extracted kinetics scheme to a practical thermal experiment.

• Composites Research
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• v.33 no.5
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• pp.268-274
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• 2020

This paper analyzed the degradation behaviors of silica nano epoxy composite based on the isoconversional method. The size of the silica nano particle was about 12 nm and the particles were mixed by three different weight ratios to make the degradation test samples. The thermogravimetric analyses were performed under six different temperature increase rates to measure the weight changes. Four different methods, Friedman, Flynn-Wall-Ozawa, Kissinger and DAEM (Distributed Activation Energy Method), were employed to calculate the activation energies depending on the conversion ratios, and their calculation results were compared. The results represented that the activation energy was increased when the silica nano particles were mixed up to 10%, indicating the definite contribution of the particles to the degradation behavior enhancements. However, the enhancement was not proportional to the particle mixture ratio by demonstrating the similar activation energies between 10% and 18% samples. The calculation results by the different methods were also compared and discussed.

• Journal of the Korean Society of Propulsion Engineers
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• v.20 no.2
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• pp.46-55
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• 2016

The kinetic analysis of a heavily aluminized cyclotrimethylene-trinitramine(RDX) is conducted using differential scanning calorimetry(DSC), and the Friedman isoconversional method is applied to the DSC experimental data. The pre-exponential factor and activation energy are extracted as a function of the product mass fraction. The extracted kinetic scheme does not assume multiple chemical steps to describe the complex response of energetic materials; instead, a set of multiple Arrhenius factors is constructed based on the local progress of the exothermic reaction. The resulting reaction kinetic scheme is applied to two thermal decomposition tests for validating the reactive flow response of a heavily aluminized RDX. The results support applicability of the present model to practical thermal explosion systems.

• Journal of the Korean Society of Propulsion Engineers
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• v.19 no.1
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• pp.33-41
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• 2015

The kinetic analysis of energetic materials using Differential Scanning Calorimetry (DSC) is proposed. Friedman Isoconversional method is applied to DSC experiment data and AKTS software is used for analysis. The proposed kinetic scheme has considerable advantage over the standard method based on One-Dimenaionl Time to Explosion (ODTX). Reaction rate and product mass fraction simulation are conducted to validate extracted kinetic scheme. Also a slow cook-off simulation is implemented on $B/KNO_3$ for validating the applicability of the extracted kinetics scheme to a practical thermal experiment.

• Korean Journal of Materials Research
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• v.11 no.9
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• pp.786-791
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• 2001

$\alpha$,$\omega$-Bis(4-glycidyloxybenzylidene-4-aminophenyl)methane (BGBAM) was synthesized from the initial materials, 4-hydroxylbenzaldehyde (HBA), 4,4'-methylenedianiline (MDA) and epichlorohydrin. The DSC trace for BGBAM shows two endotherms associated with the liquid crystalline phase transition around $104.2^{\circ}C$ and the isotropic transition around $171.2^{\circ}C$, and it also has a broad exotherm in the range of $178~300^{\circ}C$ due to the anionic homopolymerization of BGBAM. DSC curve for the curing of BGBAM with hexamethylene diamine (HMD) shows an endothermic peak around $93^{\circ}C$ attributed to the melting of BGBAM. It also has three exothermic peaks around $128.4^{\circ}C$ and $180.2^{\circ}C$ associated with the epoxide-amine reaction and weak peak in the range of $200~263^{\circ}C$ related to the anionic homopolymerization between the unreacted epoxide groups. The activation energy values of cure reaction by Kissinger method are 66.5, 67.3 and 90.6 kJ/mol for $T_{pl},\; T_{p2}\; and \;T_{p3},\; respectively$. The kinetic parameters by isoconverional method are similar value to those from Kissinger method.

• Elastomers and Composites
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• v.53 no.1
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• pp.1-5
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• 2018

In the current research, the curing kinetics of a mixture system consisting of a Bisphenol-A type vinyl ester resin and styrene monomer was studied. Methylethylketone peroxide and cobalt octoate were used as the polymerization initiator and accelerator respectively. Thermograms with several different heating rates were obtained using non-isothermal differential scanning calorimetry. Activation energy values analyzed by the Flynn-Wall-Ozawa isoconversional method showed a three-step change with conversion ${\alpha}$: a slight decrease initially for ${\alpha}$ < 0.1, a constant value of 47.9 kJ/mol in the range 0.1 < ${\alpha}$ < 0.7, and a slow increase for 0.7 < ${\alpha}$. When assuming a constant activation energy of 47.9 kJ/mol, an autocatalytic model of the Sestak-Berggren equation was considered as the proper mathematical model of the conversion function, indicating an overall order of 1.2.

• Elastomers and Composites
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• v.50 no.2
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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.