• Korean Chemical Engineering Research
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• v.47 no.6
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• pp.676-682
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• 2009

Devolatilization of the Refuse Derived Fuel(RDF) which is produced at WonJu in Korea was characterized in air atmosphere with variation of heating rate(10, 20 and $30^{\circ}C/min$) in TGA. The results of TG Analysis have shown that the pyrolysis and char combustion of the RDF occurred in the range of $350{\sim}700^{\circ}C$ depending on the heating rate. Activation energy of the RDF which was determined by using Friedman and Ozawa-Flynn-Wall method was in the range of 14.44~18.40 kcal/mol. Also, reaction order(n) and pre-exponential factors(A) were 1.219 and $3.02{\times}10^5$ by using Friedman method, respectively. In order to find out the devolatilization mechanism of the RDF, twelve solid-state mechanisms defined by Coats Redfern Method were tested. The results of the Coats Redfern Method have shown that chemical reaction is the effective mechanism by comparison with the value of the activation energy which was derived from the Friedman and Flynn-Wall-Ozawa method and correlation coefficient from twelve solid-state mechanisms of Coats Redfern Method. The solid state decomposition mechanism of the RDF was found to be a decelerated $F_1$ type, random nucleation with one nucleus on the individual particle.

• Journal of the Korean Society for Aeronautical & Space Sciences
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• v.48 no.12
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• pp.945-952
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• 2020

In this study, the effects of Low Earth Orbit(LEO) environments on the degradation behavior of epoxy nano silica composite materials were investigated. The nanocomposite materials containing silica particles in different weight ratios of 10% and 18% were prepared and degraded in a LEO simulator to compare with the neat epoxy cases. Thermogravimetric analysis (TGA) was performed on the degraded nanocomposites and the activation energies were calculated by Friedman method, Flynn-Wall-Ozawa (FWO) method, Kissinger method, and DAEM (Distributed Activation Energy Method) based on the iso-conversional method. As the results, for the neat epoxy sample cases, it was found that the average activation energy was increased as the degradation was progressed. When the nano particles were mixed, however, the energy increased to the 15 environmental test cycles, and decreased afterwards, meaning that the particle mixture contributed adversely to the thermal degradation. Discussions on the results of the different calculation methods were also given.

• Journal of the Korean Institute of Gas
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• v.26 no.5
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• pp.41-48
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• 2022

2-Chloro-N-(Cyano-2-thienyl methyl) acetamide (CCTA) is an intermediate used for synthesizing pesticides. It is stable at room temperature and pressure but can be decomposed when heat is accumulated. In this study, the decomposition characteristics were evaluated by measuring the weight change according to temperature using a Thermogravimetry analyzer(TGA), and the thermal decomposition characteristics were evaluated using Differential Scanning Calorimeter(DSC). The exothermic decomposition reaction occurred rapidly at about 91 ℃, and the activation energy determined by using Kissinger method, Kissinger-Akahira-Sunose(KAS) method, and Flynn-Wall-Ozawa(FWO) method were 162 kJ/mol, 149 kJ/mol and 139 kJ/mol, respectively. T_D24, the temperature at which the maximum heating rate is reached within 24 hours, was evaluated as 52~55 ℃ using the estimated activation energy.

• Korean Chemical Engineering Research
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• v.50 no.3
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• pp.391-397
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• 2012

The depletion of conventional oil reserves and the increasing energy need in developing countries such as China and India result in exceeding oil demand over supply. As a solution of the problem, the efficient utilization of heavy oil has been receiving more and more interest. In order to utilize heavy oil, upgrading processes are required. Among the upgrading processes, thermal decomposition is thought to be relatively simple and economical. In this study, to understand basic characteristics of thermal decomposition of heavy oil, we conducted pyrolysis experiments of deasphalted oil (DAO) produced by a solvent deasphalting process. DAO is a mixture of many components and consists mainly of materials of carbon number 20~40. For the comparison with results of DAO pyrolysis, additional pyrolysis experiments with single materials of carbon number 30 ($C_{30}H_{62}$, $C_{30}H_{58}O_4S$, $C_{30}H_{63}O_3P$) were conducted. Pyrolysis experiments were carried out non-isothermally with variation of heating rate (10, 50, $100^{\circ}C$/min) in a thermogravimetric analyzer. Average pyrolysis activation energy determined by using Arrhenius method, Ingraham and Marrier method, and Coats and Redfern method was 72~99 kJ/mol. In the activation energy calculated by Ozawa-Flynn-Wall method, DAO had wider variation than other single materials.

• 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.

• Elastomers and Composites
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• v.22 no.4
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• pp.324-332
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• 1987

The thermal degradation of the homopolymer poly(methyl methacrylate) (PMMA) and flame-retardant tetrabrormobisphenol-A(TBBA) as well as of their blends were carried out using the thermogravimetric method in the stream of nitrogen gas with 60ml/min at various heating rate from 1 to $20^{\circ}C/min$. Friedman and Ozawa mathematical methods were used to obtain the value of activation energy.

• Elastomers and Composites
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• v.49 no.2
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• pp.144-148
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• 2014

Compression set (CS) and weight loss by thermal degradation of the ACM rubber composite sample prepared for an automotive part were measured simultaneously at several given temperatures of $150^{\circ}C$, $160^{\circ}C$, $170^{\circ}C$, and $180^{\circ}C$. Using the relationship between them, thermal life of the sample could be predicted at a given operating temperature by applying Toops method which is based on the analysis of non-isothermal TGA thermograms. Conversion by weight loss showed a linear relationship with CS changes, exhibiting 4.2% at CS 40%. Activation energy of thermal degradation was calculated as 120.2 kJ/mol at 4.2% of weight loss from Flynn-Wall-Ozawa analysis. When the expected life was set as time to reach CS 40% at $120^{\circ}C$, the life time of the sample was calculated as 9,700 hrs when Toops method was applied.

• Journal of Adhesion and Interface
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• v.10 no.4
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• pp.191-198
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• 2009

UV-curable aliphatic epoxy acrylates were prepared by the reaction of glycerol diglycidyl ether (GDE) with 2-carboxyethyl acrylate (2-CEA) or 2-hydroxyethyl acrylate (2-HEA). The structures of the epoxy acrylates were characterized by FT-IR, $^1H$-NMR, and $^{13}C$-NMR and the yield was obtained by prep-LC. The UV- and the thermal-curing behaviors of the product were investigated using photo-DSC and DSC, respectively. The reactivity of 2-CEA was higher than 2-HEA and the yield of the product (GEA-C) which was prepared using 2-CEA was about 83%. The maximum UV-curing time ($T_{max}$) of the GEA-C contained non-reactive components and by-product was about 10 seconds. The GEA-C showed low color difference (${\Delta}E^*$), low viscosity, and good thermal stability - its value was 2.51, 192 cps, and $299^{\circ}C$ (at 5% weight loss), respectively. The activation energies ($E_a$) of thermal-curing reaction calculated from Kissinger and Ozawa-Flynn-Wall method were 91~92 kJ/mol.

• Elastomers and Composites
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• v.35 no.4
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• pp.272-280
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• 2000

The experimental kinetics was analyzed for commercial rubbers such as NR, IR, BR, SBR 1500, and SBR 1700. Kinetic analysis for the commercial rubbers was performed using a thermogravimetric method, which the activation energies of NR obtained by Kissinger, Friedman, ana Ozawa's method were 195.0, 198.3, and 186.3 kJ/mol, respectively. whereas that of SBR 1500 were 246.4, 247.5, and 254.8 kJ/mol, respectively. It was shown that the yield of pyrolytic oil was generally increased with increasing the final temperature. Considering the effect of heating rate. it was found that the yield of pyrolytic oil was not consistent for each sample. The number average molecular weight of pyrolitic oil of SBR 1500 was in the range of 740-2486. The calorific value of SBR 1500 was 39-40 kJ/g, and it might be a considerable energy potential although it was lower than the conventional fuel such as kerosene, diesel, light fuel, and heavy fuel.

• Journal of the Korean Institute of Telematics and Electronics
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• v.26 no.9
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• pp.1436-1443
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• 1989

In this paper, we propose a maximum-likelihood estimation(MLE) method to obtain the location and the amplitude of the pulses in MPE( multi-pulse excitation)-LPC speech synthesis using multi-pulses as excitation source. This MLE method computes the value maximizing the likelihood function with respect to unknown parameters(amplitude and position of the pulses) for the observed data sequence. Thus in the case of overlapped pulses, the method is equivalent to Ozawa's crosscorrelation method, resulting in equal amount of computation and sound quality with the cross-correlation method. We show by computer simulation: the multi-pulses obtained by MLE method are(1) pseudo-periodic in pitch in the case of voicde sound, (2) the pulses are random for unvoiced sound, (3) the pulses change from random to periodic in the interval where the original speech signal changes from unvoiced to voiced. Short time power specta of original speech and syunthesized speech obtained by using multi-pulses as excitation source are quite similar to each other at the formants.