• 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 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.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.

• Applied Chemistry for Engineering
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• v.10 no.4
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• pp.548-556
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• 1999

The thermal degradation of polyethylene has been studied using a nonisothermal thermogravimetric technique under a nitrogen atmosphere condition at several heating rates from 10 to $50^{\circ}C/min$. To obtain information on the kinetic parameters, the dynamic thermogravimetric analysis curve and its derivative have been analyzed by a variety of analytical methods such as Kissinger, Freeman-Carroll, Flynn-Wall, Coats-Redfern, Chatterjee-Conrad, Friedman, Horowitz-Metzger, Ozawa and Denq methods. The comparative works for the kinetic results obtained from various methods should be performed to determine the kinetic parameters, because three are tremendous differences in the calculated kinetic parameters depending upon the mathematical method taken in the analysis. From this work, it was found that the apparent activation energy of HDPE was larger than those of LDPE and LLDPE.

• Proceedings of the Korean Society For Composite Materials Conference
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• 2002.10a
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• pp.273-275
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• 2002

In this studies, curing behavior and mechanical properties of tetrafunctional epoxy resin (4EP)/ fluorine-containing epoxy resin (FEP) blend systems was investigated with 4, 4'-diaminodiphenol methane (DDM) as a curing agent. The cure activation energies $(E_a)$) were studied by Flynn-Wall-Ozawa's equation with dynamic DSC method. For the fracture toughness of the casting specimens, the critical stress intensity factor ($K_{IC}$) and the specific fracture energy ($G_{IC}$) were determined by fracture toughness test.

• 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.

• Korean Chemical Engineering Research
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• v.54 no.3
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• pp.404-409
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• 2016

Thermal Characteristics and kinetic parameters of $LaMnO_3$ synthesis reaction were investigated by means of TGA (Thermogravimetric analysis) at non-isothermal heating conditions (5.0, 10.0, 15.0 and 20.0 K/min). The reaction was occurred rapidly at 450~600K (X=0.4~0.7) depending on the heating rate. Activation energy for the synthesis of $LaMnO_3$ from the precursor, which was determined by different method such as Friedman, Ozawa-Flynn-Wall and Vyazovkin methods, was in the range of 23~243 kJ/g-mol depending on the fractional conversion level and estimation method. The reaction order decreased with increasing heating rate and fractional conversional level. The average reaction order was 4.50 in case of X=0.1~0.3, while it was 1.87 in case of X=0.7~0.9, respectively. The value of frequency factor of reaction rate increased with inceasing heating rate and fractional conversion level. The aveage value of frequency factor was 205.6 ($min^{-1}$) when X=0.1~0.3, while it was 475.2 ($min^{-1}$) when X=0.7~0.9, respectively.

• Polymer(Korea)
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• v.25 no.1
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• pp.78-89
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• 2001

Morphological changes of unsaturated polyester/polyvinylacetate semi-IPN were studied while the phase separation and the cure reaction occurred in a competing fashion. The light scattering and thermal analysis techniques were used to investigate the phase separation rates and mechanical properties resultantly induced by molecular diffusion of thermoplastic polymer during the curing process of thermosetting polymer. The reaction activation energy was calculated by using Flynn-Wall method and the semi-IPN structure exhibited various phase-separation morphological characteristics. When PVAc composition was 10 wt%, the phase separation was not observed during the curing reaction, but the phase separation occurred in a similar fashion to nucleation and growth(NG) mechanism at room temperature. On the other hand, when PVAc composition was over 11.65 wt%, the phase separation was generated in the middle of the curing process. Consequently, the phase separation seemed to influence the curing reaction rate, which was also supported by the changing activation energy with conversion and PVAc composition. Finally, the total scattered intensity was measured at various temperature, and subsequently the diffusion rates of phase separation R(${\beta}m$) were evaluated.

• Korean Chemical Engineering Research
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• v.45 no.6
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• pp.604-610
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• 2007

Characteristics of steam gasification and combustion of naphtha tar pitch, which is the bottom product of naphtha cracking process, were investigated by using the thermo gravimetric analyzer to develop the technology for obtaining syngas by using the naphtha tar pitch as a carbon source. Friedman's and Ozawa-Flynn-Wall method were used to calculate activation energy, reaction order and frequency factor of reaction rate constant for both of steam gasification and combustion. The activation energy of combustion of naphtha tar pitch based on the fractional conversion by Friedman's method was in the range of 41.58 ~ 68.14 kJ/g-mol when the fractional conversion level was in the range of 0.2~0.6, but 183.07~191.17 kJ/g-mol when the conversion level was 0.9~1.0, respectively. In case of steam gasification of naphtha tar pitch, the activation energy was in the range of 31.87~44.87 kJ/g-mol in the relatively lower conversion level (0.2~0.6), but 70.63~87.79 kJ/g-mol in the relatively higher conversion level (0.8~0.95), respectively. Those results exhibited that the steam gasification as well as combustion would occur by means of two steps such as devolitilization followed by combustion or gasification.

• Macromolecular Research
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• v.14 no.5
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• pp.491-498
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• 2006

The thermal degradation of poly(hexamethylene guanidine) phosphate (PHMG) was studied by dynamic thermogravimetric analysis (TGA) and pyrolysis-GC/MS (p-GC). Thermal degradation of PHMG occurs in three different processes, such as dephosphorylation, sublimation/vaporization of amine compounds and decomposition/ recombination of hydrocarbon residues. The kinetic parameters of each stage were calculated from the Kissinger, Friedman and Flynn-Wall-Ozawa methods. The Chang method was also used for comparison study. To investigate the degradation mechanisms of the three different stages, the Coats-Redfern and the Phadnis-Deshpande methods were employed. The probable degradation mechanism for the first stage was a nucleation and growth mechanism, $A_n$ type. However, a power law and a diffusion mechanism, $D_n$ type, were operated for the second degradation stage, whereas a nucleation and growth mechanism, $A_n$ type, were operated again for the third degradation stage of PHMG. The theoretical weight loss against temperature curves, calculated by the estimated kinetic parameters, well fit the experimental data, thereby confirming the validity of the analysis method used in this work. The life-time predicted from the kinetic equation is a valuable guide for the thermal processing of PHMG.