• Polymer(Korea)
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• v.26 no.3
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• pp.344-352
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• 2002

In this work, two thermal cationic latent catalysts, i.e., triphenyl benzyl phosphonium hexafluoroantimonate (TBPH) and benzyl 2-methylpyrazinium hexafluoroantimonate (BMPH) were newly synthesized. And the thermal and mechanical properties of difunctional epoxy (diglycidylether of bisphenol h, DGEBA) resins initiated by 1 phr of either TBPH or BMPH catalyst were investigated. As experimental results, the epoxy/TBPH system showed higher curing temperature and critical stress intensity factor ($K_{IC}$) than those of epoxy/BMPH. This could be interpreted in terms of slow thermal diffusion rate and bulk structure of four phenyl groups in TBPH. However, the decomposed activation energy determined from Coats-Redfern method was lower in the case of epoxy/TBPH. This result was probably due to the fact that broken short chain structure was developed by steric hindrance of TBPH.

• KOREAN JOURNAL OF PACKAGING SCIENCE & TECHNOLOGY
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• v.21 no.3
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• pp.107-113
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• 2015

This work focused on the study of thermal properties and kinetic behavior of LDPE-nanoclay composite films. The effect of nanoclay content (0.5, 1, 3, and 5 wt%) on thermal stability and crystallization characteristics of the nanocomposites were investigated by Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC). The results from endothermic curve showed that the nanoclay played an important role in the crystallization of nanocomposites by acting as nucleating agent. From exothermic curve, there was a crystallization temperature shift which was attributed to crystallization process induced by nanoclay. The TGA results showed that the addition of nanoclay significantly increased the thermal stability of LDPE matrix, which was likely due to the characteristic of layered silicates/clays dispersed in LDPE matrix as well as the formation of multilayered carbonaceous-silicate char. A well-known Coats-Redfern method was used to evaluate the decomposition activation energy of nanocomposite. It was demonstrated that introducing of nanoclay to LDPE matrix escalated the activation energy of nanocomposite decomposition resulting in thermal stability improvement.

• 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.

• Polymer(Korea)
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• v.26 no.1
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• pp.80-87
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• 2002

A comparative study using electron-beam(EB) and thermal curing techniques was carried out to determine the effect of cure behavior and thermal stability of epoxy resins. In this work, benzylquinoxalinium hexafluoroantimonate(BQH) was used as a latent cationic catalyst for an epoxy resin. According to the thermogravimetric analysis(TGA), the decomposed activation energy based on Coats-Redfern method was higher in the case of thermal curing technique. This could be interpreted in terms of slow thermal diffusion rate resulted from high crosslink density of the thermally cured epoxy resin. However, the increase of hydroxyl group in the epoxy resin cured by EB technique was observed in near-infrared spectroscopy(NIRS) measurements, resulting in improving the stable short aromatic chain structure, integral procedural decomposition temperature, and finally ductile properties for high impact strengths.

• 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.

• Applied Microscopy
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• v.47 no.3
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• pp.110-120
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• 2017

Non-isothermal thermogravimetry (TG) measurements on melt-quenched $Bi_xSe_{100-x}$ specimens (x=0, 2.5, 7.5 at%) were made at a heating rate ${\beta}=10^{\circ}C/min$ in the range $T=35^{\circ}C{\sim}950^{\circ}C$. The as-measured TG curves confirm that $Bi_xSe_{100-x}$ samples were thermally stable with minor loss at $T{\leq}400^{\circ}C$ and mass loss starts to decrease up to $600^{\circ}C$, beyond which trivial mass loss was observed. These TG curves were used to estimate molar (Se/Bi)-ratios of $Bi_xSe_{100-x}$ samples, which were not in accordance with initial composition. Shaping features of conversion curves ${\alpha}(T)-T$ of $Bi_xSe_{100-x}$ samples combined with a reliable flow chart were used to reduce kinetic mechanisms that would have caused their thermal mass loss to few nth-order reaction models of the form $f[{\alpha}(T)]{\propto}[1-{\alpha}(T)]^n$ (n=1/2, 2/3, and 1). The constructed ${\alpha}(T)-T$ and $(d{\alpha}(T)/dT)-T$ curves were analyzed using Coats-Redfern (CR) and Achar-Brindley-Sharp (ABS) kinetic formulas on basis of these model functions, but the linearity of attained plots were good in a limited ${\alpha}(T)-region$. The applicability of CR and ABS methods, with model function of kinetic reaction mechanism R0 (n=0), was notable as they gave best linear fits over much broader ${\alpha}(T)-range$.

• 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.

• Polymer(Korea)
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• v.26 no.6
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• pp.767-777
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• 2002

In this work, biodegradable modified aliphatic polyester (MAP) in tetrafunctional epoxy (4EP) resin was investigated in terms of cure kinetics, thermal stabilities, rheological properties, and mechanical interfacial properties. DSC results of the blends show that the cure activation energies (E$\_$a/) were increased in 10 wt% of MAP compared with neat 4EP, due to the increasing intermolecular interaction between 4EP and MAP. The decomposed activation energies (E$\_$t/) derived from Coats-Redfern method, were increased within the 10∼30 wt% composition range of MAP contents, resulting from increasing the cross-linking density of the blend system. Rheological properties of the blend system were investigated under isothermal condition using a rheometer. Cross-linking activation energies (E$\_$c/) were determined from the Arrhenius equation based on gel time and curing temperature. As a result, the E$\_$c/ showed a similar behavior with E$\_$a/. The fracture toughness (K$\_$IC/) of the mechanical interfacial properties was discussed in semi-IPN behaviors of the casting specimen.

• Environmental Engineering Research
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• v.22 no.3
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• pp.320-328
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• 2017

This paper describes the non-isothermal pyrolysis of wood pellet and saw dust, and their blends with bituminous coal. The blends showed the distinct, two peaks in thermogravimetric curves, and the first peak came from the biomass pyrolysis and the second one came from the coal pyrolysis. The interaction in the blend was evaluated in terms of the maximum rate of weight loss, characteristic temperatures, char yields, and the calculated and experimental thermogravimetric curves. The activation energies and frequency factors for the blends were obtained with the multi-stage, Coats and Redfern method. The respective activation energies of 73 and 67 kJ/mol and the frequency factors of 725,100 and $65,262min^{-1}$ were obtained for the present wood pellet and saw dust samples. The thermogravimetric study shows that there is no significant interaction between the present biomass and coal in the blends, and the pyrolysis behavior can be described with the additive rule.

• Journal of the Korea Safety Management & Science
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• v.10 no.4
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• pp.111-120
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• 2008

The combustion reaction of polypropylene was investigated using a thermogravimetric technique under an air 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 were analyzed by a variety of analytical methods such as Kissinger, Friedman, Freeman-Carroll, Chatterjee-Conrad, Ozawa and Coats-Redfern methods. The comparative works for the kinetic results obtained from various methods should be performed to determine the kinetic parameters, because there are tremendous differences in the calculated kinetic parameters depending upon the mathematical method taken in the analysis.