• The Korean Journal of Rheology
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• v.10 no.4
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• pp.227-233
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• 1998

The effects of 1 mol% N-benzylpyrazinium hexafluoroantimonate(BPH) as a thermal latent initiator and blend compositions composed of cycloaliphatic and DGEBA epoxies were investigated in the rheological properties and cure kinetics. Latent properties were performed by measurement of the conversion as a function of reaction time using isothermal DSC at $150^{\circ}C$ and $50^{\circ}C$ Rheological properties of the blend systems were investigated in terms of isothermal experiments using a rheometer. The gelation time was obtained from the evaluation of storage modulus (G'), loss modulus (G") and damping factor (tan$\delta$)). Cross-linking activation energy ($E_c$) was also determined from the Arrhenius equation based on gel time and curing temperature. As a result, the gel time and cross-linking activation energy increased with increasing DGEBA composition. The cure activation energies ($E_a$) were obtained by Kissinger method using dynamic DSC thermograms. In this work, the cure activation energy decreased with increasing CAE concentration, which might be resulted from the short repeat units, simple side-groups and viscosity of reaction media.edia.

• Polymer(Korea)
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• v.27 no.3
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• pp.176-182
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• 2003

The fluorine-containing epoxy resin, 2-trifluorotoluene diglycidylether (FER) was prepared by reaction of 2-chloro-${\alpha}$,${\alpha}$,${\alpha}$-trifluorotoluene with glycerol diglycidylether in the presence of pyridine catalyst. Curing behavior of FER/DDM system was investigated using dynamic and isothermal DSC. Cure activation energy (Ea) was determined by Flynn-Wall-Ozawa's equation. The rheological properties of FER/DDM system were studied under isothermal condition using a rheometer. Cross-linking activation energy (Ec) was determined from the Arrhenius equation based on gel time and curing temperature. As a result, the chemical structure of FER was confirmed by FT-IR, $\^$13/C NMR, and $\^$19/F NMR spectroscopy. The cure activation energy of FER/DDM system was 55.4 kJ/mol and conversion and conversion rate were increased with the curing temperature. The cross-linking activation energy of FER/DDM system was 41.6 kJ/mol and gel time was decreased with the curing temperature.

• Applied Chemistry for Engineering
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• v.10 no.3
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• pp.419-426
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• 1999

In this study, the reaction rate constant, activation energy, total crosslinking density, elastic constant, cure properties ($t_5,\;t_{90}$), modulus, and abrasion resistance of rubber compounds were investigated as a function of cure temperatures, cure systems and reinforcing filler loadings. Reaction rate constants showed strong dependence on thc carbon black loading, cure temperature and cure system, and increased sharply with increasing the reaction temperatures. The lowest activation energy was obtained in the efficient cure (EC) system which corresponds to the high level of sulfur to accelerator ratio, and the activation energy was decreased with decreasing the carbon black loadings. The change of carbon black loadings directly affects the modulus and abrasion resistance, but the change of cure system showed various effects on the rubber compounds. Increased carbon black loadings showed the high modulus, improved abrasion resistance and short scorch time but decrease in crosslinking density and elastic constant. Higher crosslinking density and elastic constant were shown in the EC cure system regardless of carbon black loadings, but scorch timc ($t_5$) was not affected by the change of the ratio of sulfur to accelerator. Rapid optimum cure time ($t_{90}$) were showen in the EC cure system. Also, the equivalent cure curve coefficient of rubber compound was 0.96 for conventional cure (CC) system, and 0.94 for semi-efficient cure (SEC) and EC system regardless carbon black loadings. As regarding the abrasion resistance, wear volume showed the logarithmic increase for the loaded weight.

• Polymer(Korea)
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• v.26 no.5
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• pp.599-606
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• 2002

In this study, 4,4'-tetraglycidyl diaminodiphenyl methane (TGDDM)/polyamideimide (PAI) blends were cured using diaminodiphenyl sulfone (DDS). And the effect of addition of different PAI contents to neat TGDDM was investigated in the thermal, mechanical, and morphological properties of the blends. The cure behavior and thermal stability of the cured specimens were monitored by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. Also, the critical stress intensity factor (K$\_$IC/) was measured in UTM, and the phase separation behavior and final morphology of TGDDM/PAI blends were examined in scanning electron microscopy(SEM). As a result, the cure temperature and cure activation energy (E$\_$a/) were decreased with increasing the PAI content. The decreasing of cure temperature and cure activation energy were probably due to the presence of secondary amine group of PAI backbone used as co-initiator. But, the decomposition activation energy (E$\_$t/) and K$\_$IC/ value were increased up to 5. 10 phr of PAI content, respectively and they were decreased above the PAI contents. These results were explained on the basis of chain scission reaction by etherification. And morphology of blends observed from SEM was confirmed in co-continuous structures.

• 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.

• Macromolecular Research
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• v.17 no.2
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• pp.121-127
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• 2009

The cure kinetics of the epoxy-layered, silicate nanocomposites were studied by differential scanning calorimetry under isothermal and dynamic conditions. The materials used in this study were o-cresol novolac epoxy resin and phenol novolac hardener, with organically modified layered silicates. Various kinetic parameters, including the reaction order, activation energy, and kinetic rate constants, were investigated, and the storage stability of the epoxy-layered silicate nanocomposites was measured. To synthesize the epoxy-layered silicate nanocomposites, the phenolic hardener underwent pre-intercalation by layered silicate. From the cure kinetics analyses, the organically modified layered silicate decreased the activation energy during cure reaction in the epoxy/phenolic hardener system. In addition, the storage stability of the nanocomposite with the pre-intercalated phenolic hardener was significantly increased compared to that of the nanocomposite with direct mixing of epoxy, phenolic hardener, and layered silicate. This was due to the protective effect of the reaction between onium ions and epoxide groups.

• Transactions on Electrical and Electronic Materials
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• v.13 no.4
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• pp.204-207
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• 2012

Epoxy nanocomposite was synthesized through the exfoliation of organoclay in an epoxy matrix, which was composed of diglycidyl ether of bisphenol A (DGEBA), 4,4'-methylene dianiline (MDA) and malononitrile (MN). Organoclay was prepared by treating the montmorillonite with octadecyl trimethyl ammonium bromide (ODTMA). The exfoliation of the organoclay was estimated by wide angle X-ray diffraction (WAXD) analysis. In order to measure the cure rate of DGEBA/MDA (30 phr)/MN (5 phr)/organoclay (3 phr), differential scanning calorimetry (DSC) analysis was performed at various heating rates, and the data were interpreted by Kissinger equation. Thermal degradation kinetics of the epoxy nanocomposite were studied by thermogravimetric analysis (TGA), and the data were introduced to the Ozawa equation. The activation energy for cure reaction was 45.8 kJ/mol, and the activation energy for thermal degradation was 143 kJ/mol.

• Elastomers and Composites
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• v.46 no.2
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• pp.144-151
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• 2011

Intermittent CSR testing was used to investigate the degradation of a hydrogenated NBR(HNBR) O-rings, and also the prediction of its life-time. The cure system of HNBR O-ring was controlled as sulfur cure and peroxide cure system. An intermittent CSR jig was designed taking into consideration the O-ring's environment under use. The testing allowed observation of the effects of friction, heat loss, and stress relaxation by the Mullins effect. Degradation of O-rings by thermal aging was observed between 100 and $120^{\circ}C$. In the temperature range of $100-120^{\circ}C$, O-rings showed linear degradation behavior and satisfied the Arrhenius relationship. The activation energy of HNBR-S was about 70.6 kJ/mol. From Arrhenius plots, predicted life-times of HNBR-S O-ring were 31.1 years and 33.7 years for 50% and 40% failure conditions, respectively. In case of HNBR-P, the activation energy was about 72.1kJ/mol, and predicted life-times were 34.0 years and 36.5 years for 50% and 40% failure conditions, respectively. The peroxide cure system showed slower degradation rate and higher activation energy than the sulfur cure system.

• Elastomers and Composites
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• v.35 no.2
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• pp.122-131
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• 2000

In this work, the effect of chemical surface treatments on morphology of carbon blacks was investigated in terms of cure behavior and tearing energy ($G_T$) of carbon blacks/rubber composites. As experimental results, the polar or nonpolar chemical treatment led to a significant physical change of carbon black morphology. The cure activation energies (Ea) and frequency factor (A) obtained from Kissinger equation decreased with improving the dispersion of carbon flacks, resulting in high reactivity. However, a significant advantage of carbon black/rubber composites is gained by carbon blacks treated in basic (BCB) or nonpolar (NCB) chemical solution, resulting in increasing the tearing energy. These results could be explained by changes of dispersion, agglomerate, surface functional group, void volume, and cross-linking density of carbon black/rubber composites.

• Applied Chemistry for Engineering
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• v.7 no.2
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• pp.356-361
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• 1996

Cure kinetics of diglycidyl ether of bisphenol A(DGEBA)/4,4'-methylene dianiline(MDA) with hydroquinone-phenyl glycidyl ether(HQ-PGE) as a reactive additive, which was preliminarily synthesized, was investigated by DSC and FT-IR analyses. Kissinger equation and Arrhenius' equation were used to calculate activation energy and pre-exponential factor. When HQ-PGE was added to DGEBA/MDA system, it reduced activation energy of system. When the 5 phr of HQ-PGE was added to DGEBA/MDA system, activation energy was 7.8 kcal/mol by FT-IR analysis and 11.3 kcal/mol by DSC, in comparison with the system without HQ-PGE, activation energy decreased about 30% and 9%, respectively. According to these results, HQ-PGE, introducing agent of this system, acted as a catalyst.