• Macromolecular Research
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• v.10 no.1
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• pp.34-39
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• 2002

Cure behavior of an epoxy resin was investigated at different cure temperatures (110, 120, 130, 140, and 150 $^{\circ}C$) and cure times in the presence of 2 wt% of an N-benzylpyrazinium hexafluoroantimonate (BPH) cationic catalyst by means of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The glass transition temperature ( $T_{g}$) and chemical conversion (x) at the different temperatures were determined from DSC thermograms. The $T_{g}$ and x vs. In time data were superposed up to $T_{g}$ = 10$0^{\circ}C$ and x = 0.70 by shifting horizontally at a reference temperature of $T_{g}$ = 13$0^{\circ}C$. It is interesting that the $T_{g}$ and x of the superposed data increase rather slowly in the early stage of cure and rapidly thereafter. Therefore, the increase of the $T_{g}$ and x can be divided into two regions; $R_{I}$= -18.4(= $T_{go}$ ) ~5$^{\circ}C$ and $R_{II}$ = 5 ~ 10$0^{\circ}C$ in $T_{g}$, and $R_{I}$ : 0~0.24 and $R_{II}$ : 0.24~0.70 in x. The $R_{I}$ is closely related to the initiation reactions between BPH and epoxy and between hydroxy group and epoxy in this epoxy/catalyst system. From the kinetic analysis of the $T_{g}$-shift, activation energy was 12.5 kcal/mol. The relationship between $T_{g}$ and x was also considered. The gelation and vitrification times for different cure temperatures were obtained from DMA curves.urves. DMA curves.urves.

• Elastomers and Composites
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• v.34 no.4
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• pp.321-331
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• 1999

The curing process is the final step in tire manufacturing whereby a green tire built from layers of rubber compounds is formed to the desired shape and the compounds are converted to a strong, elastic materials to meet tire performance needs under elevated pressure and temperature in a press. A numerical optimization procedure was developed to improve product quality in a tire curing process. First, a dynamic constrained optimization problem was formulated to determine the optimal condition of the supplied cure media during a curing process. The objective function is subject to an equality constraint representing the process model that describes the heat transfer and cures kinetic phenomena in a cure press and is subject to inequality constraints representing temperature limits imposed on cure media. Then, the optimization problem was solved to determine optimal condition of the supplied cure media for a tire using the complex algorithm along with a finite element model solver.

• Journal of the Korean Wood Science and Technology
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• v.40 no.2
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• pp.110-122
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• 2012

This study investigated the effects of layered clay on the thermal curing behavior and tensile properties of resole phenol-formaldehyde (PF) resin/clay/cellulose nanocomposites. The thermal curing behavior of the nanocomposite was characterized using conventional differential scanning calorimetry (DSC) and temperature modulated (TMDSC). The addition of clay was found to accelerate resin curing, as measured by peak temperature ($T_p$) and heat of reaction (${\Delta}H$) of the nanocomposite’ curing reaction increasing clay addition decreased $T_p$ with a minimum at 3~5% clay. However, the reversing heat flow and heat capacity showed that the clay addition up to 3% delayed the vitrification process of the resole PF resin in the nanocomposite, indicating an inhibition effect of the clay on curing in the later stages of the reaction. Three different methods were employed to determineactivation energies for the curing reaction of the nanocomposite. Both the Ozawa and Kissinger methods showed the lowest activation energy (E) at 3% clay content. Using the isoconversional method, the activation energy ($E_{\alpha}$) as a function of the degree of conversion was measured and showed that as the degree of cure increased, the $E_{\alpha}$ showed a gradual decrease, and gave the lowest value at 3% nanoclay. The addition of clay improved the tensile strengths of the nanocomposites, although a slight decrease in the elongation at break was observed as the clay content increased. These results demonstrated that the addition of clay to resole PF resins accelerate the curing behavior of the nanocomposites with an optimum level of 3% clay based on the balance between the cure kinetics and tensile properties.

• Polymer(Korea)
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• v.37 no.2
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• pp.240-248
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• 2013

The curing behaviors of diglycidyl ether of bisphenol A (DGEBA) with mercaptan hardener were studied by the comparison with amine-adduct type hardener. Curing behaviors were evaluated by DSC at dynamic and isothermal conditions. In the DSC, the dynamic experiments were based on the method of Kissinger's equation, and the isothermal experiments were fitted to the Kamal's kinetic model. Activation energy of epoxy/amine-adduct type hardener was ca. 40 kcal/mol. As the functional group of mercaptan hardener, -SH increased, on epoxy/mercaptan hardeners, the activation energies decreased from 28 to 19 kcal/mol. Epoxy/amine-adduct type hardener was initiated at $90^{\circ}C$ or higher. However, epoxy/mercaptan hardeners reduced the initiation temperatures below $80^{\circ}C$ and shortened the durations of curing reaction within 10 min. We found out that the reaction kinetics of epoxy with mercaptan hardener followed the autocatalytic reaction models, and the maximum reaction rates were shown at the conversions of 20~40%.

• The Journal of Korean Academy of Prosthodontics
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• v.48 no.1
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• pp.55-60
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• 2010

Purpose: The shrinkage of dental resin cement may cause several clinical problems such as distortion that may jeopardize the accurate fit to the prepared tooth and internal stress within the restorations. It is important to know the polymerization shrinkage-strain of dental resin cement to reduce clinical complications. The purpose of this study was to investigate the polymerization shrinkage-strain kinetics of six commercially available dental resin cements. Material and methods: Three self-cure resin cements (Fujicem, Superbond, M-bond) and three dual-cure resin cements (Maxcem, Panavia-F, Variolink II) were investigated. Time dependent polymerization shrinkage-strain kinetics of the materials were measured by the Bonded-disk method as a function of time at $23^{\circ}C$, with values particularly noted at 1, 5, 10, 30, 60, 120 min after mixing. Five recordings were taken for each materials. The data were analyzed with one-way ANOVA and Scheffe post hoc test at the significance level of 0.05. Results: Polymerization shrinkage-strain values were 3.72%, 4.19%, 4.13%, 2.44%, 7.57%, 2.90% for Fujicem, Maxcem, M bond, Panavia F, Superbond, Variolink II, respectively at 120 minutes after the start of mixing. Panavia F exhibited maximum polymerization shrinkage-strain values, but Superbond showed minimum polymerization shrinkage-strain values among the investigated materials (P < .05). There was no significant differences of shrinkage-strain value between Maxcem and M bond at 120 minutes after the start of mixing (P > .05). Most shrinkage of the resin cement materials investigated occurred in the first 30 minutes after the start of mixing. Conclusion: The onset of polymerization shrinkage of self-cure resin cements was slower than that of dual-cure resin cements after mixing, but the net shrinkage strain values of self-cure resin cements was higher than that of dual-cure resin cements at 120 minutes after mixing. Most shrinkage of the dental resin cements occurred in the first 30 minutes after mixing.

• Composites Research
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• v.33 no.5
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• pp.302-308
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• 2020

We measured the thermal conductivity of composite materials manufactured by the autoclave and vacuum bag only processes and predicted the cure behavior of the external and internal of composite parts with a cure kinetics model. The temperature difference between the external and internal depends on the processes because of the change of thermal conductivity. In the autoclave process, the temperature and cure behavior of the internal were similar to those of the external because of the high thermal conductivity. However, the temperature of the internal of the vacuum bag only process was different from that of the external. The difference can influence the part quality and evacuation of air. Compression tests were performed to find the mechanical property using 0° unidirectional specimens. The composite of the vacuum bag only process was found to have a lower compressive strength than that of the autoclave process.

• Applied Chemistry for Engineering
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• v.5 no.5
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• pp.904-909
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• 1994

Cure kinetics of DGEBA(diglycidyl ether of bisphenol A)/MDA(4,4'-methylene dianiline)/GN(glutaronitrile) system with and without HQ(hydroquinone) as a catalyst was studied by Kissinger equation and Fractional life method. The activation energy of the system with HQ was somewhat lower and the pre-exponential factor of that was higher by about 30% than those of the system without HQ. As 1.25phr of HQ was added, reaction rates increased about 1.8 times.

• Applied Chemistry for Engineering
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• v.7 no.5
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• pp.963-969
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• 1996

Cure characteristics of DGEBA(diglycidyl ether of bisphenol A)/dicy(dicyandiamide) system containing diuron(3-(3,4-dichloro phenyl) -1,1-dimethylurea) as an accelerator was investigated. The system has shelf life of six months because dicy is insoluble in liquid/solid resins at room temperature. It is generally known that dicy is an adequate curing agent for one component adhesive due to its highly latent property. With increasing the amount of added dicy, reaction heat of DGEBA/dicy system increased and degree of conversion was not varied. For DGEBA/dicy/diuron system, cure temperature decreased about $40^{\circ}C$ and cure reaction became fast by the addition of diuron which activates dicy. $T_g$ of the mixed resin decreased with the amount of accelerator. which was interpreated with molecular structure forming loose chain. Cure kinetics of DGEBA/dicy and DGEBA/dicy/diuron system were explained using Kamal's autocatalytic reaction model. The effect of acceleration was confirmed with that reaction model.

• Proceedings of the Korean Society For Composite Materials Conference
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• 2001.05a
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• pp.118-121
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• 2001

The investigation of cure kinetics and morphology studies on DGEBA/PEI/Anhydride system were performed by differential scanning calorimetry and scanning electron microscopy. Autocatalystic kinetics model was applied by isothermal scan test. Ozawa method and Kissinger method was applied by temperature scan. Activation energy was 95kJ/mol for neat DGEBA/NMA, 120kJ/mol for DGEBA/PEI(10p.h.r.)/NMA. The generation of secondary phase of PEI was observed and its size was grown up by increasing contents of PEI.

• Proceedings of the Materials Research Society of Korea Conference
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• 1994.11a
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• pp.125-126
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• 1994

The chemorheological changes and kinetics during curing reaction of an silica filled epoxy system (DGEBA with curing agent Polyxoypropylenediamine) were investigated. This study concentrates on the influence of silica on the reaction kinetics and rheological behavior of the eopxy system. The concentration of the filler was varied 0~200phr. Curing behavior of the silica filled epoxy system was measured at various heating rates with DSC. Conversion was also measured by integrating the obtained DSC curve and Kinetic parameters measured by using the nonlinear regression method. DSC experiments showed that the presence of silica was found to accelerate the progress of the curing reaction and of reduce the heat of reaction compared with that of unfilled epoxy systems . Rheological experiments were conducted on a Physica by using a disposable parallel plate fixture. Material properites were measured such as the elastic modulus(G′), the loss modulus(G"), the loss tangent(tan $\delta$), and the viscosity was at the initial stahe, and the more the silica filler was added, and the lower the gel temperature was in the epoxy system. In this study it is concluded that the curing of the silica filled epoxy system was found to be accelerated, as silica was added to the epoxy compound.