• Proceedings of the Korean Society For Composite Materials Conference
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• 1999.11a
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• pp.73-76
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• 1999

Near infrared spectroscopy techniques were used to study the cure reactions of epoxy resin system based on diglycidyl ether of bisphenol A(DGEBA) resins cured with 4, 4' diaminodiphenyl sulfone (DDS) hardner. Stoichiometric DGEBA/DDS resin formulation was involved in this study. The infrared absorption spectra of the prepared formulation were obtained on an FTIR spectrometer operating in the region of 11000 to 4000$cm^{-l}$. The chemical group peaks of interest in a DFEBA/DDS spectrum were identified by a comparative study with individual spectra of DGEBA and DDS monomers. Where necessary, special model compounds were used to identify unknown bands, such as the primary amine band at 4535$cm^{-l}$. The absorption bands of interest were integrated to quantify the areas and then converted to molar concentrations. This series of quantitative analyses of the major chemical groups led us to understand not only the reaction mechanism but also the cure kinetics. In this paper, the reaction mechanisms observed in stoichiometric DGEBA/DDS resin formulation and the various properties of the resin system as a function of cure temperature are described.

• Journal of the Korean Society of Safety
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• v.16 no.3
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• pp.68-75
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• 2001

Photopolymerization, the utilization of electromagnetic radiation(or light) as the energy source for polymerization of functional monomers, oligomers is the basis of important commercial processes with broad applicability, including photoimaging and RV curing of coatings and inks. The objective of this study is to investigate the characteristics of environmental fraternitive photopolymerization of methyl methacrylate(MMA). This work is the first step to continue further research about alkyl methacrylate. The experiment was done in aqueous solution under the influence of photo-initiator concentration(0.05-0.25mol/l), light intensity (5000-9000 ${\mu}J/cm^2$) and monomer concentration(2-6mol/l). Methyl methacrylate was polymerized to high conversion ratio using hydrogen peroxide($H_2O_2$) and the kinetics model we have obtained is as follows. $R_p=k_p[S]^{0.41}[M]^{0.62}[L]^{2.45} exp(53.64/RT$). The differential method of thermogravimetric analysis(Friedman method) was used to obtain value of activation energy on decomposition reaction. The average value of it res 45.4Kca1/mol.

• Journal of the Korean Chemical Society
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• v.46 no.3
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• pp.233-240
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• 2002

In this work, the cure kinetics and rheological and mechanical properties of diglycidylether of bispheonol A (DGEBA, EP)/polyurethane (PU) blends were investigated. The 1 wt% N-benzylpyrazinium hexafluoroantiminate (BPH) was used as a latent thermal catalyst. Latent properties were performed by measurement of the conversion as a function of reaction temperature using DSC. And the rheological properties of the blend systems were investigated under isothermal conditions using a rheometer. Crosslinking activating energies (Ec) were also determined from the Arrhenius equation based on gel time and curing temperature. The impact strengths were measured as mechanical properties of the casting specimens. The BPH in the blend systems could be an excellent latent thermal catalyst without any co-initiator. The rheological results showed that Ec was highest when PU content was 30 wt% which was in good agreement with the impact strengths. This was probably due to the intermolecular hydrogen bonding between the hydroxyl group in PU and EP, resulting in increasing the crosslinking density.

• 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.

• Composites Research
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• v.15 no.6
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• pp.8-15
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• 2002

In this work, the effect of biodegradable poly(butylene succinate)(PBS) in difunctional epoxy(21:P) resin was investigated in terms of rheological properties, cure kinetics, thermal stabilities, and mechanical interfacial properties. Rheological properties of the blend system were measured under isothermal condition using a rheometer. Cross-linking activation energies($\textrm{E}_c$) were determined from the Arrhenius equation based on gel time and curing temperature. The $\textrm{E}_c$ was increased in the presence of 10 wt% PBS as compared with neat 2EP. From the DSC results of the blends, the cure activation energies($\textrm{E}_a$) showed a similar behavior with $\textrm{E}_c$ due to the increased intermolecular interaction between 2EP and PBS. The decomposed activation energies($\textrm{E}_t$) for the thermal stability derived from the integral method of Horowitz-Metzger equation, were also increased in 10 wt% PBS. In addition, 20 wt% PBS showed the highest critical stress intensity factor($\textrm{E}_{IC}$). which was explained by increasing the fracture toughness of the 2EP/PBS blend systems.

• Composites Research
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• v.26 no.3
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• pp.182-188
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• 2013

The purpose of this study was to measure the volumetric polymerization shrinkage kinetics and stress of a silorane-based dental restorative composite and compare it with those of conventional methacrylate-based dental composites. Two methacrylate-based composites (Z250, Z350 flowable) and one silorane-based composite (P90) were investigated. The volumetric polymerization shrinkage of the composites during light curing was measured using a laboratory-made volume shrinkage measurement instrument based on the Archimedes' principle, and the polymerization stress was also determined with the strain gage method. The shrinkage of silorane-based composites (P90) was the lowest, and that of Z350 flowable was the highest. Peak polymerization shrinkage rate was the lowest in P90 and the highest in Z350 flowable. The time to reach peak shrinkage rate of P90 was longer than those of the methacrylate-based composites. The polymerization shrinkage stress of P90 was lower than those of the methacrylate-based composites.

• Journal of the Korean Electrochemical Society
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• v.16 no.2
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• pp.91-97
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• 2013

Solid polymer electrolyte films are prepared by ultraviolet radiation in the mixtures of an ionic liquid salt (1-ethyl-3-methylimidazolium tetrafluoroborate, $EMIBF_4$) and solvent (acetonitrile (ACN) or propylene carbonate(PC)), and an oligomer (poly(ethylene glycol)diacrylate, PEGDA, 45-60 wt.%). Electrochemical properties of activated carbon supercapacitors adopting the solid polymer electrolyte films as a separator are also examined by cyclic voltammetry and impedance measurement techniques. As a result, the supercapacitor adopting the PEGDA as much as 45 wt.% exhibits a superior capacitance of $46Fg^{-1}$ at $20mVs^{-1}$. It seems that this is due to fast kinetics of ion conduction by sufficient film flexibility, which can be allowed by comparatively weak ultraviolet curing of small anount of the PEGDA.

• Journal of the Korean Chemical Society
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• v.66 no.3
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• pp.209-217
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• 2022

We have developed photosensitive electrochromic smart windows that does not require any transparent conducting oxide (TCO) substrate. In our previous study, we demonstrated that a flexible film-type device made with a low temperature curing WO₃ sol and TiO₂ sol could show a reversible and rapid switching between colored and bleached state via incorporation of platinum catalysts on the surface of WO₃ layer. However, when these devices were exposed to sunlight over 4 hour, it was confirmed that they did not return to fully bleached state in the darkened state due to their overcoloring process. In this study, we added 4-hydroxy-(2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPOL) as an additive to the electrolyte of photosensitive electrochromic device to effectively prevent the undesired overcoloring process. The resulting device with TEMPOL indeed did not undergo excessive coloration and showed great reversibility even after being exposed to sunlight for over 4 hours. Various concentrations of TEMPOL were applied to compare changes in the visible transmittance and coloring/bleaching kinetics of devices. In terms of energetic point of view, we proposed a plausible mechanism of TEMPOL to prevent excessive coloration.

• The Journal of Korean Academy of Prosthodontics
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• v.39 no.6
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• pp.709-734
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• 2001

The aims of this experiment were to investigate the strain and temperature changes simultaneously within autopolymerzing acrylic resin specimens. A computerized data acquisition system with an electrical resistance strain gauge and a thermocouple was used over time periods up to 180 minutes. The overall strain kinetics, the effects of stress relaxation and additional heat supply during the polymerization were evaluated. Stone mold replicas with an inner butt-joint rectangular cavity ($40.0{\times}25.0mm$, 5.0mm in depth) were duplicated from a brass master mold. A strain gauge (AE-11-S50N-120-EC, CAS Inc., Korea) and a thermocouple were installed within the cavity, which had been connected to a personal computer and a precision signal conditioning amplifier (DA1600 Dynamic Strain Amplifier, CAS Inc., Korea) so that real-time recordings of both polymerization-induced strain and temperature changes were performed. After each of fresh resin mixture was poured into the mold replica, data recording was done up to 180 minutes with three-second interval. Each of two poly(methyl methacrylate) products (Duralay, Vertex) and a vinyl ethyl methacrylate product (Snap) was examined repeatedly ten times. Additionally, removal procedures were done after 15, 30 and 60 minutes from the start of mixing to evaluate the effect of stress relaxation after deflasking. Six specimens for each of nine conditions were examined. After removal from the mold, the specimen continued bench-curing up to 180 minutes. Using a waterbath (Hanau Junior Curing Unit, Model No.76-0, Teledyne Hanau, New York, U.S.A.) with its temperature control maintained at $50^{\circ}C$, heat-soaking procedures with two different durations (15 and 45 minutes) were done to evaluate the effect of additional heat supply on the strain and temperature changes within the specimen during the polymerization. Five specimens for each of six conditions were examined. Within the parameters of this study the following results were drawn: 1. The mean shrinkage strains reached $-3095{\mu}{\epsilon},\;-1796{\mu}{\epsilon}$ and $-2959{\mu}{\epsilon}$ for Duralay, Snap and Vertex, respectively. The mean maximum temperature rise reached $56.7^{\circ}C,\;41.3^{\circ}C$ and $56.1^{\circ}C$ for Duralay, Snap, and Vertex, respectively. A vinyl ethyl methacrylate product (Snap) showed significantly less polymerization shrinkage strain (p<0.01) and significantly lower maximum temperature rise (p<0.01) than the other two poly(methyl methacrylate) products (Duralay, Vertex). 2. Mean maximum shrinkage rate for each resin was calculated to $-31.8{\mu}{\epsilon}/sec,\;-15.9{\mu}{\epsilon}/sec$ and $-31.8{\mu}{\epsilon}/sec$ for Duralay, Snap and Vertex, respectively. Snap showed significantly lower maximum shrinkage rate than Duralay and Vertex (p<0.01). 3. From the second experiment, some expansion was observed immediately after removal of specimen from the mold, and the amount of expansion increased as the removal time was delayed. For each removal time, Snap showed significantly less strain changes than the other two poly(methyl methacrylate) products (p<0.05). 4. During the external heat supply for the resins, higher maximum temperature rises were found. Meanwhile, the maximum shrinkage rates were not different from those of room temperature polymerizations. 5. From the third experiment, the external heat supply for the resins during polymerization could temporarily decrease or even reverse shrinkage strains of each material. But, shrinkage re-occurred in the linear nature after completion of heat supply. 6. Linear thermal expansion coefficients obtained from the end of heat supply continuing for an additional 5 minutes, showed that Snap exhibited significantly lower values than the other two poly(methyl methacrylate) products (p<0.01). Moreover, little difference was found between the mean linear thermal expansion coefficients obtained from two different heating durations (p>0.05).

• Restorative Dentistry and Endodontics
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• v.24 no.2
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• pp.265-285
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• 1999

The purposes of this investigation were to observe the reaction kinetics of five commercial dual cured resin cements (Bistite, Dual, Scotchbond, Duolink and Duo) when cured under varying thicknesses of porcelain inlays by chemical or light activation and to evaluate the effect of the porcelain disc on the rate of polymerization of dual cured resin cement during light exposure by using thermal analysis. Thermogravimetric analysis(TGA) was used to evaluate the weight change as a function of temperature during a thermal program from $25{\sim}800^{\circ}C$ at rate of $10^{\circ}C$/min and to measure inorganic filler weight %. Differential scanning calorimetry(DSC) was used to evaluate the heat of cure(${\Delta}H$), maximum rate of heat output and peak heat flow time in dual cured resin cement systems when the polymerization reaction occured by chemical cure only or by light exposure through 0mm, 1mm, 2mm and 4mm thickness of porcelain discs. In 4mm thickness of porcelain disc, the exposure time was varied from 40s to 60s to investigate the effect of the exposure time on polymerization reaction. To investigate the effect on the setting of dual cured resin cements of absorption of polymerizing light by porcelain materials used as inlays and onlays, the change of the intensity of the light attenuated by 1mm, 2mm and 4mm thickness of porcelain discs was measured using curing radiometer. The results were as follows 1. The heat of cure of resin cements was 34~60J/gm and significant differences were observed between brands (P<0.001). Inverse relationship was present between the heat of reaction and filler weight % the heat of cure decreased with increasing filler content (R=-0.967). The heat of reaction by light cure was greater than by chemical cure in Bistite, Scotchbond and Duolink(P<0.05), but there was no statistically significant difference in Dual and Duo(P>0.05). 2. The polymerization rate of chemical cure and light cure of five commercially available dual cured resin cements was found to vary greatly with brand. Setting time based on peak heat flow time was shortest in Duo during chemical cure, and shortest in Dual during light cure. Cure speed by light exposure was 5~20 times faster than by chemical cure in dual cured resin cements. The dual cured resin cements differed markedly in the ratio of light and chemical activated catalysts. 3. The peak heat flow time increased by 1.51, 1.87, and 3.24 times as light cure was done through 1mm, 2mm and 4mm thick porcelain discs. Exposure times recommended by the manufacturers were insufficient to compensate for the attenuation of light by the 4mm thick porcelain disc. 4. A strong inverse relationship was observed between peak heat flow and peak time in chemical cure(R=0.951), and a strong positive correlations hip was observed between peak heat flow and the heat of cure in light cure(R=0.928). There was no correlationship present between filler weight % or heat of cure and peak time. 5. The thermal decomposition of resin cements occured primarily between $300^{\circ}C$ and $480^{\circ}C$ with maximum decomposition rates at $335^{\circ}C$ and $440^{\circ}C$.