• Elastomers and Composites
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• v.51 no.1
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• pp.56-62
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• 2016

The isothermal crystallization behaviors of blends of poly(ethylene naphthalate) (PEN) and a thermotropic liquid crystalline polymer (TLCP) were investigated by differential scanning calorimetry (DSC) as functions of crystallization temperature and blend composition. Avrami analyses were applied to obtain information on the crystal growth geometry and the factors controlling the rate of crystallization. The crystallization kinetics of the PEN/TLCP blends followed the Avrami equation up to a high degree of crystallization, regardless of crystallization temperature. The calculated Avrami exponents for PEN/TLCP revealed three-dimensional growth of the crystalline region in each blend. The crystallization rate of each blend increased as the crystallization temperature decreased, and decreased as the TLCP content increased. The crystallization of PEN in the blend was affected by the addition of TLCP, which acts as a nucleating agent.

• Macromolecular Research
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• v.11 no.1
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• pp.25-35
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• 2003

A series of random poly(ethylene-co-1,4-butylene terephthalate)s (PEBTs), as well as poly(ethylene terephthalate) (PET) and poly(1,4-butylene terephthalate) (PBT), were synthesized by the bulk polycondensation. Their composition, molecular weight, and thermal properties were determined. All the copolymers are crystallizable, regardless of the compositions, which may originate from both even-atomic-numbered ethylene terephthalate and butylenes terephthalate units that undergo inherently crystallization. Non-isothermal crystallization exotherms were measured over the cooling rate of 2.5-20.0 K/min by calorimetry and then analyzed reasonably by the modified Avrami method rather than the Ozawa method. The results suggest that the primary crystallizations in the copolymers and the homopolymers follow a heterogeneous nucleation and spherulitic growth mechanism. However, when the cooling rate increases and the content of comonomer unit (ethylene glycol or 1,4-butylene glycol) increases, the crystallization behavior still becomes deviated slightly from the prediction of the modified Avrami analysis, which is due to the involvement of secondary crystallization and the formation of relatively low crystallinity. Overall, the crystallization rate is accelerated by increasing cooling rate but still depended on the composition. In addition, the activation energy in the non-isothermal crystallization was estimated.

• Polymer(Korea)
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• v.36 no.6
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• pp.803-809
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• 2012

The non-isothermal crystallization behavior of ethylene-tetrafluoroethylene (ETFE) copolymer was investigated by DSC and imaging FTIR analysis. Modified non-isothermal Avrami analysis was applied to interpret the crystallization behavior of ETFE. It was found that the less linearity in ln[-ln(1-X(t))] vs. ln(t) plot was obtained in thermal analysis comparison with imaging FTIR due to relatively small crystallization enthalpy change in ETFE. It means that imaging FTIR measured by overall IR absorption intensity change due to the crystallization was found to be effective to understand the non-isothermal crystallization kinetics of ETFE. In addition, the optical transmittance of ETFE was studied. The crystallite developed by slow cooling caused the light scattering and resulted in the increase of haze and the lowering of transmittance up to 8%. From our results, it was confirmed that cooling rate is an important processing parameter for maintaining optical transmittance of ETFE as a replacement material for glass.

• Korean Journal of Materials Research
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• v.26 no.1
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• pp.54-60
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• 2016

We have investigated the crystallization mechanism of the lithium disilicate ($Li_2O-2SiO_2$, LSO) glass particles with different sizes by isothermal and non-isothermal processes. The LSO glass was fabricated by rapid quenching of melt. X-ray diffraction and differential scanning calorimetry measurements were performed. Different crystallization models of Johnson-Mehl-Avrami, modified Ozawa and Arrhenius were adopted to analyze the thermal measurements. The activation energy E and the Avrami exponent n, which describe a crystallization mechanism, were obtained for three different glass particle sizes. Values of E and n for the glass particle with size under $45{\mu}m$, $75{\sim}106{\mu}m$, and $125{\sim}150{\mu}m$, were 2.28 eV, 2.21 eV, 2.19 eV, and ~1.5 for the isothermal process, respectively. Those values for the non-isothermal process were 2.4 eV, 2.3 eV, 2.2 eV, and ~1.3, for the isothermal process, respectively. The obtained values of the crystallization parameters indicate that the crystallization occurs through the decreasing nucleation rate with a diffusion controlled growth, irrespective to the particle sizes. It is also concluded that the smaller glass particles require the higher heat absorption to be crystallized.

• Korea-Australia Rheology Journal
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• v.17 no.1
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• pp.21-25
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• 2005

Rheological properties and crystallization kinetics of the polypropylene (PP) block copolymer and recycled PP block copolymer were studied by advanced rheometric expansion system (ARES), differential scanning calorimetry (DSC), and optical microscopy. In the study of the dynamic rheology, it is observed that the storage modulus and loss modulus for the PP block copolymer and recycled PP block copolymer did not change with frequency. In the study of the effect of the repeated extrusion on the crystallization rate, half crystallization time of the PP samples was increased with the number of repeated extrusion in isothermal crystallization temperature ($T_c$). From the isothermal crystallization kinetics study, the crystallization rate was decreased with the increase of the number of repeated extrusion. Also, from the result of Avrami plot, the overall crystallization rate constant (K) was decreased with the increase of the number of the repeated extrusion. From the study of the optical microscopy, the size of the spherulite of the PP samples did not change significantly with the number of repeated extrusion. However, it was clearly observed that the number of the spherulite growth sites was decreased with the number of repeated extrusion. From the results of the crystallization rate, isothermal crystallization kinetics, Avrami plots, and optical microscopy, it is suggested that the crystallization rate of the PP block copolymer is decreased with the increase of the number of repeated extrusion.

• Journal of the Korean Ceramic Society
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• v.53 no.1
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• pp.24-33
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• 2016

The grafting reaction for maleic anhydride (MA) onto high density polyethylene (HDPE) was investigated from solution process with initiators. The chemical modification of neat HDPE was carried out with various contents of MA (3-21 wt.%) and initiator (0.2-1 wt.%) at different temperature ($80-130^{\circ}C$). The grafting degree was obtained from the titration and the highest grafting degree was 3.1%. The grafting degree increased as the content of MA and initiator increased, however, the highest grafting degree was demonstrated for a particular content of MA and initiator. In the non-isothermal crystallization kinetics, the Ozawa model was unsuitable method to investigate the crystallization behavior of MA onto HDPE, whereas the Avrami and Liu models found effective. The crystallization rate was accelerated as the cooling rate increased, but postponed by combination of MA onto neat HDPE backbone.

• Macromolecular Research
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• v.12 no.1
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• pp.1-10
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• 2004

The structural changes occurring in the isothermal crystallization processes of polyethylene (PE), poly-oxymethylene (POM), and vinylidene fluoridetrifluoroethylene (VDFTrFE) copolymer have been reviewed on the basis of our recent experimental data collected by the time-resolved measurements of synchrotron-sourced wide-angle (WAXS) and small-angle X-ray scatterings (SAXS) and infrared spectra. The temperature jump from the melt to a crystallization temperature could be measured at a cooling rate of 600-1,000 $^{\circ}C$/min, during which we collected the WAXS, SAXS, and infrared spectral data successfully at time intervals of ca. 10 sec. In the case of PE, the infrared spectral data clarified the generation of chain segments of partially disordered trans conformations immediately after the jump. These segments then became transformed into more-regular all-trans-zigzag forms, followed by the formation of an orthorhombic crystal lattice. At this stage, the generation of a stacked lamella structure having an 800-${\AA}$-long period was detected in the SAXS data. This structure was found to transfer successively to a more densely packed lamella structure having a 400-${\AA}$-long period as a result of the secondary crystallization of the amorphous region in-between the original lamellae. As for POM, the formation process of a stacked lamella structure was essentially the same as that mentioned above for PE, as evidenced from the analysis of SAXS and WAXS data. The observation of morphology-sensitive infrared bands revealed the evolution of fully extended helical chains after the generation of lamella having folded chain structures. We speculate that these extended chains exist as taut tie chains passing continuously through the neighboring lamellae. In the isothermal crystallization of VDFTrFE copolymer from the melt, a paraelectric high-temperature phase was detected at first and then it transferred into the ferroelectric low-temperature phase at a later stage. By analyzing the reflection profile of the WAXS data, the structural ordering in the high-temperature phase and the ferroelectric phase transition to the low-temperature phase of the multi-domain structure were traced successfully.

• Proceedings of the Korean Fiber Society Conference
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• 1995.10a
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• pp.75-75
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• 1995

• Polymer(Korea)
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• v.39 no.2
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• pp.268-274
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• 2015

In this paper, the isothermal crystallization kinetics of a functional PP (FPP) with different grafting yields (GY)-methacryloxyethyltrimethyl ammonium chloride (DMC) grafted PP were investigated by differential scanning calorimetry (DSC). The results showed that the crystallization rate of FPP (GY=4.83%) was the highest for all of the studied samples. Furthermore, for the FPP with different GY, the value of $t_{1/2}$ became longer with increasing the grafting yield (GY). The possible explanation was that the quaternary ammonium groups introduced affected the crystallization process of the FPP in two opposite directions, i.e. promoting the nucleation and hindering the transport of the chain molecules towards the growing nuclei. Polarized optical micrographs showed that the DMC chains acted as nucleating agents, which accelerated the nucleation. In addition, the results showed the FPP had lower nucleation free energy than the PP. This study would be useful for designing the processing parameters of the grafted samples.

• Elastomers and Composites
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• v.49 no.1
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• pp.13-23
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• 2014

In this work, glycolide, L-lactide and ${\varepsilon}$-caprolactone monomers were polymerized into the triblock copolymers by two step polymerization method and their non-isothermal crystallization behaviors were studied by combination of modified Avrami and Ozawa formula for further analysis of their behaviors. The result showed that PGCLA21 gave the highest value for supercooling analysis and super cooling degree increased with L-lactide content. Crystallization velocity constant, however, showed no significant change. The result of cooling function in specific relative crystallization degree showed that the increase of L-lactide content made an effect on the more enhancement of crystallization velocity of the PGCLA than PGCL. The result of big logF(T) value with the L-lactide content above critical point for PGCLA41 and PGCLA21 showed that bigger cooling velocity needed to gain same crystal size compared with PGCL. This means that it gives negative effect in the increase of crystallization velocity.