• 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.

• 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.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.9 no.5
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• pp.1125-1129
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• 2008

Polypropylene (PP)/corn starch master batch(starch-MB) blends with different PP compositions of 90, 80, 70, and 60 wt% were prepared by melt compounding at $200^{\circ}C$, using lab scale Brabender mixer. The chemical structures, thermal properties and non-isothermal crystallization behavior of the PP/starch-MB blends were investigated by FT-infrared spectrometry (FT-IR), differential scanning calorimetry (DSC), and thermogravimetric analyzer (TGA). The fabrication of the PP/starch-MB blend was confirmed by the existence of hydroxy group in FT-IR spectrum. There was no district change in melting temperature and melting enthalpy, and TGA curve indicates a decrease in degradation temperature with starch-MB content. The non-isothermal crystallization process was analyzed using by Avrami equation. The Avrami exponents were in the range of 2.71-3.97 for PP and 1.48-1.99 for PP/starch-MB blonds. The activation energies calculated by Kissinger method were 233 kJ/mol for PP, 484 kJ/mol for PP90, 541 kJ/mol for PP80, 553 kJ/mol for PP70, and 422 kJ/mol for PP60.

• Korea-Australia Rheology Journal
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• v.12 no.2
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• pp.101-105
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• 2000

The crystallization behavior of homo polypropylene (PP) and PP in the PP-poly($\varepsilon$-caprolactone) (PCL) blends during isothermal crystallization has been investigated using differential scanning calorimeter (DSC) and advanced rheometric expansion system (ARES). From the storage modulus data of the homo PP and PP-PCL blends during isothermal crystallization, the volume fraction of crystallized material ($X_t$) of the homo PP and PP in the PP-PCL blends was calculated using the various rheological models. The results of $X_t$ of the homo PP and PP in the PP-PCL blends from ARES measurement were compared with the results from DSC. The $X_t$ of the homo PP was found to be higher in the ARES measurement than in the DSC. The crystallization rate of the homo PP was found to be faster in the rheological measurements than in the thermal analysis. The $X_t$ of PP in the PP-PCL blends with various compositions was obtained from the thermal analysis and rheological measurements. The $X_t$ of PP in the PP-PCL blends obtained from the thermal analysis and rheological measurements are not consistent. This discrepancy of $X_t$ may be due to the morphological changes resulted from the different crystallization kinetics of PP in the PP-PCL blends.

• 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.

• Polymer(Korea)
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• v.31 no.5
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• pp.385-392
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• 2007

Poly (N-vinylpyrrolidone) (PVP) groups were grafted onto a poly(3-hydroxybutyrate-co-3-hydroryvalerate) (PHBV) backbone in order to modify its properties and synthesize a novel biocompatible copolymer. The crystallization behavior of PHBV and grafted PHBV was investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). During the cooling-induced crystallization process, the crystallization temperature and the crystallization rate of the grafted PHBV decreased with increasing PVP weight fraction. On the heating scans of all grafted PHBV samples, a new crystallization exothermic peak appeared at almost the same temperature, suggesting the operation of a recrystallization process, while the melting temperature ($T_m$) and the apparent enthalpy of fusion (${\Delta}H_f$) were not affected by graft modification. During the isothermal crystallization process at the same temperature, the presence of side PVP groups decreased the spherulitic growth rate and the spherulitic band spacing with increasing PVP weight fraction in samples.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.20 no.1
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• pp.58-63
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• 2010

The glass-ceramics made from the mixture of coal bottom ash, produced from a thermal power plant mixed with $Na_2O$ and $Li_2O$ was fabricated and their crystallization behavior was studied using a non-isothermal analyzing method. The temperature for 50% crystallization was higher than the exothermic peak temperature $T_p$ at DTA curve and the quickest crystallization temperature was much the same as $T_p$ as identified from the relationships of crystallized fraction and crystallization rate with temperature. By using Kissinger equation describing a crystallization behavior, the activation energy (262 kJ/mol), the Avrami constant (1.7) and the frequency ($5.7{\times}10^{16}/s$) for crystallization were calculated from which the nepheline crystal could be expected as showing an 1~2-dimensional surface crystallization behavior mainly with some bulk crystallization tendency at the same time. The actual observation of microstructure using SEM showed the considerable amount of surface crystals of dendrite and the bulk crystals with low fraction, so the prediction by the Kissinger equation was in accord with the crystallization behavior of glass-ceramics fabricated in this study.

• Macromolecular Research
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• v.8 no.3
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• pp.103-115
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• 2000

The structural changes viewed from the molecular level have been investigated for the isothermal crystallization phenomena of polyethylene (PE) and the solvent-induced crystallization phenomenon of syndiotactic polystyrene (sPS) glassy sample. The data, which were collected by the time-resolved measurements of Fourier-transform infrared spectra, Raman spectra, synchrotron-sourced small-angle X-ray scattering, wide-angle X-ray scattering, and so on, were combined together to extract the detailed structural information in these phase transition phenomena. In the case of PE, the isothermal crystallization from the melt to the orthorhombic form was found to occur via the conformationally-disordered trans chain form, followed by the formation of the lamellar stacking structure of regular orthorhombic-type crystals. In the case of sPS, the amorphous chains in the glassy sample were found to enhance the mobility through the interaction with the injected solvent molecules, which act as a trigger to cause the conformational ordering from the random coil to the regular T$_2$G$_2$-type helical form. The thus created short helical segments were found to grow into longer helices, which gathered together to form the crystallites, as revealed by the organized coupling of the infrared, Raman and X-ray scattering data.

• Korean Journal of Metals and Materials
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• v.46 no.6
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• pp.338-344
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• 2008

The crystallization kinetics of the $Cu_{43}Zr_{43}Al_7Be_7$ bulk metallic glass were studied by differential scanning calorimetry(DSC) in the continuous heating and isothermal annealing modes. Only one major peak could be detected on the DSC traces of $Cu_{43}Zr_{43}Al_7Be_7$ bulk amorphous alloy, and the activation energy for crystallization corresponding to the peak determined by the Kissinger method was resulted of 239 kJ/mol. The isothermal kinetic, analyzed by the Johnson-Mehl-Avrami equation yielded values for the Avrami exponents in the range 1.69 to 2.37, which implied a crystallization governed by a three-dimensioned growth. Primary phases were essentially the cubic structure CuZr together with the $Cu_{10}Zr_7$ phase. At higher temperature, the CuZr disappeared while the $Cu_{10}Zr_7$ became predominant. After long term annealing at 731 K, the phases were $Cu_{10}Zr_7$, $Cu_2ZrAl$ and $Al_3Zr_5$.