Isothermal and Non-Isothermal Crystallization Kinetics of PVDF and PVDF/PMMA Blends

Background: poly(vinylidene fluoride) PVDF and PVDF/PMMA blends have been investigated with a focus on the crystal structure, immiscibility and mechanical properties. However, few reports were found on the crystallization behaviors of PVDF and PVDF/PMMA blends, especially on crystallization kinetics. The article is to report the research on isothermal and nonisothermal crystallization kinetics for PVDF and PVDF/PMMA blends using differential scanning calorimetry (DSC). Results: Besides crystallization temperature and isothermal crystallization activation energy, the Avrami equation exponent of PVDF in blends decreased compared with pure PVDF. The nonisothermal crystallization kinetics of PVDF and PVDF/PMMA (70:30) blends were investigated by Ozawa equation, Jeziorny method and crystallization rate constant (CRC) in detail. The nonisothermal crystallization energy of pure PVDF and its blends were determined by the Kissinger and Vyazovkin’s method. Conclusion: The nucleation and growth mechanism of PVDF in blends changed compared with pure PVDF. The Ozawa equation is not applicable in nonisothermal crystallization kinetics of PVDF and PVDF/PMMA blends. The decreasing of crystallization ability of PVDF in blends were found and confirmed by CRC and the decline of crystallization rate constant in Jeziorny method. Such is opposite to the results of Kissinger’s and Vyazovkin’s method, chances are that these two methods were not used to calculate the nonisothermal crystallization activation energy where the nucleation process was influenced.

Synthesis and Nonisothermal Crystallization Kinetics of Poly(Butylene Terephthalate-co-Tetramethylene Ether Glycol) Copolyesters

Poly(butylene terephthalate-co-tetramethylene ether glycol) (PBT-co-PTMEG) copolymers with PTMEG ranging from 0 to 40 wt% were synthesized through melt polymerization. The structure and composition were supported by Fourier-transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (1H NMR). All samples had excellent thermal stability at a Td−5% around 370 °C. Crystallization temperature (Tc) and enthalpy of crystallization (ΔHc) were detected by differential scanning calorimetry (DSC), revealing a decrement from 182.3 to 135.1 °C and 47.0 to 22.1 J g−1, respectively, with the increase in PTMEG concentration from 0 to 40 wt%. Moreover, nonisothermal crystallization was carried out to explore the crystallization behavior of copolymers; the crystallization rate of PBT reduced gradually when PTMEG content increased. Hence, a decrement in the spherulite growth rate was detected in polarizing light microscope (PLM) observation, observing that the PTMEG could enhance the hindrance in the molecular chain to lower the crystallinity of PBT-co-PTMEG copolyester. Moreover, thermal properties and the crystallization rate of PBT-co-PTMEG copolymers can be amended via the regulation of PTMEG contents.

Nonisothermal crystallization behaviors of ethylene–acrylic acid copolymer and ethylene–acrylic acid copolymer/chloroprene rubber thermoplastic vulcanizate

Nonisothermal crystallization kinetics of ethylene–acrylic acid copolymer (EAA) and thermoplastic vulcanizate (TPV) based on EAA/chloroprene rubber (CR) were extensively studied using differential scanning calorimetry. Several methods, including the Avrami, Ozawa, and Mo equations, were carried out to analyze the process of nonisothermal crystallization kinetics of EAA and EAA/CR TPV. The results showed that the Avrami analysis modified by Jeziorny and a method developed by Mo could describe the nonisothermal crystallizations of pure EAA and the EAA/CR TPV very well. However, the Ozawa analysis did not give an adequate description. The crystallization processes of pure EAA and the EAA/CR TPV were accelerated by increasing the cooling rates. Moreover, the initial crystallization temperature and the crystallization termination temperature of EAA/CR TPV were higher than those of pure EAA at the same cooling rate, thus showing the nucleating function of CR in the beginning. While the crystallization half time of EAA/CR TPV was apparently longer than that of pure EAA, meaning that the more CR could cause the steric effect and retard the crystallization process of the TPV during the late stages of crystallizing. Although the CR phase of EAA/CR TPV could provide more nucleation sites, the presence of more CR phase must impose a much more significant confinement effect on the crystal growth of EAA. It was believed that this confinement effect overweighed the nucleation effect, thereby slowing down the overall crystallization rate.