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101.
Qingsheng Liu Bingyao Deng Chia‐Hsin Tung Meifang Zhu Tien‐Wei Shyr 《Journal of Polymer Science.Polymer Physics》2010,48(21):2288-2295
The poly(3‐hydroxbutyrate‐co‐3‐hydroxyvalerate)/poly(ε‐caprolactone) block copolymers (PHCLs) with three different weight ratios of PCL blocks (38%, named PHCL‐38; 53%, named PHCL‐53; and 60%, named PHCL‐60) were synthesized by using PHBV with two hydroxyl end groups to initiate ring‐opening polymerization of ε‐caprolactone. During DSC cooling process, melt crystallization of PHCL‐53 at relatively high cooling rates (9, 12, and 15 °C min?1) and PHCL‐60 at all the selected cooling rates corresponded to PCL blocks so that PHCL‐53 and PHCL‐60 were used to study the nonisothermal crystallization behaviors of PCL blocks. The kinetics of PCL blocks in PHCL‐53 and PHCL‐60 under nonisothermal crystallization conditions were analyzed by Mo equation. Mo equation was successful in describing the nonisothermal crystallization kinetics of PCL blocks in PHCLs. Crystallization activation energy were estimated using Kissinger's method. The results of kinetic parameters showed that both blocks crystallized more difficultly than corresponding homopolymers. With the increase of PCL content, the crystallization rate of PCL block increased gradually. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010 相似文献
102.
Márcia M. Favaro Bruna T. Rego Márcia C. Branciforti Rosario E. S. Bretas 《Journal of Polymer Science.Polymer Physics》2010,48(2):113-127
An intercalated nanocomposite made of montmorillonite nanoclay, MMT, and poly(trimethylene terephthalate), PTT, was produced by twin screw extrusion and characterized by wide angle X‐ray diffraction, WAXD, and transmission electron microscopy, TEM. The quiescent isothermal and non‐isothermal and the flow‐induced crystallization of the nanocomposite were studied by differential scanning calorimetry, DSC, polarized light optical microscopy, PLOM, and rheometry. The quiescent results showed that the nanoclay acted as an efficient nucleating agent for the PTT, which result in an anticipation of the transition temperature between regimes II and III of crystallization. The fold interfacial free energy, σe, of the PTT in the nanocomposite during regime III was lower than in the pure state; that is, the pure PTT developed spherulites, whereas in the nanocomposite it produced a paracrystalline morphology. Under shear rate, the total times for crystallization in the nanocomposite were higher than in the pure PTT. In flow‐induced crystallization, a fibrillar nucleus must be formed as a result of chain orientation. In the nanocomposite, chain orientation only occurred after the percolated structure was broken. Therefore, the formation of a fibrillar nucleus in the nanocomposite took more time, which increased the total crystallization time. Inc. J Polym Sci Part B: Polym Phys 48: 113–127, 2010 相似文献
103.
用差示扫描量热分析研究了间规聚苯乙烯(sPS)的非等温结晶及其动力学,并分别用Ozawa和Jeziorny两种方法来处理sPS的非等温结晶数据.结果表明,在25~40℃/min的冷却速率范围内,sPS的半结晶时间随冷却速率增大而呈指数式下降,sPS非等温结晶过程遵循Ozawa动力学方程,但不符合Jeziorny方法中的Avrami动力学方程.所得到的sPS非等温结晶Avrami指数n在36~41之间,高于等温结晶时的n值 相似文献
104.
J. Nieto T. Oswald F. Blanco Joao B. P. Soares Benjamin Monrabal 《Journal of Polymer Science.Polymer Physics》2001,39(14):1616-1628
The effect of molecular weight and long‐chain branching on the crystallization analysis fractionation (CRYSTAF) of ethylene homopolymers was investigated. Several ethylene homopolymers were prepared with different molecular weights and levels of long‐chain branching to isolate these effects from the dominant effect of comonomer content on crystallizability measured by CRYSTAF. Molecular weight effects might be significant for samples with number‐average molecular weights below 5000, but this effect can be corrected if terminal methyl groups are taken into account. Long‐chain branching has only a very small effect on the CRYSTAF profile of the samples investigated in this study. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1616–1628, 2001 相似文献
105.
Chen‐Rui Tseng Hsin‐Yi Lee Feng‐Chih Chang 《Journal of Polymer Science.Polymer Physics》2001,39(17):2097-2107
We investigated the effects of montmorillonite (clay) on the crystallization kinetics of syndiotactic polystyrene (sPS) with isothermal differential scanning calorimetry analyses. The clay was dispersed into the sPS matrix via melt blending on a scale of 1–2 nm or up to about 100 nm, depending on the surfactant treatment. For a crystallization temperature of 240 °C, the isothermal crystallization data were fitted well with the Avrami crystallization equation. Crystallization data on the kinetic parameters (i.e., the crystallization rate constant, Avrami exponent, clay content, and clay/surfactant cation‐exchange ratio) were also investigated. Experimental results indicated that the crystallization rate constant of the sPS nanocomposite increased with increasing clay content. The clay played a vital role in facilitating the formation on the thermodynamically more favorable all‐β‐form crystal when the sPS was melt‐crystallized. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2097–2107, 2001 相似文献
106.
Abstract An optical autoclave for phase studies on mixtures in the temperature range from 80 to 373 K and for pressures up to 200 MPa is described. The cell is fitted with sapphire windows and employs magnetic stirring. Measurements are performed according to the synthetical (e.g. by visual observation) or analytical method (e.g. by sampling and online gaschromatography). Results for the crystallization and fluid phase equilibria of the binary systems nitrogen + trifluoromethane and argon + trifluoromethane from 110 K to 230 K and up to 200 MPa are presented and discussed in comparison with other N2- and CHF3-systems. 相似文献
107.
We report the inverse Meyer–Neldel (MN) rule in the thermally activated crystallization of a hybrid composite of phenol formaldehyde using two experimental approaches. In the first experiment, the annealing time dependence of the pre-exponential factor K 0 and the activation energy of crystallization E c were studied. In the second experiment, the annealing temperature dependence of the same parameters was investigated. We observed the inverse Meyer–Neldel rule between the pre-exponential factor K 0 and the activation energy of crystallization E c in both cases. 相似文献
108.
Toshimitsu Ichimori Shinichi Yamazaki Kunio Kimura 《Journal of polymer science. Part A, Polymer chemistry》2013,51(20):4301-4308
Composition control of aromatic poly(thioester‐amide) was examined by the reaction‐induced phase separation during polymerization of S‐acetyl‐4‐mercaptobenzoic acid (AMBA) and p‐acetylaminobenzoic acid (AABA) in aromatic solvent. The poly(thioester‐amide)s were obtained as precipitates and their yields became lower at the middle range of the content of AMBA in feed (χf). The contents of p‐mercaptobenzoyl (MB) moiety (χp) in the precipitates prepared without shearing were in good agreement with the χf values. In contrast to this, the χp values of the precipitates prepared at χf of 50–70 mol % under shearing were much lower than the χf values. The reaction rate of AMBA increased with shearing, whereas that of AABA was unchanged by shearing. This shearing effect on the reaction rates accelerated to form the homo‐oligomers. The solubility of MB oligomers enhanced by shearing, whereas that of p‐benzamide oligomers did not enhance owing to the strong interaction through hydrogen bonding. The MB oligomers were inhibited to be precipitated, resulting in the lower χp values than the χf values. The composition could be controlled by the application of the shearing to the heterogeneous polymerization. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4301–4308 相似文献
109.
《Journal of Polymer Science.Polymer Physics》2018,56(7):588-597
Polymer blends based on poly(vinylidene fluoride) (PVDF) and poly(ethylene oxide) (PEO) have been prepared to analyze the crystallization kinetics of poly(ethylene oxide) confined in semicrystalline PVDF with different ratios of both polymers. Both blend components were dissolved in a common solvent, dimethyl formamide. Blend films were obtained by casting from the solution at 70 °C. Thus, PVDF crystals are formed by crystallization from the solution while PEO (which is in the liquid state during the whole process) is confined between PVDF crystallites. The kinetics of crystallization of the confined PEO phase was studied by isothermal and nonisothermal experiments. Fitting of Avrami model to the experimental DSC traces allows a quantitative comparison of the influence of the PVDF/PEO ratio in the blend on the crystallization behavior. The effect of melting and further recrystallization of the PVDF matrix on PEO confinement is also studied. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 588–597 相似文献
110.
Crystallization in ultrathin Poly(Ethylene Oxide)/Poly(Methyl Methacrylate) (PEO/PMMA) blend films with thickness of ca. 10 nm was investigated by means of microscopic and in situ spectroscopic methods. It was revealed that the blend films undergo a phase ordering in a humid atmosphere before or during crystallization, with PEO de-mixing with PMMA and segregating to the free film interface on the PMMA layer. The de-mixed PEO chains crystallize into a fractal-like morphology by a diffusion-limited process, and the crystal growth is 1-dimensional with Avrami exponent n ≈ 1, resulting in flat-on crystal lamellae with the PEO chains oriented normal to the film plane. 相似文献