Summary: The polymorphisms in poly(hexamethylene terephthalate) (PHT), along with their associated melting and spherulite morphologies, were examined by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), and polarized‐light microscopy (PLM). The morphology and crystal cells were dependent on the temperature of crystallization. When melt‐crystallized at low temperatures (90–135 °C), PHT showed at least five melting peaks and two re‐crystallization peaks upon DSC scanning, and the samples displayed various fractions of both α and β crystals. However, only a single melting peak was obtained in PHT melt‐crystallized at 140 °C or above, which displayed a single type of β crystal. In addition, two different forms of spherulites were identified in melt‐crystallized PHT, with one being a typical Maltese‐cross spherulite containing the α crystal, and the other being a dendrite‐type packed mainly with the β crystal. This study provides timely evidence for a critical interpretation of the relationship between multiple melting and polymorphisms (unit cells and spherulites) in polymers, including semi‐crystalline polyesters.
WAXD diffractograms for PHT melt‐crystallized at 140 °C, revealing a single type of β‐crystal cell. 相似文献
The design of a differential thermal analysis apparatus for use at elevated pressure is described. Experiments on melting and crystallization of folded-chain crystals of polyethylene and poly(ethylene–butene-1) copolymer, and melting of extended-chain polyethylene crystals have been conducted at pressures up to 4200 bars. The precision in transition temperature measurement was ±1°C. The Clausius-Clapeyron equation predicts the melting point increase with pressure at atmospheric pressure to be 32.0°C/kb. The melting point depression due to copolymerization remained constant over the complete pressure range analyzed on the poly(ethylene–butene-1) used in this study. Crystallization of polyethylene is retarded at elevated pressures, and a 50% larger degree of supercooling is necessary at 5000 bars to give a crystallization rate equal to that observed at atmospheric pressure. The difference in melting point between folded-chain and extended-chain polyethylene increases from 8.4°C at 1 bar to 25.6°C at 3000 bars. 相似文献
Precise melting and crystallization temperatures of extended-chain and folded-chain crystals of form I and folded-chain crystals of form II poly(vinylidene fluoride) under high pressure have been obtained by microdifferential thermal analysis (DTA). Upon heating at pressures above 4000 kg/cm2, the micro-DTA thermogram of form II crystallized from the melt at atmospheric pressure shows melting of the form II structure and the melting of the folded-chain and extended-chain crystals of form I, formed through recrystallization processes. These features were clarified by supplemental methods. The bandwidth seen in electron micrographs of the extended-chain crystal of form I obtained by crystallization under high pressure was in the range of 1500 to 2000 Å. At atmospheric pressure, the extended-chain crystal of form I melted at 207°C, approximately 17°C higher than the folded-chain crystal of form I and 31°C higher than the folded-chain crystal of form II. 相似文献
The polymorphous crystallization and multiple melting behavior of poly(l-lactic acid) (PLLA) with an optical purity of 92 % were investigated after isothermally crystallized from the melt state by wide-angle X-ray diffraction and differential scanning calorimetry. Owing to the low optical purity, it was found that the disordered (α′) and ordered (α) crystalline phases of PLLA were formed in the samples crystallized at lower (<95 °C) and higher (≥95 °C) temperatures, respectively. The melting behavior of PLLA is different in three regions of crystallization temperature (Tc) divided into Region I (Tc < 95 °C), Region II (95 °C ≤ Tc < 120 °C), and Region III (Tc ≥ 120 °C). In Region I, an exothermic peak was observed between the low-temperature and high-temperature endothermic peaks, which results from the solid–solid phase transition of α′-form crystal to α one. In Region II, the double-melting peaks can be mainly ascribed to the melting–recrystallization–remelting of less stable α crystals. In Region III, the single endotherm shows that the α crystals formed at higher temperatures are stable enough and melt directly without the recrystallization process during heating. 相似文献
Ultrahigh molecular mass polyethylene (UHMMPE) is filled with carbon nano-tubes (CNTs) by solution in the presence of maleic
anhydride grafted styrene-(ethylene-co-butylene)-styrene copolymer (MA-SEBS) as a compatibilizer. The UHMMPE/CNT composites
crystallized from melt were prepared at a cooling rate of 20°C min-1. The melting and crystallization behaviors of UHMMPE/ CNT composites were investigated by differential scanning calorimetry.
The results showed that onset melting temperature (Tm) and degree of crystallinity (Xc) of UHMMPE/CNT composites crystallized from solution are higher than those from melt due to the larger crystalline lamellar
thickness. The onset crystallization temperature (Tc) of UHMMPE/CNT composites tends to shift to higher temperature region with increasing CNT content in the composites. Tm and
Tc of UHMMPE phase in UHMMPE/CNT composites decrease with the addition of MA-SEBS. Moreover, the crystallization rate of UHMMPE
phase in UHMMPE/CNT composite is increased due to the introduction of CNTs. MA-SEBS acts as compatilizer, enhances the dispersion
of CNTs in the UHMMPE matrix. Thereby, the crystallization rate of UHMMPE phase in UHMMPE/CNT composite is further increased
with the addition of MA-SEBS.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
Dilatometric, calorimetric, and dissolution studies have been made of two crystalline modifications of trans-1,4-polyisoprene in order to determine their equilibrium melting temperatures. This parameter is of fundamental importance in the formal treatment of polymorphism in crystalline polymers. A consistent set of thermodynamic parameters has been derived for both crystalline modifications. The equilibrium melting temperature of the polymorph, which was previously observed to melt from carefully crystallized bulk material at 64°C, was calculated to be at least 82.4°C. The other form, which melts from the bulk at 74°C, has an equilibrium melting temperature of 79.5 ± 0.5°C. The trans-1,4-polyisoprene, crystallized by stirring n-butyl acetate solutions at 49°C, was found by x-ray diffraction to be in the first form and melts at 81.2 ± 0.5°C when very slow heating rates are applied. This melting temperature is very close to the independently derived equilibrium melting temperature and lends support to the possibility that extended chain crystals are present in these solution crystallized crystals. Using the newly found melting temperatures of the two crystalline modifications it can be derived from the free energies of fusion that the first crystalline form is more stable at temperatures above approximately 66°C, whereas the other form is more stable below this temperature. 相似文献
A report on crystallization of polyethylene at elevated pressures to an extended-chain morphology is presented. The crystals have been characterized by electron microscopy and density determination. Pressure, supercooling (temperature), and crystallization time have been varied to find the best conditions for production of perfect crystals. At 10–30°C supercooling completely crystallized polyethylene was obtained between 4.5 and 7 kb crystallization pressure in 1–8 hr. Analysis of fracture surfaces of samples crystallized for different lengths of time shows an increase in size and number of crystal lamellae and an improvement of extended chain crystals in the early stages of crystallization. A further improvement of the less well crystallized material between the lamellae occurs after 15 min of crystallization time. 相似文献
The Morphology of quenched poly(ethylene terephthalate) (PET) films crystallized by low-molecular-weight organic penetrants is studied by scanning electron microscopy. Films with thicknesses from ca. 1 mil (0.0025 cm) to ca. 35 mil (0.1 cm) were exposed to methylene chloride (MeCl2) and N,N-dimethylformamide (DMF) in the temperature ranges 0–38°C and 22–70°C, respectively. The effects on the surface and internal structures of contact with liquids and saturated vapors were examined. Severe porosity at the surface results from contact with the liquids, but only minor surface roughness appears following contact with vapors. Internal porosity developed in the thinnest films (ca. 1 mil) during crystallization in liquid environments. Here, the internal void fraction is greatest along the film centerline and decreases with increasing crystallization temperature. A mathematical model discussed previously accounts for the observed behavior. 相似文献