The melting, crystallization, and self-packed ring patterns in the spherulites of miscible blends comprising poly(trimethylene
terephthalate) (PTT) and poly(ether imide) (PEI) were revealed by optical, scanning electron microscopies (PLM and SEM) and
differential scanning calorimetry (DSC). Morphology and melting behavior of the miscible PTT/PEI blends were compared with
the neat PTT. Ringed spherulites appeared in the miscible PTT/PEI blends at all crystallization temperatures up to 220 °C,
whereas at this high temperature no rings were seen in the neat PTT. A postulation was proposed, and interrelations between
rings in spherulites and the multiple lamellae distributions were investigated. The specific interactions and the segregation
of amorphous PEI were discussed for interpreting the morphological changes of 220 °C-melt-crystallized PTT/PEI samples. Interlamellar
segregation of PEI might be associated with multiple lamellae in the spherulites of PTT/PEI blends; therefore, rings were
more easily formed in the PTT/PEI blends at all crystallization temperatures. A postulated model of uneven lamellar growth,
coupled with periodical spiraling, more properly describes the possible origin of ring bands from combined effects of both
interactions and segregation between the amorphous PEI and PTT in blends. 相似文献
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
A novel phosphorus-containing copolyester (PTTP), poly(trimethylene terephthalate) (PTT) copolyester with a bulky linking pendent group of 9,10-dihydro-10-[2,3-di(hydroxycarbonyl) propyl]-10-phosphaphenanthrene-10-oxide (DDP) was prepared, and its crystallization, crystal morphology and interference color were investigated in this article for the first time. Differential scanning calorimeter (DSC) results showed that with the increase of DDP content, the melting point (T(m)) and crystallization ability of PTTP decreased. WAXD results suggests that the three samples share one crystal structure, however the crystallinity decreases with increasing DDP content. Polarized optical microscope (POM) observation indicated that the samples showed non-banded spherulites at a lower and higher temperature, and banded spherulites at the middle temperature range. From the micrographs obtained from scanning electronic microscopy (SEM) and atomic force microscopy (AFM), ringed patterns with many defects could be found for samples with higher DDP contents, which crystallized at a lower temperature, and a transformation from square-shaped spherulites to circular spherulites was noted for samples with higher DDP contents, which crystallized at a higher temperature. The interference color of the spherulites was also studied and it was shown that with the increase of film thickness or decrease of DDP content, the spherulites became more colorful under POM observation, indicating that the hindering effect and randomness caused by incorporating the DDP monomer with a bulky pendent group into the PTT molecular chain exhibited a negative influence on the molecular mobility and crystallization ability of the copolyester, and led to the formation of the defective band morphology and the less colorful interference color of the PTTP spherulites. 相似文献
The wide-angle X-ray diffraction (WAXD) patterns of isothermally crystallized Nylon 1212 show that γ-form crystals form below 90℃ and the α-form crystals can exist above 140℃. In the temperature range of 90-140℃, the α-form and γ-form crystals coexist. Variable-temperature WAXD exhibits that the nylon 1212 γ-form does not show crystal transition on heating, while α-form isothermally crystallized at 160℃ exhibits Brill transition at a little higher than 180℃ on heating. The multiple melting behaviors of Nylon 1212 isothermally crystallized from melt come from a complex mechanism of different crystal structures, dual lamellar population and melting-recrystallization. In polarized optical microscope (POM) observations, Nylon 1212 isothermally crystallized at 175℃ shows the ringed banded spherulites. However, at temperatures below 160℃ the ringed banded image disappears, and cross-extinct spherulites are formed. 相似文献
The multiple melting behavior of poly(ethylene terephthalate) (PET) was investigated with differential scanning calorimetry (DSC) by examining PET samples having been subjected to special schemes of crystallization and annealing treatment at multiple descending temperatures. Upon such step-wise annealing in decreasing temperatures, the existence of doublet melting peaks in addition to a series of multiple minor peaks in the PET has been demonstrated using carefully designed thermal schemes. Using the Hoffman theory, multiple lamellae populations, might be suggested to be simultaneously present in the PET subjected to such thermal treatments. However, direct experimental evidence has yet to be provided. The low-temperature minor crystals simply melt during normal scanning without having time enough to reorganize into higher-melt crystals. Nevertheless, the effect of scanning on non-isothermal crystallization does exist but is primarily confined to the temperature range much below the main melting region where the crystallization of polymer chains can progress at a reasonable rate. At higher temperatures near the main melting region, annealing for extended times is required in order to result in relative changes of the melting endotherms of the upper and lower peaks in the main melting doublet. In all we have shown that interpretations of the multiple melting phenomenon in semicrystalline polymers can be better refined. 相似文献
Melting behavior of poly(trimethylene terephthalate) (PTT) after isothermal crystallization from the melt state was studied using differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) techniques. The subsequent melting thermograms for PTT isothermally crystallized within the temperature range of 182-215 °C exhibited triple (for crystallization temperatures lower than ≈192 °C), double (for crystallization temperatures greater than ≈192 °C but lower than ≈210 °C), or single (for crystallization temperatures greater than ≈210 °C) endothermic melting phenomenon. These peaks were denoted peaks I, II, and III for low-, middle-, and high-temperature melting endotherms, respectively. For the triple melting phenomenon, it was postulated that the occurrence of peak I was a result of the melting of the primary crystallites, peak II was a result of the melting of recrystallized crystallites, and peak III was a result of the melting of the recrystallized crystallites of different stabilities. In addition, determination of the equilibrium melting temperature Tm0 for this PTT resin according to the linear and non-linear Hoffmann-Weeks extrapolation provided values of 243.6 and 277.6 °C, respectively. 相似文献
The crystallization behavior of poly(e-caprolactone)/poly(ethylene glycol) (PCL/PEG) blend was investigated by differential scanning calorimetry (DSC) and polarized microscopy (POM). Individual phase transition peaks in the DSC curves for both PEG and PCL in all the polymer blends with different PCL contents were observed. The crystallization and melting peak temperatures of PEG were at 41 and 65°C, respectively; while the crystallization and melting temperatures of PCL located at 28 and 56°C, respectively. In-situ POM results demonstrated that spherulites crystalline morphology was formed for both PCL and PEG homopolymers. In PEG/PCL blend, however, both the phase separation morphology and spherulitic morphology can be observed. In blends with 30 or 50 wt % PCL, the PCL component formed dispersed phase and crystallized at lower temperature. However, in blends with 70% PCL, the phase inversion behavior occurred. The continuous PCL phase crystallized at 35°C, while the PEG dispersed phase crystallized at a lower temperature. Fractional crystallization behavior of PEG and PCL was controlled by temperature. The spherulites growth rate of PEG was greatly influenced by temperature, instead of the content of PCL component in the PCL/PEG blends. 相似文献
The melting behavior of poly(butylene terephthalate) (PBT) has been investigated, and a simulation has been performed to determine whether the multiple melting endotherms observed during the thermal analysis of PBT can be explained by the simultaneous melting and recrystallization of an initial distribution of crystal melting temperatures that contains only one maximum and two inflection points. Specimens that were cooled at constant rates from the melt showed between one and three melting endotherms upon heating in a differential scanning calorimeter (DSC). The position and breadth of the crystallization exotherms upon cooling from the melt and small-angle x-ray scattering showed that as the cooling rate is increased, the distribution of melting temperatures broadens and shifts to lower temperatures. By combining temperature-dependent recrystallization with an initial distribution of melting temperatures, simulated DSC curves were produced that agreed well with experimental DSC curves. In instances of triple peaked curves, the high temperature peak was due to crystals formed during the scanning process, and the middle and low temperature peaks were due to crystals originally present in the material. Satisfactory agreement between the experimental and simulated curves was found without considering additional crystallization from the amorphous regions during the scanning process. 相似文献