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crystallinity calculated from the heat of fusion. In the present work, the effect of the rigid amorphous fraction (RAF) on the traditional amorphous fraction (TAF) will be discussed: the hysteresis peak at the glass transition of the TAF disappears under

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Abstract  

Volumetric thermal analysis of semicrystalline poly(ethylene terephthalate), PET, with different content of crystalline phase was carried out using mercury-in-glass dilatometry. The effect of crystals on the thermal properties of amorphous phase (glass transition temperature, T g, thermal expansion coefficients, α) were determined. At cold-crystallization (106°C, up to 4 h), crystalline content of 2.4–25.3 vol.% was achieved. Increasing content of crystalline phase broadens the glass transition region and increases T g. The change of thermal expansion coefficient during glass transition is lower than that predicted by the two-phase model, which indicates the presence of a third fraction — rigid amorphous fraction (RAF), whose content steadily increases during crystallization. However, its relative portion (specific RAF) is significantly reduced. Further significant decrease in specific RAF appears after annealing at a higher temperature.

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Abstract  

A three-phase model, comprising crystalline, mobile amorphous, and rigid amorphous fractions (χ c, χ MA, χ RA, respectively) has been applied in the study of semicrystalline Nylon-6. The samples studied were Nylon-6 alpha phase prepared by subsequent annealing of a parent sample slowly cooled from the melt. The treated samples were annealed at 110°C, then briefly heated to 136°C, then re-annealed at 110°C. Temperature-modulated differential scanning calorimetry (TMDSC) measurements allow the devitrification of the rigid amorphous fraction to be examined. We observe a lower endotherm, termed the ‘annealing’ peak in the non-reversing heat flow after annealing at 110°C. By brief heating above this lower endotherm and immediately quenching in LN2-cooled glass beads, the glass transition temperature and χ RA decrease substantially, χ MA increases, and the annealing peak disappears. The annealing peak corresponds to the point at which partial de-vitrification of the rigid amorphous fraction (RAF) occurs. Re-annealing at 110°C causes the glass transition and χ RA to increase, and χ MA to decrease. None of these treatments affected the measured degree of crystallinity, but it cannot be excluded that crystal reorganization or recrystallization may also occur at the annealing peak, contributing to the de-vitrification of the rigid amorphous fraction. Using a combined approach of thermal analysis with wide and small angle X-ray scattering, we analyze the location of the rigid amorphous and mobile amorphous fractions within the context of the Heterogeneous and Homogeneous Stack Models. Results show the homogeneous stack model is the correct one for Nylon-6. The cooperativity length (ξA) increases with a decrease of rigid amorphous fraction, or, increase of the mobile amorphous fraction. Devitrification of some of the RAF leads to the broadening of the glass transition region and shift of T g.

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Abstract  

The increment of heat capacity at the glass transition for semi-crystalline poly(ethylene terephthalate) (PET) observed by temperature-modulated differential scanning calorimetry (TMDSC) shows significant deviations from a simple crystalline/amorphous two-phase model. Introduction of a rigid amorphous fraction, which is non-crystalline but which also does not participate in the normal glass transition, allows a much better description of the transition behaviour in semi-crystalline PET. Certain questions arise such as what is the rigid amorphous fraction and over what temperature range do these rigid amorphous segments devitrify? These TMDSC results show that the rigid amorphous component may be treated as an interphase between amorphous and crystalline phases. This interphase does not exhibit a separate glass transition temperature at temperatures above the normal Tg. The suggestion is made that the glass transition of the rigid amorphous component occurs continually between the glass transition temperature of the amorphous phase and up to about 135C for this particular sample of PET.

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An analysis of the crystallization behaviour of a new poly(aryl-ether-ether-ketone-ketone), PK99, by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) is presented. Isothermal crystallization TG were obtained in the whole range between the glass transition temperature (T g) and the melting temperature (T m) as a consequence of the slow crystallization kinetics stemming from the closeness of these transitions. The calorimetric results, compared with WAXD data, were applied to determine the theoretical melting temperature and crystallization enthalpy. The DSC and WAXD data were combined in order to calculate the total amount of the crystallizable fraction of the polymer, and a model was proposed to explain the difference between the fractions of crystallinity observed with these techniques. The thermal and X-ray data were also correlated with different lamellar morphologies arising from the crystallization conditions. Finally, DSC experiments on the crystallized sample were used to detect the presence of a rigid amorphous phase which does not relax at T g.

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Semi-crystalline polymers

Two phases or three? An overview and perspective

Journal of Thermal Analysis and Calorimetry
Author: R. Seyler
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hindering the large-amplitude motion close to boundaries to a more rigid phase or by applying external strain, as in drawn fibers. Both of these latter restraints may produce a rigid amorphous fractions ( RAF ) [ 18 ]. The ATHAS Data Bank provides the

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Abstract  

We report a thermal analysis study of the effect of molecular weight on the amorphous phase structure of poly(phenylene sulfide), PPS, crystallized at temperatures just above the glass transition temperature. Thermal properties of Fortron PPS, having viscosity average molecular weights of 30000 to 91000, were characterized using temperature modulated differential scanning calorimetry (MDSC). We find that while crystallinity varies little with molecular weight, the heat capacity increment at the glass transition decreases as molecular weight decreases. This leads to a smaller liquid-like amorphous phase, and a larger rigid amorphous fraction, in the lower molecular weight PPS. For all molecular weights, constrained fraction decreases as the scan rate decreases.

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Abstract  

The relaxation strength at the glass transition for semi-crystalline polymers observed by different experimental methods shows significant deviations from a simple two-phase model. Introduction of a rigid amorphous fraction, which is non-crystalline but does not participate in the glass transition, allows a description of the relaxation behavior of such systems. The question arises when does this amorphous material vitrify. Our measurements on PET identify no separate glass transition and no devitrification over a broad temperature range. Measurements on a low molecular weight compound which partly crystallizes supports the idea that vitrification of the rigid amorphous material occurs during formation of crystallites. The reason for vitrification is the immobilization of co-operative motions due to the fixation of parts of the molecules in the crystallites. Local movements (Β-relaxation) are only slightly influenced by the crystallites and occur in the whole non-crystalline fraction.

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