Quenched melt regions

Photomicrographic microdensitometry was used to generate quantitative distribution data for the additives. Calibration was conducted using standard quenched samples with a known additive concentration, photographed under the same conditions. Quenched melt regions, dis-... 

One possible reason suggested by Flory and Mandelkern (1956) for or contribution to the discrepancies indicated in Table 2 is the inability of the penetrometer method to detect the maximum temperature of melting because of its relative insensitivity and because of the upper "tail to the crystallinity-temperature curve as deduced from the copolymer crystallinity theory of Flory (1955). Dole and Wunderlich (1957, 1959) found, however, that two melting regions each of the quenched 80/20 and 60/40 copolymers could be observed in the calorimetric experiments. The specific heat curves of these two copolyesters are illustrated in... 

Table 5.1. Effect of experimental conditions on the reversing and non-reversing heat flows in the melt region. The sum of the heat flow signals is quantitative and is defined as the initial crystallinity of the quenched PET sample (courtesy of TA Instruments Inc.)...

Transitions. Samples containing 50 mol % tetrafluoroethylene with ca 92% alternation were quenched in ice water or cooled slowly from the melt to minimise or maximize crystallinity, respectively (19). Internal motions were studied by dynamic mechanical and dielectric measurements, and by nuclear magnetic resonance. The dynamic mechanical behavior showed that the CC relaxation occurs at 110°C in the quenched sample in the slowly cooled sample it is shifted to 135°C. The P relaxation appears near —25°C. The y relaxation at — 120°C in the quenched sample is reduced in peak height in the slowly cooled sample and shifted to a slightly higher temperature. The CC and y relaxations reflect motions in the amorphous regions, whereas the P relaxation occurs in the crystalline regions. The y relaxation at — 120°C in dynamic mechanical measurements at 1 H2 appears at —35°C in dielectric measurements at 10 H2. The temperature of the CC relaxation varies from 145°C at 100 H2 to 170°C at 10 H2. In the mechanical measurement, it is 110°C. There is no evidence for relaxation in the dielectric data. 

On the basis of the concept described above, we propose a model for the homogeneous crystallization mechanism of one component polymers, which is schematically shown in Fig. 31. When the crystallization temperature is in the coexistence region above the binodal temperature Tb, crystal nucleation occurs directly from the melt, which is the well-known mechanism of polymer crystal nucleation. However, the rate of crystallization from the coexistence region is considered to be extremely slow, resulting in single crystals in the melt matrix. Crystallization at a greater rate always involves phase separation the quench below Tb causes phase separations. The most popular case... 

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