The microphase morphology of a series of polystyrene-b-polybutadiene-b-poly( -caprolactone) ABC triblock copolymers (SBC) was studied by transmission electron microscopy (TEM) and synchrotron radiation small-angle X-ray scattering (SAXS) for selected samples. The studies were performed as a function of annealing time at high temperature (150 °C). Interestingly, even though crystallization took place under similar conditions (5 h at 40 °C), the annealing time at high temperature can influence the final morphology in such a way that within a copolymer (S 51B09C40), a morphological transition from a lamellar-cylindrical (lc) to a cylindrical-ring (cr) morphology can occur. It was also observed that the copolymers reach varied levels of long-range order of the microdomains, depending on the composition. These results combined with the observation or not of well-defined spherulites in the bulk illustrate the strong "conflict" between microphase separation and crystallization, especially when the PCL content is relatively high. The morphological changes are directly related to the thermal behavior of the triblock copolymers, in particular, the melting temperature and Avrami parameter associated with the crystallization kinetics.
In conclusion, our data indicate that type 1 AIH predisposition in a Venezuelan mestizo population of different ethnic backgrounds is associated with DRB1*1301 and DRB1*0301 alleles. In addition, our findings suggest that protection against disease might be conferred by the DQB1*04 allele, with distinct ethnic differences from other populations.
The melting behavior as well as the crystallization kinetics of a series of polystyrene-bpolybutadiene-b-poly( -caprolactone) ABC triblock copolymers was investigated by differential scanning calorimetry (DSC). The studies were performed as a function of annealing time at high temperature (150 °C), maintaining invariable the crystallization conditions. While a copolymer with only 16 wt % PCL does not show significant changes with the annealing time, it influences strongly the melting behavior and crystallization kinetics of copolymers with higher PCL content. Thus, higher melting points and degree of crystallinity can be observed by increasing annealing time, suggesting the results show a clear "conflict" between microphase separation and crystallization. This is more evident when the thermodynamic force to form spherulites and the thermodynamic force to maintain the microphase morphology formed in the melt compete. The analysis of the crystallization kinetics through the Avrami theory demonstrated that when the nucleation step proceeds heterogeneously, the Avrami exponent effectively reflects the dimensionality of crystal growth.
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