Effect of molar mass distribution (MMD) and composition distribution (CD) on crystallization behavior of linear low-density polyethylene materials at moderate and high supercooling was studied using differential scanning calorimetry, hotstage polarized light microscopy, small-angle light scattering, and chip nanocalorimetry methods. A set of uni-and bimodal materials having small variation in average molar mass, density, and melt flow rate, but large differences in MMD and CD, was investigated. The results indicate a clear effect of structural heterogeneity on morphology and crystallization behavior of the materials. Broader MMD and CD increased in average radius of superstructures, melting, crystallization temperatures, and isothermal crystallization rate at different supercoolings. Origin of such behavior is discussed.
Crystallization behaviour of polylactic acid/cellulose (PLA/CELL) and linear low-density polyethylene/cellulose (LDPE/CELL) composites was studied by differential scanning calorimetry (DSC) and polarized light microscopy equipped with hot-stage. The effect of addition of cellulose on thermal properties of PLA/CELL and LDPE/CELL composites was considered. The DSC experiments were performed at different scanning rates.For pure PLA the crystallization peak at r= 98.8 °C was observed in DSC scans at 20°C/min with the corresponding melting peak at 110.1°C. With addition of cellulose no crystallization peaks and melting peaks related to them were found. For all samples cold ciystallization peaks at around 130°C and corresponding melting peaks at 152-153 °C were observed in endotherms. Cold crystallinity is strongly affected by cellulose content: the higher the cellulose content, the higher is the cold crystallinity of the samples. At the same time overall crystallinity for all PLA/cellulose composites is negligible contrary to pure PLA, which is slightly crystalline.Unlike PLA, LDPE and its composites have no cold crystallization, which is a usual behaviour for LDPE materials. A general crystallization/melting behaviour of LDPE/cellulose composites is identical to that of pure LDPE. However, the crystallinity of LDPE/composites decreases with increasing cellulose content.
Blends of high-density polyethylene (HDPE), moderate and hyper-branched LLDPEs (LLDPE and HbPE, respectively) have attained widespread commercial applications, though the understanding of the mechanical and melt-flow properties of such blends has been handicapped by the absence of a consensus concerning the degrees of mixing of the components. Moreover, usually the blends are obtained by melt blending, which may not ensure the initial homogeneity of the components. In our work the mixtures were prepared by dissolving the conventional LLDPE having branching content 7.2 wt% with HbPE with comonomer content 17.8 wt% in xylene at 130°C and stirring for 2 hours. The same procedure was applied for the blending of HDPE with HbPE. After dissolving the mixtures were cooled in liquid nitrogen and after that freeze dried in vacuum line. The ratio of components in the blends was varied. Differential scanning calorimetry has been used to investigate the miscibility and thermal behavior of the blends. For this purpose isothermal and non-isothermal treatment of prepared blends were conducted. By preliminary study the double melting peaks in non-isothermal endotherms have been observed in all the studied blends. The presence of two peaks in DSC scan can be attributed to the formation of separated crystals from both the high density/linear low density and highly branched components. However, certain limited degree of co-crystallization is detected in all the LLDPE/HbPE blends and HDPE/HbPE blend rich in HbPE component.
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