The effects of the ultra-high-molecular-weight (UHMW) component of polypropylene (PP) on its rheological properties, crystallization behavior, and solid-state mechanical properties were investigated using various measurement techniques. The terminal relaxation time—determined by measuring the linear viscoelasticity—was increased by adding the UHMW component. The increase in the melt elasticity produced by adding the UHMW component was observed by measuring the steady-state shear flow, although the shear viscosity was not greatly affected. Owing to the long characteristic time of the Rouse relaxation of the UHMW component, PP with the UHMW component formed highly oriented structures through a shear-induced crystallization process. The addition of the UHMW component enhanced the orientation and regularity of crystalline structure for extruded films. Therefore, the Young′s modulus, yield stress, and strength were higher in the PP film containing the UHMW component than in one without the UHMW component, irrespective of the direction of tensile deformation.
The effect of thermal and shear histories on the crystallization rate of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) was studied. As with other crystalline polymers, the shear history greatly affected the crystallization rate when the shear rate was beyond a critical value, i.e., the inverse of the Rouse relaxation time. Even after the formation of extended chain crystals, spherulite texture was clearly discernable. It grew from certain points on the extended chain crystals. Consequently, a row of spherulites appeared along the flow direction. The resin temperature in the molten state was also significant. When the sample was heated to 170 °C, which is beyond the main melting peak in the differential scanning calorimetry curve, unmolten crystals did not affect the linear viscoelastic properties. They acted as effective nucleating agents for the rest of the polymer during cooling. Therefore, the shear history hardly affected the crystallization rate and the number of spherulites.
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