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In this paper, the effect of uniaxial extension on the crystallization of an ethylene-based butane plastomer is examined by using rheometry coupled with differential scanning calorimetry (DSC). Uniaxial extension experiments were performed at temperatures below and above the peak melting point of the polyethylene in order to characterize its flow-induced crystallization behavior at extensional rates relevant to processing. The degree of crystallinity of the stretched samples was quantified by DSC, i.e., by analyzing the thermal behavior of samples after stretching. Analysis of the tensile strain-hardening behavior very near the peak melt temperature revealed that crystallization depends on temperature, strain, and strain rate. In addition, it was revealed that a very small window of temperatures spanning just 1–2°C can have a dramatic effect on polymer crystallization. Finally, flow-induced crystallization experiments at temperatures close to the peak melting point have shown the recrystallization of multiple crystalline structures within a polymer matrix, witnessed by double peaks within a narrow window of 89–93°C in the DSC thermographs, with the most demonstrable double peak behavior occurring at a temperature of 91°C, a temperature that is just 1°C cooler than the peak melt temperature of the polymer.

The processing behavior of a number of LLDPE/LDPE blends with emphasis on the effects of manufacturing technology of LLDPE and long chain branching is presented. A single low-density polyethylene was blended with two Ziegler-Natta linear-low-density polyethylenes LLDPE's and two metallocene-LLDPE's having distinctly different molecular structures. The weight fractions of the LDPEs used in the blends were 1 wt.%, 5 wt.%, 10 wt.%, 20 wt.%, 50 wt.% and 75 wt.%. Capillary extrusion reveals that the onset of sharkskin and gross melt fracture are slightly influenced with the addition of LDPE into LLDPE. However, the amplitude of the oscillations in the stick-slip flow regime was found to scale well with the weight fraction of LDPE even at amounts as low as 1 wt.%. Furthermore, it was observed that the onset of this flow regime was shifted to higher shear rates with increase of LDPE content. Shear rheology was found to be insensitive to detect small levels of LDPE. On the other hand, extensional rheology was found to be capable of detecting levels of LDPE as low as 1 wt.% at high Hencky strain rates (typically greater than 5 s−1) although only for certain blends.

The thermorheological behavior of a number of LLDPE/LDPE blends was studied with emphasis on the effects of the production technology of the linear low- density polyethylene (LLDPE) and the effects of long chain branching (LCB). Two Ziegler-Natta LLDPE's (LL3001.32 and Dowlex2045G) and two metallocene LLDPEs (AffinityPL1840 and Exact 3128) were blended with a single low-density polyethylene (LDPE), with all LLDPEs having distinctly different molecular weight. The weight fractions of the LDPEs used in the blends were 1, 5, 10, 20, 50, and 75%. DSC analy- sis has shown that the blends with metallocence LLDPEs are miscible in the crystal state, whereas for the Ziegler-Natta, apart from the two distinct peaks of the individ- ual components, a third peak appears which indicates the existence of a third phase that is created from the cocrystallization of components from the two blended poly- mers. The linear viscoelastic characterization was performed and mastercurves at 150 8C were constructed for all blends to check miscibility using the time tempera- ture superposition principle. In addition, Van Gurp Palmen and zero-shear viscosity versus composition were constructed to check the thermorheological behavior of all blends. In general, good agreement is found among these various methods. It was concluded that metallocene LLDPEs are more compatible with LDPE at all LDPE compositions when compared with their Ziegler-Natta counterparts. Finally, the extensional properties of all blends were studied to examine the effects of different levels of LCB on their extensional rheological properties. It was concluded that exten- sional rheology is a sensitive tool capable of detecting subtle changes in the polyethyl- ene macrostructure, that is, low levels of LCB. V C 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1669-1683, 2008

The “rise time” required to achieve a steady pressure reading in a capillary rheometer operated at constant piston speed can be very short or very long depending on the amount of the material in the barrel, its isothermal compressibility, the flow rate and the geometrical characteristics of the dies used [S.G. Hatzikiriakos, J.M. Dealy, Start-up pressure transients in a capillary rheometer, Polym. Eng. Sci. 34 (1994) 493–499]. When a short die having a large diameter is used, a maximum can also be obtained in the pressure transient, which is solely due to the compressibility of the material. This phenomenon is explained by means of a viscous mathematical model including compressibility, whose predictions are compared with experiments for a molten linear low-density polyethylene (LLDPE).

The thermorheological behavior of a number of linear low-density polyethylene and low-density polyethylene (LLDPE/LDPE) blends was studied with emphasis on the effects of long chain branching. A Ziegler–Natta, LLDPE (LL3001.32) was blended with four LDPEs having distinctly different molecular weights. The weight fractions of the LDPEs used in the blends were 1, 5, 10, 20, 50, and 75%. Differential scanning calorimetry (DSC) analysis has shown that all blends exhibited more than one crystal type. At high LDPE weight fractions, apart from the two distinct peaks of the individual components, a third peak appears which indicates the existence of a third phase that is created from the co-crystallization of the two components. The linear viscoelastic characterization was performed, and mastercurves at 150 °C were constructed for all blends to check miscibility. In addition, Van Gurp Palmen, zero-shear viscosity vs composition, Cole–Cole, and the weighted relaxation spectra plots were constructed to check the thermorheological behavior of all blends. In general, good agreement is found among these various methods. The elongational behavior of the blends was studied using a uniaxial extensional rheometer, the SER universal testing platform from Xpansion Instruments. The blends exhibit strain-hardening behavior at high rates of deformation even at LDPE concentrations as low as 1%, which suggests the strong effect of branching added by the LDPE component.

The processing behavior of a number of linear low-density polyethylenes/low density polyethylene (LLDPE/ LDPE) blends with emphasis on the effects of long chain branches is presented. A Ziegler-Natta linear low-density polyethylene was blended with four low-density polyethylene LDPE's having distinctly different molecular weights. The weight fractions of the LDPEs used in the blends were 1, 5, 10, 20, 50, and 75 wt%. Capillary extrusion reveals that the onset of sharkskin and gross melt fracture are slightly influenced with the addition of LDPE into LLDPE. However, the amplitude of the oscillations in the stick-slip flow regime was found to scale well with the weight fraction of LDPE. Amounts as low as 1 wt% LDPE have a significant effect on the amplitude of pressure oscillations. These effects are clearly due to the presence of long chain branching (LCB); furthermore, it was observed that the onset of this flow regime was shifted to higher shear rates with increase of LDPE content. On the other hand, shear rheology is not sensitive to detect addition of small levels of LDPE up to 20 wt%. Extensional rheology can detect levels of LDPE as small as 1 wt% only at high Hencky strain rates (typically greater than 5s−1) and only for certain blends, typically those that contain LDPE of high molecular weight. It is suggested that the magnitude of oscillations in the oscillating melt fracture flow regime is a sensitive method capable of detecting low levels of LCB. POLYM. ENG. SCI., 47:1317–1326, 2007. © 2007 Society of Plastics Engineers