The aim of this paper is to investigate how the molecular structure of linear polypropylenes can be modified by electron beam irradiation. For this purpose a linear precursor was irradiated with different doses. The samples were analyzed by size-exclusion chromatography coupled with a light scattering detector. With increasing doses, a reduction of molar mass and an increasing number of longchain branches were found. Moreover, conclusions with respect to the topography of the long-chain branches obtained were drawn from the molar mass dependence of the zero shear viscosity of the irradiated samples, which deviates significantly from that of linear polypropylenes. The experimental results can be interpreted in a way that at low doses very few but long branches occur. At higher doses more and shorter branches per molecule exist. The elongational experiments clearly exhibit a change of the strainhardening behavior with irradiation dose, which is in agreement with the structural changes concluded from the shear measurements. The results from rheology and their interpretation demonstrate two features. First, rheological experiments conducted on irradiated polypropylenes are much more sensitive with respect to long-chain branching than the classical characterization methods based on size-exclusion chromatography coupled with light scattering. Second, from a comparison of the rheological behavior of linear and irradiated polypropylenes some conclusions can be drawn regarding the topography of the long-chain branches generated.
This article investigates how rheological properties of polypropylenes with different molecular structures influence their foaming behavior. The molecular structure of the different polypropylenes is analyzed by size exclusion chromatography coupled with a light scattering detector, and by rheological means, such as the molar mass dependence of the zero shear-rate viscosity. The main focus of the rheological experiments is laid on the strain hardening and failure behavior of the melts in uniaxial elongational flow. For all linear polypropylenes investigated, a rupture of samples occurred before the maximum strain—accessible with the instrument used—was achieved. For the linear polypropylenes, a growth of the stress to rupture and the elongation at break were found with increasing molar mass, which go along with an increase of the expansion ratio in the foaming experiments. Besides the linear polypropylenes, which do not show strain hardening, several so-called high melt strength polypropylenes were investigated. It was found that the strain hardening of those polypropylenes causes not only a high melt strength, but also a more uniform sample deformation in the elongational experiments, and thus high elongations at break or even no rupture of the samples. Due to the superior homogeneity of deformation, the foams of polypropylenes, which show pronounced strain hardening at the strain rates relevant for foaming, possess higher expansion ratios than linear samples of the same melt strength. Furthermore, it was found that the foaming behavior of the polypropylenes is governed by the elongational behavior of the melts independently of the molecular constitution, which is responsible for it. This means that different molecular structures, which cause a similar elongational behavior of the melt, lead to a comparable foaming behavior.
Two polyethylene and two polypropylene melts were characterized in uniaxial elongational flow. They exhibit significant differences with respect to strain hardening. For the polypropylenes it was shown that the elongational behavior found in uniaxial elongation is qualitatively reflected in biaxial deformation too. From the polyethylenes, films were blown using laboratory equipment, and the polypropylenes were processed into beakers by thermoforming. For both materials it could be shown that strain hardening is of advantage for the geometrical uniformity of the processed items. POLYM. ENG. SCI., 46: 1190–1195, 2006. © 2006 Society of Plastics Engineers
In this article the influence of long-chain branching on the foaming behavior of polypropylene (PP) is investigated. Different branching contents are achieved by blending a linear PP (L-PP) and a long-chain branched PP (LCB-PP). Whereas, the L-PP does not exhibit any strain hardening in laboratory stretching experiments, blends with amounts of the LCB-PP higher than 2 wt% already show a pronounced strain-hardening behavior. The strain hardening increased with a growing amount of the long-chain branched PP. A laboratory scale foaming apparatus based on a capillary rheometer is developed for the foaming experiments. In foaming tests with azodicarbonamide as chemical blowing agent, a significant improvement of the foaming behavior with respect to a higher expansion ratio, a lower amount of connected cells, and a more homogeneous cell size distribution is found with increasing content of the LCB-PP up to a concentration of 50 wt%. At this concentration, the foaming behavior of the LCB-PP is reached. The results demonstrate that low amounts of long-chain branching can significantly improve the optimal foaming process of PPs with a chemical blowing agent, and that additions of the linear material up to 50 wt% to the LCB-PP do not have any influence on the favorable foaming performance of the long-chain branched PP.
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