Reactive processing with low-molar-mass modifiers is a well-known method to create long-chain branched (LCB) structures in a poly(ethylene terephthalate) (PET) melt. However, less is known about the elongational flow properties of LCB-PET. Therefore, the aim of this contribution is (a) to generate LCB molecules and (b) to evaluate the influence of the branching level on the transient elongational behavior. For this purpose, a commercial, linear PET and different contents (0.1− 0.3 wt %) of the tetrafunctional modifier pyromellitic dianhydride (PMDA) were reactively processed. All samples were analyzed by size exclusion chromatography coupled with a light scattering device and characterized by shear and elongational rheometry. It was found that the molar mass distribution of the modified materials exhibit a high molar mass shoulder, leading to an increase of the weight-average molar mass and a broadening of the molar mass distribution. Moreover, the Mark−Houwink plot of the modified materials displays deviations from the power law toward lower intrinsic viscosities, which indicate the existence of LCB molecules. The shear viscosity shows a pronounced shear thinning behavior and a remarkable increase at low frequencies compared to the linear PET. Considering the transient elongational viscosity, a distinguished strain hardening is observed, which increases with increasing PMDA content and with increasing strain rate. From the results of the rheological and molecular characterization and by considering the chemical reaction mechanisms, it can be concluded that the PET modified with high PMDA contents has a treelike branch-on-branch architecture, which is well-known from low-density polyethylene melts.
The spreading of an axisymmetric drop on partially and completely wetted substrates is investigated from the theoretical and experimental point of view. In particular, novel physical models considering the capillary force, the gravitational force, and a viscous friction force simultaneously are derived. The models enable the analytical mathematical description of the drop radius as a function of the spreading time, which is useful for practical applications. Moreover, the construction of a master curve for the partial wetting scenario is proposed. The theoretical models are experimentally verifi ed, using different polymer fi lms as substrates and polydimethylsiloxanes of different viscosities as liquids. The comparison shows that theory and experiment are consistent.Depending on the surface and interfacial tensions, two different wetting scenarios are possible: Either the drop forms a defi ned equilibrium contact angle or the liquid completely covers the substrate in order to reduce the surface energy of the system in the fi nal state. The fi rst situation
This paper compares the molecular structure and rheological properties of a commercial poly(ethylene terephthalate) (PET) after reactive processing with different concentrations of either pyromellitic dianhydride (PMDA) or a multifunctional epoxide (Joncryl®ADR-4368) as a chain extender. By size exclusion chromatography with triple detection, an increase of molar mass, a broadening of molar mass distribution, and the generation of long-chain branched molecules were found for both chain extenders. While gel-free materials were obtained with PMDA, the processing with Joncryl leads to the formation of gels. The effect of branching, indicated by the Mark-Houwink exponent, is more pronounced for materials with Joncryl compared to PMDA and points to a more compact branching structure of the PET/Joncryl molecules. Rheological measurements in shear and elongation support the analysis from SEC and reveal a complex tree-like branching structure for both chain extenders. In addition, the role of the two modifiers with respect to processing was assessed.
Film blowing of Poly(ethylene terephthalate) (PET) is challenging due its inherently low melt viscosity and poor melt strength. In this study, it is shown how the rheological properties of a commercial PET can be altered by reactive extrusion using either pyromellitic dianhydride (PMDA) or a multifunctional epoxy (Joncryl® ADR 4368) as chain extender, in order to improve the processing behavior during film blowing. The modified materials were characterized by shear and elongation rheometry and relevant processing characteristics, like melt pressure, bubble stability, and film thickness uniformity, were used to assess the influence of the type of modifier on processing and product performance. It is shown that PMDA is useful to increase the melt strength which leads to an improved bubble stability, while epoxy modified PET shows a reduced drawability that can cause problems at high take-up ratios. On the other hand, the epoxy modifier indicates a pronounced strain hardening during elongational deformation, and therefore leads to a better film thickness uniformity compared to the neat PET and the PET modified with PMDA. The differences with respect to processing performance are discussed and ascribed to the molecular structure of the materials.
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