Papers by Keyword: Amorphous Polymers

Abstract: The development of high performance products at lowest possible product development-time and costs is the demand of the plastics industry today. A successful use of process simulation to describe the behavior of complex structures and to minimize the technical and economic risks for companies requires application and process-relevant material data.The pvT-behavior of polymers is an essential parameter for process simulations. Especially the dependence of the specific volume of pressure and temperature [1, 2] under process conditions is not mapped to the existing measurement methods.In this study pvT measurements were performed on selected amorphous and semi-crystalline polymers (PP, HDPE, POM, PBT, and ABS) with a Pirouette pvT device, a combination of a dilatometer and Couette rheometer. The specific volume was determined as a function of temperature (25-300°C) and at pressures ranging between 200-1000 bar. On top of that, the influence of the cooling rate was also investigated by pvT measurements performed at cooling rates of 0.1°C/s, 1°C/s and 100°C/s.The coefficients for the 2nd domain Tait pvT-model, which is implemented in the software Autodesk Moldflow, were determined by fitting the experimental pvT data and comparing them with the measured curves. As a result, the semi-crystalline polymers show a shift of the transition temperature to lower temperatures and a reduction in the specific volume in the melt is observed. For validation, in a case study shrinkage results in real were compared with the simulation.

Abstract: Mechanical spectroscopy is a powerful tool for the investigation of molecular dynamics of amorphous polymers over a large temperature range and frequency scale. In this work, by using high precision shear mechanical spectroscopy tool, we have investigated the segmental dynamics from local segmental relaxation to sub-Rouse modes in a series of amorphous polymers. We have demonstrated the existence of sub-Rouse modes slower than the local segmental motion in amorphous polymers. The sub-Rouse modes exhibit a similar change of dynamics at the same temperature T_B ~1.2 T_g, as the local segmental relaxation through the temperature dependence of relaxation time and relaxation strength. Furthermore, the crossover relaxation time of the sub-Rouse modes at T_B is almost the same for all the polymers investigated, i.e. τ_α'(T_B) = 10^-1±0.5 s, which is independent of molecular weight and molecular structure. This remarkable finding indicates that solely the time scale of the relaxation determines the change in dynamics of the sub-Rouse modes. According to the coupling model, the crossover is suggested to be caused by the onset of strong intermolecular cooperativity below T_B. Hence the results suggest that the sub-Rouse modes and their properties are generally found in amorphous polymers by mechanical spectroscopy, and reveal the cooperative nature of the sub-Rouse modes.

Abstract: Positron annihilation lifetime measurements on polymethylmethacrylate (PMMA) at low temperature were performed. Different discrete fitting procedures have been used to analyze the experimental data. It shows that the extracted parameters depend strongly on the fitting procedure. The physical meaning of the results is discussed. The blob model seems to give the best annihilation parameters.