Molecular Rheology of Complex Fluids

The processing of polymer materials is highly governed by its rheology, and influences the properties of the final product. For example, a recurring problem is instability in extrusion that leads to imperfect plastic parts. The ability to predict and control the rheological behavior of polymer fluids as a function of molecular chemistry has attracted a long history of collaboration between industry and academia. In industrial polymer processes, there is usually a combination of both shear and extensional flows. In some processing operations such as blow molding and fiber spinning,
extensional flow is the dominant type of deformation. The polymer molecules experience a significant amount of chain orientation and stretching during these processes. Shear rheology measured by conventional shear rheometers is good at describing chain orientation, whereas extensional rheology gives a good way of inducing chain stretching. Accurate and reliable stress–strain measurements of extensional flow play a crucial role in the understanding of non–linear rheological properties of polymers. However, the non–linear extensional rheology has not been extensively studied. It is known that the rheology of polymer melts is highly sensitive to molecular architecture, but the precise connection between architecture and non–linear rheology is still not fully understood. For example, linear polymer melts have the simplest architecture, but the possible existence of a qualitative difference on extensional steady–state viscosity between melts and solutions is still an open question. Branched polymer melts have more complex molecular structures. A stress maximum during the start–up of uniaxial extensional flow was reported in 1979 for a low–density polyethylene (LDPE)
melt. Subsequently observations of a steady stress following a stress maximum were reported for two LDPE melts. However the rheological significance of the stress maximum as well as the existence of steady flow conditions following the maximum is still a matter of some debate. This thesis focuses on the experimental study of extensional rheology of linear and branched polymer melts. We report the stress–strain measurements in extensional flows using a unique Filament Stretching Rheometer (FSR) in controlled strain rate mode and controlled stress mode. Extensional flow is difficult to measure reliably in Laboratory circumstances. In this thesis we first present an updated control scheme that allows us to control the kinematics of polymer melts in an FSR, which is the foundation of
our experimental work. Next we investigate four categories of polymer melts from the simplest system to the most complicated system, including 1) the narrow molar mass distribution (NMMD) linear polystyrene melts and solutions; 2) the bidisperse and polydisperse linear polystyrene melts; 3) the NMMD branched polystyrene melts; and 4) the polydisperse branched polyethylene melts. The experimental results are also compared with some developing theoretical models. Finally, to ensure the experimental data is accurate, the measurements from the FSR are compared with the data from some other extensional rheometers as well.