Relationships between structure and rheology in polymer nanocomposites probed via X-ray scattering

Polymer nanocomposites have received intense attention due to their potential for significantly enhanced polymer properties like mechanical strength, thermal stability, electrical conductivity, etc. Melt state processing of these materials exposes the nanofillers to complex flow fields, which can induce changes in nanocomposite microstructure, including particle dispersion and the orientation of anisotropic nanoparticles in the polymer matrix. Since nanocomposite properties are strongly correlated with both these structural features, it is essential to develop methods to characterize such microstructural changes. This thesis reports extensive measurements of mechanical rheology and particle orientation during flow of nanocomposites based on multi-walled carbon nanotubes, clays, and graphene nanosheets. Changes in orientation of anisotropic nanoparticles are manifested in x-ray scattering images collected during shear. In-situ studies of orientation are enabled by custom designed x-ray adapted shear cells and high energy synchrotron radiation at the Advanced Photon Source in Argonne National Laboratory where these experiments were conducted.;Studies of flow induced orientation in model nanotube dispersions revealed increasing sample anisotropy with increasing shear rate across concentrations and aspect ratios. In dilute dispersions the orientation dynamics was dominated by flow induced aggregation/disaggregation of MWNTs, with anisotropy primarily attributed to individually dispersed nanotubes. In concentrated suspensions, sample anisotropy resulted from flow induced elastic deformation within entangled MWNT clusters. Release of elastic energy upon flow cessation resulted in an unexpected relaxation of induced anisotropy. These studies were followed with study of more complex, but, industrially relevant nanocomposites made with polypropylene as the dispersing matrix. The high viscosity of polypropylene makes dispersion of nanoparticles difficult, and hence a careful study of dispersing techniques was performed. In these nanocomposites, shear flow could not induce particle alignment, while unidirectional extension was more effective at inducing nanotube orientation.;Model clay dispersions revealed important differences between orientation dynamics at two structural length scales -- individual particles and network of particles. Close connection between rheology and structure was observed, with Brownian effects dominating the relaxation of induced anisotropy following flow cessation. In graphene/polystyrene nanocomposites, both unidirectional and large amplitude oscillatory flows were capable of orienting nanoparticles. However, orientation was largely independent of deformation rate.