Mechanical Reinforcement and Segmental Dynamics of Polymer Nanocomposites

Open Access
Gong, Shushan
Graduate Program:
Materials Science and Engineering
Doctor of Philosophy
Document Type:
Date of Defense:
January 06, 2016
Committee Members:
  • Ralph H Colby, Dissertation Advisor
  • Ralph H Colby, Committee Chair
  • James Patrick Runt, Committee Member
  • James Hansell Adair, Committee Member
  • Thomas E Mallouk, Committee Member
  • Polymer Nanocomposites
  • Mechanical Reinforcement
  • glassy bridge
  • rheology
  • dielectric
  • network
The addition of nanofiller into a polymer matrix will dramatically change the physical properties of polymer. The introduction of nanofiller makes the polymer more applicable in many industries, such as automobile tires, coatings, semiconductors, and packaging. The altered properties are not the simple combination of the characters from the two components. The interactions in polymer nanocomposites play an important role in determining the physical properties. This dissertation focuses on the mechanical properties of polymer nanocomposites (silica/poly-2-vinylpyridine) above their glass transition temperature Tg, as a model for automobile tires, which utilize small silica particles in crosslinked rubber far above Tg. We also investigate the impacts of the interaction between particle filler and polymer matrix on the altered mechanical properties. Dielectric relaxation spectroscopy (DRS) is used to study the glassy bound polymer layers formed around the particles. The results show evidence of the existence of immobilized polymer layers at the surface of each nanoparticle. At the same time, the thickness of the immobilized polymer layers is quantified and formed to be around 2 nm. Then we consider particles with glassy bound polymer layers are bridged together (either rubbery bridge or glassy bridge) by polymer chains and form small clusters. Clusters finally percolate to form a particle-polymer network as loading fraction increases. Rheology is used to study the network formation, and to predict the boundary of rubbery bridge and glassy bridge regimes. The distance between particles determines the type of polymer bridging. The particle spacing larger than Kuhn length makes flexible (rubbery) bridge with rheology described by a flexible Rouse model for percolation. When the spacing is shorter than the Kuhn length (~ 1nm), stiffer bridge forms instead, which is called glassy bridge. The mechanical differences between rubbery bridge and glassy bridge, and the effect of Mw on the formation of glassy bridge, are also discussed.