Polymer Nanocomposites: Polymer And Particle Dynamics And Its Application As Lubricant

Abstract

My thesis is prepared upon two separate yet interdisciplinary projects. First, I present a project entitled 'Polymer Nanocomposites: Polymer and Particle Dynamics' where I investigate dynamics of polymer and particle upon their mixing. On second part of the thesis, I present one of the application of polymer nanocomposites (PNC) entitled 'Nanoscale Organic-Inorganic Hybrid Lubricants'. Understanding nanoscale dynamics of polymer and particle upon mixing will be a useful guide to improve its application. Polymer Nanocomposites: Polymer and Particle Dynamics - Polymer nanocomposites containing nanoparticles smaller than the random coil size of their host polymer chains are known to exhibit unique properties, such as lower viscosity and glass transition temperature relative to the neat polymer melt. It has been hypothesized that these unusual properties result from fast diffusion of the nanostructures in the host polymer, which facilitates polymer chain relaxation by constraint release and other processes. In this study, the effects of addition of sterically stabilized inorganic nanoparticles to entangled cis-1,4-polyisoprene and polydimethylsiloxane on the overall rheology of nanocomposites are discussed. In addition, insights about the relaxation of the host polymer chains and transport properties of nanoparticles in entangled polymer nanocomposites are presented. The nanoparticles are found to act as effective plasticizers for their entangled linear hosts, and below a critical, chemistry and molecular-weight dependent particle volume fraction, lead to reduced viscosity, glass transition temperature, number of entanglements, and polymer relaxation time. We also find that the particle motions in the polymer host are hyperdiffusive and at the nanoparticle length scale, the polymer host acts like a simple, ideal fluid and the composites' viscosity rises with increasing particle concentration. Nanoscale Organic-Inorganic Hybrid Lubricants - Silica (SiO2) nanoparticles densely grafted with amphiphilic organic chains are used to create a family of organicinorganic hybrid lubricants. Short sulfonate-functionalized alkylaryl chains covalently tethered to the particles form a dense corona brush that stabilizes them against aggregation. When these hybrid particles are dispersed in poly-[alpha]-olefin (PAO) oligomers, they form homogeneous nanocomposite fluids at both low and high particle loadings. By varying the volume fraction of the SiO2 nanostructures in the PAO nanocomposites, we show that exceptionally stable hybrid lubricants can be created and that their mechanical properties can be tuned to span the spectrum from simple liquids to complex gels. We further show that these hybrid lubricants simultaneously exhibit lower interfacial friction coefficients, enhanced wear and mechanical properties, and superior thermal stability in comparison with either PAO or its nanocomposites created at low nanoparticle loadings. Profilometry and energy dispersive X-ray spectroscopic analysis of the wear track show that the enhanced wear characteristics in PAO-SiO2 composite lubricants originate from two sources: localization of the SiO2 particles into the wear track and extension of the elastohydrodynamic lubrication regime to Sommerfeld numbers more than an order of magnitude larger than for PAO. ii