Polymer-Particle Nanocomposites: Size and Dispersion Effects

摘要

Polymer-particle nanocomposites are used in industrial processes to enhance a broad range of material properties (e.g. mechanical, optical, electrical and gas permeability properties). This dissertation will focus on explanation and quantification of mechanical property improvements upon the addition of nanoparticles to polymeric materials. Nanoparticles, as enhancers of mechanical properties, are ubiquitous in synthetic and natural materials (e.g. automobile tires, packaging, bone), however, to date, there is no thorough understanding of the mechanism of their action. In this dissertation, silica (SiO2) nanoparticles, both bare and grafted with polystyrene (PS), are studied in polymeric matrices. Several variables of interest are considered, including particle dispersion state, particle size, length and density of grafted polymer chains, and volume fraction of SiO2. Polymer grafted nanoparticles behave akin to block copolymers, and this is critically leveraged to systematically vary nanoparticle dispersion and examine its role on the mechanical reinforcement in polymer based nanocomposites in the melt state. Rheology unequivocally shows that reinforcement is maximized by the formation of a transient, but long-lived, percolating polymer-particle network with the particles serving as the network junctions. The effects of dispersion and weight fraction of filler on nanocomposite mechanical properties are also studied in a bare particle system. Due to the interest in directional properties for many different materials, different means of inducing directional ordering of particle structures are also studied. Using a combination of electron microscopy and x-ray scattering, it is shown that shearing anisotropic NP assemblies (sheets or strings) causes them to orient, one in front of the other, into macroscopic two-dimensional structures along the flow direction. In contrast, no such flow-induced ordering occurs for well dispersed NPs or spherical NP aggregates! This work also addresses the interfacial, rigid polymer layer, or `bound layer' which has long been of interest in polymer nanocomposites and polymer thin films. The divergent properties of the `bound layer' as compared to the bulk material can have very important effects on properties, including mechanical properties. This is especially true in polymer nanocomposites, where at high weight fractions, `bound layer' polymer can easily make up 20% or more of total material! Here we quantify this layer of bound polymer as a function of particle size, polymer molecular weight and other variables, primarily using thermogravimetric analysis but also dynamic light scattering and differential scanning calorimetry. We find that as nanoparticles become smaller, the `bound layer' systematically decreases in thickness. This result is quite relevant to explanations of many polymer nanocomposite properties that depend on size, including mechanical and barrier properties. Many additional important and new results are reported herein. These include the importance of dispersion state in the resulting mechanical properties of polymer-particle nanocomposites, where a systematic study showed an optimal dispersion state of a connected particle network. An additional and unexpected finding in this system was the critical dependence of composite properties on grafted chain length of particles. As the grafted chain length is increased, the strain which leads to yielding in a steady shear experiment is increased in a linear relationship. At very high rates, this yielding process completely switches mechanisms, from yielding of the particle network to yielding of the entangled polymer network! A surprising correlation between the amount of bound polymer in solution and in the bulk was also found and is interpreted herein. Self-assembly was further explored in a range of different systems and it was found that grafted particles and there mimics have vast potential in the creation of a wide array of particle superstructures. In concert, these experiments provide a comprehensive picture of mechanical reinforcement in polymer-particle nanocomposites. Not only is the dispersion state of the particles crucial, but the presence of grafted chains is also so for proper reinforcement. Here many routes to ideal dispersion are detailed and the important role of grafted chains is also resolved.