Advancing Renewable Materials by Integrated Light and X-ray Scattering - Final Technical Report

Polyhydroxyalkanotes (PHAs), a group of newly developed, commercially available biopolymers, and their composites have the potential to replace petroleum-based amorphous and semicrystalline polymers currently in use for consumer packaging, adhesives, and coating applications and to have significant advantages in medical applications such as tissue engineering. While the potential of PHAs is recognized in the literature and has even been realized in some cases, knowledge of these systems is decades behind that of synthetic polymers. Composites based on PHAs, furthermore, are just emerging in the research community. We argue that widespread adoption of nano-enhanced PHA materials can only be achieved through a proper characterization of the nanofiller morphology and its impact on the polymer matrix. Our goal is to build a robust understanding of the structure-processing relationships of PHAs to make it possible to achieve fundamental control over the final properties of these biopolymers and their bionanocomposites and to develop cost-effective manufacturing technologies for them. With the ultimate goal to design PHA polymer nanocomposites with tailored properties, we have performed a systematic study of the influence of cooling rate on the thermal properties and morphology of linear PHAs (PHB Mw = 690,000 g/mol; PHBV Mw = 407,000 g/mol, 8 mol %more » HV) and branched (PHBHx, Mw = 903, 000 g/mol, 7.2 mol % Hx) copolymers. Structure-property relations for silica/PHBHx nanocomposites were also investigated. Our studies show that simple two-phase composite models do not account for the molecular weight dependent enhancement in the modulus. Although improvement of the mechanical properties (stiffness/modulus and toughness) must be due to alteration of the matrix by the nanoparticle filler, the observed improvement was not caused by the change of crystallinity or spherulitic morphology. Since the mechanical properties of polymer nanocomposites can be affected by many factors, such as the interaction between particles and a polymer matrix, crystallinity of the polymer, spherulitic morphology, molecular weight of the polymer matrix, the PHA system studied can serve as a model system for determining the unique influence of particle characteristics on the morphology and mechanical properties of renewable polymer matrices. Motivated by our promising results, we have initiated a systematic morphology characterization studies on a series of branched PHA polymers to uncover conceptual models that predict reinforcement and toughening in renewable polymer nanocomposites as a function particle characteristics, molecular weight and polymer backbone structure. Thus how enhancement in the mechanical properties occurs in PHAs is the focus of our work. In March 2010, the PI discovered a process that will allow better control of particle dispersion in PHA matrices. A graduate student (Sandip Argekar) was added to the project to help test this discovery and the scale up potential for the low-cost manufacture of renewable polymer nanocomposite films. If successful, the PI and co-PI will submit an SBIR proposal to facilitate technology transfer of the discoveries under this award.« less