Combining Polarization Analysis and Isothermal Crystallization Behavior Elucidated by Two-Dimensional Correlation Spectroscopy for Understanding the Crystallization Properties of Poly[(R)-3-hydroxybutyrate- <i>co</i> -(R)-3-hydroxyhexanoate

Poly(3-hydrxybutyrate-<i>co</i>-3-hydroxyhexanoate) (PHBHx) is a biopolymer that is produced and degraded by microbes. Because of the potential to replace polymers derived from petrochemicals with these materials, there is a high level of expectation for its commercial uses if its physical and chemical properties can be understood and controlled. Among other things these properties are determined by the polymer's morphology - that is its crystallinity, and orientation of both crystalline and amorphous phases. The focus on the Raman characteristics of the crystalline phase enables elucidation of the characteristics of the polymer experiencing dynamic crystallization under various conditions. In this article we will start by reviewing the changes in the Raman spectrum from an amorphous to a crystalline material in an isothermal crystallization study. In that study a correlation field splitting between a CH stretching band that interacts with the carbonyl group on the opposite chain in the unit cell was identified. Then we will show the polarized Raman spectra of single crystals which enable an explanation of the residual amorphous material seen in the spectra of single crystals. Using the information from the single crystal measurements we can then study the Raman behavior of spherulites and confirm the model that proposes an explanation for the appearance of rings in the polarized light microscope (PLM) images of some spherulites. The polarized Raman studies confirm that the crystal ribbons that grow along the radii are twisting about the growth direction. The two-dimensional correlation spectroscopy (2D-COS) analysis of the polarized spectra of spherulites suggest the presence of strain that has been proposed to induce the twisting.