Crystal Orientation switching in Spherulites Grown from Miscible Blends of Poly-3-hydroxybutyrate with Cellulose tributyrate

Fully miscible blends over the whole composition range are obtained by melt mixing bacterial poly(3hydroxybutyate), PHB, and trisubstituted cellulose butyrate, CTB. Blends containing up to 50wt% CTB are partially crystalline. Isothermal crystallization experiments show formation of PHB spherulites that grow until impingement. Depending on composition, radial growth rate is either constant or it suddenly increases in a very unusual manner leading to peculiar morphologies. In the latter case, in concomitance to the crystal growth acceleration, the sign of birefringence changes and rotation of the PHB unit cell orientation is observed. These results are discussed in terms of the influence of both composition and Tc on the relative crystallization kinetics of the two blend components. A strong effect played by the not yet crystallized CTB component that in the presence of the highly mobile PHB component forms a liquid crystallike phase is proposed.