IntroductionPoly(3-hydroxybutyrate)(PHB) is produced by a wide variety of microorganisms as intracellular carbon and energy storage material [1], and has been extensively studied as a biodegradable and biocompatible thermoplastic [2][3][4]. However, it is well known that the processing of PHB and its copolymers into fibers, films, and other products is very hard. These polyesters have a glass transition point below room temperature, and the crystallization rate is quite low [5]. Because of these properties, the melt cools down to the room temperature without crystallization and the spherulitic crystallization occurs after processing resulting in the brittle character. Further the defect in the spherulites formed during the secondary crystallization deteriorates the mechanical properties [6,7].Several groups have attempted to improve the mechanical properties of PHB solution cast films. Holmes tried to obtain uniaxially and biaxially oriented films of PHB to improve the mechanical properties [4]. However, these films were too brittle to draw either uniaxially or biaxially to high ratio. De Koning et al. have reported that the stiffness and brittleness of PHB film was avoided by annealing at elevated temperatures [8]. This procedure seems to eliminate the defect in the spherulites. Barham and Keller [9] reported that the ductility of PHB films can be significantly improved by the application of cold drawing. The elongation at break measured at room temperature increases up to 300 % after 300 % of elongation by rolling, while as compression molded PHB film shows the elongation at break as low as 7 %. One can apply similar process to obtain highly oriented PHBH films with good mechanical properties.In this study, the roll drawing was applied to the compression molded poly ( 3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) films. While brittle spherulite structure tends to break easily by extension, it is possible to make a crystal orientation to some extent, without breaking in roll drawing. Roll drawn PHBH films are ductile and can be stretched to high extension ratio without breaking. Films obtained were further annealed at an elevated temperature. The objective of this study is to investigate the changes in mechanical properties and higher order structures of PHBH films during these processes.Abstract : Bacterial poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)(PHBH) highly oriented films were prepared by the combination of roll and uniaxial drawing processes. Compression molded films, which is rather brittle, turned to be ductile after roll drawing up to x 2, and the films were further uniaxially drawn to a draw ratio as high as 1000 %. The PHBH film with the tensile strength of 178 MPa and the modulus of 1.4 GPa were obtained. The roll drawn PHB film showed a slight crystalline orientation of α-form. The orientation advanced with uniaxial draw ratio and the formation of β-form crystal was observed. Relations among the processing conditions, higher order structures and mechanical properties were investigated using...