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Two-Dimensional Raman Correlation Spectroscopy Study of Poly[(R)-3-hydroxybutyrate- co-(R)-3-hydroxyhexanoate] Copolymers.

Two-dimensional correlation analysis was applied to the time-dependent evolution of Raman spectra during the isothermal crystallization of bioplastic, poly[(R)-3-hydroxybutyrate- co-(R)-3-hydroxyhexanoate] or PHBHx copolymer. Simultaneous Raman measurement of both carbonyl stretching and low-frequency crystalline lattice mode regions made it possible to carry out the highly informative hetero-mode correlation analysis. The crystallization process of PHBHx involves: (1) the early nucleation stage; (2) the primary growth of well-ordered crystals of PHBHx; and (3) the secondary crystal growth phase. The latter stage probably occurs in the inter-lamellar region, with an accompanying reduction of the amorphous component, which occurs most dominantly during the primary crystal growth. The development of a fully formed lamellar structure comprising the 21 helices occurs after the primary growth of crystals. In the later stage, secondary inter lamellar space crystallization occurs after the full formation of packed helices comprising the lamellae.

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