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Nucleation Ability of Thermally Reduced Graphene Oxide for Polylactide: Role of Size and Structural Integrity

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journal contribution
posted on 02.04.2015, 00:00 by Yuan-Ying Liang, Su Yang, Xin Jiang, Gan-Ji Zhong, Jia-Zhuang Xu, Zhong-Ming Li
Following our previous work on graphene oxide-induced polylactide (PLA) crystallization [Macromolecules 2010, 43, 5000−5008], in the current work, we further revealed the role of size and structural integrity of thermally reduced graphene oxide (RGO) in PLA crystallization. RGO nanoplatelets with different architectures were obtained via bath and probe ultrasound (RGOw and RGOp). The average size of RGO decreased substantially with ultrasound intensity and time, where the generation of RGO edges constituted the translocation of functional group sites from in-plane to edges. The formation of sp3-configuration dominated in RGOw, whereas the partial recovery of sp2-configuration occurred in RGOp, giving rise to either the escalation of sp3/sp2 ratio for RGOw or retrogradation of that for RGOp. Isothermal crystallization kinetics of PLA nanocomposites containing RGOw and RGOp was determined by in situ synchrotron wide-angle X-ray diffraction. The induction period and overall crystallization rate of PLA/RGOw nanocomposites were strengthened with diminishing platelet size because of more nucleation sites encouraged by redistribution of functional groups. However, the adverse situation was found in PLA/RGOp nanocomposites. The observed phenomenon was ascribed to the disruption of the internal structure, i.e., the CC sp2 π-bond network, which deteriorated the CH−π interaction between PLA and RGO. These results conclusively suggested that the size and structural integrity of RGO had a concerted effort to determine the final nucleation ability of RGO dispersed by ultrasound.