We reported a new method to prepare polyvinyl alcohol (PVA)/thermoplastic starch (TPS) composites by using polyvinyl alcohol microspheres (PVAMS). The PVAMS/TPS composites were characterized using tensile test, scanning electron microscopy (SEM), dynamic mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA). The results exhibited that adding small amounts of PVAMSs can effectively improve the mechanical strength and toughness of the composites, especially for the 1 wt %PVAMS in TPS matrix, with a tensile strength of 3.5 MPa, an elongation at break at 71.73% and an impact strength of 33.4 kJ/m2
. Furthermore, the SEM and shift in the tan δ peak (Tα
) at the maximum value of 69.87 and −36.52 °C indicates that the PVAMS decreased the mobility of the amorphous starch molecules due to the strong intermolecular hydrogen bonds between PVAMS and TPS. The peak temperature of maximum decomposition rate (Tp) of 1 wt % PVAMS/TPS composites increased about 5 °C compared with TPS in TGA curves.
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