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This study focuses on the fabrication of polymer nanocomposite films using polyvinyl alcohol (PVA)/graphene quantum dots (GQDs). We investigate the relationship between the structural, thermal, and nanoscale morphological properties of these films and their photoluminescent response. Although according to X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and differential thermal analysis (DTA), the incorporation of GQDs does not significantly affect the percentage crystallinity of the PVA matrix, for a range of added GQD concentrations, atomic force microscopy (AFM) showed the formation of islands with apparent crystalline morphology on the surface of the PVA/GQD films. This observation suggests that GQDs presumably act as nucleating agents for island growth. The incorporation of GQDs also led to the formation of characteristic surface pores with increased stiffness and frictional contrast, as indicated by ultrasonic force microscopy (UFM) and frictional force microscopy (FFM) data. The photoluminescence (PL) spectra of the films were found to depend both on the amount of GQDs incorporated and on the film morphology. For GQD loads >1.2%wt, a GQD-related band was observed at ~1650 cm -1 in FT-IR, along with an increase in the PL band at lower energy. For a load of ~2%wt GQDs, the surface morphology was characterized by extended cluster aggregates with lower stiffness and friction than the surrounding matrix, and the PL signal decreased.

The mechanical behavior of polymer materials is heavily influenced by a phenomenon known as crazing. Crazing is a precursor to damage and leads to the formation of cracks as it grows in both thickness and tip size. The current research employs an in situ SEM method to investigate the initiation and progression of crazing in all-biopolymeric blends based on Polyhydroxyalkanoates (PHAs). To this end, two chemically different grades of PHA, namely poly(hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV), were melt-blended with polybutyrate adipate terephthalate (PBAT). The obtained morphologies of blends, the droplet/fibrillar matrix, were highly influenced by the plasticity of the matrices as well as the content of the minor phase. Increasing the concentration of PBAT from 15 to 30 wt.% resulted in the brittle to ductile transition. It changed the mechanism of plastic deformation from single craze-cracking to homogeneous and heterogeneous intensified crazing for PHB and PHBHV matrices, respectively. Homogeneous tensile crazes formed perpendicularly to the draw direction at the initial stages of deformation, transformed into shear crazes characterized by oblique edge propagation for the PHBHV/PBAT blend. Such angled crazes suggested that the displacement might be caused by shear localized deformation. The crazes' strength and the time to failure increased with the minor phase fibers. These fibers, aligned with the tensile direction and spanning the width of the crazes, were in the order of a few micrometers in diameter depending on the concentration. The network of fibrillar PBAT provided additional integrity for larger plastic deformation values. This study elucidates the mechanism of crazing in PHA blends and provides strategies for controlling it.