Nanoscale Investigations of α- and γ-Crystal Phases in PVDF-Based Nanocomposites

The impact of carbon nanotube (CNT) incorporation into semicrystalline poly(vinylidene fluoride), PVDF, was investigated at both the macro and nanoscales. A special effort was devoted to probe the local morphology and the mechanical, ferroelectric, piezoelectric, and electrical conductivity response by means of atomic force microscopy. Incorporation of CNTs mainly induces the development of the polar γ-phase, and as a consequence, the coexistence of the γ-phase with the most stable nonpolar α-phase is observed. A maximum γ-phase content is reached at 0.7 wt % CNT loading. The spherulitic morphology of the PVDF α-phase is assessed, in conjunction with the lack of any ferroelectric response, while the presence of the polar γ-phase is confirmed, owing to clear piezoresponse signals. Local piezoelectric measurements on γ-phase domains yield a maximum effective coefficient | d₃₃| ≈ 13 pm/V, thus underlining the potential for applications of such functional PVDF-based nanocomposites in advanced piezoelectric devices. An increase in macroscopic conductivity with CNT content is observed, with a percolation threshold achieved for a composition close to 0.7 wt %. Nanoscale investigation of the electrical conductivity confirms the presence of some infinite CNT cluster homogeneously distributed over the surface. The macroscopic viscoelastic behavior of the composite reflects the reinforcing effect of CNTs, while the nanomechanical characterization yields a local contact modulus of the γ-phase domains larger than that of its α-phase counterpart, in agreement with the fact that the CNTs act as γ-phase promoters and subsequently reinforce the γ-domains.