Tailoring the Conductivity and Flexibility of Natural Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)-Based Biocomposites by Introduction of Carbon Nanomaterials and Atactic Poly-3-hydroxybutyrate

In the present work, we provide the development results of highly efficient conductive biopolymer composite films with potential use as piezoresistive sensors. Natural isotactic biopolymer poly(3-hydroxybutyrate-<i>co</i>-3-hydroxyvalerate) (PHBV) was selected as the primary biopolymer material. To reduce the crystallinity and improve the processability of PHBV, the synthetic atactic (R,S)poly-3-hydroxybutyrate ((R,S)-PHB) polyester was blended with the semicrystalline PHBV biopolyester. Graphene nanomaterials with different structures, comprising crude multi-walled carbon nanotubes (MWCNTs), oxidatively functionalized multi-walled carbon nanotubes (ox-MWCNTs) and graphene nanoplatelets (GNPs), were proposed as electroactive fillers. The preparation of the composites was based on a simplified solvent casting method and the conductive graphene fillers were dispersed into the biopolyester matrix without any further routines. As a result of the optimization, a PHBV/((R,S)-PHB) mass ratio of 70:30 was found to be the most promising composition to obtain composite films with the expected mechanical characteristics. The influence of graphene filler structure on the degree of crystallinity, viscoelastic, electrical, and piezoresistive properties obtained for of the composites was determined. The lowest PHBV/PHB matrix crystallinities of 37% (DSC) and 39% (XRD) were recorded for the composite with 1% ox-MWCNTs and 1% GNPs. The most promising piezoresistive responses were noted for composites filled simultaneously with 1% GNPs and 1% ox-MWCNTs or MWCNTs. However, a 1.5% deformation and recovery did not affect the initial conductivity of the PHBV/(R,S)-PHB +1%MWCNTs+1%GNP system (9 × 10^-5 S/cm), while for the system with oxidized carbon nanotubes, the resistance increases by approximately 0.2% in relation to the initial value (8 × 10^-6 S/cm).