Comprehensive Characterization of Solution-Cast Pristine and Reduced Graphene Oxide Composite Polyvinylidene Fluoride Films for Sensory Applications

Abstract

Pristine and doped polyvinylidene fluoride (PVDF) are actively investigated for a broad range of applications in pressure sensing, energy harvesting, transducers, porous membranes, etc. There have been numerous reports on the improved piezoelectric and electric performance of PVDF-doped reduced graphene oxide (rGO) structures. However, the common in situ doping methods have proven to be expensive and less desirable. Furthermore, there is a lack of explicit extraction of the compression mode piezoelectric coefficient (d33) in ex situ rGO doped PVDF composite films prepared using low-cost, solution-cast processes. In this work, we describe an optimal procedure for preparing high-quality pristine and nano-composite PVDF films using solution-casting and thermal poling. We then verify their electromechanical properties by rigorously characterizing β-phase concentration, crystallinity, piezoelectric coefficient, dielectric permittivity, and loss tangent. We also demonstrate a novel stationary atomic force microscope (AFM) technique designed to reduce non-piezoelectric influences on the extraction of d33 in PVDF films. We then discuss the benefits of our d33 measurements technique over commercially sourced piezometers and conventional piezoforce microscopy (PFM). Characterization outcomes from our in-house synthesized films demonstrate that the introduction of 0.3%w.t. rGO nanoparticles in a solution-cast only marginally changes the β-phase concentration from 83.7% to 81.7% and decreases the crystallinity from 42.4% to 37.3%, whereas doping increases the piezoelectric coefficient by 28% from d33 = 45 pm/V to d33 = 58 pm/V, while also improving the dielectric by 28%. The piezoelectric coefficients of our films were generally higher but comparable to other in situ prepared PVDF/rGO composite films, while the dielectric permittivity and β-phase concentrations were found to be lower.