Influence of the solvent evaporation rate on the β-Phase content of electrosprayed PVDF particles and films studied by a fast Multi-Overtone QCM

A combination of an electrospray setup and a quartz crystal microbalance with dissipation monitoring (QCM-D) was employed to study the drying of droplets of poly(vinylidene fluoride) (PVDF) dissolved in dimethylformamide (DMF). A novel variant of the QCM was used, which interrogates the resonance frequency and the resonance bandwidth on four overtones at the same time, achieving a time resolution of 2 ms. This instrument allowed to elucidate the mechanism of β-phase formation in electrospray deposition of PVDF. When the distance between the nozzle and the substrate was small, the droplets landed in a partially wet state, as evidenced from an increase in the resonance bandwidth. No such increase in bandwidth was observed when the distance was large. From the flight time (milliseconds) and the drying time on the substrate (seconds), one concludes that drying in the plume is faster than drying on the substrate. IR spectra show that the β–phase content is close to 100 % for particles, which dried in the plume. It is less than 50 % for particles having dried on the substrate. Fast drying promotes the formation of the β-phase. Follow-up experiments with thicker films on steel substrates also show increased β-phase content for larger distances.