VDF-based
polymers, such as poly(vinylidene fluoride) (PVDF) and
its copolymers, are well-known ferroelectrics of interest for numerous
applications, from energy storage to electrocaloric refrigeration.
However, their often complex thermal phase behavior that typically
leads to a low phase-stability can drastically affect the long-term
dielectric properties of this materials family. Here, we demonstrate
on the example of the terpolymer P(VDF-ter-TrFE-ter-CFE) (molar ratio: 64/29/7) that by limiting mass transport/segmental
chain motion both during solidification and in the solid state, a
drastically smaller “burn-in” in relative permittivity,
εr, is observed. Indeed, εr decreases
little over time and saturates rapidly at 96–97% of its initial
value. Mass transport thereby is limited by using highly entangled
systems via the selection of a suitable polymer solution concentration
and molecular weight. In addition, rapid solvent extraction assists
in reducing unwanted relaxation processes. Accordingly, increased
control of the phase stability of P(VDF-ter-TrFE-ter-CFE) is gained. Moreover, pathways are opened to reliably
identify processing routes for any given VDF-based polymer, with critical
information being obtained from thermal analysis and rheometry data
only, enabling rapid feedback to material design, including the prediction
of required molecular weights without the need for complex characterization
methodologies.