Tailoring poly(vinylidene fluoride-co-chlorotrifluoroethylene) microstructure and physicochemical properties by exploring its binary phase diagram with dimethylformamide

Poly(vinylidene fluoride-co-chlorotrifluoroethylene), PVDF-CTFE, membranes were prepared by solven casting from dimethylformamide, DMF. The preparation conditions involved a systematic variation of polymer/solvent ratio and solvent evaporation temperature. The microstructural variations of the PVDF-CTFE membranes depend on the different regions of the PVDF-CTFE/DMF phase diagram, explained by the Flory-Huggins theory. The effect of the polymer/solvent ratio and solvent evaporation temperature on the morphology, degree of porosity, β-phase content, degree of crystallinity, mechanical, dielectric and piezoelectric properties of the PVDF-CTFE polymer were evaluated. In this binary system, the porous microstructure is attributed to a spinodal decomposition of the liquid-liquid phase separation. For a given polymer/solvent ratio, 20 wt%, and higher evaporation solvent temperature, the β-phase content is around 82% and the piezoelectric coefficient, d33, is - 4 pC/N.

This work is funded by FEDER funds through the “Programa Operacional Factores de Competitividade – COMPETE” and by national funds from FCT – Fundação para a Ciência e a Tecnologia, in the framework of the strategic project Strategic Project PEST-C/FIS/UI607/2014 and PEST-C/QUI/UI0686/2013). The authors also thank funding from Matepro –Optimizing Materials and Processes”, ref. NORTE-07-0124FEDER-000037”, co-funded by the “Programa Operacional Regional do Norte” (ON.2 – O Novo Norte), under the “Quadro de Referência Estratégico Nacional” (QREN), through the “Fundo Europeu de Desenvolvimento Regional” (FEDER), and grant SFRH/BD/68499/2010 (C.M.C.). The authors thank Solvay for kindly supplying the high quality materials and the Departmento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Spain, for hosting a research stay in which the theoretical work was performed.