Multifunctional PVDF/BaFe12O19 Composite Membranes: Filler-Controlled β-Phase Evolution, Thermal Behavior, Optical, Dielectric, and Magnetic Properties

Multifunctional polymer–ferrite composites based on poly(vinylidene fluoride) (PVDF) and magnetic fillers are of increasing interest for applications requiring coupled electrical, dielectric, and magnetic responses. However, the relationship between magnetic filler concentration, PVDF phase composition, and the resulting multifunctional properties remains insufficiently understood. In this work, PVDF/BaFe12O19 (PVDF/BaF) composite membranes containing 2–20 wt.% BaF were fabricated using a combined non-solvent and thermally induced phase-inversion (NIPS–TIPS) method. Structural evolution was analyzed by X-ray diffraction and quantitative FTIR spectroscopy, thermal behavior by differential scanning calorimetry, optical properties by diffuse reflectance spectroscopy, dielectric response in the frequency range 103–106 Hz, and magnetic characteristics by vibrating sample magnetometry. At moderate filler concentrations (2–10 wt.%), BaFe12O19 nanoparticles acted as effective β-phase nucleating centers, leading to electroactive phase fractions of 97.7–99.9% and a maximum β-phase content of 86.7% for PVDF/BaF10. At higher loadings (15–20 wt.%), particle agglomeration and restricted chain mobility promoted a transition toward α-phase-dominated crystallization. Thermal analysis indicated competing nucleation and confined crystallization processes, while optical and dielectric measurements revealed nonmonotonic changes associated with interfacial interactions and Maxwell–Wagner–Sillars polarization. Magnetic measurements showed a linear increase in saturation magnetization with filler concentration and a nonmonotonic coercivity dependence with a pronounced change near the critical agglomeration concentration. These results demonstrate that the multifunctional response of PVDF/BaFe12O19 membranes is governed by the interplay between β-phase nucleation, interfacial polarization, and magnetic particle interactions, with approximately 10 wt.% ferrite providing the most balanced electrical, dielectric, and magnetic characteristics.