Tailoring Thermal Conductivity Anisotropy in Poly(vinylidene fluoride)/Boron Nitride Nanosheet Composites via Processing-Induced Filler Orientation

To address the thermal management challenges in electronic devices, this study systematically investigates the effects of injection molding and compression molding on the microstructure and thermal conductivity of poly(vinylidene fluoride)/boron nitride nanosheet (PVDF/BNNs) composites. Using 10 μm diameter BNNs as thermal conductive fillers and PVDF as the matrix, the composites were characterized via scanning electron microscopy (SEM), thermal conductivity measurements, rheological analysis, X-ray diffraction (XRD), and mechanical tests. The results demonstrate that the strong shear stress in injection molding induces significant alignment of BNNs along the flow direction, leading to remarkable thermal conductivity anisotropy. At a PVDF/BNNs mass ratio of 90/10, the in-plane thermal conductivity of the injection-molded composite reaches 1.26 W/(m·K), while the through-plane conductivity is only 0.40 W/(m·K). In contrast, compression molding, which involves minimal shear, results in randomly dispersed BNNs and isotropic thermal conductivity, with both in-plane and through-plane values around 0.41 W/(m·K) at the same filler loading. Both processing methods preserve the coexistence of α- and β-crystalline phases in PVDF. However, injection molding enhances matrix crystallinity through stress-induced crystallization, yielding composites with higher density and superior tensile properties. Compression molding, due to slower cooling, leads to incomplete PVDF crystallization, as evidenced by a shoulder peak near 164 °C in differential scanning calorimetry (DSC) curves. This study elucidates the mechanism by which processing methods regulate the structure and properties of PVDF/BNNs composites, offering theoretical and practical guidance for designing high-performance thermally conductive materials.