Investigation of Molecular Mechanisms of Polyvinylidene Fluoride under the Effects of Temperature, Electric Poling, and Mechanical Stretching Using Molecular Dynamics Simulations.

This study uses molecular dynamics (MD) simulations to investigate the molecular mechanisms of polyvinylidene fluoride (PVDF) influenced by temperature, electric poling, and mechanical stretching. The β-phase, with all-trans ⟨T⟩ planar zigzag conformation, is known to have the best potential of energy harvesting, while α-phase, with alternating trans ⟨T⟩ and gauche ⟨G⟩ linkages, is more stable in terms of potential energy. By applying an electric field and uniaxial deformation to an amorphous PVDF system, we study the transformation from α- to β-phase and corresponding molecular mechanisms by tracking the molecular chain conformation using the trans percentages (PT). After complete relaxation of molecular chains, the chain conformations and PT values indicate a typical distribution pattern of α-phase. Next, we observe that the dipole moment of the system increases significantly with the presence of a strong electric field without immediately affecting the chain conformations. The increment of dipole moment is due to the aligning of side atoms within the chains and the increment becomes more significant with elevated temperature. In contrast, chain conformations change significantly under mechanical stretching. Specifically, before yielding, the total dipole moments are still governed by local orientations of atoms. Later, the chain segments begin to straighten in the large deformation stage, which leads to the increment of the total dipole moment. Our results also show that there exists an optimal temperature window for maximum ⟨G⟩ to ⟨T⟩ transformation rate. Moreover, we look into the synergistic effect of electric poling and mechanical stretching and explain molecular-level mechanisms for this effect. This study contributes to the fundamental understanding of the underlying molecular mechanisms for the piezoelectric PVDF system under different processing conditions.