Effect of solvents on the crystal formation of poly(vinylidene fluoride) film prepared by a spin-coating process

• Published in: Polymer journal Vol. 49; no. 3; pp. 319 - 325
• Main Authors: Nishiyama, Takashi, Sumihara, Takayuki, Sato, Eriko, Horibe, Hideo
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.03.2017; Nature Publishing Group
• Subjects: 639/301/923/1028; 639/638/455/958; Beta phase; Biomaterials; Bioorganic Chemistry; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Coating effects; Crystal structure; Crystallinity; Crystals; Dipole moments; Evaporation rate; Fluorides; Gamma phase; Ions; original-article; Phase transformations; Polymer Sciences; Polymers; Polyvinylidene fluorides; Potential energy; Solvents; Spin coating; Surfaces and Interfaces; Thin Films; Vinylidene fluoride
• ISSN: 0032-3896; 1349-0540
• DOI: 10.1038/pj.2016.116

The effect of the solvent evaporation rate and solvent type on the crystal formation of poly(vinylidene fluoride) (PVDF) prepared by spin-coating was evaluated over time. In the much-solvent-remaining state, the crystalline phase of PVDF changed in the order of α, γ and β with the increasing dipole moment of the solvent. In the almost-all-solvent-evaporated state, the crystalline structure of PVDF/hexamethylphosphoramide with a higher dipole moment was dominantly dependent on the evaporation rate and varied in the order of β, γ and α with the increasing solvent evaporation rate. However, PVDF/triethyl phosphate, having a lower dipole moment, always formed the α phase, regardless of the evaporation rate. The PVDF α phase in the concentrated solution state is difficult to transform into the β and γ phases because the potential energy of each PVDF crystalline phase increases in the order of α, γ and β. The PVDF crystalline phase in the spin-coating method is strongly affected by both the polymer–solvent electrostatic interactions and the evaporation conditions. From the results of the crystal transition behavior, it was experimentally supported that the potential energy of the PVDF crystalline structure increases in the order of α, γ and β. The crystalline phase of PVDF film prepared by spin-coating changes both of the polymer–solvent interaction and the evaporation rate. In the much solvent remained state, the crystalline phase changes in the order of α, γ and β phase with increasing the dipole moment of solvent. In the solvent-evaporated state, the crystalline phase of PVDF and solvent with higher dipole moment system changes in the order of β, γ and α phase with increasing the solvent evaporation rate, whereas the PVDF and solvent with lower dipole moment system forms into α phase regardless of the evaporation rate.