Molecular Dynamics Study on Wettability of Poly(vinylidene fluoride) Crystalline and Amorphous Surfaces

Abstract

The present study investigates the effect of microscopic structure on the wettability of poly(vinylidene fluoride) (PVDF) surfaces using all-atom molecular dynamics simulations of water droplets brought into contact with both crystal and amorphous PVDF surfaces. For each case, computations were performed using five different droplet diameters, and the corresponding water droplet contact angles θ were obtained. Using the fact that the cosine of these contact angles for both surfaces are inversely proportional to the radius of the droplet contact surface ( rdr( Z0)), the contact angle θ∞ of the macroscopic water droplet was obtained by extrapolating cos θ to 1/ rdr( Z0) = 0. The estimated values of θ∞ on the crystal and amorphous surfaces were 96° and 86°, respectively, showing that the amorphous surface is less hydrophobic than the crystal surface. The contact angle of the crystalline/amorphous mixed surface was estimated using the Cassie equation to be 91°. This value agrees well with experimental measurement of the water contact angle on the PVDF film. Furthermore, the interaction energy, interface structure, and electrostatic potential were analyzed to clarify the reason for the lower hydrophobicity of the amorphous surface. This surface interacts more favorably with water than the crystal surface. Such an interaction reduces the excess free energy (interfacial tension) at the PVDF and water interface and makes the amorphous surface less hydrophobic. The amorphous interfacial region contains more water molecules than the crystal one, and water molecules are oriented toward the PVDF. This interface structure makes water strongly interact with the PVDF.