Surface structure,topology, and liquid wetting behavior in oriented polymers

The structure and the properties of oriented polymer surfaces were studied for three series of uniaxially oriented films of polypropylene (PP), polystyrene (PS), and poly(ethylene terephthalate) (PET). The surface structure was characterized in terms of relative crystallinity and molecular orientation along with topology and roughness by using FT-IR-ATR dichroism technique, optical microscopy and surface profilometer. In all three polymers, the surface orientation function increases with draw ratio. The relative surface crystallinity and the trans con-former also increases for PP and PET, respectively. In uniaxially drawn PP, the surface becomes rough with increasing draw ratio and the roughness is anisotropic with peaks and valleys elongated along the draw direction. For drawn PP, the equilibrium contact angles for four different liquids all exhibit anisotropy with higher values in perpendicular direction than that in parallel to the draw direction. In contrast, both drawn PET and PS films show smooth surfaces, and the equilibrium contact angles were all isotropic. When roughness is removed from the drawn PP by polishing without altering the molecular orientation, the anisotropy becomes negligible and the contact angles approach the value for undrawn PP. When surface roughness was created deliberately on undrawn PET and PS films, the contact angle anisotropy was clearly observed. Therefore, the anisotropy in surface topology rather than the molecular orientation seems to play a dominant role in developing anisotropic wetting behavior. The equilibrium contact angles for smooth surfaces have been calculated using the experimentally obtained roughness and anisotropic contact angle data from the rough surface. These values are in reasonable agreement with the measured contact angles for smooth surfaces, suggesting that the observed contact angle anisotropy can be attributed entirely to the roughness anisotropy rather than to the molecular orientation.