Unusual Morphologies of Poly(vinyl alcohol) Thin Films Adsorbed on Poly(dimethylsiloxane) Substrates

Adsorption of poly(vinyl alcohol) (PVOH), 99% and 88% hydrolyzed poly(vinyl acetate), to poly(dimethylsiloxane) (PDMS) substrates was studied. The substrates were prepared by covalently attaching linear PDMS polymers of 2, 9, 17, 49, and 116 kDa onto silicon wafers. As the PDMS molecular weight/thickness increases, the adsorbed PVOH thin films progressively transition from continuous to discontinuous morphologies, including honeycomb and fractal/droplet. The structures are the result of thin film dewetting that occurs upon exposure to air. The PVOH film thickness does not vary significantly on these PDMS substrates, implicating the PDMS thickness as the cause for the morphology differences. The adsorbed PVOH thin films are less stable and have a stronger tendency to dewet on thicker, more liquid-like PDMS layers. When PVOH(99%) and PVOH(88%) thin films are compared, fractal and droplet morphologies are observed on high molecular weight PDMS substrates, respectively. The formation of the unique fractal features in the PVOH(99%) thin films as well as other crystalline and semicrystalline thin films is most likely driven by crystallization during the dehydration process in a diffusion-limited aggregation fashion. The only significant enhancement in hydrophilicity via PVOH adsorption was obtained on PDMS(2k), which is completely covered with a PVOH thin film. To mimic the lower receding contact angle and less liquid-like character of the PDMS(2k) substrate, light plasma treatment of the higher molecular weight PDMS substrates was carried out. On the treated PDMS substrates, the adsorbed PVOH thin films are in the more continuous honeycomb morphology, giving rise to significantly enhanced wettability. Furthermore, hydrophobic recovery of the hydrophilized PDMS substrates was not observed during a 1 week period. Thus, light plasma oxidation and subsequent PVOH adsorption can be utilized as a means to effectively hydrophilize conventional PDMS substrates. This study illustrates that the stability and morphology of adsorbed polymer thin films depend on polymer crystallinity as well as substrate physical properties.