Constructing robust 3-dimensionally conformal micropatterns: vulcanization of honeycomb structured polymeric films

Here, we present the static breath figure process for constructing 3-dimensionally conformal microporous films on nonplanar substrates, with a commercially available triblock polymer, polystyrene-b-polyisoprene-b-polystyrene. The polymer can cover the surface of nonplanar substrates with ordered porous morphology despite the sharp corners and irregular shapes, which was ascribed to the fluid-like character of the matrix. In the subsequent vulcanization, the micro-patterned polymer films were effectively crosslinked and became self-supported even after removing the sacrificial templates. The 3D structures became resistant to a wide range of organic solvents and thermally stable up to 350 degrees C, an increase of more than 300 K as compared to the un-crosslinked films. The surface features on the 3D structures along the direction of the descending solvent level were investigated in detail by scanning electron microscopy. Furthermore, the versatility of this patterning method was also demonstrated by forming hierarchical micro-structures on bas-relief Si substrates with different patterns. Particularly, hydroxy groups were introduced into another commercially available triblock polymer, polystyrene-b-polybutadiene-b-polystyrene by hydroboration. The functionalized 3D micropatterns feasible for site-directed grafting were created by the hydroxyl-containing polymers.