Effect of Sequential Layer-by-Layer Surface Modifications on the Surface Energy of Plasma-Modified Poly(dimethylsiloxane)

Surface-initiated grafting of N,N-dimethylacrylamide, styrenesulfonate (SS), and (ar-vinylbenzyl)trimethylammonium chloride (VBTAC) from microwave plasma carboxylated, initiator-functionalized poly(dimethylsiloxane) (PDMS) surfaces was accomplished utilizing reversible addition−fragmentation chain transfer (RAFT) polymerization. Surface spectroscopic attenuated total reflectance (ATR) FT-IR analysis and atomic force microscopy (AFM) measurements were utilized to determine surface grafting and morphological surface features. The VBTAC-grafted PDMS provided a smooth, hydrophilic cationic surface for creating layer-by-layer (LBL) surfaces via alternating deposition of well-defined poly(SS) and poly(VBTAC), also prepared via aqueous RAFT. Comparisons of the ATR FT-IR spectra of the LBL assemblies and those of respective anionic poly(SS) and cationic poly(VBTAC) components confirmed strong electrostatic complexation of a fraction of the sulfonate and quarternary ammonium species in the layers as well as the existence of noncomplexed species. AFM images of surface topology indicated the presence of domains, likely phase-separated segments of the respective homopolymers, as well as interlayer mixing. The employed LBL methodology results in formation of stable, highly hydrophilic surfaces on a PDMS substrate. To our knowledge, this is the first study that illustrates surface functionalization of PDMS using microwave plasma and RAFT polymerization, followed by LBL deposition of polyelectrolytes.