Synthesis And Morphology Of Polydimethylsiloxane Nylon6 Diblock Copolymers PDF Download

The thin film morphology characteristics of polydimethylsiloxane-containing block copolymers have been investigated. For this investigation, a commercially available hydroxyl terminated PDMS was purchased from Gelest and attached to a carboxylic acid functional reversible addition-fragmentation chain transfer (RAFT) agent by Steglich esterification. This produced macro-RAFT agents to which styrene monomer was polymerized. By using this approach the generation of low polydispersity polystyrene-block-polydimethylsiloxane (PS-block-PDMS) copolymers of various molecular weights spanning a wide volume fraction range in which the PDMS block remained the same in each polymerization. Synthesized block copolymers were characterized by gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. Bulk and thin film characterization of PS-block-PDMS copolymers was done by small-angle x-ray scattering (SAXS), transmission electron microscopy (TEM), contact angle measurements, scanning force microscopy (SFM), and grazing incidence small-angle X-ray scattering (GISAXS). The following observations have been made. For PS-rich PS-block-PDMS copolymer thin films the low surface tension of PDMS caused it to migrate to the film surface regardless of solvent choice. The surface morphology was found to depend strongly on the solubility parameter of the solvent and exhibited SFM images consistent with parallel cylinder, perforated lamellar, and lamellar surface layers with increasing solvent solubility parameter. This behavior was due to the selective swelling of the individual blocks under slightly selective, good solvent conditions. A custom solvent annealing apparatus provided similar results in which order-order transitions in the thin films were observed with increasing solvent solubility parameter. Additionally improvements in the long-range order were observed after 1 h of solvent annealing. PS-rich PS-block-PDMS copolymer thin films also displayed PDMS rich surfaces after casting. Etching of this wetting layer by exposure to ultraviolet/ozone (UVO) cleaner allowed characterization of the interior film morphology. GISAXS was also able to characterize domain orientation in the as-cast and selectively etched thin films. PDMS cylinder orientation in PS-block-PDMS copolymer was found to be dependent on solvent choice and polymer molecular weight. The likely mechanism for perpendicularly oriented PDMS cylinders in selective solvents was an order-order transition to spheres where cylinders would nucleate at the air/film surface and template a perpendicularly oriented morphology during evaporation induced ordering. Perpendicularly oriented PDMS cylinders were observed in the lower molecular weight PS-rich PS-block-PDMS thin film samples indicating a preferential molecular weight range for the formation of perpendicular domains. Solvent annealing in PS selective chlorobenzene improved the long range order, but was not a strong driving force in altering domain orientation.