Date of Award


Document Type

Open Access Dissertation

Degree Name

Doctor of Philosophy (PhD)

Degree Program

Polymer Science and Engineering

First Advisor

E. Bryan Coughlin

Second Advisor

Alfred J. Crosby

Third Advisor

Anthony D. Dinsmore

Subject Categories

Polymer Science


Hybrid organic-inorganic materials represent a new class of materials having scientific and technological potential. In this thesis, Polyhedral Oligomeric Silsesquioxanes (POSS) are used as an inorganic building block which has been tethered to an organic polymer. POSS are silica precusors, having a well defined silsesquioxane cental core surrounded by an organic periphery which makes them compatible with monomers and possibly polymers. The objectives of this study are to (1) study the basic structures of POSS homopolymers, (2) to incorporate POSS building blocks by a bottomup approach into polymer chains and study the resulting morphologies, and (3) to study the thin film behavior of POSS block copolymers. PMA and styryl POSS homopolymers of different peripheries were synthesized by ATRP and mass spectrometry studies were carried out by MALDI-TOF and ESI. PMA POSS chains undergo a number of fragmentations while styrly POSS chains have a relatively robust backbone. Poly(ethylene-butylene-b-MAPOSS), AB type copolymers and poly(MAPOSS-b-styrene-b-MAPOSS), ABA type copolymers were synthesized by a combination of anionic and ATRP polymerization. Spheres, inverse cylinders, lamellar and crystalline lamellar morphologies were observed for the poly(ethylene-butylene-b- MAPOSS) copolymers. In the poly(MAPOSS-b-styrene-b-MAPOSS) copolymers, cylindrical, lamellar and perforated lamellar morphologies were obtained. Beyond the interaction parameter (χ), total degree of polymerization (N) and volume fraction (f), the conformational asymmetry (ε) also plays an important role in determining the morphology of these block copolymer. Crystallization of the POSS phase and better thermal properties were observed in the both block copolymers. Thin film studies of poly(MAPOSS-b-styrene-b-MAPOSS) copolymers showed that the microdomains can be oriented either parallel or perpendicular to the substrate depending upon the film thickness, morphology and relative volume fractions of the connecting blocks. By removal of the organic phase, ordered mesoporous low dielectric constant silica films were obtained. These hybrid block copolymers are a potential candidate for nanopatterning applications.