Date of Award

Fall 2010

Degree Type


Degree Name

Doctor of Philosophy (PhD)


Polymers and High Performance Materials

Committee Chair

James Rawlins

Committee Chair Department

Polymers and High Performance Materials

Committee Member 2

Sergei Nazarenko

Committee Member 2 Department

Polymers and High Performance Materials

Committee Member 3

Janice Paige Buchanan

Committee Member 3 Department

Chemistry and Biochemistry

Committee Member 4

Daniel Savin

Committee Member 4 Department

Polymers and High Performance Materials


Matrices employed in composite materials directly influence overall composite properties. In all thermoset materials, molecular level interactions and transformations during cure result in heterogeneous architecture. Variability in connectivity results from the often dramatic spatial and topological changes that occur during the crosslinking process. Compatibility (fillers, pigments, additives), temperature gradients and reactivity differences in the precursors only serve to increase the complexity of network formation. The objective of the research herein is to characterize and understand the relationships between cure conditions, conversion, connectivity, network architecture and properties in glassy thermosetting matrix resins.

In this research, epoxy and vinyl ester resins (VERs) were characterized to identify controlling factors in the development of network architecture and understand how they affect the mechanical properties. VERs cure under low temperature conditions (< 50 °C) via redox catalysis resulted in vitrification limiting conversion with resulting glass transition temperatures (Tgs) approximately 15 °C above the cure temperature. Subsequently, in situ ligand exchange altered the activity of the metal catalyst, and the reduced connectivity of the resulting networks translated into a 30% reduction in stiffness above Tg. Network architecture was further manipulated by changing the chemical composition of the backbone. Incorporation of POSS nanoparticles into VERs resulted in changes to initial network development, with higher levels of conversion prior to vitrification. 3,3’-DDS was cured with a variety of epoxies and examined for conversion, connectivity and mechanical properties. Comparison with 4,4’-DDS revealed significant correlations between molecular level structure and properties.

The research established relationships between cure conditions, conversion, connectivity and properties in glassy thermosetting matrix resins. Specifically, the importance of early stages of network development was correlated to ultimate properties. Network architecture is sensitive to the mobility, concentration and rate of matrix development. These parameters can be altered through changes in temperature or initiating system. Control of the network architecture and ultimately mechanical properties can be achieved by tailoring reaction rate and mobility appropriately. Rapid conversion with inadequate mobility increases heterogeneity and reduces mechanical viability through poor connectivity. Conversion must occur at rates comparable to mobility to ensure high conversion and excellent connectivity to maximize mechanical properties.