Date of Award

Spring 2020

Degree Type


Degree Name

Doctor of Philosophy (PhD)


Polymer Science and Engineering

Committee Chair

Jeffrey Wiggins

Committee Chair School

Polymer Science and Engineering

Committee Member 2

Robson F. Storey

Committee Member 2 School

Polymer Science and Engineering

Committee Member 3

Derek L. Patton

Committee Member 3 School

Polymer Science and Engineering

Committee Member 4

Yoan Simon

Committee Member 4 School

Polymer Science and Engineering

Committee Member 5

Xiaodan Gu

Committee Member 5 School

Polymer Science and Engineering


The research presented addresses the design of novel materials for additive manufacturing through a dual-cure approach that combines UV initiated free-radical polymerization of an acrylic network combined with the thermally initiated ring opening polymerization of a benzoxazine network. This work is split into three primary sections: the first and second sections focus on the synthesis and characterization of networks based on dual-cure BOX monomers, while the third develops simulation tools to further investigate thermoset networks prepared via additive manufacturing. A novel 3D printing formulation based on a multifunctional benzoxazine (BOX) monomer possessing both photo and thermally polymerizable functional groups is reported. Printing formulation viscosity is readily tuned using a monofunctional reactive diluent to enable Stereolithography (SLA) 3D printing. In the primary curing step, the printing formulation is UV-cured by SLA 3D printing to prepare accurate parts on the millimeter size scale. The 3D printed parts are then heated in the secondary curing step to activate a thermally initiated BOX ring opening polymerization. The last chapter of this research applies a combined computational and experimental approach to study the photo initiated free radical polymerization of an acrylate during SLA 3D printing at an atomistic level. After simulated crosslinking, network properties including crosslink density and glass transition temperature are calculated and compared to experimental results.

Available for download on Thursday, May 14, 2020