Degree
Doctor of Philosophy (PhD)
Department
Chemistry
Document Type
Dissertation
Abstract
Frontal polymerization is a rapid, energy-efficient, and sustainable technique for transforming liquid monomers into polymeric materials. It allows for the production of thermoplastics, thermosets, and composite systems, and is used in a vast array of applications. In this work, experimental investigations, namely kinetic studies on thermoset materials, were employed to study applications in coatings, additive manufacturing, flexible materials, and bubble-free materials.
Chapters 2 and 3 investigate initiators in free-radical frontal polymerization (FRFP) systems that produce bubble-free polymers. The shelf-life and temperature dependence on the front velocity of a synthesized persulfate initiator were investigated in Chapter 2. Contrary to a previously published work on the initiator, it was determined that the initiator had a short shelf-life, and the temperature at which it was stored did not significantly affect its overall shelf-life. In Chapter 3, another bubble-free initiator was studied. The first studied use of benzopinacol (or TPED) was in radical-induced cationic frontal polymerization methods. In this study, FRFP was employed with trimethylolpropane triacrylate as the monomer, and the effect of initiator concentration on front kinetics was investigated. This system produced bubble-free polymers, although major cracking within the polymers was observed.
Chapter 4 introduces a new imaging technique that involves observing fluorescent tracer particle movement within thin-layer acrylate coatings during FRFP. The function of layer thickness, initiator (Luperox 231) concentration, and filler (fumed silica) loading was studied, and instabilities such as Marangoni convection, buoyancy-driven convection, and viscous fingering were investigated.
The use of RICFP in additive manufacturing (3D printing) applications was demonstrated in Chapter 5. The influence of resin composition, initiator concentration, layer thickness, filler type, and loading was examined. Lastly, Chapter 6 presents a hybrid polymerization system using a thiol-ene free-radical and vinyl ether cationic hybrid system. The effect of thiol and initiator concentration on front velocity and temperature was investigated, and studies supporting the hybridization polymerization were employed. Mechanical testing on the flexible polymers produced was also conducted.
Date
3-26-2026
Recommended Citation
Aucoin, Alexandra V., "Experimental Investigations of Frontal Polymerization: Applications in Coatings, 3D Printing, Flexible Polymers, and Bubble-Free Initiators" (2026). LSU Doctoral Dissertations. 7053.
https://repository.lsu.edu/gradschool_dissertations/7053
Committee Chair
Pojman, John A.
LSU Acknowledgement
1
LSU Accessibility Acknowledgment
1