Electronic Thesis and Dissertation Repository

Thesis Format

Integrated Article


Doctor of Philosophy




Ragogna, Paul J.


Photopolymer networks with phosphonium cation, alkyl phosphine and olefin functionality were designed, synthesized and functionalized with metals by metathesis, coordination and hydrometallation reactions, respectively. The materials were strategically designed so that the metal functionalization step could be monitored and quantified. In some cases, this involved characterization by IR, NMR, or X-ray spectroscopic techniques, or by comparison to molecular analogues. It was found that by using a bi-functional photopolymer network, the material could be bi-metallized by orthogonal mechanisms. All metallized polymer networks were tested for their suitability as precursors to metal-containing ceramics. The polymers were pyrolyzed, and on analysis it was found that this methodology mostly favors metal oxides, but metal phosphates and phosphides can also be achieved. Further findings showed that tuning the amount of metal in the polymer precursor has the effect of controlling the amount of metal in the ceramics after pyrolysis. Selected polymer networks were patterned before being metallized and pyrolyzed and this was found to be an effective way of forming patterned ceramics.

Summary for Lay Audience

We live in an age with a constant demand for more out of less. For example, the growing use of digital electronic devices has fostered an expectation of perpetually faster, higher performing yet smaller device components. With growing concern for the environment, consumers expect green vehicles that can travel farther on less or alternative fuel than older models. While these tasks are daunting, scientists have discovered materials that show promise in accomplishing them. These materials are called ceramics. Ceramics can be composed of elements spanning the periodic table and can occur in many different forms. Some ceramics can be easily synthesized, while others can be difficult to access, especially in the context of using them in applications which have specific requirements. The research in this dissertation is targeted towards developing general methods for making ceramics. The work is based in using specialized plastic as a precursor. Throughout the thesis different types of plastic, with different chemical functionality is explored for its ability to be functionalized with a diverse range of elements. Interestingly, if the element-containing plastic is pyrolyzed, it will leave an imprint of itself in the form of element-containing ceramic. While this research is targeted towards improving the production of useful ceramics, the focus in this early stage of the work is on understanding the fundamental structure and bonding in the new element-containing plastic and ultimately the effects that they have on the resulting ceramic materials.