Fundamental and applied studies of polymeric photonic crystals: the role of polymer architecture and 3D printing
Date
2020
Authors
Boyle, Bret Michael, author
Miyake, Garret, advisor
McNally, Andrew, committee member
Menoni, Carmen, committee member
Prawel, David, committee member
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Abstract
Block copolymers (BCP) provide a bottom-up, economical approach to synthesizing polymeric photonic crystals (PC) through the process of self-assembly. Photonic crystals (PC) are defined as periodic, dielectric nanostructures able to reflect certain wavelengths of light within a photonic band gap. The ability to directly tailor the synthesis, conformation, and self- assembly of a BCP to affect the properties of the resulting PC material creates a modular platform for PC materials design. Even though this platform exists for polymeric PC materials, the direct result of modulating the polymer architecture on the dynamics, self-assembly, and application of PC materials remains relatively unexplored. To help close this gap, this dissertation presents the polymer synthesis, characterization, and self-assembly of macromolecules within two unique classes of polymer architecture, dendritic block copolymers (DBCP) and bottlebrush block copolymers (BBCP). DBCPs were shown to possess many characteristics similar to those of bottlebrush polymers such as a rod-like conformation, a reduced capability for chain entanglement, and lower glassy moduli compared to non-rigid, linear polymers. Further, DBCPs possess high free energy parameters, as well as glass transition temperatures below melt extrusion 3D printing operating conditions, and were shown to self- assemble into PCs during the process of 3D printing. DBCP PCs represented the first example of 3D printing structural color. For BBCPs, the backbone composition's effect on the global BBCP conformation and in modulating self-assembly processes was examined. The backbone composition was shown to dramatically shift the wavelength of reflection of the PC material at similar molecular weights as well as improve the fidelity of the nanostructure morphology as the molecular weight increases from 50,000 g/mol to 2 million g/mol. The structure-property relationships illuminated herein have laid the groundwork for new research efforts into engineering BCPs for novel PC applications.
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Subject
architecture
polymer
structural color
photonic crystals
powder melt extrusion
3D printing