Download or read book Synthesis, Self-Assembly, and Modification of Poly(vinylpyridine) Based Block Copolymers for the Creation of Well-Ordered Charged Nanostructures written by Brandon Aubrey Fultz and published by . This book was released on 2020 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation investigates the use of block copolymer self-assembly to create nanostructures with unique domain properties. Precise control over nanoscale feature size and properties of materials has become increasingly more important to keep up the ever-decreasing size of technology. Bottom-up approaches using block copolymers has been progressively more attractive due to their ability to autonomously self-assembly into an array of complex morphologies with features sizes as small as 2-3 nanometers. Modifications of these systems has generally been limited to only one domain as the processes under which modifications are carried out generally result in the disruption or destruction of the underlying morphology. We originally set out to create a block polymer system containing poly(vinylpyridine) (PVP) segments which can undergo several transformations such as protonation, metal coordination, or quaternization. By coupling PVP segments with poly(tert-butyl methacrylate), we believed that a well-ordered charged mosaic containing segregated opposite charges could be created without disruption of the underlying morphology. Thin films of hexagonally packed P4VP cylinders were self-assembled perpendicular to the surface and subsequently treated with bromoethane vapor at various durations to quaternize pyridinyl nitrogens. The PtBMA matrix was then partially hydrolyzed to poly(methacrylic acid), PMAA, through HCl vapor treatment followed by neutralization by brief submersion in KOH solution. Using techniques such as AFM, contact angle testing, and ToF-SIMS, we were able to determine the success of these transformations as well as methodologies in which structural morphology was maintained. An additional exploration into the use of tris(trimethylsilyl)silane (TTMSS) as non-toxic alternative to tin hydrides using only light was investigated as a method to remove reversible addition-fragmentation transfer (RAFT) chain transfer agents. As the end group removal from PVP polymers derived from RAFT has to our knowledge never been reported, we felt that these results would be invaluable to the scientific community due to the ubiquitous use of PVP in many systems. Not only was TTMSS found to be an effective reagent for RAFT removal of PVP polymers, it was also found to be effective for the removal of RAFT end groups from polystyrene which has been generally reported in literature to be difficult due to the stability of the benzyl radical. Reactions were found to be complete for most polymers in less than 2 hours whereas, other reported reagents typically took 24 hours or as much as 1 week.