Well-defined functional block copolymers containing either a fluorinated or a hydrophilic segment can be synthesized via a controlled free-radical technique, known as atom transfer radical polymerization (ATRP). Their self assembly characteristics in the solid state and in solution were examined in this work with the aim of developing ultralow dielectric constant materials and templates for conductive polymer synthesis, respectively. We demonstrated the controlled synthesis via ATRP of block copolymers containing poly(pentafluorostyrene) (PPFS) and a degradable polymer, such as poly(methyl methacrylate) (PMMA), poly([epsilon]-caprolactone) (PCL), or poly(D,L-lactide) (PLA). These block copolymers microphase separate in the solid state to form periodic nanostructures, such as alternating lamellae, a bicontinuous gyroid on a cubic lattice, cylinders on a hexagonal lattice, or spheres on a body-centered-cubic lattice, depending on the volume fraction of each block and the interblock segregation strength. Additionally, we quantified the interblock segregation strength of PPFS/PMMA, demonstrating that this block copolymer is only approximately twice as segregated as its nonfluorinated counterpart poly(styrene-[beta]-methyl methacrylate) due to the symmetric placement of the polar C-F bonds on the benzene ring in PPFS. We also showed that the self-assembly characteristics of PPFS-containing block copolymers can be used to create nanoporous fluorinated films with ultra-low dielectric constants in the range of 1.7 - 1.9. The dielectric constants are tunable through manipulation of the volume fraction of the degradable block in the parent block copolymers. We also demonstrated the controlled synthesis via ATRP of block copolymers containing poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAAMPSA) with either poly(oligo(ethylene glycol) methyl ether methacrylate) (PEGMA) or poly(methyl acrylate) (PMA). We showed that PEGMA/PAAMPSA formed well-ordered nanostructures in the solid state when cast from strong hydrogen bond accepting solvents, such as DMSO and DMF. PEGMA/PAAMPSA can also be used as the acid dopant in the synthesis of conductive polyaniline (PANI). Additionally, we studied the micelle formation of PMA/PAAMPSA and subsequently used these micelles as templates to create spherical conductive PANI nanoparticles. The size and size distribution of these PANI nanoparticles were dictated by the corresponding characteristics of the micellar template. / text

Thesis (Ph.D.)--University of Delaware, 2008. / Principal faculty advisor: Kristi L. Kiick, Dept. of Materials Science & Engineering. Includes bibliographical references.

Yes / Uniform onion micelles formed from up to ten nano-structured polymer layers were produced by the aqueous self-assembly of highly-branched copolymers. Highly-branched poly(alkyl methacrylate)s were chain extended with poly(acrylic acid) in a two-step reversible addition–fragmentation chain transfer-self-condensing vinyl polymerization (RAFT-SCVP) in solution. The resulting polymers were dispersed into water from oxolane (THF) using a self-organized precipitation-like method and the self-assembled particles were studied by phase-analysis light scattering, small-angle neutron scattering, and electron microscopy techniques. The relative hydrophobicity of the blocks was varied by changing the alkyl methacrylate (methyl, butyl, or lauryl) and this was found to affect the morphology of the particles. Only the poly(butyl methacrylate)-containing macromolecule formed an onion micelle structure. The formation of this morphology was observed to depend on: the evaporation of the good solvent (THF) during the self assembly process causing kinetic trapping of structures; the pH of the aqueous phase; and also on the ratio of hydrophobic to hydrophilic segments within the copolymer. The lamellar structure could be removed by annealing the dispersion above the glass transition temperature of the poly(butyl methacrylate). To exemplify how these onion micelles can be used to encapsulate and release an active compound, a dye, rhodamine B (Rh B), was encapsulated and released. The release behaviour was dependent on the morphology of the particles. Particles formed containing the poly(methyl methacrylate) or poly (lauryl methacrylate) core did not form onions and although these materials absorbed Rh B, it was continuously released at room temperature. On the other hand, the lamellar structure formed from branchpoly( butyl methacrylate)-[poly(butyl methacrylate)-block-poly(acrylic acid)] allowed for encapsulation of approximately 45% of the dye, without release, until heating disrupted the lamellar structure. / EPSRC and Domino UK Ltd for a Nanotechnology KTN CASE studentship to support SLC, Experiments at the ISIS Pulsed Neutron and Muon Source were supported by a beam time allocation from the Science and Technology Facilities Council (experiment numbers RB1220108 and RB1320167).

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Siu Man Hin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references. / Abstracts in English and Chinese. / Abstract --- p.i / Abstract in Chinese --- p.iv / Acknowledgement --- p.vi / Content --- p.vii / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Protein folding - Coil-to-globule transition --- p.1 / Chapter 1.2 --- Quaternary structure of proteins - Aggregation --- p.5 / Chapter 1.3 --- The effect of fast and slow heating rate to the aggregation of copolymers --- p.11 / Chapter 1.4 --- Main goal in thesis --- p.14 / Chapter 1.5 --- References --- p.18 / Chapter Chapter 2 --- Fundamentals of light scattering and instrumentation / Chapter 2.1 --- Static laser light scattering --- p.21 / Chapter 2.2 --- Dynamic light scattering --- p.22 / Chapter 2.3 --- Correlation function profile analysis --- p.24 / Chapter 2.4 --- Molar mass distribution and conformation of polymers --- p.25 / Chapter 2.5 --- Instrumentation / Chapter 2.5.1 --- Light source --- p.27 / Chapter 2.5.2 --- Cell design --- p.28 / Chapter 2.5.3 --- Detector --- p.28 / Chapter 2.5.4 --- Differential refractometer --- p.29 / References --- p.30 / Chapter Chapter 3 --- The effect of comonomer distribution on the coil-to-globule transition of a single AB copolymer chain in dilute solution / Chapter 3.1 --- Introduction --- p.32 / Chapter 3.2 --- Experimental / Chapter 3.2.1 --- Sample preparation and characterization --- p.35 / Chapter 3.2.2 --- Differential Scanning Calorimeter --- p.37 / Chapter 3.3 --- Results and discussion --- p.38 / Chapter 3.4 --- References --- p.49 / Chapter Chapter 4 --- Formation of mesoglobular phase of amphiphilic copolymer chains in dilute solution: 1. Effect of comonomer distribution / Chapter 4.1 --- Introduction --- p.50 / Chapter 4.2 --- Sample preparation and characterization --- p.53 / Chapter 4.3 --- Results and discussion --- p.54 / Chapter 4.4 --- References --- p.65 / Chapter Chapter 5 --- Formation of mesoglobular phase of amphiphilic copolymer chains in dilute solution: 2. Effect of comonomer distribution / Chapter 5.1 --- Introduction --- p.66 / Chapter 5.2 --- Sample preparation and characterization --- p.69 / Chapter 5.3 --- Results and discussion --- p.71 / Chapter 4.4 --- References --- p.80

Chen, Qianjin. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.