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Structure-Property Relationships of Polymeric Materials at the Solid-Polymer Melt Interfaces

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dc.contributor.advisor Koga, Tadanori en_US
dc.contributor.author Jiang, Naisheng en_US
dc.contributor.other Department of Materials Science and Engineering en_US
dc.date.accessioned 2017-09-20T16:50:00Z
dc.date.available 2017-09-20T16:50:00Z
dc.date.issued 2015-08-01
dc.identifier.uri http://hdl.handle.net/11401/76313 en_US
dc.description 189 pgs en_US
dc.description.abstract In this thesis, by combining various surface and interface characterization techniques, I report the structures, dynamics, and physical and mechanical properties of polymeric materials at the solid-polymer melt interface. Following the introduction, in Chapter 2, I show the experimental evidence of irreversibly adsorbed polymer layers (several nanometers thick) on silicon substrates regardless of the magnitude of attractive polymer-solid interactions. Interestingly, the adsorbed layers are composed of an inner, higher density region (~ 2 nm in thickness regardless of molecular weight (M<sub>w<sub>) with a more flattened chain conformation (' flattened layer' ) and an outer bulk-like density region whose thickness increases with M<sub>w<sub> (' loosely adsorbed layer' )). In Chapter 3, I show the impact of the adsorbed layer on the local viscosity of single polystyrene (PS) thin films, overcoming the effects of a surface mobile layer at the air/polymer interface. In Chapter 4, I reveal the novel adhesive properties of the two adsorbed PS layers (i.e., flattened layer and loosely adsorbed layer), which have contrasting roles in thermodynamic stability of a polymer film when prepared on the two adsorbed layers. In chapter 5, I further examine the swelling behavior of the adsorbed PS layer in supercritical CO<sub>2<sub>. The neutron reflectivity results demonstrate that the loosely adsorbed PS layer, which is found to be immobile even at temperatures far above the glass transition temperature, swells in CO<sub>2<sub>. Further interdiffusion experiments using bilayers of PS and deuterated PS in CO<sub>2<sub> indicate that swollen PS thin films have a mobility gradient in the direction normal to the film surface associated with the adsorbed layer. In Chapter 6, I exhibit work related to polymer structures and dynamics at the polymer-' curved' solid surface. For this purpose, I use polybutadiene (PB) chains bound to carbon black (CB) filler surfaces, known as ' bound rubber' in the rubber industry, by extracting with solvent leaching. Small-angle neutron scattering and neutron spin echo experiments for the ' bound rubber-coated' CB fillers dispersed in deuterated toluene reveal similar heterogeneous chain conformations on the curved surface: flattened chains constitute the inner unswollen region of the bound rubber layer and loosely adsorbed polymer chains form the outer swollen region. In addition, results show that the outer loosely adsorbed chains display similar collective relaxation to the ' breathing' dynamics that have been reported in end-grafted polymer chains in a good solvent. en_US
dc.description.sponsorship This work is sponsored by the Stony Brook University Graduate School in compliance with the requirements for completion of degree. en_US
dc.format Monograph en_US
dc.format.medium Electronic Resource en_US
dc.language.iso en_US en_US
dc.publisher The Graduate School, Stony Brook University: Stony Brook, NY. en_US
dc.subject.lcsh Materials Science en_US
dc.subject.other adsorption, interfaces, nanoconfinment, physical properties, polymer thin film, structures en_US
dc.title Structure-Property Relationships of Polymeric Materials at the Solid-Polymer Melt Interfaces en_US
dc.type Dissertation en_US
dc.mimetype Application/PDF en_US
dc.contributor.committeemember Sokolov, Jonathan en_US
dc.contributor.committeemember Venkatesh, T.A. en_US
dc.contributor.committeemember Fukuto, Masafumi en_US

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