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dc.contributor.authorMargaretta, Evan Daviden_US
dc.date.accessioned2018-02-21T07:00:18Z
dc.date.available2018-02-21T07:00:18Z
dc.date.issued2016-08-29
dc.identifier.othervt_gsexam:8532en_US
dc.identifier.urihttp://hdl.handle.net/10919/82226
dc.description.abstractPolymeric materials with inherent stimulus response represent an ever-growing area of research. In particular, block copolymers demonstrate exciting properties owing to their enhanced mechanical strength and microphase separation. Incorporating functionality into block copolymers proves useful in enhancing their utility. Presently, synthesis and subsequent post-polymerization modification achieved this for a range of block copolymers. In particular, neutralization of acid-containing polymers readily imparted ionic functionality and yielded microphase-separated block copolymer domains, enhancing polymer thermomechanical properties and ion transport. An ABA triblock copolymer composed of mechanically reinforcing polystyrene outer blocks and ionic central poly(1-methylimidazolium acrylate) block acted as a host for ionic liquid that caused an evolution in bulk morphology, resulting in enhanced ionic conductivity. The resulting membrane also exhibited a strong electromechanical actuation response under applied potential. Adding ionic liquid doped with a corresponding lithium salt enabled evaluation of sulfonated block copolymers as components of ternary polymer electrolytes, relevant for battery applications. Modification of a sulfonic acid-containing pentablock copolymer presented photocurable functional groups to the ionic domains which enabled their UV irradiation-induced curing. This novel route of modifying ion-containing block copolymers resulted in enhanced thermomechanical properties and enabled healing of physical defects in the film, unprecedented for ion-containing block copolymers. Covalent networks represent a relevant area of research for a wide variety of applications such as coatings, adhesives, and scaffolds. Careful design of degradable crosslinkers enables stimulus response in these networks by eliminating covalent crosslinks and affording a soluble product. Extension of poly(ethylene glycol) methacrylate-based network formation into three dimensions using microstereolithography resulted in novel acid-degradable 3D-printed parts. An additional study investigated mixtures of acrylamide-modified poly(vinyl alcohol) and poly(ethylene glycol) diacrylate as water-soluble resins for the direct formation of hydrogels from solution. Photorheology and photocalorimetry investigated the thermal and mechanical changes inherent in the curing process and evaluated the mixtures as a platform for microstereolithography.en_US
dc.format.mediumETDen_US
dc.publisherVirginia Techen_US
dc.rightsThis Item is protected by copyright and/or related rights. Some uses of this Item may be deemed fair and permitted by law even without permission from the rights holder(s), or the rights holder(s) may have licensed the work for use under certain conditions. For other uses you need to obtain permission from the rights holder(s).en_US
dc.subjectIon-containing polymersen_US
dc.subjectblock copolymersen_US
dc.subjectstimulus responseen_US
dc.subjectpost-polymerization modificationen_US
dc.titleImparting Functionality to Macromolecules for Selective Stimulus Responseen_US
dc.typeDissertationen_US
dc.contributor.departmentChemistryen_US
dc.description.degreePHDen_US
thesis.degree.namePHDen_US
thesis.degree.leveldoctoralen_US
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen_US
thesis.degree.disciplineChemistryen_US
dc.contributor.committeechairLong, Timothy Een_US
dc.contributor.committeememberMoore, Robert Bowenen_US
dc.contributor.committeememberTurner, Sam Richarden_US
dc.contributor.committeememberHeflin, James Randyen_US


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