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Process-morphology-property Relationships in Strut-like Poly(ether ether ketone) Aerogels Prepared through Thermally Induced Phase Separation

dc.contributor.authorSpiering, Glenn Allenen
dc.contributor.committeechairMoore, Robert Bowenen
dc.contributor.committeememberDavis, Richey M.en
dc.contributor.committeememberBortner, Michael J.en
dc.contributor.committeememberAshkar, Ranaen
dc.contributor.departmentGraduate Schoolen
dc.date.accessioned2025-11-26T09:00:35Zen
dc.date.available2025-11-26T09:00:35Zen
dc.date.issued2025-11-25en
dc.description.abstractPoly(ether ether ketone) (PEEK) aerogels resulting from gelation in 1,3-diphenyl acetone (DPA) were prepared for the first time. The phase separation mechanism was determined to be solid-liquid phase separation which resulted in the formation of aerogels consisting of crystalline axialites. These axialites formed a strut-like network that had superior compressive properties compared to the globular aerogels previous prepared from the gelation of PEEK in 4-chlorophenol and dichloroacetic acid. It was also found that strut-like PEEK or poly(phenylene sulfide) (PPS) aerogels prepared from gelation in DPA were mechanically robust such that they could resist the forces imposed on the gel during drying. Monolithic strut-like PEEK or PPS aerogels were prepared with vacuum-drying, freeze-drying, and supercritical CO2 extraction with minimal shrinkage and deformation. The weaker globular PEEK aerogel morphologies suffered from considerable shrinkage due to capillary forces or ice crystal growth induced on vacuum-drying or freeze-drying, respectively. Determining the gelation mechanism of PEEK in DPA allowed for effective manipulation of the processing parameters. It was found that changing the gelation temperature improved the mechanical properties of PEEK aerogels. Dissolution temperature can also be lowered to improve the nucleation density of PEEK aerogels.en
dc.description.abstractgeneralAerogels are interesting nanoporous materials with unique properties that stem from their fine microstructure. The phase separation process of forming a solid gel from a liquid solution is known as gelation. The route of phase separation is critical to the final morphology and properties of the resulting gel. In this work we prepare semicrystalline gels using a system of poly(ether ether ketone) (PEEK), a high performance semicrystalline polymer, and 1,3-diphenylacetone (DPA), a benign, high boiling point solvent. In this thermally induced phase separation process, the PEEK is dissolved in DPA at elevated temperatures. On cooling, the PEEK crystalizes into a 3-dimensional network that entraps the DPA. Replacing the solvent with air results in a PEEK aerogel consisting of a strut-like morphology with impressive mechanical properties. These gels were found to be strong enough to resist collapse on solvent removal using the cheaper, but more destructive drying methods. Further, understanding the phase separation process allowed us to explore the impact of changing processing parameters on aerogel morphology and properties.en
dc.description.degreeDoctor of Philosophyen
dc.format.mediumETDen
dc.identifier.othervt_gsexam:44786en
dc.identifier.urihttps://hdl.handle.net/10919/139766en
dc.language.isoenen
dc.publisherVirginia Techen
dc.rightsCreative Commons Attribution-NonCommercial-ShareAlike 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by-nc-sa/4.0/en
dc.subjectaerogelen
dc.subjectpoly(ether ether ketone)en
dc.subjectmorphologyen
dc.subjectX-ray scatteringen
dc.subjectgel drying methodsen
dc.titleProcess-morphology-property Relationships in Strut-like Poly(ether ether ketone) Aerogels Prepared through Thermally Induced Phase Separationen
dc.typeDissertationen
thesis.degree.disciplineMacromolecular Science and Engineeringen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.leveldoctoralen
thesis.degree.nameDoctor of Philosophyen

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