The phase diagrams for the thermoreversible gelation of poly(ether ether ketone) (PEEK) in dichloroacetic acid (DCA) and 4-chlorophenol (4CP) were constructed over broad temperature and concentration ranges, revealing that PEEK is capable of dissolving and forming gels in DCA and 4CP up to a weight fraction of 25 wt.%. Highly porous aerogels of PEEK were prepared through simple solvent exchange and solvent removal of the PEEK/DCA or PEEK/4CP gels. Solvent removal utilized freeze-drying (sublimation) methods or supercritical CO2 drying methods. Varying the weight fraction of PEEK dissolved in solution determined PEEK aerogel density. Mechanical properties (in compression) were shown to improve with increasing density, resulting in equivalent compressive moduli at comparable density regardless of preparation method (concentration variation, gelation solvent, solvent removal method, or annealing parameters). Additionally, density-matched aerogels from various MW PEEK showed a correlation between increasing MW and increasing compressive modulus. Contact angle and contact angle hysteresis revealed that PEEK aerogels have a high contact angle, exceeding the conditions necessary to be classified as superhydrophobic materials. PEEK aerogel contact angle decreases with increasing density and a very low contact angle hysteresis that increases with increasing density, regardless of gelation solvent or drying method. Small angle neutron scattering (SANS) contrast-matching experiments were used to elucidate the morphological origin of scattering features, wherein it was determined that the origin of the scattering feature present in the small angle scattering region was stacked crystalline lamella. Ultra-small angle X-ray scattering (USAXS)/SAXS/Wide angle X-ray scattering (WAXS) was then used to probe the hierarchical nanostructure of PEEK aerogels across a broad range of length scales. The Unified Fit Model was used to extract structural information, which was then used to determine the specific surface areas of PEEK aerogels. Regardless of gelation solvent, gel concentration, or solvent removal method, all PEEK aerogels display high surface areas as determined by SAXS and high surface areas as determined by nitrogen adsorption methods. Surface area values determined from SAXS data were consistently higher than that measured directly using nitrogen adsorption, suggesting that pore densification diminishes the accessible aerogel surface area. / Ph. D. / Poly(ether ether ketone) (PEEK) is a semicrystalline polymer with high temperature thermal transitions and excellent mechanical strength, making it an ideal candidate for many high-performance polymer applications. When PEEK is dissolved in particular solvents, it will form a 3-dimensional network where crystalline polymer is the cross-linking unit of the network. Careful solvent removal does not significantly perturb the gel network structure and produces a low-density aerogel. This work details the first reported instance of the monolithic gelation of PEEK and the first examples of PEEK aerogels. The nanostructure of these gels and aerogels is fully characterized to relate structural features to physical properties such as mechanical stiffness and wettability.

This work investigates the influence of microstructure and cooling and heating rates on the physical and chemical properties of fast crystallizing polymers. The primary objectives were to 1) utilize advanced methodologies to accurately determine the fundamental thermodynamic value of equilibrium melting temperature (Tmo) for the semi-crystalline polymer poly(ether ketone ketone) (PEKK), 2) increase understanding of the influence of microstructure (random versus blocky) of functionalized semi-crystalline polymers on physical and chemical properties, and 3) understand the influence of additive manufacturing process parameters on semi-crystalline polymer crystallization and final properties. All objectives utilized the advanced characterization technique of fast scanning calorimetry (FSC) using the Mettler Toledo Flash DSC 1. The first half of this work focuses on the high-performance semi-crystalline aromatic polymer poly(ether ketone ketone) (PEKK) with a copolymerization ratio of terephthalate to isophthalate moieties (i.e., T/I ratio) of 80/20. Due to the fast heating and cooling rates of the Flash DSC, PEKK underwent melt-reorganization upon heating at slow heating rates. This discovery resulted in utilizing a Hoffman-Weeks linear extrapolation of the zero-entropy production temperature to establish a new equilibrium melting temperature of 382 oC. Additionally, a new NMR solvent, dichloroacetic acid, was discovered for PEKK, allowing for comprehensive NMR analysis of PEKK for the first time. Diphenyl acetone (DPA) was discovered as a novel, benign gelation solvent for PEKK, enabling heterogeneous gel-state bromination and sulfonation to afford blocky microstructures. The gel state functionalization process resulted in a blocky microstructure with runs of pristine crystallizable PEKK retained within the crystalline domains, and amorphous domains containing the functionalized PEKK monomers. The preservation of the pristine crystalline domains resulted in enhanced physical and chemical properties compared to the randomly functionalized analogs. Additionally, heterogeneous gel state functionalization of PEKK gels prepared from different solvents and gelation temperatures resulted in differences in crystallization behavior between blocky microstructures of the same degree of functionalization. This result demonstrates that the blocky microstructure can be tuned through controlling the starting gel morphology. The second half of this work focuses on understanding the influence of cooling and heating rates on the melting, crystal morphology, and crystallization kinetics on isotactic polypropylene (iPP), iPP-polyethylene copolymers (iPP-PE), and iPP/iPP-PE blends and using this information to gain understanding of how these polymers crystallize during the additive manufacturing processes of powder bed fusion (PBF) and material extrusion (MatEx). The crystallization kinetics of iPP, iPP-PE copolymers, and iPP/iPP-PE blends exhibited bimodal parabolic-like behavior attributed to crystallization of the mesomorphic crystal polymorph at low temperatures and the α-form crystal at high temperatures. Incorporation of non-crystallizable polyethylene fractions both covalently and blended as a secondary component, resulted in decreasing crystallization rates, inhibition of crystallization, and decreased crystallizability. Additionally, the non-isothermal crystallization behavior of these systems shows that the non-crystallizable fractions influence the crystal nucleation density and temperature at which polymorphic crystallization occurs. Utilizing in-situ IR thermography in the PBF system, the heating and cooling rates observed for a single-layer PBF print were used to mimic the PBF process by FSC. Partial melting in the printing process leads to self-seeding and increased crystallization onset temperatures upon cooling, which influences the final part melting morphology. Nucleation from surrounding powder and partially melted crystals greatly influences the crystallization kinetics and crystal morphology of the final part. Utilizing rheological experiments and process-relevant cooling rates observed in the MatEx process, the miscibility of iPP/iPP-PE blends influenced the nucleation behavior and crystallization rates, subsequently leading to differences in printed part properties. / Doctor of Philosophy / The crystalline morphology of semi-crystalline polymers depends on their microstructure and thermal history. The resultant crystalline morphology greatly affects the physical and chemical properties. In the first part of this work, the effect of microstructure on material properties is explored. Block copolymer microstructures consist of two or more blocks of distinct polymer segments covalently bonded to one another. This leads to self-organization of the components into unique structural order that would not be attainable if the polymer segments were randomly bonded together. This structural order enhances material properties; thus, block copolymers are advantageous for many applications. However, synthesis of block copolymers can be tedious and expensive. Thus, additional methodologies for block copolymer synthesis are desired. In this work blocky (i.e., statistically non-random) copolymers are synthesized through a facile post-polymerization functionalization method. These blocky copolymers result in enhanced physical and chemical properties compared to the randomly synthesized analogs. This work shows blocky functionalization of a new polymer under new post-polymerization conditions and expands upon the synthesis methodology for block copolymers. In the second part of this work, the effect of heating and cooling rates on the formation of crystals during additive manufacturing is explored. Additive manufacturing modalities of powder bed fusion and material extrusion consist of rapid heating and cooling processes, which can affect how crystals form and ultimately affect the final printed part properties. Using a technique called fast scanning calorimetry, the different heating and cooling rates that the polymer witnesses during printing can be mimicked, and the formation of crystals under these different conditions can be replicated. This mimicking analysis can be related to the printing process and be used to help guide printing processes to enhance printed part properties.