This thesis has focused on the synthesis and characterization of amino functional monomers, principally monomers containing aryl phosphine oxide units. Utilization of these monomers was demonstrated in various types of linear and network polymerizations. The diamines monomers included bis(3-aminophenyl) methyl phosphine oxide (DAMPO), bis(3-aminophenyl) phenyl phosphine oxide (DAPPO), bis(3-aminophenoxy phenyl) phenyl phosphine oxide (BAPPO) and bis(3-aminophenoxy phenyl) methyl Phosphine oxide (BAMPO). From these monomers high molecular weight poly(ether imides), polyurea-urethanes, poly(arylene ether ketones) poly(arylene ether sulfones) and poly(arylene ether phosphine oxides) were. Internal and external fire testing methodologies showed that the new polymers containing phosphine oxide units were fire resistant while maintaining the desirable physical characteristics of carefully selected control systems. In addition, suitable curing schedules for epoxy networks were determined by using dielectric monitoring techniques. The curing rates varied with the structure of the monomers and were slowest for the deactivated control (4,4'aminophenyl sulfone). Epoxy networks containing aryl phosphine oxide units had higher char yields in dynamic thermogravimetric analyses than control specimens. This correlated with their superior flame resistance. The brittle epoxy matrices were subsequently modified with reactive or non-reactive thermoplastic polymers in order to improve their fracture toughness. Poly(ether imides) and poly(ether sulfones) showed good phase separation behavior with tetrafunctional epoxy matrices during the curing reactions, as confirmed by scanning electron microscopy (SEM) and dynamic mechanical analysis (DMA). Mechanical tests showed that reactive thermoplastic modification of the epoxy networks improved the fracture toughness of the systems, without noticeable decreases in other characteristics such as flexural modulus. Reactive systems also maintained chemical resistance in contrast to non-reactive thermoplastic controls. / Ph. D.

Biopsy is a standard practice in the diagnosis and treatment of many cancers. Despite its integral role in cancer diagnosis, in some instances, the biopsy tool facilitates metastasis by transferring cancerous cells attached to its exterior into the healthy tissue or the blood circulation during its retraction from the tumor. These few cancer cells can then serve as seeds for the malignant tumor to grow in the healthy tissue. Cauterization using extreme heat or cold can destroy cells in the region and minimize the chance of seeding but this can be an inexact process that increases damage to otherwise healthy tissue and prolongs healing time following a biopsy procedure. In our laboratory, we have developed the concept of a new smart biopsy tool that can reduce the chance of cancer cell dissemination during a biopsy. This tool improves on the conventional biopsy needle by introducing an impedance sensor on the biopsy tool which is housed in a sliding sheath. Due to the significant difference in the electrical conductivity of the tumor and the healthy tissue, the sensor is able to distinguish between the two and locate the exact tumor interface. The protective sheath placed around the instrumented biopsy tool and above the interface isolates the healthy tissue and prevents or at least minimizes the transfer of tumor cells. Delivering an RF dose through the sheath can kill any malignant cells that might be lurking around the interface. This thesis, in particular, will concentrate on the development of the design, fabrication and calibration of the impedance sensor and its integration with the biopsy tool. The impedance sensor essentially consists of conductive electrodes sandwiched between insulating layers. They are built on thin-film polymer, Polyimide, using conventional microfabrication techniques. These sensors are further calibrated to estimate the cell constant. Once calibrated, these probes are used to measure the conductivity of porcine tissues, and in-house prepared agar phantoms. / Master of Science

Polyimides epitomize one of the most versatile high-performance engineering polymers. Polyimides are inherently mechanically robust, chemically inert, and thermooxidatively stable to 400+ °C depending on their chemical structure, enabling their function in numerous aerospace, electronic, medical, and flame-retardant applications. Polyimides can be highly modular even within synthetic limitations, which promotes and sustains innovative research. One recent interest concerns the innovation of fire suppression foams. Aqueous film-forming foams (AFFFs) are regularly sought when engaging liquid fuel (gasoline, jet fuel) fires. AFFFs utilize perfluorinated compounds (PFCs) like perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), which exhibit toxicity, bioaccumulation, and persistence in the environment resulting in the presence of fluorosurfactant chemicals in environments either through direct or secondary exposure via chemical migration. Recently, the USEPA has even detected PFAS in drinking water at hundreds of military training facilities and civilian airports. While fluorinated compounds provide desirable thermooxidative stability and excellent fire retardancy, the environmental impact imposed by these chemicals strongly encourages research that targets the complete removal of PFCs in conventional formulations. This thesis focuses on the fundamental development of water-soluble sulfonated polyimide (sPI) and poly(amic acid) (sPAA) systems for next-generation polymer-based fire suppression foams. The use of sulfonated monomers and poly(amic acid) salt formation enables tunable structures and water solubilities. The polymers maintain competitive thermal stabilities to conventional polyimides and, when combined with readily available, non-toxic surfactants (SDS), produce stable foams. The MIL-F-24385F performance requirement evaluates foam quality/stability, drainage time, and burnback resistance to access viability and provides comparison to other systems; preliminary testing shows that sPI/sPAA formulations perform well. Solution rheology offers insights into fundamental scaling relationships of specific viscosity vs. concentration in both salt and salt-free solution that are important to future foam development. Additionally, the structural nature of the sPIs/ sPAAs allows for their modification with phosphonium moieties or siloxanes, which are slated to have positive effects on performance. Overall, these sPIs and sPAAs provide a promising platform for the future direction of fire suppression foams. / Master of Science / High-performance polymers are used in the most demanding of engineering applications. Polyimides represent one of the most versatile high-performance polymers. Polyimides are mechanically strong, chemically inert, and resistant to extreme temperatures depending on their chemical structure, allowing their use in numerous aerospace, electronic, medical, and flame-retardant applications. Polyimides are synthetically versatile, which enables the discovery of new uses after decades of research. One new targeted application is fire suppression foams. Aqueous film-forming foams (AFFFs) are the standard when battling liquid fuel (gasoline, jet fuel) fires. AFFFs contain perfluorinated compounds (PFCs), which are toxic and persist in the environment; they migrate easily to affect indirectly exposed ecosystems. Recently, the USEPA has even detected PFAS in drinking water at hundreds of military training facilities and civilian airports. While AFFFs with PFCs are highly effective, replacement materials are needed. This thesis focuses on the fundamental development of water-soluble sulfonated polyimide (sPI) and poly(amic acid) (sPAA) systems for fire suppression foams. The polymers remain thermally stable, and when combined with readily available surfactants (SDS), produce stable foams. Preliminary fire testing shows that sPI/sPAA formulations perform well against military specifications. Solution rheology (study of flow) explores the solution behavior of sPI, which offers insights into fundamental concentration-viscosity relationships that are important to future foam development. Additionally, the structural nature of the sPIs/ sPAAs allows for their modification with phosphonium groups or siloxanes, which changes their characteristics. Overall, these sPIs and sPAAs are initially promising for the future direction of fire suppression foams.

Nesse trabalho são discutidos os resultados a respeito de materiais híbridos baseados na poliimida, PI, obtida por reações de policondensação entre a diamina 4,4\'-Oxidianilina (ODA) e o dianidrido 4,4\'-Oxidiftálico (ODPA), seguida de imidização térmica. O estudo foca na influência do tempo de tratamento (1, 15 e 60 min) e na temperatura de decomposição térmica (500°C) sobre as propriedades da PI. Os experimentos foram realizados sob fluxo de Argônio e os materiais obtidos apresentam características intermediárias entre PI e materiais carbonáceos. Dados de Nanoindentação (NI) revelaram aumento de até 50% de dureza para os filmes tratados por 60 min. ODPA e ODA serviu ainda de base para a preparação do revestimento híbrido contendo ORMOSIL gerado in situ por catálise ácida via processo sol-gel a partir do (3-aminopropil)trietóxissilano (APTES) e Tetraetil Ortossilicato (TEOS). O revestimento obtido é homogêneo e tem boa interação com o substrato (aço inoxidável 316L). A polarização potenciodinâmica revelou uma proteção elevada tanto em solução de NaCl 3,5% em massa quanto em H2SO4 0,5 mol L-1, em relação ao aço sem revestimento, com densidade de corrente da ordem de 10-9 A cm-2, na faixa de -700 a 500 mV vs Ag/AgCl. Por fim, filmes híbridos baseados em ODPA, ODA, APTES e TEOS, adicionados de Ácido Fosfotungstico (HPW) foram preparados e avaliados por Espectroscopia na região do Infravermelho com Transformada de Fourier e Ressonância Magnética Nuclear de Silício e Fósforo (29Si e 31P MAS NMR) que confirmaram a formação da PI e da rede ORMOSIL, bem como revelam que a estrutura do HPW permaneceu intacta após o processo de síntese. Mapeamentos realizados por Micro-fluorescência de Raios X assistida por Luz Síncrotron (μ-XRF) mostram uma boa dispersão da fase inorgânica (ORMOSIL e HPW) na orgânica (POO), e todos os materiais são termicamente estáveis até aproximadamente 500°C, de acordo com as curvas obtidas por Termogravimetria (TGA). Outras técnicas de caracterização também foram usadas para uma investigação mais detalhada dos materiais. / In this thesis are presented the results and considerations related to several hybrid materials derived from the polyimide, PI, obtained by polycondensation reactions between 4,4\'-Oxydianiline (ODA) and 4,4\'-Oxydiphthalic (ODA), followed by thermal imidization. The study focuses on the effect of thermal treatment time (1, 15 and 60 min) and the temperature of beginning of thermal decomposition (773 K) on the properties of PI. The experiments were performed under Argon flow, and the materials presented intermingled properties of PI and carbonaceous materials. The hardness, evaluated by Nanoindentation (NI), reached an increase of 50% for POO films treated for 60 min. POO was also used for the preparation of the hybrid coating containing ORMOSIL obtained in situ by acid catalysis via sol-gel process from (3-aminopropyl)triethoxysilane (APTES) and Tetraethyl Orthosilicate (TEOS). The coating is homogeneous and present a good interaction with the substrate (316L stainless steel). Data of potendynamic polarization revealed a high protection both under NaCl 3.5 wt% and H2SO4 0.5 mol L-1 solutions related to the neat substrate, with current density of order 10-9 A cm-2, in range potential of -700 to 500 mV vs Ag/AgCl. Finally, hybrid films were prepared based on ODPA, ODA, APTES and TEOS, in addition to Phosphotungstic Acid (HPW). The characteristics of all materials were evaluated by Fourier Transform Infrared Spectroscopy in Middle and Near Infrared region (FTMIR and FTNIR), and Magic Angle Spinning-Nuclear Magnetic Resonance of Silicon 29 and Phosphorus 31 (29Si and 31P MAS NMR) which confirmed the ORMOSIL network formation, as well as revealed that the HPW structure remained intact after the synthesis process. Mapping performed by Assisted Synchrotron Light X-ray Micro Fluorescence (μ-XRF) the good dispersion of the inorganic phase (ORMOSIL and HPW) in the organic phase (POO). All materials are thermally stable up to 773 K, according to Thermogravimetric Analysis (TGA). Other techniques of characterization were also used to further investigation of the materials.

L'objectif de cette étude est d'évaluer les potentialités du polyimide pour la passivation des composants de puissance en carbure de silicium (SiC), laquelle sera soumise à des températures et des champs électriques nettement supérieurs à ceux rencontrés dans l'environnement des puces en silicium (jusqu'à 350°C et 3 MV/cm respectivement).<br />Pour quantifier les propriétés ‘intrinsèques' du polyimide, des caractérisations électriques ont été réalisées dans une gamme de température étendue jusqu'à 260 °C, sur des structures MIM (Métal Isolant Métal), avec des films de polyimide élaborés selon le procédé de fabrication standard préconisé par le fabricant. Les résultats ont montré de bonnes propriétés électriques à température ambiante et jusqu'à 180 °C. Cependant, des valeurs de facteur de pertes et de permittivité diélectrique trop élevées pour satisfaire l'application visée ont été montrées au-delà de 180°C. Une amélioration des propriétés diélectriques et d'isolation a été cependant observée après la réalisation d'un traitement thermique additionnel, dans lequel les échantillons sont exposés longuement à des températures élevées, indiquant que la stabilité des propriétés du matériau n'est pas atteinte à l'issue du recuit d'imidisation du film polyimide.<br />L'analyse des caractérisations électriques et physico-chimiques montrent que cette instabilité est liée à l'évolution du taux d'imidisation de l'acide polyamique en polyimide, et de la concentration d'impuretés résiduelles (eau, solvant) lesquels dépendent des paramètres (durée, température) du recuit final d'élaboration du polyimide. Cette étude a permis de mettre en évidence la nécessité d'optimiser le recuit d'imidisation du procédé d'élaboration du film de polyimide afin d'obtenir des propriétés électriques adaptées au cahier des charges de l'application visée, dans une gamme de température étendue jusqu'à 350 °C.

Robust industrially relevant membranes for CO₂ removal from aggressive natural gas feed streams were developed and characterized. Asymmetric hollow fiber membranes with defect-free selective skin layers on an optimized porous support substructure were successfully spun and subsequently stabilized by covalent crosslinking within the economical membrane formation process. Thermal treatment conditions, which promote sufficient crosslinking without introducing defects or undesired substructure resistance, were identified. It was found that crosslinking improves membrane efficiency and plasticization resistance as well as mechanical strength of fibers. The capability to maintain attractive separation performance under realistic operating conditions and durability against deleterious impurities suggests that the crosslinked fibers have great potential for use in diverse aggressive applications, even beyond the CO₂/CH₄ example explored in this work.

The existence of polymer constituent in piezoelectric fiber composites (PFCs) could lead to significant viscoelastic behaviors, affecting overall performance of PFCs. High mechanical and electrical stimuli often generate significant amount of heat, increasing temperatures of the PFCs. At elevated temperatures, most materials, especially polymers show pronounced time-dependent behaviors. Predicting time-dependent responses of the PFCs becomes important to improve reliability in using PFCs. We study overall performance of PFCs having unidirectional piezoceramic fibers, such as PZT fibers, dispersed in viscoelastic polymer matrix. Two types of PFCs are studied, which are active fiber composites (AFCs) and macro fiber composites (MFCs). AFCs and MFCs consist of unidirectional PZT fibers dispersed in epoxy placed between two interdigitated electrode and kapton layers. The AFCs have a circular fiber cross-section while the MFCs have a square fiber cross-section. Finite element (FE) models of representative volume elements (RVEs) of active PFCs, having square and circular fiber cross-sections, are generated for composites with 20, 40, and 60 percent fiber contents. Two FE micromechanical models having one fiber embedded in epoxy matrix and five fibers placed in epoxy matrix are considered. A continuum 3D piezoelectric element in ABAQUS FE is used. A general time-integral function is applied for the mechanical, electrical, and piezoelectric properties in order to incorporate the time-dependent effect and histories of loadings. The effective properties of PZT-5A/epoxy and PZT-7A/LaRC-SI piezocomposites determined from the FE micromechanical models are compared to available experimental data and analytical solutions in the literature. Furthermore, the effect of viscoelastic behaviors of the LaRC-SI matrix at an elevated temperature on the overall electro-mechanical and piezoelectric constants are examined.

Mixed matrix nanocomposite membranes composed of a crosslinkable polyimide matrix and high-silica molecular sieve particles were developed for purifying natural gas. It was shown that ideal mixed matrix effects were not possible without sieve surface modification. A previously developed Grignard procedure was utilized to deposit magnesium hydroxide nanostructures on the sieve surface in order to enhance polymer adhesion. Analyses of Grignard-treated sieves pointed to the formation of non-selective voids within the surface deposited layer. These voids were suspected to lead to lower-than-expected membrane performance. In order to improve membrane transport, a reactive sizing procedure was developed to fill these voids with polyimide-miscible material. In a serendipitous discovery, as-received sieves--when treated with this reactive sizing procedure--resulted in nearly identical membrane performance as reactive-sized, Grignard-treated sieves. This observation lead to the speculation of a non-ideal transport mechanism in mixed matrix membranes.

Natural gas is one of the fastest growing primary energy sources in the world today. The increasing world demand for energy requires increased production of high quality natural gas. For the natural gas to be fed into the mainline gas transportation system, it must meet the pipe-line quality standards. Natural gas produced at the wellhead is usually "sub-quality" and contains various impurities such as CO2, H2S, and higher hydrocarbons, which must be removed to meet specifications. Carbon dioxide is usually the most abundant impurity in natural gas feeds and high CO2 partial pressures in the feed can lead to plasticization, which causes loss of some methane product and may ultimately render the membrane ineffective. Moreover, the presence of highly sorbing higher hydrocarbons in the feed can further reduce membrane performance. Covalent crosslinking has been shown to increase plasticization resistance in dense films by suppressing the degree of swelling and segmental chain mobility in the polymer, thereby preserving the selectivity of the membrane. This research focuses on extending the dense film success to asymmetric hollow fibers. In this work, the effect of high pressure CO2 (up to 400 psia CO2 partial pressure) on CO2/CH4 mixed gas separation performance was investigated on defect-free the hollow fiber membrane at different degrees of crosslinking. All the crosslinked fibers were shown to exhibit good resistance to selectivity losses from CO2 induced plasticization, significantly more than the uncrosslinked fibers. Robust resistance of the hollow fiber membranes in the presence of toluene (a highly sorbing contaminant) was also demonstrated as the membranes showed no plasticization. Antiplasticization was found to occur in the presence of toluene feeds with the crosslinkable fibers used in this work.

Membrane separations are rapidly growing alternatives to traditionally expensive gas separation processes. For natural gas purification, membranes are used to remove carbon dioxide to prevent pipeline corrosion and increase the heating value of the natural gas. The robust chemical and physical properties of polyimide membranes make them ideal for the numerous components and high pressures associated with natural gas production. Typically, the performance of membranes changes over time as a result of physical aging of the polymer. Previous work shows that the thin selective layer of an asymmetric hollow fiber membrane, the morphology of choice for gas separations, ages differently than a thick dense film of the same material. Also, carbon dioxide, which is highly soluble in most polymers, can actively swell and plasticize polymer membranes at higher pressures. In this work, free acid groups present in the model polyimide are covalently crosslinked to stabilize the matrix against plasticization. Physical aging of two different crosslinked derivatives are compared to the free acid polyimide through gas permeation, gas sorption, and refractive index measurements. Thick (~50 m) and thin (~650 nm) films are examined to determine the effects of sample dimension on physical aging. The crosslinking mechanism employs diol substituents to form ester linkages through the free acid group. However, the annealing treatment, above the glass transition temperature, used to "reset" the thermal history of the films is found to form a new crosslinked polymer. Characterization of this new crosslinking mechanism reveals a high-temperature decarboxylation of the free acid creates free-radical phenyl groups which form covalent crosslinks through other portions of the polymer structure. Since ester crosslinks may be vulnerable to hydrolysis in aggressive gas feed streams, this new mechanism of crosslinking may create a more robust membrane for aggressive separations. In addition to the physical aging study, supercritical carbon dioxide conditioning of the two glycol crosslinked polyimides is compared to the free acid polymer. In this case, the free acid polymer is not crosslinked since the esterification crosslinking reaction occurs at much lower temperature than the decarboxylation mechanism. The free acid polymer displays an atypical permeation response under supercritical carbon dioxide conditions which suggests a structural reorganization of the polymer occurs. The crosslinked polymers do not exhibit this type of response. Mixed gas permeation confirms a substantial decrease in the productivity of the free acid polyimide and reveals the enhanced stability of the crosslinked polyimides following the supercritical carbon dioxide conditioning. Finally, examination of structurally similar fluorine-containing polyimides following approximately 18 years of aging allows the study of polymer structure on physical aging. A 6FDA-based polyimide is compared to a BPDA-based polyimide to understand the effects of bulky, CF3 groups on physical aging, and polyimides with diamine isomers reveal the effects of structural symmetry on physical aging.