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.

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The thesis contains a background and reflections section, an introduction, and three appended articles. The first section is reserved for some of the background and basics on polymers and polymer composites and a discussion on their effect on our everyday lives. The introduction gives a brief recap of the project. The articles contain the research that was performed on the thermal oxidation of thermosetting polyimides and their composites during the project. The first article covered the thermal oxidative degradation of satin weave and thin-ply composites made by resin transfer molding with carbon fibers and thermosetting polyimide. The degradation was studied by weight loss measurements and X-ray computed microtomography. The weight loss measurements showed that the initial desorption stage during ageing followed Fickian behavior and the proposed model. It was also observed that the satin weave composites formed crack clusters that grew into a network of cracks, voids and delaminations throughout the specimens as the ageing time progressed, while the thin-ply composites only formed delaminations at the free edges. The second manuscript studied the behavior of the neat polyimide resin when aged for up to 1500 hours in ambient air, and compared it with a newly developed polyimide formulation, with slightly altered chemical composition. The reduced amount of internal crosslinkers in the newer formulation was expected to enhance the fracture toughness of the material. Three-point bending, differential scanning calorimetry, dilatometry, weight loss, light optical microscopy and nanoindentation experiments were performed and highlighted the differences in the thermal and mechanical properties of the two formulations. A slight increase in the fracture toughness was observed, while the glass transition of the new formulation had decreased. The third manuscript was aimed at continuing the discussion from the second article on the differences between the two thermosetting polyimides. Thermogravimetric scans showed that the polyimide formulations behaved very similarly under thermal oxidative tests. The initial analysis gave indications that the model could capture well the degradation at high temperatures, but is not adequate in predicting long-term degradation at temperatures around 288–400 °C.

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Phosphorus-containing high performance polymers have been extensively studied during the last 10 years. These materials are of interest for a variety of optical and fire resistant properties, as well as for their ability to complex with the inorganic salts. This dissertation has focused on the nature of the phosphonyl group interactions with hydroxyl containing polymers, such as the poly(hydroxy ether)s. These may be considered linear models of epoxy resins and are also closely related to dimethacrylate (vinyl ester) matrix resins that are important for composite systems. It has been shown that bisphenol A poly(arylene ether phosphine oxide/sulfone) homo- or statistical copolymers are miscible with a bisphenol A-epichlorohydrin based poly(hydroxy ethers) (PHE), as shown by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC), infrared spectroscopy and , solid state cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS). These measurements illustrate the strong hydrogen bonding between the phosphonyl groups of the copolymers and the pendent hydroxyl groups of the PHE as the miscibility inducing mechanism. Complete miscibility at all blend compositions was achieved with as little as 20 mole% of phosphine oxide units in the poly(arylene ether) copolymer. Replacement of the bisphenol A moiety by other diphenols, such as hydroquinone, hexafluorobisphenol A and biphenol did not significantly affect blend miscibilities. Miscible polymer blends with PHE were also made by blending poly(arylene thioether phosphine oxide), and fully cyclized phosphine oxide containing polyimides based on (prepared from 2,2'-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) and bis(m-aminophenyl) methyl phosphine oxide (DAMPO)) or bis(m-aminophenyl) phenyl phosphine oxide). Additional research has focused on the influence of these materials on the property characteristics of vinyl ester matrix resins and has shown that the concentration of phosphonyl groups controls the homogeneity of both oligomers and the resulting networks. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and fracture toughness measurements further confirmed the qualitative observations. Metal salts, such as CoCl2 and CuCl2 had earlier been demonstrated to form complexes/nanocomposites with phosphorus-containing poly(arylene ethers). It has been possible to prepare transparent films with 100 mol% of metal chlorides, based upon the phosphonyl groups. The films are transparent, unlike the opaque polysulfone control systems. FTIR results suggested the formation of inorganic salt and polymer complexes at low concentrations. TEM showed homogeneous morphology at low concentrations and excellent dispersion even at high mole % of salts. Cobalt materials reinforce the basic poly(arylene ether)s to provide higher modulus values and influence positively the char yield generated after TGA experiments in air. The cobalt salt/BPADA-DAMPO polyimide composites also yield transparent films, implying very small dimensions. Silica-polymer nanocomposites were also produced by mixing commercial silica colloid/N,N-dimethylacetamide (DMAc) fine dispersions (~ 12 nm) with bisphenol A poly(arylene ether phenyl phosphine oxide). The dry films produced by solution casting are transparent and silica colloids are evenly dispersed (~ 12 nm) into the polymer matrix as shown by TEM. These nanocomposites increased char yield compared with the polymer control, suggesting their fire retardant character. In comparison, the silica/polysulfone hybrid films prepared by the same methods were opaque and the char yield was not improved. This different phase behavior has been explained to be due to the hydrogen bonding between phosphonyl groups and silanol hydroxyl groups on the surface of the nanosilica. / Ph. D.

In this thesis, microelectrode arrays of micropumps have been designed, fabricated and characterized for transporting microfluid by AC electro-osmosis (ACEO). In particular, the 3D stepped electrode design which shows superior performance to others in literature is adopted for making micropumps, and the performance of such devices has been studied and explored. A novel fabrication process has also been developed in the work, realizing 3D stepped electrodes on a flexible substrate, which is suitable for biomedical use, for example glaucoma implant. There are three major contributions to ACEO pumping in the work. First, a novel design of 3D “T-shaped” discrete electrode arrays was made using PolyMUMPs® process. The breakthrough of this work was discretizing the continuous 3D stepped electrodes which were commonly seen in the past research. The “T-shaped” electrodes did not only create ACEO flows on the top surfaces of electrodes but also along the side walls between separated electrodes. Secondly, four 3D stepped electrode arrays were designed, fabricated and tested. It was found from the experiment that PolyMUMPs® ACEO electrodes usually required a higher driving voltage than gold electrodes for operation. It was also noticed that a simulation based on the modified model taking into account the surface oxide of electrodes showed a better agreement with the experimental results. It thus demonstrated the possibility that the surface oxide of electrodes had impact on fluidic pumping. This methodology could also be applied to metal electrodes with a native oxide layer such as titanium and aluminum. Thirdly, a prototype of the ACEO pump with 3D stepped electrode arrays was first time realized on a flexible substrate using Kapton polyimide sheets and packaged with PDMS encapsulants. Comprehensive experimental testing was also conducted to evaluate the mechanical properties as well as the pumping performance. The experimental findings indicated that this fabrication process was a promising method to create flexible ACEO pumps that can be used as medical implants and wearable devices. / Thesis (Ph.D, Mechanical and Materials Engineering) -- Queen's University, 2013-05-06 10:57:48.077

<p>Flexible printed circuit boards (flex PCBs) are used in a wide range of electronic devices today due to their light weight, bendability, extensive wiring possibilities, and low-cost manufacturing techniques. The general trend in the flex PCB industry is further miniaturization alongside increasing functionality per device and reduced costs. To meet these demands, a new generation of low cost manufacturing technologies is being developed to enable structures with smaller lateral dimensions and higher packing densities.</p><p>Wet etching is today the most cost-efficient method for producing a large number of through-foil structures in flex PCBs. However, conventional wet etch techniques do not allow for through-foil structures with aspect ratios over 1 – a fact that either necessitates thin and mechanically weak foils or puts severe limitations on the packing density. The fabrication techniques presented in this thesis allow for through-foil structures with higher aspect ratios and packing densities using wet etching. To achieve high aspect ratios with wet etching, the flex PCB foils are pre-treated with irradiation by swift heavy ions. Each ion that passes through the foil leaves a track of damaged material which can be subsequently etched to form highly vertical pores. By using conventional flex PCB process techniques on the porous foils, high aspect ratio metallized through-foil structures are demonstrated.</p><p>The resulting structures consist of multiple sub-micrometer sized wires. These structures are superior to their conventional counterparts when it comes to their higher aspect ratios, higher possible packing densities and low metallic cross-section. Furthermore, metallized through-foil structures with larger areas and more complicated geometries are possible without losing the mechanical stability of the foil. This in turn enables applications that are not possible using conventional techniques and structures. In this thesis, two such applications are demonstrated: flex PCB vertical thermopile sensors and substrate integrated waveguides for use in millimeter wave applications.</p>

Flexible printed circuit boards (flex PCBs) are used in a wide range of electronic devices today due to their light weight, bendability, extensive wiring possibilities, and low-cost manufacturing techniques. The general trend in the flex PCB industry is further miniaturization alongside increasing functionality per device and reduced costs. To meet these demands, a new generation of low cost manufacturing technologies is being developed to enable structures with smaller lateral dimensions and higher packing densities. Wet etching is today the most cost-efficient method for producing a large number of through-foil structures in flex PCBs. However, conventional wet etch techniques do not allow for through-foil structures with aspect ratios over 1 – a fact that either necessitates thin and mechanically weak foils or puts severe limitations on the packing density. The fabrication techniques presented in this thesis allow for through-foil structures with higher aspect ratios and packing densities using wet etching. To achieve high aspect ratios with wet etching, the flex PCB foils are pre-treated with irradiation by swift heavy ions. Each ion that passes through the foil leaves a track of damaged material which can be subsequently etched to form highly vertical pores. By using conventional flex PCB process techniques on the porous foils, high aspect ratio metallized through-foil structures are demonstrated. The resulting structures consist of multiple sub-micrometer sized wires. These structures are superior to their conventional counterparts when it comes to their higher aspect ratios, higher possible packing densities and low metallic cross-section. Furthermore, metallized through-foil structures with larger areas and more complicated geometries are possible without losing the mechanical stability of the foil. This in turn enables applications that are not possible using conventional techniques and structures. In this thesis, two such applications are demonstrated: flex PCB vertical thermopile sensors and substrate integrated waveguides for use in millimeter wave applications. / wisenet

Cette étude présente une démarche expérimentale originale permettant de sonder la dynamique de l'eau dans les membranes polymères échangeuses d'ions utilisées pour l'application pile à combustible. Grâce à l'utilisation de trois techniques complémentaires, la diffusion des molécules d'eau a été suivie à l'échelle moléculaire (diffusion quasi-élastique des neutrons ; 1 pico s < t < 1 nano s), à l'échelle macroscopique (RMN à gradient de champ pulsé ; 1 milli s < t < 1 s) et à l'échelle dite « intermédiaire » (relaxométrie RMN ; 1 nano s < t < 10 micro sec). Les expériences ont été menées en fonction de la quantité d'eau adsorbée, dans la membrane Nafion® et dans des polyimides sulfonés naphtaléniques. L'analyse des données expérimentales permet de préciser les échelles spatiales des ralentissements de la diffusion dans les deux matériaux, ainsi que de mettre en évidence les aspects structuraux qui permettent à l'eau d'être plus mobile dans le Nafion® que dans les polyimides sulfonés, et ce, quelle que soit la teneur en eau.