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Microvascular composites are materials with an inner hollow network which allows thecirculation of fluids. This functionalizes the composite materials, giving them furtherapplications such as self-healing or active cooling. Some of the already existingmicrovascular composites are made with fiber reinforced epoxy resin with cavitiescreated by removal of a sacrificial low temperature resistant polymer insert. Currentresearch is focused on the obtention of microvascular composites that can withstandhigher service temperatures than epoxy, using polyimide as the high-temperature resinmatrix. The aim of this project is to find a suitable sacrificial material that will withstandthe higher curing temperatures of the polyimide while allowing its easy removal fromthe matrix. Three different candidate sacrificial materials were studied for this purpose:PEEK, PPS, and PC. Preliminary DSC test showed that the melting temperature of the PEEK was close to therange of the chosen resin. PPS melting temperature and PC glass transition temperaturewere below this range of curing temperatures. TGA test revealed that the degradationsuffered by the different materials at the curing temperature of the polyimide wasconsiderably low. A small-scale test mimicking the actual microvascular compositemanufacturing conditions was designed to study the actual behavior of the differentmaterials when heated. It was seen that both the PEEK and the PPS could not flowwithout applying extra pressure for the desired range of temperatures. Furthermore, ascaled model test revealed that there was no visible interaction between the differentmaterials tested and the polyimide resin. The initial study showed that PEEK and PPS arenot readily viable to use due to the apparent difficulties to remove them from thecomposite by just applying heat. PC was also considered not viable for this applicationsince it softened too much a too low temperature.

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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.

Ces travaux exposent et analysent les performances d’un composite à matrice thermoplastique semi-cristallin au passage et au-delà de la transition vitreuse. Il est nécessaire de donner des éléments objectifs afin d’évaluer et discuter dans quelles mesures ce matériau peut être utilisé de manière innovante. L’objectif visé est de donner des perspectives en termes de plage de températures d’utilisation des matériaux composites à matrice thermoplastique et plus spécifiquement pour des applications à hautes températures. Le composite à fibres continues de carbone et matrice polyétheréthercétone PEEK a ainsi été étudié sur une large gamme de température, avant et après sa température de transition vitreuse (Tg = 143°C).La phase de caractérisation quasi-statique a mis en évidence l’importance du renfort et le bon transfert de charge de la matrice au-delà de la Tg pour les différentes sollicitations. En particulier, la résistance à la rupture en compression s’est avérée intéressante dans l’optique d’une application structurelle. De plus, les observations fractographiques ont mis en évidence des comportements radicalement différents au passage de la transition vitreuse. Le caractère plus ductile de la matrice permet de limiter la propagation de fissures au travers des plis par dissipation de l’énergie : la plastification de la matrice augmente la capacité du composite à dissiper de l’énergie en limitant ainsi la fissuration. Cependant pour des chargements où la matrice pilote la réponse mécanique du composite tels que des efforts de cisaillement, les comportements non linéaires sont fortement accentués. Des mécanismes de déformations dépendant du temps ont été observés à travers des essais de charge-décharge et de fluage au-delà de la Tg : le caractère visqueux de la matrice joue un rôle prépondérant.Ces mécanismes non linéaires étant identifiables sur des temps longs, il était intéressant de proposer des méthodes de modélisation pour prédire le comportement du composite. C’est pourquoi des modèles à l’échelle du pli ont été adaptés en fonction de la température et de la prépondérance des caractères viscoélastique et viscoplastique. Différents essais de fluage-recouvrance en torsion rectangulaire menés sur un rhéomètre ont permis d’évaluer les composantes viscoélastiques et viscoplastiques de la déformation à des températures inférieures et supérieures à la Tg. / The present study shows and analyses the specifications of a semi-crystalline thermoplastic composite as function of temperature, below and above the glass transition. In order to assess and discuss about what extent this material could be innovately use, objective facts must be necessary exposed: the main target is to give the outlooks about the temperature range, in particular the high temperatures. The studied material is a continuous carbon fibre composite with a polyetheretherketone (PEEK) matrix. Its glass transition temperature is around 143°C. It has been characterized throughout a wide temperature range.For several kinds of quasi-static loadings, the load transfer from the matrix to the fibre reinforcement is good even above the glass transition temperature. The compression strength is indeed very interesting for an aeronautical application. In addition, the fracture surface analysis have significantly revealed a different behaviour above the glass transition temperature: the matrix is more ductile and thus the crack propagation is limited thanks to the energy dissipation. However when the mechanical response is driven by the matrix behaviour such as shear loadings, the nonlinear mechanical behaviour of the composite are highly increased. Therefore the time-dependent behaviours have been characterized by using creep experiments and loading-unloading tensile tests as function of the temperature.In order to predict those non-linear behaviours, meso-models have been developed as function of the temperature. Thus viscoelasticity and viscoplasticity have been taken into account to model the nonlinear mechanical behaviour of the composite material, thanks to creep-recovery tests which have been carried out with a torsion rheometer.

Made available in DSpace on 2014-12-17T14:58:15Z (GMT). No. of bitstreams: 1 MayaraSCFL_DISSERT.pdf: 5165682 bytes, checksum: c5b249c3b897f27db4e517452be9b9ce (MD5) Previous issue date: 2012-04-30 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Composites based on PEEK + PTFE + CARBON FIBER + Graphite (G_CFRP) has increased application in the top industries, as Aerospace, Aeronautical, Petroleum, Biomedical, Mechanical and Electronics Engineering challenges. A commercially available G_CFRP was warmed up to three different levels of thermal energy to identify the main damage mechanisms and some evidences for their intrinsic transitions. An experimental test rig for systematize a heat flux was developed in this dissertation, based on the Joule Effect. It was built using an isothermal container, an internal heat source and a real-time measurement system for test a sample by time. A standard conical-cylindrical tip was inserted into a soldering iron, commercially available and identified by three different levels of nominal electrical power, 40W (manufacturer A), 40W (manufacturer B), 100W and 150W, selected after screening tests: these power levels for the heat source, after one hour of heating and one hour of cooling in situ, carried out three different zones of degradation in the composite surface. The bench was instrumented with twelve thermocouples, a wattmeter and a video camera. The twelve specimens tested suffered different degradation mechanisms, analyzed by DSC (Differential Scanning Calorimetry) and TG (Thermogravimetry) techniques, Scanning Electron Microscopy (SEM) and Energy-Dispersive X-Rays (EDX) Analysis. Before and after each testing, it was measured the hardness of the sample by HRM (Hardness Rockwell M). Excellent correlations (R2=1) were obtained in the plots of the evaporated area after one hour of heating and one hour of cooling in situ versus (1) the respective power of heat source and (2) the central temperature of the sample. However, as resulting of the differential degradation of G_CFRP and their anisotropy, confirmed by their variable thermal properties, viscoelastic and plastic properties, there were both linear and non-linear behaviour between the temperature field and Rockwell M hardness measured in the radial and circumferential directions of the samples. Some morphological features of the damaged zones are presented and discussed, as, for example, the crazing and skeletonization mechanism of G_CFRP / Comp?sitos baseados em matrizes polim?ricas de PEEK e PTFE, refor?adas com fibra de carbono e grafite (G_CFRP) apresentam crescente aplica??o e desafios ? Engenharia nas ind?strias Aeroespacial, Aeron?utica, de Petr?leo, Biom?dica, Mec?nica e Eletr?nica. Um comp?sito G_CFRP foi aquecido em tr?s n?veis de energia t?rmica para identificar os principais mecanismos de dano e algumas evid?ncias em suas transi??es de mecanismos. Uma bancada experimental foi desenvolvida para sistematizar o fluxo t?rmico com base no Efeito Joule. Foi constru?da usando-se um recipiente isot?rmico, uma fonte quente interna e um sistema de medidas em tempo real para ensaiar um corpo-de-prova (CP) de cada vez. Uma ponta c?nica-cil?ndrica foi inserida em um ferro de soldar, comercialmente dispon?vel e identificado por tr?s diferentes n?veis de pot?ncia el?trica, 40W (fabricante A), 40W (fabricante B), 100W e 150W, selecionados ap?s ensaios piloto: estes n?veis de pot?ncia para a fonte quente, ap?s uma hora de aquecimento e uma hora de resfriamento in situ, promoveu tr?s zonas diferentes de degrada??o na superf?cie do comp?sito. A bancada foi instrumentada com doze termopares, um watt?metro e uma c?mera de v?deo. Os doze C.P. ensaiados apresentaram diferentes mecanismos de degrada??o, analisados pelas t?cnicas de Calorimetria Diferencial Explorat?ria (DSC) e Termogravimetria (TG), e pelas an?lises de Microscopia Eletr?nica de Varredura (MEV) e Energia Dispersiva de Raios-X (EDS). Antes e ap?s cada ensaio, foram feitos ensaios de dureza Rockwell M (HRM). Excelentes correla??es (R2=1) foram obtidas nas curvas da ?rea evaporada ap?s uma hora de aquecimento e uma hora de resfriamento in situ versus (1) a respectiva pot?ncia da fonte quente e (2) a temperatura central do C.P. entretanto, como resultado da degrada??o diferencial do G_CFRP e da sua anisotropia, confirmadas por suas propriedades t?rmicas vari?veis, propriedades viscoel?sticas e viscopl?sticas, houve comportamentos linear e n?o-linear entre o campo de temperatura e a HRM medidos nas dire??es radial e circunferencial dos C.P. Algumas peculiaridades morfol?gicas das zonas de dano s?o apresentadas e discutidas, como, por exemplo, os mecanismos de dano por crazing e esqueletiza??o do G_CFRP

In dieser Arbeit wurde die Grenzfläche zwischen Ti-3Al-2,5V und CF/PEEK in thermoplastischen Ti-CF/PEEK-Laminaten untersucht. Vergleichende Untersuchungen von mechanischen, chemischen, chemisch-physikalischen und physikalischen Oberflächenvorbehandlungen im Zugscherversuch haben gezeigt, dass sich durch die Vorbehandlung mit einem Nd:YAG-Laser ein stabiles und feuchtigkeitsbeständiges Grenzflächensystem erzeugen lässt. Ti-CF/PEEK-Laminate wurden bruchmechanisch im Mixed-Mode-Bending-Versuch sowohl bei reiner als auch bei überlagerter Mode I- und Mode II-Belastung geprüft. Die Versagensmechanismen wurden an den Bruchflächen der Mixed-Mode-Bending-Proben und an den Bruchflächen der Zugscherproben mittels mikroskopischer und spektroskopischer Methoden bestimmt. Verschiedene Analyseverfahren wurden eingesetzt, um Ti-3Al-2,5V-Oberflächen vor und nach der Laservorbehandlung, um laserbehandelte und wärmebehandelte Ti-3Al-2,5V-Oberflächen und um das Grenzflächensystem im Verbund zwischen Ti-3Al-2,5V und CF/PEEK vor und nach Alterung in 80°C warmem Wasser zu analysieren. Dabei wurden sowohl die grenzflächennahen Phasen im Ti-3Al-2,5V als auch die grenzflächennahen Phasen im PEEK berücksichtigt. Die Untersuchgen zeigen, dass sich nicht alle eingesetzten Analyseverfahren zur Charakterisierung eignen und dass nicht jedes Analyseverfahren eindeutig interpretierbare Ergebnisse liefert. Die eingesetzten Analyseverfahren werden in dieser Arbeit miteinander verglichen und in Bezug zu ihrer Einsetzbarkeit und zu ihren Einsatzgrenzen bewertet. Titan-PEEK-Verbindungen zeigen je nach eingesetzter Vorbehandlungsmethode unterschiedliche Adhäsions-, Versagens- und Alterungsmechanismen. Die Ergebnisse aus den Untersuchungen der Verbindung zwischen PEEK und laserbehandeltem Ti-3Al-2,5V zeigen, dass neben mechanischer Adhäsion auf Mikro- und Nanoebene weitere Adhäsionsmechanismen in Frage kommen. Die Aluminiumanreicherung an der Oberfläche und die erhöhte Reaktivität durch mikro- und nanostrukturierte Oberflächen können chemische Wechselwirkungen zwischen PEEK und laserbehandeltem Ti-3Al-2,5V begünstigen. Die Untersuchungen geben ebenfalls Hinweise darauf, dass die Verbundeigenschaften im Titan-PEEK-Verbund durch die Morphologie von PEEK beeinflusst wird. An der Titan-PEEK-Grenzfläche wurde Grenzflächenkristallisation nachgewiesen, von der bekannt ist, dass sie die Verbundeigenschaften von faserverstärkten Kunststoffen senkrecht zur Faserorientierung verbessern. Nicht nachgewiesen, aber durchaus möglich ist, dass sich mechanisch verklammertes PEEK in der porösen Oxidschicht aufgrund thermischer Eigenspannungen während der Abkühlung orientiert und die mechanischen Eigenschaften an der Grenzfläche in Analogie zu selbst verstärkten Polymeren verbessert. Dieser Ansatz kann eine Erklärung dafür sein, warum im MMB-Versuch nicht nur hohe kritische Energiefreisetzungsraten bei reiner Mode II-Belastung, sondern vor allem auch bei reiner Mode I-Belastung beobachtet wird. Die auf PEEK basierenden Mechanismen sind materialspezifisch und nicht auf chemisch aushärtbare Klebstoffe anwendbar. Der Einfluss der Größenordnung von Oberflächenstrukturen auf die Langzeit- und Feuchtigkeitsbeständigkeit, der bereits aus der Literatur bekannt ist, wird in dieser Arbeit bestätigt. Mit mikrostrukturierten Oberflächen, die mittels Sandstrahlen erzeugt werden, lassen sich im Gegensatz zu nanostrukturierten Oberflächen, die mittels Laserbehandlung erzeugt werden, keine langzeit- und feuchtigkeitsbeständige Verbindungen zwischen PEEK und Ti-3Al-2,5V erzeugen. In Titan-PEEK-Verbindungen ist nicht nur die Haftung zwischen PEEK und Ti-3Al-2,5V entscheidend, sondern auch die Stabilität der Phasen im Grenzflächensystem, wie am Beispiel der Verbindung zwischen anodisiertem Ti-3Al-2,5V und PEEK gezeigt wird. Geringe Verbundfestigkeiten können somit als Folge thermischer Alterung während der Verbundherstellung verursacht werden, bei der die Oxidschicht durch Sauerstoffdiffusion geschädigt wird. Thermische Eigenspannungen, die sowohl zur Rissbildung im Oxid als auch im martensitischen Bereich führen, und ungenügende Verbundqualität, die beispielsweise durch eingeschlossene Luft bei großflächigen Klebungen entsteht, begünstigen die Alterung in hydrothermischer Umgebung. Zum Verständnis von Adhäsions- und Alterungsmechanismen an der Grenzfläche zwischen Ti-3Al-2,5V und PEEK trägt nicht nur das Eigenschaftsbild der Metall-, Oxid- und Polymerphasen im Grenzflächensystem bei, sondern auch Änderungen in den einzelnen grenzflächennahen Phasen während Oberflächenvorbehandlung und der Konsolidierung. Bei der Verwendung von thermoplastischen Klebstoffen sind im Gegensatz zu Reaktionsklebstoffen besonders die vergleichsweise hohen Konsolidierungstemperaturen, die Kristallisationskinetik und die Schmelzviskosität zu berücksichtigen. So sollte bereits bei der Oberflächenvorbehandlung die Bildung thermisch unstabiler Oberflächenphasen vermieden werden, da diese während der Herstellung thermisch geschädigt werden können. Der Verbindungsprozess erfordert besonders bei großen Klebeflächen Maßnahmen, um das Phänomen der «eingeschlossenen Luft» zu vermeiden, da sich schlecht infiltrierte Bereiche negativ auf die Alterungsbeständigkeit auswirken. Bei porösen Oberflächenstrukturen auf Nanoskala ist ebenso eine Abstimmung zwischen Porengröße und Schmelzviskosität des Thermoplasten erforderlich, um ausreichende Infiltration des Thermoplasten an porösen Oberflächenstrukturen zu gewährleisten. Die grenzflächennahen Phasen von PEEK wurden erstmals an der Ti-3Al-2,5V-Oberfläche nachgewiesen. Die Einflussfaktoren und die Eigenschaften der grenzflächennahen Phasen von PEEK sind bereits aus Untersuchungen von CF/PEEK-Verbunden bekannt. Die Ergebnisse zeigen großes Potential der Übertragbarkeit auf die Titan-PEEK-Grenzfläche. So kann beispielsweise die PEEK-Morphologie durch gezielte Temperaturführung beim Kleben beeinflusst werden. Die Mechanismen an der Grenzfläche und die daraus resultierenden Verbundeigenschaften, die sich an der Grenzfläche zwischen Ti-3Al-2,5V und PEEK ergeben, zeigen großes Potential. Die Erkenntnisse aus dieser Arbeit zur Herstellung von Ti-PEEK-Grenzflächen mit hoher Verbundfestigkeit und Alterungsbeständigkeit zeigen ebenfalls großes Potential der Übertragbarkeit auf andere Metall-Thermoplast-Verbindungen. / The interface between titanium Ti-3Al-2,5V and Polyetheretherketone (PEEK) in Ti-CF/PEEK laminates are investigated. Comparative investigations of mechanical, chemical, chemo-physical and physical surface pre-treatments evidenced that surface pre-treatment by a pulsed Nd:YAG laser (physical pre-treatment) offers both good adhesion and superior moisture resistance of the titanium-PEEK interface. The titanium-PEEK interface modified by laser pre-treatment is characterized mechanically and analytical in detail. This investigation takes into account all process steps (surface pre-treatment, bonding, and ageing) as well as all the phases and interfaces in the titanium-PEEK system (i.e. titanium, oxide, and also PEEK). The delamination behavior is investigated mechanically with the mixed mode bending experiment (MMB). The MMB loading was represented by a superposition of simple mode I and mode II loadings. Based on MMB fracture surface analysis, a failure and damaging mechanism could be assumed. The analytical methods used in this investigation are a cryo-fracture, X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), secondary electron microscopy (SEM, EDX, transmission electron microscopy (TEM), analytical TEM (EDX, EFTEM, EELS), adsorption/desorption experiments (Krypton-BET), Laser scanning microscopy (LSM), contact angle measurements, and Raman microscopy. The adhesion and degradation mechanism observed at the titanium-PEEK interface strongly depends on the applied surface pre-treatment. The interface properties between pretreated Ti-3Al-2.5V and PEEK show an influence of the morphology of PEEK. For the first time, interfacial crystallization of PEEK at the Ti-3Al-2.5V surface was confirmed by experimental results. Interfacial crystallization is known for its strengthening effect perpendicular to C-fibers within CF/PEEK laminates and implies a strong interaction between PEEK and the oxide layer on the Ti-3Al-2.5V joining partner. Moreover, the investigations of the interface between laser treated Ti-3Al-2.5V and PEEK indicate that adhesion is not only due to mechanical interlocking on micro- and nano-scale. Chemical interactions between the polymer and the joining surface seem be promoted byan increased surface reactivity due to the high surface area structures on micro- and nano-scale. In addition, an aluminum-enrichment was detected with TEM at the treated surface that may play a role in the bonding. During the cooling phase of the consolidation of the thermoplastic, thermal stress arise at the interface due to suppressed expansion and contraction of the individual components. It can be assumed that PEEK, which is interlocked within the oxide pores, reduces the stress by relaxation processes. Relaxation induced re-orientation of the molecule structure is able strengthen the interface as it is known from self-reinforced polymers. This assumption could explain the interface behavior characterized by mode I and mode II loadings. High energy release rates observed at mode I loadings could be traced back to the re-orientated molecule structure which is equal to the direction of mode I loading. This mechanism is material specific and can be applied only to cure-free thermoplastics. The long-term durability is enhanced significantly when of surface structures on nano-scale are formed by the pretreatment. This result is in good agreement with the literature. However, during the bonding process not only on the formation of adhesion between PEEK and Ti-3Al-2.5V is important but also the stability of the interfacial phases within the Ti-PEEK interfacial system as shown on the interface properties between anodized Ti-3Al-2.5V. Anodized oxide phases, for example, which degrade during the bonding by oxidation diffusion, were found to result in low interfacial strength and low long-term durability. Aging in hydro-thermal environment are enhanced by further factors. Residual stress which arises during the bonding process leads to cracks within the oxide and within martensitic region. Entrapped air which especially develop when large areas are bonded enhance water diffusion along the interface and hydrothermal aging. A basic understanding of the titanium-PEEK system requires that all phases and interfaces in the titanium-PEEK system as well as all process steps are taken into account. Although the polymer will be neglected in most cases this investigation reveals that even the polymer morphology significantly influences the interface properties.