The major directions of this thesis involve (1) the synthesis, immobilization, and characterization of tridentate phosphine linkers on silica, (2) the study of unprecedented Si2C bond cleavage in Rh and Ir phosphine complexes, and (3) the study of performance polymers with solid2state NMR techniques. First a brief overview of solid2state NMR and its relevance to the various areas of chemistry covered in this thesis is given. Following the synthesis, immobilization, and characterization of tridentate phosphine ligands, EtOSi[(CH2)nPPh2]3 (n = 4, 7, 11) and [MeP((CH2)nPPh2)3]+I? (n = 4, 7, 11) on silica is detailed. Both, immobilization by electrostatic interactions and by a covalent siloxane bond to the support, is studied and compared. Ligand exchange with Wilkinson?s catalyst affords immobilized Rh complexes. These materials are applied to catalytic olefin hydrogenation. In either case active hydrogenation catalysts are obtained that can easily and efficiently be recycled up to 30 times. Detailed investigations reveal that irrespective of the linkage to the support the catalysts consist initially of well2defined molecular species that form supported Rh nanoparticles with a narrow size distribution in the course of the catalytic reaction. The nanoparticles are active hydrogenation catalysts as well, and no metal leaching into solution is detected. The reaction of the tridentate phosphine ligands EtOSi[(CH2)2PPh2]3 and MeSi[(CH2)2PPh2]3 with Rh and Ir complexes is investigated. This reaction does not lead to the anticipated Wilkinson2type complexes with the metal in the +I oxidation state, but instead to oxidative addition of the C(sp3)2Si bond to Rh or Ir centers to yield octahedral complexes with the metal in the +III oxidation state. These complexes are fully characterized by multinuclear NMR in solution and in the solid state. Preliminary density functional theory (DFT) calculations corroborate the preference for oxidative addition. Subsequently the study of performance thermoplastics which are important materials for the oil and gas industry is presented. The polymer morphology is studied by solid2state NMR techniques. Special attention is devoted to potential decomposition pathways at elevated temperatures for polyetheretherketone (PEEK) and polyphenylene sulfide (PPS) polymers. 13C CP/MAS (cross polarization with magic angle spinning) NMR and IR spectroscopy reveal that PEEK polymers show no detectable chemical change on the molecular level, while PPS polymers display signs of oxidation of the thioether group and branching via formation of ether, thioether, and biphenyl linkages. Furthermore, the water absorption of polybenzimidazole (PBI), polyetherketoneketone (PEKK), and their blend PEKK2PBI is studied. It is demonstrated that steam2treatment even at high temperatures and pressures does not cause chemical decomposition and that the changes, which are morphological in nature, are fully reversible.

Les thermoplastiques hautes performances poly(éther-cétone-cétone) (PEKK) sont actuellement étudiés avec un grand intérêt dans l’industrie aéronautique comme matrice pour la fabrication de pièces de structure composites renforcées par des fibres de carbone. En effet, les composites thermoplastiques PEKK ont l’avantage d’être consolidables hors autoclave et ont des températures de mise en œuvre plus faibles que les composites PEEK.L’objectif de cette étude est de comprendre et prédire l’évolution des propriétés mécaniques des composites PEKK suivant le cycle thermique de mise en œuvre pour déterminer les paramètres de mise en œuvre optimaux pour la fabrication des pièces composites PEKK concernant les temps de mise en œuvre et les performances mécaniques finales.Une première partie traite de la modélisation des cinétiques de cristallisation des matrices PEKK ainsi que l’influence de la cristallinité et des morphologies cristallines sur les propriétés mécaniques des matrices PEKK. Une deuxième partie se concentre sur les modifications macromoléculaires des matrices PEKK pour des hautes températures de mise en œuvre sous air et sous azote et leurs impacts sur la cristallisation et les performances mécaniques des matrices PEKK. Enfin une dernière partie présente l’influence des fibres de carbones sur les morphologies cristallines et les cinétiques de cristallisation, la fabrication de composites PEKK unidirectionnels et tissés à ± 45° sous presse et sous autoclave et enfin l’impact de la cristallinité et des morphologies cristallines sur les performances mécaniques finales des composites PEKK. / Poly(ether-ketone-ketone) (PEKK) high performance thermoplastics are currently studied with a great interest by the aeronautic industry as matrix for carbon fiber reinforced structural parts. In fact, PEKK composites can be consolidated out of autoclave and they have lower processing temperatures than PEEK composites.The aim of the study was to investigate and predict the evolution of PEKK composite mechanical properties depending on the processing thermal cycle to determine the best processing parameters for PEKK composite part manufacturing regarding processing times and final mechanical performances.A first part investigates the crystallization kinetics modelling of PEKK matrices and the influence of crystallinity and crystalline morphologies on PEKK matrix mechanical properties. A second part focuses on the macromolecular modifications of PEKK matrices at high processing temperatures under air and nitrogen and their impact on PEKK matrices crystallization and mechanical properties. A last part presents the influence of carbon fibers on crystalline morphologies and crystallization kinetics, the manufacturing of unidirectional and ± 45° PEKK composites under press and autoclave and finally the impact of crystallinity and crystalline morphologies on PEKK composite mechanical properties.

Syfte Syftet med föreliggande studie är att genom en systematisk översikt identifiera skillnaderna i de kemiska och mekaniska egenskaperna hos materialen PEEK och PEKK och till vilka dentala applikationer materialen kan användas.  Material och metod Materialens kemiska och mekaniska egenskaper identifierades genom litteratursökning med PRISMA och PICO-systemet. Databaserna som användes var PubMed, Scopus samt Web of Science. Granskning gjordes på titel-, abstrakt- och fulltextnivå, baserat på inklusions- och exklusionskriterier. Resultat Sökningen resulterade i totalt 226 artiklar varav 210 artiklar i PubMed, nio artiklar i Scopus och sju artiklar i Web of Science. Efter kontroll av dubbletter och bedömning utifrån inklusions- och exklusionskriterier var det totalt sju artiklar som analyserades på fulltextnivå. Av dessa sju artiklarna utvärderades olika materialegenskaper där de använda materialtesterna skiljde sig åt. I fem artiklar utvärderades bindningsstyrkan mellan fasadmaterial och PEEK och/eller PEKK. En artikel undersökte ytan hos materialen beroende på ytbehandling och en artikel testade tryckhållfasthet på tre-ledsbroar av PEEK och PEKK. Båda materialen uppvisade liknande mekaniska och kemiska egenskaper vid jämförelse mot varandra.  Slutsats PEEK och PEKKs mekaniska och kemiska egenskaper skiljer sig inte åt. Mer forskning och kliniska data behövs om materialens dentala applikationer. Nyckelord: Avtagbar protetik, fast protetik, högpresterande polymer, PAEK, tandvård / Purpose The purpose of the present study is to carry out a systematic review to identify the differences in mechanical and chemical properties of the materials PEEK and PEKK, as well as which  dental applications the materials can be used for.  Material and method The materials’ mechanical and chemical properties were identified using PRISMA and PICO system through a literature search. The databases used were PubMed, Scopus and Web of Science. Screening and assessing were done at title, abstract and full text level, based on the inclusion and exclusion criteria. Results The search resulted in a total of 226 articles, whereon 210 articles in PubMed, nine articles in Scopus and seven articles in Web of Science. After removal of duplicates and assessment of the studies according to the inclusion and exclusion criteria, the total amount of studies reviewed was seven. In these seven articles, different properties were evaluated, and the tests used differed. In five articles, the shear bond strength between veneering materials and PEEK and/or PEKK was tested. In one article the surface roughness depending on surface treatment was tested and in another, the strength of three-unit fixed dental prostheses made of PEEK and PEKK was tested. PEEK and PEKK showed similar mechanical and chemical properties in comparison to each other.  Conclusion The mechanical and chemical properties of PEEK and PEKK do not differ. More research and clinical data are needed on the dental applications of the materials.Keywords: Dentistry, fixed dental prosthesis, high-performance polymer, removable dental prothesis, PAEK.

RTM6 has for more than 20 years been the main commercial epoxy system for infusion processing qualified by the aerospace industry. In common with other aerospace-grade epoxy systems RTM6 is mechanically strong but brittle, producing carbon-fibre (CF) composites with relatively low impact resistance and damage tolerance. This thesis reports an approach to toughening epoxy-CF composites without modification of the resin. Thus, a T300 carbon fabric (ES-fabric) coated with 20 weight % of a poly (aryl ether ketone) (PAEK) was used to toughen the composite. The initial stage of the study was the manufacturing process. DSC and oscillatory-shear rheology were used to determine flow times and cure conditions, and to produce laminates with fibre volume fractions ≥55% a hybrid resin infusion/hot-press process was developed. Dynamic mechanical thermal analysis also showed that the PAEK coating produced relatively little plasticization of the epoxy matrix, with values of the matrix glass transition temperature shifting from 186±4.4 to 181± 1.4 ºC when using the ES-fabric. The main body of the study focussed on the toughening effect afforded by the PAEK coating relative to an uncoated fabric system as a reference. Mode I and Mode II interlaminar fracture toughness behaviour were studied using dual cantilever beam (DCB) and four-point end-notch flexure (4ENF) tests, respectively. The measured mode-I fracture energy, GIC, increased three-fold, from 216 ± 7.2 Jm-2 to 751 ± 105 Jm-2, due to the toughening effect of the PAEK coating; whereas the mode-II fracture energy, GIIC, increased almost four-fold from 857 ± 99 Jm-2 to 3316 ± 372 Jm-2. Damage resistance was studied using low-velocity impact testing and damage tolerance using a miniature compression-after-impact (CAI). A comparative study of damage tolerance was performed using open-hole compression (OHC) testing. The impact damage resistance significantly improved with the use of the PAEK-coated ES-fabric as well as the CAI and OHC behaviour. Impact testing showed the PAEK -toughened system exhibited higher energy abortion than the untoughened system, larger damage area was created in the T300/RTM6-2 after impacted with same energy. The CAI results indicated that the normalized CAI strength is major related that damage width rather than other factor. OHC results are predicted by using W-N criteria, for ES/RTM6-2: ASC a0 = 9.35 mm and PSC d0 = 2.72mm; whereas for T300/RTM6-2: ASC a0 = 7.95 mm and PSC d0 =2.43 mm, indicates that the compressive strength of T300/RTM6-2 is more sensitive to the size of the hole, thus ES/RTM6-2 perform better damage tolerance. The results from mechanical testing indicate that the PAEK coating toughened the composite system and significantly improved damage tolerance. Scanning electron microscopy indicated that these improvements in fracture behaviour were due to morphological changes induced by the PAEK coating in the matrix-CF interfacial region, where such changes can provide the maximum benefit. Small particles of RTM (approximately 1 µm in diameter) were observed imbedded within a continuous PAEK phase. Thus, during testing crack propagation was deflected (or bifurcated) by the RTM6 particles or stopped by shearing of the continuous PAEK phase of this multiphase region. This morphology is proposed to have formed in the interfacial region during processing by dissolution of the PAEK coating within the matrix resin system, followed by reaction-induced phase separation and then phase-inversion as the matrix cures.

Le développement d'une nouvelle voie de synthèse de poly(éther cétone cétone),polymères thermostables, a été étudiée pour des matériaux composites à matrice thermoplastique obtenus par le procédé de moulage par injection de résine RTM. Pour cela,nous nous sommes orientés vers une polymérisation par couplage réactif entre des monomères difonctionnels et des agents de couplage. Neuf monomères X-EKKE-X avec différentes extrémités réactives ont été synthétisés par acylation de Friedel-Crafts ou substitution nucléophile aromatique puis caractérisés structurellement et thermiquement.Des essais de couplage à partir de monomères à extrémités COOH sur des bisoxazoline sont permis la synthèse en masse de quatre polymères, semi-cristallins ou amorphes, de faibles masses molaires. A travers l'étude du comportement thermique de molécules modèles, une fragilité thermique à partir de 250°C a été mise en évidence pour ces polymères et attribuée au pont ester-amide entre deux unités EKKE. / A new synthetic route to poly(ether ketone ketone), thermostable and semi-crystalline polymers, has been studied towards composite materials with a thermoplastic matrix obtained by a resin transfer molding process (RTM). This original synthesis was conducted by coupling reactions between difunctionals monomers and coupling agents. Nine X-EKKE-X monomers with different reactive extremities have been synthesized by Friedel-Crafts acylation or nucleophilic aromatic substitution. Thermal and structural properties were thoroughly investigated. Four polymers with semi-crystalline or amorphous morphologies and low molecular weights were obtained by coupling reactions between monomers with COOH functional extremities and bisoxazolines. Through the study of the thermal behavior of models molecules, a thermal fragility was highlighted for these polymers from 250°C and assigned to the amide-ester bridge between two EKKE units.

yes / Advanced engineering polymers of the Polyaryletherketone (PAEK) family with carbon fibre reinforcement are finding application in engineering systems as tribological bearing surfaces under severe operating conditions that cyclically move the polymer into and beyond the glass transition temperature region. To support such an application, the friction in high speed and low load PAEK-steel sliding contacts was investigated both unlubricated and lubricated with a trinonyl trimellitate ester, a base fluid for high temperature industrial lubricants. Four polymers in the PAEK family, PEEK, PEK, PEKEKK and PEKK, with 30%wt of carbon fibre whiskers were tested against an AISI 4140 steel disc. When unlubricated, low friction depended upon the formation of a PAEK transfer film on the steel disc and when this became unstable in the glass transition region the friction increased to much higher levels with associated polymer surface damage. Frictional heating due to the high sliding speed dominated the differences in glass transition behaviour between the four PAEKs. When lubricated, the lubricant film controlled friction and there was no significant effect of the glass transition of any of the PAEKs. The irreversible nature of the glass transition in PAEKs in such tribological applications, due to high surface damage at high temperature, means that it is essential to ensure effective lubrication in both fluid film and boundary lubrication. / Innovate UK, Knowledge Transfer Partnership

Certaines applications (notamment dans l'aéronautique) demandent des polymères thermostables semi-cristallins avec des résistances et des températures de fonctionnement de plus en plus élevées (Tg supérieures à 170°C) tout en conservant de bonnes propriétés de mise en œuvre (Tf ne dépassant pas 350°C) aptes aux procédés industriels. Ce projet de thèse porte sur la synthèse et la caractérisation de nouveaux polymères hautes performances de type poly(aryl éther cétone amide)s à partir d'un monomère de type EKKE aux extrémités acide carboxylique. Ainsi, trois voies de synthèse des amides par condensation ont été étudiées : entre les acides carboxyliques et les isocyanates, entre les chlorures d'acyle et les amines, et entre les acides carboxyliques et les amines par phosphorylation. La comparaison des propriétés thermiques et leurs corrélations avec les structures chimiques des poly(aryl éther cétone amide)s aromatiques et semi-aromatiques obtenus sont particulièrement détaillées. / Some demanding applications (especially in aerospace) require more and more semi-crystalline thermostable polymers with high temperature resistance and durability (Tg above 170 °C) while maintaining good processing properties (Tm not exceeding 350°C) suitable for industrial manufacturing.This work deals with the synthesis and characterization of new high performance poly(aryl ether ketone amide)s polymers from an EKKE monomer with carboxylic acid extremities. Thus, three amide condensation synthetic routes were studied: between carboxylic acids and isocyanates, between acyl chlorides and amines, and between carboxylic acids and amines by phosphorylation. The thermal properties and their correlation with the chemical structures of the obtained aromatic and semi-aromatic poly(aryl ether ketone amide)s are compared and especially detailed.