The E-beam curable BMI resin systems and phenylethynyl terminated AFR-PEPA-4 oligomer together with an imide model compound N-phenyl-[4-(phenylethynyl) phthalimide] were synthesized and characterized. E-beam exposure cannot propagate the polymerization of BMI system until the temperature goes up to 100oC. However, a small amount of oligomers may be generated from solid-state cure reaction under low E-beam intensity radiation. Higher intensity E-beam at 40 kGy per pass can give above 75% reaction conversion of BMI with thermal cure mechanism involved. NVP is a good reactive diluent for BMI resin. The cure extents of BMI/NVP increase with the increase of the dosage and applied dosage per pass. The reaction rate is much higher at the beginning of the E-beam cure and slows down after 2 dose passes due to diffusion control. Free radical initiator dicumyl peroxide can accelerate the reaction rate at the beginning of E-beam cure reaction but doesn’t affect final cure conversion very much. According to the results from FT-IR, 200 kGy total dosage E- beam exposure at 10 kGy per pass can give 70% reaction conversion of BMI/NVP with the temperature rise no more than 50oC. The product has a Tg of 180oC. The predicted ultimate Tg of cured AFR-PEPA-4 polyimide is found to be 437.2oC by simulation of DSC Tg as a function of cure. The activation energy of thermal cure reaction of AFR-PEPA-4 oligomer is 142.6 ± 10.0 kJ/mol with the kinetic order of 1 when the reaction conversion is less than 80%. The kinetics analysis of the thermal cure of N-phenyl-[4-(phenylethynyl) phthalimide] was determined by FT-IR spectroscopy by following the absorbance of the phenylethynyl triple bond and conjugated bonds. The thermal crosslinking of N-phenyl-[4-(phenylethynyl) phthalimide] through phenylethynyl addition reaction has a reaction order of 0.95 and an activation energy of 173.5 ± 8.2 kJ/mol. The conjugated bond addition reactions have a lower reaction order of 0.94 and lower activation energy (102.7 ± 15.9 kJ/mol). The cure reaction of N-phenyl-[4-(phenylethynyl) phthalimide] can be described as a fast first-order reaction stage followed by a slow second stage that is kinetically controlled by diffusion.

No description available.

Bismaleimide resins are important in aerospace applications as matrix component of composite materials due to their high thermal and mechanical properties. 4,4&rsquo / -bismaleimidodiphenylmethane (BMI) which is the most widely used bismaleimide, was synthesized starting from maleic anhydride and 4,4&rsquo / -diaminodiphenylmethane (MDA). N,N&rsquo / -diallylaminodiphenyl methane (ADM), N,N&rsquo / -diallylaminodiphenyl sulfone (ADS) and N,N&rsquo / -diallyl p-phenyl diamine (PDA) were synthesized by allylating primary aromatic diamines. Nine different prepolymers with 1:1, 1.5:1 and 2:1 molar ratios of BMI/diallyl compound were prepared and cured. The effect of increase in BMI ratio on thermal properties of the resin systems were investigated via Differential Scanning Calorimetry (DSC) and Thermal Gravimetric Analyzer (TGA). DSC results showed that the curing temperature of the resins increased due to the increase in BMI ratio in the resins. Thermal gravimetric analysis showed that incorporation of BMI monomer improved the thermal stability of the resins. BMI/ADM resin system showed better thermal stability compared to BMI/ADS and BMI/PDA resins. Processing characteristics of resins having 1:1 and 1.5:1 mole ratio of BMI/ADM were investigated by viscosity measurements and these resins were found to be suitable for composite production with Resin Transfer Molding (RTM). Composites were manufactured by RTM technique using two different mole ratios of BMI/ADM resins as matrix component. The effect of different matrix composition on thermal and mechanical properties of the composites were investigated. The concept of this thesis work was arised from the requirements of some projects carried out in T&uuml / bitak-SAGE. Keywords: Bismaleimide resins, composite, thermal properties, resin transfer molding.

No description available.

Corrosion represents the single most frequent cause for product replacement or loss of product functionality with a 5% coat to the industrial revenue generation of any country in this dissertation the efficacy of using filled coatings as a protection coating are investigated. Fillers disrupt the polymer-substrate coating interfacial area and lead to poor adhesion. Conflicting benefits of increasing surface hardness and corrosion with long term durability through loss of adhesion to the substrate are investigated. The effects of filler type, filler concentration and exposure to harsh environments such as supercritical carbon dioxide on salt water corrosion are systematically investigated. The constants maintained in the design of experiments were the substrate, AISI-SAE 1018 steel substrate, and the corrosive fluid synthetic sea salt solution (4.2 wt%) and the polymer, Bismaleimide (BMI). Adhesion strength through pull-off, lap shear and shear peel tests were determined. Corrosion using Tafel plots and electrochemical impedance spectroscopy was conducted. Vickers hardness was used to determine mechanical strength of the coatings. SEM and optical microscopy were used to examine dispersion and coating integrity. A comparison of fillers such as alumina, silica, hexagonal boron nitride, and organophilic montmorillonite clay (OMMT) at different concentrations revealed OMMT to be most effective with the least decrease in adhesion from filler-substrate contact. Subsequently examining filler concentration, a 3 wt% OMMT was found to be most effective. A comparison of unmodified and modified BMI with 3 wt% OMMT exposed and not exposed to supercritical carbon dioxide showed that the BMI provided better corrosion protection; however, OMMT provided better wear, shear, and hardness performance.

No description available.

Le composite HexTOOL TM à base de la matrice bismaléimide renforcé par des fibres de carbone fait partie d’une famille de matériaux composites récemment utilisés pour des applications à haute température. Vu la part croissante de l’utilisation de ce matériau dans les domaines industriels, il est inconcevable de ne pas s’intéresser aux endommagements (fissuration et usure…), engendrés par des sollicitations de contact, en particulier vis-à-vis de matériaux métalliques. L’une des sources de ces endommagements est associée aux vibrations apparaissant lors de sollicitations de petits débattements (fretting).L’objectif de ce travail est de développer une méthodologie expérimentale, permettant d’expertiser le comportement à long terme en fretting du composite HexTOOL TM. Deux résultats essentiels sont mis en avant au cours de cette étude. Le premier concerne l’étude de l’endommagement de la matrice bismaléimide (BMI). Pour cela, les conditions d’amorçage et de propagation des fissures ainsi que l’usure ont été analysées en fonction des conditions de sollicitation locale. Le deuxième résultat est le développement d’une stratégie d’analyse de l’usure du composite HexTOOL TM. L’orientation locale des fibres a une influence notable sur le phénomène de l’usure du composite. Des essais effectués sous des niveaux de force normale et des conditions de température différentes ont mis en évidence une meilleure résistance à l’usure dans les zones où les fibres sont parallèles à la direction de glissement. En outre, des essais menés en fonction de la température ont montré l’influence de la matrice et du troisième corps sur la cinétique d’usure. / Carbon fibre/bismaleimide composite or HexTOOL TM is one of a family of composite materials recently developed for high temperature applications. Given the increasing use of this material in industrial fields, it is interesting to study damage (cracking and wear ...), caused by contact stresses, in particular in the contact with metallic materials. One source of this damage is associated to vibration occurring when a small displacement amplitude oscillatory motion is conducted (fretting). The objective of this work is to develop an experimental methodology, allowing the analyzing of the long-term behavior of composite HexTOOLTM under fretting conditions.Two main results are put ahead during this research. The first concerns the study of damage of the bismaleimide matrix. Two types of damage, depending on local stress conditions: the Cracking and Wear, were analyzed. These experimental data conditions were used for the fretting maps to better visualize the behavior of the composite matrix. The second result is the development of a wear analysis strategy of the composite HexTOOLTM. Influence of the local fibre orientation on the wear kinetics of composite is here presented. Tests performed under constant normal force and different temperature conditions show the best wear resistant performance of composite with parallel fibre orientation to the sliding direction. In addition, the influence of the matrix behaviour (viscous response) and the third body on the wear is shown.

Les structures aéronautiques font de plus en plus appel aux matériaux composites pour alléger les structures dans le but d’améliorer leurs performances et de limiter la consommation de carburant. Les composites à matrice organiques représentent aujourd’hui plus de 50% de la structure des avions civils de dernière génération (A350 et B787). Les matériaux utilisés sont essentiellement des composites à matrice époxy avec des températures d’utilisation en service continu pour de longues durées ne dépassant pas 110°C. Continuer à augmenter cette part de matériaux composites passe par leur introduction dans des zones plus chaudes, proches des réacteurs ou des turbines. Les matériaux composites à matrice bismaléimides sont compatibles avec des températures d’application d’au moins 200°C, mais sont très sensibles aux impacts et présentent une fragilité beaucoup trop importante pour des pièces de structure. Les composites à matrice époxy ont fait l’objet de développements pour améliorer ces propriétés, en incorporant dans les formulations des thermoplastiques solubles et insolubles qui ont pour effet de freiner la propagation des délaminages induits par des impacts. En s’inspirant des méthodologies et des connaissances acquises sur les formulations époxys, l’objectif de ces travaux est de développer des systèmes réactifs de type bismaléimide à propriétés optimisées et d’identifier les paramètres clé pour y parvenir. / Aeronautics use more and more composite materials to reduce structures weight, in order to improve performance and to limit fuel consumption. Polymer matrix composite materials represent today more than 50% of last generation civil aircrafts structure (A350, B787). Most of thermoset matrices are epoxies with service temperatures below 110°C for long time services. To further optimize the composite part ratio, it is now necessary to use those materials in structural parts exposed to higher temperatures, for instance, near engines. Among high performance thermoset matrices, bismaleimides offer potential in service temperature up to at least 200°C, but their brittleness makes them non-suitable for structural applications. Epoxy-based composite materials have gone through improvements, increasing their toughness by mixing with soluble and non-soluble thermoplastics to hold in delamination crack propagation. Starting with methods and knowledge from epoxies toughening strategies, this work is dedicated to develop toughened bismaleimide systems and to identify relevant parameters to reach this aim.