The purpose of this study was to determine the effect of exposure conditions, resin composition, and resin treatment on film formation on metal surfaces exposed to epoxy resin. Epoxy rods were prepared from novolac hardened by 4-4' methylenedianiline (MDA). The curing and post curing temperatures were 60, 125 °C and 125, 160 °C. The composition of the epoxies used were 27.0 and 31. 5 parts (MDA) per 100 parts epoxy. The metals investigated were pure gold, silver, and copper; gold-copper alloys; gold-silver alloys; and electroformed gold-copper alloys. The alloys ranged in composition from 75 to 92 per cent gold. These samples were cleaned, weighed, placed in individual, covered, glass containers with the epoxy rods, and then were exposed at 30, 60, and 90 °C. The change in weight of the metal samples was determined at intervals of about. 30 days for five months. Weight increases of 0.1 to 0.4 milligram were observed for the samples exposed to the epoxy rods, and were negligible for samples stored without epoxy rods. The contaminating materials, apparently, are organic compounds consisting of unreacted monomer and degradation products. The film forms from a heavy, stagnant, low-lying, vapor-phase from the epoxy, with the vapors adsorbed or reacted on the surface of the metal samples. Film formation is not affected to any appreciable extent by the combined effect of increased curing temperatures and increased hardener content. The effect of increasing the temperature from 30 °C to 60 or 90 °C, on the rate of film formation was inconclusive. Epoxy film formation was observed on all metal samples tested, pure gold, copper, and silver; gold-copper and gold-silver alloys. The metal composition affects the rate of film formation with the rate increasing with decreased golJ composition for both copper and silver alloys. / Master of Science

Corrosion of iron and copper pipes can produce leaks and loss of efficiency in the water distribution system, elevate levels of contaminants at the tap, and cost billions of dollars annually in pipe replacement or rehabilitation. In situ pipe rehabilitation using cement mortar, polyurethane, and epoxy is a commonly employed method of dealing with aging yet structurally sound pipes because it is less expensive and less invasive than replacing pipe infrastructure. Although epoxy has been shown to be an effective solution to pipe corrosion, little research has been conducted regarding its impact on a comprehensive list of water quality parameters. This research addressed that gap in the literature by conducting short-term immersion tests in which new epoxy linings were exposed to reference tap waters containing one of three disinfectant treatments: no disinfectant, free chlorine, or chloramines. As a comparison, an aged epoxy-lined field sample was also tested. Water exposed to the liners under stagnant conditions was analyzed for the following water quality parameters: pH, ammonia, alkalinity, hardness, metals, disinfectant consumption, total organic carbon (TOC), semi-volatile organic compounds (SVOCs), disinfectant byproduct (DBP) formation, and odor. Results of the study showed relatively low impacts on water quality, as all USEPA drinking water regulations were met. Impacts were highest during the first 24 hour exposure period during which time significant disinfectant consumption was shown (> 90% free chlorine consumed, 13% chloramines consumed), high TOC was leached (2.6-6.2 mg/L), trihalomethanes and haloacetic acids were formed (both < 15 ug/L), Bisphenol-A, an endocrine disrupter, was detected (< 35 ug/L), and odor was reported by panelists at a moderate intensity and described as sweet/chemical/burning/chlorinous. Impacts were much less after the initial 24 hours, although odor remained noticeable throughout the 30 day study. Overall, water quality impacts were greatest in chlorinated waters and both new and aged epoxy showed slight differences in results. / Master of Science

There are instances where efficiency and safety may be compromised as a result of wear and tear of fluid transporting pipe systems. Consequently, it is sometimes necessary to shut down the entire operation to fix the problem. Thus, it is worth evaluating other methods that can repair the damage for a temporary period without shutting down the operation while a new pipe is being constructed. The objective was to evaluate the durability of the epoxy bonded steel in aqueous environments that might be the conditions of such a repair. EPON(registered mark)828 was chosen as the epoxy resin, and dicyandiamide and polyamidoamine were two types of curing agent evaluated in this study. The epoxy bonded steels were exposed in either distilled water or 3.4% NaCl solution for various time periods. The mechanical strengths of the bonded joints were evaluated using a three-point flexure test. The neat epoxy samples were also aged under the same conditions, and three-point flexure test and dynamic mechanical analysis (DMA) were performed to evaluate their mechanical properties. The moisture uptake of the neat epoxy increased with exposure time, and the bending modulus of the neat epoxy decreased with aging time and moisture uptake. It was found that the interfacial shear strength decreased with aging time for both epoxy bonded systems. Scanning Electron Microscopy (SEM), optical microscopy, and X-ray Photoelectron Spectroscopy (XPS) were used to determine the locus of failure of the bonded joints. It was concluded that failure occurred cohesively within the oxide layer if oxides were present on the substrate surface prior to the bonding procedure. / Master of Science

Montmorillonite reinforced polymers are a new development in the area of nanocomposite materials. Since reinforcement of epoxy is important to the development of high strength adhesives and composite matrices, the introduction of montmorillonite to epoxy is of interest. Compositional effects on epoxy reactivity, on molecular relaxation, and on mechanical properties were investigated. Change in reactivity was determined by Differential Scanning Calorimetry. Tensile properties at room temperature indicated improved modulus and retention of strength of the epoxy matrix but a decreased elongation to failure. Depression of dry nanocomposite glass transition was observed for nanocomposites beyond 5% by weight montmorillonite. Samples that were saturated with water showed lower moduli due to the epoxy matrix. The greatest moisture absorption rate was found at 7%, the least at 3%.

A study has been undertaken with the aim of preparing appropriately functionalised polyhedral oligomeric silsesquioxane (POSS) compounds to be used in ambient-cure chemistry. Numerous epoxy-functionalised compounds have been designed and synthesised and these materials have been characterised in order to determine their chemical structure. These compounds have also been incorporated into existing polymerisation reactions to test whether these materials could be used in the protective coatings industry. A glycidyl-functionalised POSS compound was prepared and reacted with a series of amines to produce ambient-cured polymers which could be used in the coatings industry. There were also a series of experiments undertaken on these polymers to identify the processes at work and to test how they compare to industry standards. As a direct comparator to this work, another set of results was obtained with a cyclic-siloxane material incorporated into the systems in place of the POSS. A linear analogue was also tested. The reactions proved to be a success and an appropriate data-set was yielded. During the synthesis of POSS precursors there are a series of residual materials produced. These materials have also been studied in this project. It was anticipated that these would behave in a similar way to the POSS compounds however the same functionality was never achieved as had been with the POSS. Ambient-cured polymers have also been targeted from a basic hydride-functionalised POSS compound and a polybutadiene system. The appropriate reactions unfortunately never took place as anticipated but there were a series of tests undertaken to identify the processes at work. A study has also been undertaken using near-I.R. to track the curing reactions. From this data, the extent of cure could be studied and the make-up of the reaction could be investigated in more detail.

L'objectif de notre étude est de mettre en évidence les synergies existantes entre les différents facteurs de vieillissement lors de la dégradation d’un revêtement polymère modèle, représentatif d’une peinture anticorrosion.Notre travail a consisté à suivre le vieillissement hygrothermique du système DGEBA/TETA sous forme de film libre et de revêtement déposé sur substrat acier dans différentes solutions (eau pure et NaCl 3%) pour différentes températures et contraintes mécaniques visco-élastique appliquées. Nos résultats ont montré que le programme de cuisson affectait les propriétés physico-chimiques et mécaniques du système initial et que l’absorption d’eau, non homogène, suivait une loi non-Fickienne, suite à un phénomène de gonflement.La prise en eau et la diffusion ont été caractérisées par gravimétrie et spectroscopie d’impédance électrochimique. Nos résultats montrent que les propriétés barrière du revêtement diminuent avec la quantité d’eau absorbée et avec la température de vieillissement. Cependant, la contrainte plane appliquée sur le système tend à contrarier cet effet. La formalisation de nos observations expérimentales dans le cadre d’une approche thermodynamique a montré l’effet prépondérant de la partie entropique par rapport à la partie enthalpique de l’énergie d’activation des processus de transport de l’eau, en raison de l’orientation des chaînes sous l’action de la contrainte. De plus, une diminution de la permittivité relative du revêtement sec a été observée en fonction de la température et de la contrainte appliquée, indépendamment de son signe (tension ou compression). Dans ce cas, la contribution enthalpique semble être prépondérante. / The objective of this study is to highlight synergies existing between different ageing factors during the degradation of a polymer model coating system, representing an anti-corrosion coating.We first monitored the hygrothermal ageing of DGEBA/TETA system as free films and as attached films onto a steel substrate in different solutions (water and NaCl 3wt% solution) for different temperatures and applied mechanical visco-elastic stresses. Our results showed that the curing programs affected the physic-chemical and mechanical properties of the cured systems and that the non-homogeneous water uptake process followed a non-Fickian law, due to a swelling phenomenon.The water uptake and diffusion were characterized by gravimetry and electrochemical impedance spectroscopy. The results indicate that the barrier properties of the coating decrease with the quantity of absorbed water in system and with the increasing of the ageing temperature. However, the planar stress applied onto the system tends to counteract this effect. The formalization of our experimental observations within a thermodynamic approach showed the predominant effect of the entropic part in comparison with enthalpic part of the activation energy of the water uptake process, due to the reorientation of polymer chains under the applied stress. In addition, a decrease in the relative permittivity of the initial dry coating was observed as a function of the temperature and the applied stress, regardless of its sign (tension and compression). In this case, the enthalpic contribution seems to be predominant.

Dans le cadre de cette thèse, nous rechercherons comment éliminer les opérations de non-valeur-ajoutée dans la fabrication des pièces en matériaux composites incluant la fixation des puces RFID directement dans les pièces en matériaux composites utilisées dans les industries aéronautiques et spatiales. Nous proposerons une nouvelle méthode innovante. Cette méthode industrielle utilise la technologie RFID pour aider éliminer les étapes de non-valeur-ajoutée qui empêchent des améliorations opérationnelles. En plus d’aider à éliminer des opérations de non-valeur-ajoutée, cette technologie peut permettre d’augmenter la communication transverse entre des processus opérationnels. L'utilisation appropriée de technologie RFID peut aussi aider à augmenter la visibilité des produits, des données et des outils dans la fabrication. Les étapes de contrôle inutiles qui induisent des délais de processus plus importants et des coûts additionnels plus élevés peuvent automatiquement être éliminées. De plus, cette méthode permet d’assurer une macro et micro traçabilité. La technologie RFID marche très bien tant avec la fibre de verre qu'avec les composés de fibre de carbone industriels. L’intégration de ces aides technologiques dans les pièces composites permet de créer des matériaux "intelligents" et de communiquer avec d'autres systèmes industriels qui sont voisins, ou dans un autre pays via le logiciel. Et cette capacité peut aider à réduire la documentation et améliorer la traçabilité pendant les phases industrielles transverses de l'entreprise. Les Informations peuvent être stockées sur la puce à l’avance ou bien après chaque processus. Ceci permet aussi d’élaborer de nouveaux processus et des occasions de traitement de la part de la société pour les parties qui sont en service. De cette façon, la puce peut permettre une communication entre le fabricant et le client. Les informations sur l'Étiquette RFID permettent aux pièces d'être gérées plus rapidement et à distance pendant tout le cycle de vie de la pièce. Les informations enregistrées sur la puce pendant la fabrication de la pièce composite peuvent même être lues, avec un ajout d’information, pendant que la pièce est en service. La méthode que nous proposons est la fixation la puce RFID dans les pièces en matériaux composites. Le dépistage et le contrôle automatiques de ces parties permettra à nos processus industriels d'être plus efficaces et visibles pendant la fabrication, aussi bien que le support après la livraison du produit. Dans un proche avenir, des entreprises nationales et internationales transformeront leur ingénierie et procédés de fabrication en appliquant cette méthode novatrice qui accélère les cycles de vie, maximise l'efficacité et élimine des étapes inutiles dans le processus. En conséquence, ces entreprises seront dans une bien meilleure position pour maximiser leur productivité et des nouvelles occasions de produit/marché aussi bien que la documentation de produit efficace et les processus de production aideront des entreprise ou les clients à abaisser leurs coûts d'exploitation, à augmenter la productivité des salariés, à améliorer la conformité, le délai de diminution et à faire des progrès plus rapides dans le domaine de la durabilité. En résumé, le fait de diminuer le délai de livraison à chaque étape dans le processus "On-Target" soutiendra) grandement la performance de " On-Cost" et " On-Quality". En utilisant cette méthode, les fabricants deviendront capables de diminuer considérablement leurs coûts, d’améliorer de façon significative les améliorations de processus, d’augmenter l’innovation à chaque étape du processus et de lancer dans l’entreprise des actions qui lui conféreront une vaste excellence opérationnelle. / The main objective of this thesis is to improve the traditional manufacturing processes in the company and to replace the traditional manufacturing methodology by new method in order to improve the manufacturing efficiency (time, cost, quality, safety of the products etc.). In the frame of this thesis, we will focus on how to eliminate the non-value added operations in the manufacturing by the embedding RFID tags directly in the composite parts used in aerospace companies. We will propose a new innovative state of the art composite manufacturing method that uses RFID technology to help eliminate non-value added manual steps that impede operational improvements. This technology can help to eliminate non-value added operations and increase the communication across operational processes. The appropriate use of RFID technology can also help increase the visibility of the products, data, and tools in manufacturing. The unnecessary control steps which induce higher process lead-times and higher additional costs can automatically be eliminated. The macro and micro traceability of processes and products (such as the part information, lifecycle, movement history and location) can all be automated and digitized with less manual intervention and less paper documentation. Carefully using this technology across our production processes, we can rapidly transform operational processes and improve their accuracy, control and efficiency. This is a lean, innovative and value adding innovative approach that significantly increases the visibility and monitoring of processes. RFID technology works very well with both glass and carbon fibre composites’ manufacturing. This technology helps makes the composite parts “smart” and communicate with other manufacturing systems that are nearby or in another country via software. And this capability can help reduce documentation and improve traceability during the manufacturing phases and across the company. Information can be stored on the tag before and/or after each process. This also enables new process and company service opportunities for parts that are in-service. In this way, the tag can enable a communication between the manufacturer and customer. The information on the RFID Tag enables the parts to be managed faster and remotely across the full lifecycle of the part. The information recorded on the RFID Tag during the manufacturing of the composite parts can even be read and more information can be read during in-service. This information can create an advantage for any modification of the parts, repair, and maintenance in the future. In this way, RFID based processes can reduce unnecessary steps across the whole supply chain and reduce the high workload of manual processes and documentation. Furthermore, costs can be minimized due to increased visibility and elimination of unnecessary steps across processes. Using RFID technology by direct embedding of the RFID Tag in the composite parts intends to measure and reduce “Process Variation”. The idea here is not to move the tasks, but to optimize and eliminating the non-value added tasks by using RFID based production method “embedding of RFID Tag in Composite parts”. The method that we propose is embedding the RFID tag in the composite parts. Automatically tracking and monitoring these parts will enable our industrial processes to be more efficient and visible during manufacturing as well as in service-processes that occur after delivery of the product. As mentioned previously, the intention here to enable our composite parts to be “smart” so they can be communicated to automatically across their lifecycle. This will help create an industrial "Internet of Things”. [...]

Les principaux enjeux de la fabrication de pièces en matériaux composites (coût, temps de fabrication, performances,...) sont intimement liés aux moyens de mise en oeuvre, principalement les autoclaves; qui engendrent non seulement des coûts très élevés en termes d'installation et d'entretien, mais limitent également les cadences de production à cause de la longueur des cycles. Afin de réduire cette dépendance, des procédés de fabrication hors autoclave ont été envisagés (Quickstep, Roctool, VARTM, VBO...) entrainant par conséquent des modifications dans la conception des matériaux destinés à ces procédés (cinétique, rhéologie, façon dont sont imprégnées les fibres...). Afin de limiter les changements en termes de procédé de fabrication, de matières premières, de produits d'environnement et de conditions de mise en oeuvre, c'est sur le procédé Vacuum Bag Only que porte cette étude. Plusieurs développement de semi-produits ces dernières années ont permis d'augmenter la robustesse de ce procédé de fabrication, palliant ainsi à cette absence de pression externe durant la cuisson en étuve. Il reste toutefois à démontrer la viabilité de ces produits par rapport à leur mise en oeuvre, à comprendre les mécanismes d'extraction de l'air et à estimer les propriétés mécaniques atteignables par rapport à leur équivalent autoclave. / The main issues concerning composite part manufacturing (cost, manufacturing time, mechanical performances, etc.) are closely linked to the means of curing, mainly autoclaves; which do not only generate very high installation and maintenance costs, but also limit production rates because of the length of the cycles. In order to reduce this dependence, non-autoclave manufacturing processes have been envisaged (Quickstep, Roctool, VARTM, VBO ...) therefore leading to modifications in the design of the materials intended for these processes (including kinetics, rheology, fiber impregnation methods). In order to limit the changes in terms of manufacturing process, raw materials, environment products and implementation conditions, this study is based on the Vacuum Bag Only process. Several semi-product developments in recent years have made it possible to increase the robustness of this manufacturing process, thereby overcoming the lack of external pressure during an oven cure. However, the viability of these products in relation to their implementation still needs to be demonstrated, as well as the understanding of the air removal mechanisms and the estimation of the achievable mechanical properties compared to their autoclave counterpart.

Cette étude porte sur la production et à la caractérisation de matériaux composites à base de matrices d’époxy modifiées par incorporation de particules de caoutchouc recyclées et dévulcanisées. Ces matrices sont renforcées par des fibres d'alumine (Al2O3- FA) et/ou par des nanoplaquettes de graphène (GnPs). Principalement, la fabrication, la caractérisation générale des composites ainsi que l’identification des mécanismes de renforcement à l’échelle micro et nano ont été réalisées. En outre, la fabrication de composites multifonctionnels à base de caoutchouc dévulcanisé et d'époxy a été réalisée pour des applications diverses potentielles dans les industries aéronautique et automobile. Dans un premier temps, les propriétés mécaniques et thermomécaniques des composites ont été étudiées de manière approfondie. L’étude mécanique a consisté à mesurer le module d’élasticité, la ténacité et la température de transition vitreuse. / Recycling of rubber is gaining importance across the world in many industries due to shrinking resources, increasing cost of raw materials, growing conscious about sustainable development as well as environmental issues. In the frame of the common research program between Michigan Tech University/USA and Supmeca/Paris-FRANCE, this PhD work is devoted to the design, development and characterization of recycled rubber modified epoxy-based composites . Additionally, alumina (Al2O3) fibers (AFs) and/or graphene nano platelets (GnPs) have been used as the basic reinforcements. A detailed experimental approach was adapted to these multifunctional composites for explaining of toughening mechanisms by means of fracture toughness test methods and scanning electron microscopy (SEM) on the fracture surfaces. Also, different case studies were included at the end of this work for various potential applications in aeronautic and automotive industries.

Thesis (Elec.E)--Massachusetts Institute of Technology, Dept. of Electrical Engineering and Computer Science, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING / Includes bibliographical references. / by Huan Lim Lee. / Elec.E