Master of Science / Department of Civil Engineering / Robert J. Peterman / Epoxy polymer overlays have been used for decades on existing bridge decks to protect the deck and extend its service life. The polymer overlay’s ability to seal a bridge deck is now being specified for new construction. Questions exist about the amount of drying time needed to achieve an acceptable concrete moisture content to ensure an adequate bond to the polymer overlay. Current Kansas Department of Transportation (KDOT) specifications for new bridge decks call a 14 day wet curing period followed by 21 days of drying (Kansas DOT, 2007) If not enough drying is provided, the moisture within the concrete can form water vapor pressure at the overlay interface and induce delamination. If too much drying time is provided projects are delayed, which can increase the total project cost or even delay overlay placement until the next spring. A testing procedure was developed to simulate a bridge deck in order to test the concrete moisture content and bonding strength of the overlay. Concrete slabs were cast to test typical concrete and curing conditions for a new bridge deck. Three concrete mixtures were tested to see what effect the water –cement ratio and the addition of fly ash might have on the overlay bond strength. Wet curing occurred at 3 different temperatures (40°F, 73°F, and 100°F) to see if temperature played a part in the bond strength as well. The concrete was then allowed to dry for 3, 7, 14, or 21 days. Five epoxy-polymer overlay systems that had been preapproved by KDOT were each used in conjunction with the previously mentioned concrete and curing conditions. After, the slabs were setup to perform pull-off tests to test the tensile rupture strength. The concrete slabs with the different epoxy overlays were heated to 122-125°F to replicate summer bridge deck temperatures. Half of the pull-off tests were performed when the slabs were heated and half were performed once the slabs had cooled back down to 73°±5°F. Results from the pull-off tests as well as results from a moisture meter taken on the concrete prior to the overlay placement were compared and analyzed. Testing conditions were compared with each other to see which had a larger effect on the epoxy polymer overlay’s bond strength.

Ce travail constitue une approche innovante mettant en complémentarité diverses techniques de caractérisation physicochimique, électrique et structurale. Menées sur un polymère époxyde, ces études ont pour principal objectif la compréhension des phénomènes et propriétés diélectriques associés aux charges d’espace, ainsi que le suivi de leur évolution dans le temps ou suite à l’application de contraintes extérieures. Les mesures de spectroscopie d’impédance et de courant de dépolarisation thermo-stimulé (CDTS), ont mis en évidence des processus de relaxations dipolaires et interfaciales. L’origine de ces phénomènes a pu être expliquée à partir des analyses physico-chimiques et structurales. Tout d’abord à l’aide des mesures de fluorescence X qui ont révélé la présence de deux types d’impuretés, pouvant créer des états énergétiques plus ou moins profonds dans la bande interdite. Ensuite, par des mesures en réflectométrie X qui ont mis en évidence plusieurs structures ordonnées au sein d’une matrice amorphe. Cette hétérogénéité structurale explique les mécanismes de piégeage et d’accumulation des charges d’espaces aux interfaces. De même, l’ordre local favorisant la mobilité des charges, ces résultats donnent une première réponse quant à la valeur relativement élevée de la conductivité électrique du polymère, telle qu’elle a pu être déterminée à partir des mesures des caractéristiques courant-tension. Des études de vieillissement accéléré ont également été menées. Les différents recuits appliqués ont contribué à la création de charges qui sont piégées dans des niveaux énergétiques de plus en plus profonds. Cela s’est traduit par une diminution de la quantité de charges qui relaxent par activation thermique ainsi que par une diminution de la conductivité électrique des échantillons. Ces changements de propriétés électriques ont été corrélés aux changements structuraux qui se sont produits au sein du polymère, et dont la principale manifestation est la disparition progressive des structures ordonnées. Cette disparition de l’ordre local a aussi été observée en l’absence de contraintes thermiques (vieillissement naturel), où il a été montré que le comportement superficiel et en volume des échantillons n’était pas identique. / This work constitutes an innovative approach in epoxy based polymer characterization, where complementary physico-chemical, electric and structural techniques are used. The main objective of these studies is to understand both dielectric phenomena and properties associated to the space charges, as well as to follow-up their evolution in time or after the application of external constraints.Impedance spectroscopy and thermo-stimulated depolarization current (TSDC), measurements have highlighted dipolar and interfacial relaxations processes. Origin of these phenomena has been explained from physico-chemical and structural analyses. First, X-ray fluorescence measurements revealed the presence of two types of impurities, which are able to create deep energetic levels in the forbidden energy band. Then, X ray reflectometry measurements highlighted several periodic structures within an amorphous matrix. This structural heterogeneity explains the mechanisms of trapping and accumulation of space charges at the interfaces and gives a first reply as for the relatively high value of the polymer electric conductivity, calculated from current-voltage measurements.Accelerated ageing studies have been also carried out. They have shown that annealing creates charges which are trapped in increasingly deep energetic levels. Consequently, both the quantity of released charges and annealed samples conductivities have decreased.These electric properties changes have been correlated with the structural changes occurring within the polymer, and whose principal manifestation is the progressive disappearance of the ordered structures. This disappearance of the local periodicity has also been observed in the absence of thermal constraints (natural ageing), where it was shown that samples surface’s behavior is different from the bulk.

[pt] O nanocompósito estudado com função de revestimento anticorrosivo é constituído de Epóxi Novolac Tipo II aditivado com grafeno, sintetizado através do processo de esfoliação/redução do grafite empregando microondas. O sistema epóxi utilizado é composto pelos componentes: A, baseado em bisfenol F e cargas inorgânicas, e o B, endurecedor baseado em um polímero aminado. A síntese do grafeno e sua aditivação no componente A, foram realizadas pelo CTNano - UFMG. O principal objetivo desta dissertação é o estudo da aplicabilidade do nanocompósito, onde o grafeno é utilizado como aditivo complementar em matriz polimérica (epóxi), como alternativa de maximizar a proteção anticorrosiva. Foram estudadas diferentes aditivações: CR (sem aditivo), e aditivadas (0.1 por cento e 0.5 por cento). O substrato utilizado foi o aço carbono 1020, cuja superfície foi preparada com jateamento abrasivo e em seguida revestida com uma pistola de ar comprimido e com solvente para auxiliar o processo. Para avaliar a eficiência destes revestimentos foram realizados ensaios de corrosão (Célula Atlas e Ensaios Cíclicos), teste de aderência (Pull Off), medida de espessura (MEV) e rugosidade do substrato através do rugosímetro analógico e microscopia óptica. Para a dispersão do grafeno foi adicionado diglidil éter de bisfenol A (DGEBA) como um diluente. Os resultados obtidos indicaram que o grafeno apresentava boa dispersão na matriz polimérica. Concentrações de grafeno acima de 0,1 por cento em massa levam à falha da proteção anticorrosiva. Este comportamento pode estar relacionado à presença de solvente residual ou DGEBA não reagido no sistema com grafeno, além de possível atuação de grafeno agregado como ponto de tensão. O mecanismo de adesão revestimento/substrato permaneceu inalterado para todas as aditivações estudadas. / [en] The studied nanocomposite with anticorrosive coating function is composed of Novolac Type II epoxy added with graphene, synthesized through the process of exfoliation / reduction of graphite using microwaves. The epoxy system used consists of the following components: A, based on bisphenol F and inorganic fillers, and B, hardener based on an amino polymer. The synthesis of graphene and its additivation in component A were performed by CTNano - UFMG. The main objective of this dissertation is the study of the applicability of the nanocomposite, where graphene is used as complementary additive in polymer matrix (epoxy), as an alternative to maximize anticorrosive protection. Different additives were studied: CR (without additive), and additives (0.1 percent and 0.5 percent). The substrate used was carbon steel 1020, the surface of which was prepared with abrasive blasting and then coated with a compressed air and solvent gun to aid the process. To evaluate the efficiency of these coatings were performed corrosion tests (Atlas Cell and Cyclic Tests), Pull Off test, thickness measurement (MEV) and roughness of the substrate through the analogous rugosimeter and optical microscopy. For the dispersion of graphene, diglycidyl ether of bisphenol A (DGEBA) was added as a diluent. The results indicated that graphene showed good dispersion in the polymer matrix. Concentrations of graphene above 0.1 percent by mass lead to failure of the anticorrosive protection. This behavior may be related to the presence of residual solvent or unreacted DGEBA in the graphene system, in addition to the possibility of aggregated graphene as voltage point. The coating / substrate adhesion mechanism remained unchanged for all additives studied.

Cette thèse est une contribution à la compréhension du comportement des composites carbone-époxy en compression par l’étude de l’influence des constituants (fibres et matrices). L’incidence d’un chargement mécanique d’amplitude constante ou variable sur la durabilité est étudiée et un modèle numérique permettant la prédiction de la résistance résiduelle est proposé. Une première partie des travaux s’intéresse aux mécanismes spécifiques engagés dans la résistance en compression. Un modèle analytique est retenu pour une confrontation expérimentale. Ce modèle propose de considérer d’une part le micro-flambage de la fibre comme contenu par le comportement en cisaillement de la matrice (Budiansky et Fleck, 1993). En complément, une partie supplémentaire de structure considérant, entre autres, l’influence du gradient de déformation induit dans une sollicitation en flexion 4 points est étudiée (Grandidier, 2002). Afin de valider la pertinence du modèle, une campagne expérimentale est menée sur six matrices époxy différentes (de fragile à ductile) dans des empilements stratifiés monolithiques identiques réalisés en cuisson autoclave. Ces résultats ont permis de valider la capacité du modèle à prédire l’influence de la rigidité de la matrice sur la résistance en compression. Le partie micro-flambage est validée pour la prise en compte de la matrice. La partie effet de structure (gradient ici) est validée par une comparaison avec des résultats supplémentaires obtenus sur des éprouvettes sandwich sollicitées en flexion. Ces dernières éprouvettes ont fait l’objet d’une conception spécifique afin de favoriser la rupture en compression pure (sans gradient de déformation). Une seconde partie est consacrée à l’étude de la durabilité en compression. Une campagne expérimentale d’essais de fatigue est menée en flexion 4 points sur les éprouvettes sandwich précédemment conçues. Les essais sont conduits à une fréquence de 10 Hz et différents rapports de charge dans une optique de dégager l’évolution de la résistance résiduelle. Un modèle numérique de changement d’échelles (stratifié, plis, constituants) est parallèlement développé, basé sur la dégradation et la plasticité de la matrice. On fait l’hypothèse de simplicité thermo-rhéologique de la matrice pour établir des courbes de maitresses à partir d’une série d’essais identifiés (fluage, relaxation, fatigue…). On utilise les propriétés résiduelles du pli (rigidité, résistance) pour estimer un indicateur d’endommagement. Ce dommage est répercuté dans les propriétés de la matrice au moyen d’une loi de dégradation linéaire. Une loi de cumul de dommage de type Miner est alors introduite pour tenir compte de la variabilité des chargements appliqués. Un solveur micro- mécanique est développé pour extraire le comportement non-linéaire du pli en cisaillement tenant compte de la dégradation. Ce comportement est paramétré par une loi de Ramberg-Osgood utilisée dans le modèle analytique validé précédemment. Les travaux des deux parties permettent donc la mise en place d’un outil de prédiction de la résistance résiduelle des plis sollicités dans un chargement biaxial plan, avec en particulier le traitement de la compression / This PhD dissertation is a contribution to the modelling of Carbon-Fiber-Epoxy-Polymer laminates, undergoing specifically compression loadings, according to components. The aim is to build a design tool for composites structures taking into account this compression specificity for dimensioning racing yachts parts (masts, daggerboards, foils), which is the expertise of HDS/GSea-Design, the company associated to this work. Emphasis was put on the influence of linear or non-linear properties of each phase by varying the type of fibre (from high stiffness to high strength) and the type of matrix (from brittle to ductile). The effect of a mechanical loading, static, constant (creep, relaxation) or variable (fatigue) on durability is studied and a numerical model for predicting the residual strength is proposed. The first part of this work deals with the mechanisms involved in compressive strength. An analytical model is used for an experimental validation. It considers a contribution linked to the micro-buckling of the fibre as contained by the shear behaviour of the matrix (Budiansky et Fleck [1993]). It considers also a contribution of the deformation gradient induced for instance in a bending loading (Gardin et al. [2002]). To validate this model, an experimental campaign was conducted on six different epoxy matrices (from brittle to ductile) on identical monolithic stackings processed in autoclave. The results allowed the validation of the model capability to predict the influence of the matrix stiffness on the compressive strength of unidirectional laminas. Taking into account the matrix behaviour validates the micro-buckling contribution. Regarding the deformation gradient contribution, it is validated through a comparison using additional experimental results on sandwich samples in bending. The latter samples were specifically designed to favour a pure compression fracture (without any deformation gradient). The second part examines durability in compression. Another experimental campaign with fatigue tests was conducted with four points bending tests on the same sandwich samples. Experiments were carried out at 10 Hz and different load ratios were used to study their influence on the compressive residual strength. A numerical model involving different scales (laminate, laminas, fibres and matrix) is developed in parallel (Huang et al. [2012a]), based on the degradation and the plasticity of the matrix. The assumption of thermo-rheological simplicity of the matrix is made to build master curves from dedicated experiments (creep, relaxation). We then use the residual properties (stiffness, strength) of the ply to estimate a damage level. This latter parameter is used to modify the elastic stiffness of the matrix with a linear law. A Miner-type cumulative law is used in fatigue to take into account the different possible loadings. A micro-mechanical solver is developed to extract the non-linear shear behaviour of the ply accounting for this degradation. This behaviour is described by a Ramberg-Osgood law used in the analytical model described in the first part of this work. The joint contributions of these two parts allowed us to program a numerical tool for predicting the residual strength of plies undergoing a biaxial in- plane loading, being monotonous, constant or with a variable amplitude, with emphasis on the particular case of compression loading.

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