The thesis showed preliminary evaluation of novel biodegradable and biocompatible agmatine-containing PAA crosslinkers. Hydrogels fabricated by this crosslinker can obtain controllable stiffness and excellent cell adhesion. The PAA contained thermo-sensitive hydrogel reported here is first employed as filler for depressed defects in rats. Results showed that such hydrogel can be injectable and biocompatible, might become a new material in plastic surgery in the clinic. The thesis also demonstrated a novel macro gels with self-healing capability and biocompatibility. The reversible photodimerization and photocleavage reactivity of coumarin has been successfully imparted to the polymer. / February 2015

Epoxy coatings are currently the most popular corrosion protection mechanism for steel reinforcement in structural concrete. However, these coatings are easily damaged on worksites, negating their intended purpose. This study investigates self-healing coatings for steel reinforcement to introduce an autonomous healing mechanism for damaged coatings. Coatings were applied to steel coupons, intentionally damaged, and introduced to a corrosive environment via aerated salt-water tanks. Performance of the experimental coatings was evaluated qualitatively and quantitatively. Adhesion strength and effects of coating thickness were also studied. Results from coated steel coupons subjected to damage and submerged in salt-water aeration tanks exhibited improved corrosion resistance performance with self-healing coatings. However, self-healing coatings have comparable poor adhesion to the substrate as do conventional coatings. This paper shows preliminary results demonstrating the potential benefits of self-healing coatings for steel reinforcement and identifies numerous avenues for future research.

Recent interest in environmentally friendly alternatives to chromate-based corrosion inhibitors has led to the development of a range of novel coating formulations. The work described in this thesis has been aimed at investigating the mechanism of self-healing and active corrosion protection of the new coatings by searching for active components that have migrated from the coating to a controlled defect. The use of glow discharge optical emission spectroscopy (GDOES) has been investigated as a tool for both the generation of a reproducible controlled defect and for elemental depth profiling of the coatings and corroded substrates. Conclusions drawn from the elemental depth profiles have been validated by a range of characterisation techniques including optical microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDX) and electrochemical techniques. The work has focused particularly on a comparison of hybrid coatings doped with inhibitors encapsulated in nano-containers, as compared with the direct addition of inhibitor species to the coating matrix. The work also investigates the effects of inhibitor addition to sol-gel coatings or primer systems or both, highlighting possible synergistic effects of mixed inhibitor systems (for example, sol-gel coating doped with strontium aluminium polyphosphate (SAPP)) supporting primers doped with benzotriazol (BZT) or mercaptobenzothiazol (MBT). The various coatings have also been studied in the absence of inhibitor species to assess the effectiveness of the coatings as barriers between the substrate and the corrosive environment. This aspect of the study has highlighted minor inhibitive effects of some of the reagents used in the coating formulations and a major inhibitive effect of the nano-containers. The work therefore concludes with recommendations for a possible coating formulation combining the most beneficial elements of the various coatings investigated.

No description available.

Nos últimos anos, as indústrias têm mostrado muito interesse em procurar sistemas de pinturas que possam ser mais eficientes na proteção do substrato metálico. Os sistemas comuns de pinturas criam uma barreira passiva sobre substrato que evita o contato com a água e outras espécies agressivas. No entanto, a degradação do revestimento pode ocorrer como consequência de fatores externos como radiação UV, temperatura ou ação mecânica. Por este motivo, pesquisadores têm buscado sistemas de pintura com proteção ativa que sejam capazes de se autorreparar (self-healing), levando o substrato a um tempo de vida em serviço mais prolongado. Uma maneira para atingir este efeito ativo é a incorporação de sistemas de nanocontainers ou nanorreservatórios com material ativo encapsulado (inibidores de corrosão) na matriz do revestimento. O objetivo deste trabalho é avaliar o efeito na resistência à corrosão do aço carbono ABNT 1020 numa solução de NaCl 0,01 mol/L quando seja submetido a um prétratamento com camada de tinta alquídica aditivada com nanocontainers contendo o inibidor de corrosão dodecilamina. Três tipos de nanocontainers foram avaliados: 1) nanocontainers a base de nanopartículas de sílica revestida com diferentes camadas de polieletrólitos. 2) nanocontainers a base do mineral haloisita. 3) nanocontainers a base de uma sílica mesoporosa com arranjo ordenado hexagonal tipo SBA-15. Também foi estudada a cinética de liberação do inibidor dodecilamina dos diferentes tipos de nanocontainers usando a técnica de impedância eletroquímica. Os métodos eletroquímicos utilizados para avaliar a resistência a corrosão e o efeito de autorreparação ou self healing foram a técnica de varredura do eletrodo vibratório (SVET) e espectroscopia de impedância eletroquímica (EIS), obtidas em solução aerada de NaCl 0,01 mol/L para chapas de aço carbono revestidas. Testes acelerados de corrosão numa câmara de névoa salina (SSC) foram realizados seguindo a norma ASTM B 117-11. As imagens de microscopia ótica, microscopia eletrônica de varredura e microscopia eletrônica de transmissão foram obtidas para conhecer a estrutura e morfologia dos nanocontainers e o aspecto dos corpos de prova pintados. A caracterização da sílica mesoporosa foi realizada por termogravimetria (TGA), adsorção e dessorção de nitrogênio e difração de raios-X. Os estudos de cinética de liberação do inibidor foram realizados numa solução de NaCl 0,1 mol/L a diferentes valores de pH (2, 9 e 6.2) e contendo 1% m/m de nanocontainers carregados com inibidor dodecilamina, onde foi possível demonstrar que a pH 2 a velocidade de liberação do inibidor foi maior para os três tipos de nanocontainers estudados. Com relação aos resultados de espectroscopia de impedância eletroquímica (EIS) e técnica de varredura com eletrodo vibratório (SVET) para os corpos de prova revestidos com uma tinta alquídica contendo 10 % m/m de nanopartículas de sílica obtidas por Lb-L ou haloisita e 15 % m/m de sílica mesoporosa foi comprovado o efeito selfhealing da tinta pela liberação do inibidor dodecilamina encapsulado dentro da estrutura do nanocontainer. Este efeito também foi notado nos testes de névoa salina, onde o inibidor de corrosão é liberado pelo abaixamento do pH nas regiões anódicas ou de corrosão retardando o processo de corrosão na região do defeito. / In the last years, the industries have shown much interest in searching painting systems that may be more effective in protecting the metallic substrate. Common painting systems create a passive barrier over the substrate that avoids contact with the water and other aggressive species. However, degradation of the coating may occur as a result of external factors such as UV radiation, temperature or mechanical action. For this reason, researchers have sought paint active protection systems that are able to self-repair (self-healing) leading to a longer lifetime of the substrate. One way to achieve this active effect is the incorporation of nanocontainer systems with encapsulated active material (corrosion inhibitors) to the coating matrix. The objective of this study is to evaluate the effect on corrosion resistance of carbon steel ABNT 1020 in aerated 0.1 mol/L NaCl solution when it is subjected to a pretreatment with alkyd paint layer doped with nanocontainers containing dodecylamine as corrosion inhibitor. Three types of nanocontainers were evaluated: 1) SiO2 nanoparticles coated with polyelectrolytes multilayers. 2) halloysite nanoparticles. 3) type SBA-15 mesoporous silica particles of. The kinetics of release of the inhibitor dodecylamine from the different types of nanocontainers was also determined indirectly using electrochemical impedance spectroscopy technique. Electrochemical measurements were performed to evaluate the self-healing effect of coated carbon steel panels after a provoked defect with scanning vibrating electrode technique (SVET) and electrochemical impedance spectroscopy (EIS), all measurements were performed in an aerated NaCl 0.01 mol/L solution. Accelerated corrosion tests in salt spray chamber (SSC) were also carried out following the prescriptions of ASTM B 117-11 standard. The images from optical, scanning electron and transmission electron microscopy were obtained to show the morphology and structure of the nanocontainers and the aspect of coated samples. The characterization of mesoporous silica was made by transmission electron microscopy, thermogravimetry (TGA), adsorption/desorption of N2 and X-ray diffraction. Kinetic studies of the release of encapsulated corrosion inhibitor were performed in NaCl 0.1 mol/L solution at different pH values (2, 9 and 6.2) containing 1 wt. % of dispersed nanocontainers loaded with dodecylamine inhibitor, and it was possible to confirm that at pH 2 condition the release of inhibitor was more efficient in comparison to other pH conditions (9 and 6.2). On the other hand, the results obtained by electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode technique (SVET) of the coated carbon steel panels with alkyd paint loaded with 10 wt. % (SiO2 nanoparticles or halloysite) and 15 wt. % (mesoporous silica) has proven the self-healing effect by the release of corrosion inhibitor from nanocontainers on the defect area triggered by the pH decrease typical of anodic or corroding areas. This self-healing and protective effect was also noticed in salt spray tests, where the corrosion inhibitor was released slowing down the corrosion process on the defective region.

Nos últimos anos, as indústrias têm mostrado muito interesse em procurar sistemas de pinturas que possam ser mais eficientes na proteção do substrato metálico. Os sistemas comuns de pinturas criam uma barreira passiva sobre substrato que evita o contato com a água e outras espécies agressivas. No entanto, a degradação do revestimento pode ocorrer como consequência de fatores externos como radiação UV, temperatura ou ação mecânica. Por este motivo, pesquisadores têm buscado sistemas de pintura com proteção ativa que sejam capazes de se autorreparar (self-healing), levando o substrato a um tempo de vida em serviço mais prolongado. Uma maneira para atingir este efeito ativo é a incorporação de sistemas de nanocontainers ou nanorreservatórios com material ativo encapsulado (inibidores de corrosão) na matriz do revestimento. O objetivo deste trabalho é avaliar o efeito na resistência à corrosão do aço carbono ABNT 1020 numa solução de NaCl 0,01 mol/L quando seja submetido a um prétratamento com camada de tinta alquídica aditivada com nanocontainers contendo o inibidor de corrosão dodecilamina. Três tipos de nanocontainers foram avaliados: 1) nanocontainers a base de nanopartículas de sílica revestida com diferentes camadas de polieletrólitos. 2) nanocontainers a base do mineral haloisita. 3) nanocontainers a base de uma sílica mesoporosa com arranjo ordenado hexagonal tipo SBA-15. Também foi estudada a cinética de liberação do inibidor dodecilamina dos diferentes tipos de nanocontainers usando a técnica de impedância eletroquímica. Os métodos eletroquímicos utilizados para avaliar a resistência a corrosão e o efeito de autorreparação ou self healing foram a técnica de varredura do eletrodo vibratório (SVET) e espectroscopia de impedância eletroquímica (EIS), obtidas em solução aerada de NaCl 0,01 mol/L para chapas de aço carbono revestidas. Testes acelerados de corrosão numa câmara de névoa salina (SSC) foram realizados seguindo a norma ASTM B 117-11. As imagens de microscopia ótica, microscopia eletrônica de varredura e microscopia eletrônica de transmissão foram obtidas para conhecer a estrutura e morfologia dos nanocontainers e o aspecto dos corpos de prova pintados. A caracterização da sílica mesoporosa foi realizada por termogravimetria (TGA), adsorção e dessorção de nitrogênio e difração de raios-X. Os estudos de cinética de liberação do inibidor foram realizados numa solução de NaCl 0,1 mol/L a diferentes valores de pH (2, 9 e 6.2) e contendo 1% m/m de nanocontainers carregados com inibidor dodecilamina, onde foi possível demonstrar que a pH 2 a velocidade de liberação do inibidor foi maior para os três tipos de nanocontainers estudados. Com relação aos resultados de espectroscopia de impedância eletroquímica (EIS) e técnica de varredura com eletrodo vibratório (SVET) para os corpos de prova revestidos com uma tinta alquídica contendo 10 % m/m de nanopartículas de sílica obtidas por Lb-L ou haloisita e 15 % m/m de sílica mesoporosa foi comprovado o efeito selfhealing da tinta pela liberação do inibidor dodecilamina encapsulado dentro da estrutura do nanocontainer. Este efeito também foi notado nos testes de névoa salina, onde o inibidor de corrosão é liberado pelo abaixamento do pH nas regiões anódicas ou de corrosão retardando o processo de corrosão na região do defeito. / In the last years, the industries have shown much interest in searching painting systems that may be more effective in protecting the metallic substrate. Common painting systems create a passive barrier over the substrate that avoids contact with the water and other aggressive species. However, degradation of the coating may occur as a result of external factors such as UV radiation, temperature or mechanical action. For this reason, researchers have sought paint active protection systems that are able to self-repair (self-healing) leading to a longer lifetime of the substrate. One way to achieve this active effect is the incorporation of nanocontainer systems with encapsulated active material (corrosion inhibitors) to the coating matrix. The objective of this study is to evaluate the effect on corrosion resistance of carbon steel ABNT 1020 in aerated 0.1 mol/L NaCl solution when it is subjected to a pretreatment with alkyd paint layer doped with nanocontainers containing dodecylamine as corrosion inhibitor. Three types of nanocontainers were evaluated: 1) SiO2 nanoparticles coated with polyelectrolytes multilayers. 2) halloysite nanoparticles. 3) type SBA-15 mesoporous silica particles of. The kinetics of release of the inhibitor dodecylamine from the different types of nanocontainers was also determined indirectly using electrochemical impedance spectroscopy technique. Electrochemical measurements were performed to evaluate the self-healing effect of coated carbon steel panels after a provoked defect with scanning vibrating electrode technique (SVET) and electrochemical impedance spectroscopy (EIS), all measurements were performed in an aerated NaCl 0.01 mol/L solution. Accelerated corrosion tests in salt spray chamber (SSC) were also carried out following the prescriptions of ASTM B 117-11 standard. The images from optical, scanning electron and transmission electron microscopy were obtained to show the morphology and structure of the nanocontainers and the aspect of coated samples. The characterization of mesoporous silica was made by transmission electron microscopy, thermogravimetry (TGA), adsorption/desorption of N2 and X-ray diffraction. Kinetic studies of the release of encapsulated corrosion inhibitor were performed in NaCl 0.1 mol/L solution at different pH values (2, 9 and 6.2) containing 1 wt. % of dispersed nanocontainers loaded with dodecylamine inhibitor, and it was possible to confirm that at pH 2 condition the release of inhibitor was more efficient in comparison to other pH conditions (9 and 6.2). On the other hand, the results obtained by electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode technique (SVET) of the coated carbon steel panels with alkyd paint loaded with 10 wt. % (SiO2 nanoparticles or halloysite) and 15 wt. % (mesoporous silica) has proven the self-healing effect by the release of corrosion inhibitor from nanocontainers on the defect area triggered by the pH decrease typical of anodic or corroding areas. This self-healing and protective effect was also noticed in salt spray tests, where the corrosion inhibitor was released slowing down the corrosion process on the defective region.

Au cours des dernières décennies, le concept de « matériaux intelligents » a suscité un intérêt en croissance rapide en raison de l'apparition de plusieurs nouveaux types de matériaux polymères qui sont capables d'accomplir une fonction désirée en réponse à un stimulus spécifique de façon prédéterminée et contrôlée. Deux exemples représentatifs sont les polymères à mémoire de forme (SMPs) et les polymères autoréparables or réparables par un stimulus (SHPs). Ils sont sujets de cette thèse. D'une part, les SMPs sont des matériaux qui ont la capacité de mémoriser une forme spécifique. Après avoir été déformés et fixés à une forme temporaire, ils peuvent récupérer la forme originale et permanente sous l'effet d'un signal stimulant comme la chaleur, la lumière ou un champ électrique. Bénéficiant de la mise en œuvre relativement facile, les SMPs sont une alternative intéressante aux alliages à mémoire de forme bien établis; et ils ont trouvé un large éventail d'applications potentielles allant des implants pour la chirurgie non-invasive aux actionneurs sensibles aux environnements. D'autre part, les SHPs sont des matériaux qui sont capables de réparer des dommages mécaniques (fissures ou fractures) par eux-mêmes ou avec l'aide d’un stimulus externe. Leur développement a un grand intérêt pour améliorer la sécurité, prolonger la durée de vie et réduire le coût de l'entretien des matériaux. Sauf quelques matériaux souples (certains gels et élastomères) qui sont guérissables de façon vraiment autonome, la plupart des SHPs nécessitent l'intervention d'un stimulus comme c’est le cas pour les SMPs. L'objectif principal de cette thèse est de développer de nouveaux SMPs et SHPs contrôlables par un rayonnement lumineux. La stratégie que nous avons utilisée est basée sur l'ajout d'une petite quantité de nanoparticules d'or (AuNPs ) ou de nanotiges d'or (AuNRs) dans un SMP ou SHP pour absorber la lumière visible ou proche infrarouge. L’idée est d’utiliser la chaleur dégagée par les nanoparticules lors de l’absorption de la lumière due à la résonance plasmonique de surface (SPR) pour contrôler les transitions de phase dans les polymères et, par conséquent, de dicter leurs processus de mémoire de forme ou de guérison. Bien qu’un effet photothermique est à l'origine de ces processus, tous les avantages de l'utilisation de la lumière comme stimulus sont conservés, tels que l'activation à distance et le contrôle spatiotemporel. Plusieurs travaux de recherche ont été réalisés au cours de cette thèse, dont les résultats, nous l'espérons, peuvent constituer une contribution de base faisant l'utilisation d’AuNPs et AuNRs une technologie de plate-forme pour le développement des SMPs et SHPs contrôlables par la lumière. En ce qui concerne les SMPs, nous avons d’abord préparé un nouveau matériau nanocomposite AuNP-polymère à base d’oligo(ε-caprolactone) ramifié et réticulé. En faisant usage de chauffage localisé induit par la lumière, nous avons prouvé que la lumière visible peut être utilisée pour activer un processus de récupération de forme de manière sélective spatialement, et pour réaliser plusieurs formes intermédiaires sur-demande. En outre, nous avons constaté qu'en ajustant l'intensité de la lumière laser ou la quantité d’AuNPs, l'élévation locale de la température dans le matériau peut être importante et atteindre une amplitude prédéterminée sans influence défavorable sur ses environs. Cette caractéristique intéressante permet d'utiliser le même SMP pour des applications couvrant un large domaine de températures environnantes. De plus, dans cette étude, nous avons démontré comment l'énergie libérée dans un processus de récupération de forme contrôlé par la lumière peut être utilisée pour accomplir un travail mécanique. Sur la base du projet précédent, nous avons ensuite fait la première démonstration que la polarisation de la lumière peut également être utilisée pour contrôler l'effet de mémoire de forme ainsi que le processus de récupération de forme. À cette fin, nous avons conçu et préparé un SMP anisotrope contenant des AuNRs orientés par étirage de films de poly(alcool de vinyle) (PVA). L'idée est que la quantité de chaleur dégagée par les nanotiges d’or lors de l'exposition à la lumière proche infrarouge, est déterminée par l’absorption de photons qui, pour un matériau anisotrope, est dépendante de la polarisation de la lumière incidente. Nous avons montré qu’en effet, changeant la direction de polarisation du laser incident par rapport à la direction d'étirage du film tout en conservant toutes les autres conditions inchangées, permet de contrôler le degré d'élévation de température dans le matériau, ce qui détermine le processus de récupération de forme. En découvrant ce nouveau moyen de control, cette étude a élargi la boîte à outils pour les SMPs contrôlables par voie optique. Sur le côté SHPs, notre motivation d’exploiter l'approche photothermique est d'aborder la question difficile de la guérison de matériaux mécaniquement forts et dues. En général, une force mécanique élevée (ou une grande dureté) d'un matériau entrave sa capacité d’auto-guérison ou guérison induite par des stimuli en raison du manque de mobilité de chaînes du polymère, sachant que cette mobilité est cruciale pour la diffusion du polymère dans une région fracturée conduisant à la cicatrisation. Nous avons proposé la stratégie consistant à utiliser l'effet photothermique pour provoquer la transition de phase « fusion – cristallisation » pour la réparation. Dans une première étude, par le chargement d'une très petite quantité d’AuNPs dans deux polymères cristallins, le poly(oxyde d' éthylène ) (PEO, T[indice inférieur m~]63 °C) et le polyéthylène de basse densité (LDPE , T[indice inférieur m~]103 °C), nous avons réussi une guérison optique très rapide et efficace, fusionnant deux morceaux de polymère en contact en un seul avec des propriétés mécaniques bien récupérées. Nous avons confirmé le mécanisme de guérison basé sur la fusion des chaînes cristallisées lors de l’exposition à la lumière, suivie de la cristallisation lors du refroidissement après l'extinction du laser. Cette cristallisation des chaines ayant diffusé à travers les surfaces de coupe a pour effet de les fusionner pour la guérison. En plus de l'activation à distance et la capacité de cicatrisation rapide, nous avons aussi démontré le control spatial de la guérison optique car elle a lieu uniquement dans les régions fracturées exposées au laser. Après avoir appris comment utiliser l'effet photothermique découlant de la SPR d’AuNPs pour réaliser le control des processus de mémoire de forme et de guérison dans des polymères séparés, nous avons continué notre effort pour développer des matériaux qui possèdent les deux fonctions de mémoire de forme et de guérison commandées par la lumière. La réalisation d’un tel matériau est aussi une tâche difficile en raison de l'incompatibilité structurelle entre les SMPs et SHPs, puisque la structure de réseau réticulé nécessaire pour le mémoire de forme réduit généralement la mobilité de chaînes requise pour la guérison. Grâce aux connaissances générées par nos recherches, nous avons proposé un design de matériau consistant à réticuler chimiquement un polymère cristallin (PEO) chargé d’une petite quantité d’AuNPs. Notre étude a montré que ce matériau polymère acquise l’effet de mémoire de forme contrôlable par la lumière et la guérison optique rapide dus au même effet de chauffage localisé induit par un laser. En effet, l'effet photothermique peut activer le processus de récupération de la forme du matériau en élevant sa température au-dessus de la T[indice inférieur m] de la phase cristalline et, dans le même temps, permet la cicatrisation de fissures par l'intermédiaire de fusion des chaînes cristallisées sous exposition au laser et la cristallisation ultérieure lors du refroidissement après l’éteinte du laser. De plus, nous avons démontré que ces deux fonctions peuvent être exécutées de manière séquentielle sur le même matériau, sans interférence entre elles. La mise en œuvre simultanée des deux fonctions distinctes dans un seul matériau peut élargir les applications possibles de SMPs et SHPs. Par la suite, nous avons appliqué la stratégie établie avec des polymères cristallins aux hydrogels polymères. Il est connu depuis longtemps qu’il est très difficile d’obtenir des hydrogels mécaniquement robustes pouvant être réparés par effets de stimuli. Nous avons conçu et préparé un hydrogel hybride en chargeant une petite quantité d’AuNPs dans un hydrogel formé par copolymérisation du N, N-diméthylacrylamide (DMA), de l'acrylate de stéaryle (SA) et du N, N'- méthylène bisacrylamide (MBA). La force mécanique de cet hydrogel est donnée par une réticulation chimique qui coexiste avec une réticulation physique due aux chaînes latérales d’alkyles hydrophobes cristallisées. Encore une fois, par le contrôle de la transition de phase de « fusion-cristallisation » des chaînes SA à l'aide d'un laser, l'hydrogel hybride montre à la fois la fonction de mémoire de forme contrôlé par la lumière et la fonction de guérison optique efficace. Une grande contrainte à la rupture supérieure à 2 MPa a été obtenue pour un hydrogel coupé en deux et puis réparé par la lumièr. La dernière, mais non la moindre, contribution portée par l’étude dans cette thèse est une découverte que nous avons faite sur les SHPs. Nous avons observé que l’hydrogel de PVA physiquement réticulé, étant préparé par la méthode de congélation/décongélation, peut s’auto-guérir à la température ambiante sans l’utilisation d’un stimulus ou d'un agent de guérison. Cette découverte est importante étant donné que cet hydrogel est biocompatible et un matériau largement utilisé pour des applications. Notre étude a montré que la clé pour obtenir une guérison autonome efficace de l'hydrogel de PVA ayant une force mécanique relativement élevée est d'avoir une quantité suffisante de groupements hydroxyle libres sur les chaînes de PVA pour ponts-hydrogène et une bonne mobilité de chaîne assurant la diffusion du polymère à travers les surfaces de coupe.

The recent development of materials with autonomous repair capabilities has opened an exciting new field of polymer science expected to impact nearly every facet of modern society. Similar to natural systems, these "self-healing" materials sense when their structural integrity has been compromised (e.g., due to wear or damage) and respond with a viable repair mechanism. Despite the extraordinary number of successes and advances in this area, a means to ascertain instantaneous knowledge of a material's structural integrity, and more importantly, when it has been compromised, remains a considerable challenge in current systems and materials. To address this challenge, we report recent efforts toward the development of an electronically conductive material that is structurally dynamic and responds to various types of external stimuli. In particular, we have developed new synthetic methodology to prepare a variety of organometallic polymers containing a novel benzobisimidazolylidene or bis(benzoimidazolylidene) ligand, which is comprised of two linearly opposed N-heterocyclic carbenes (NHCs) annulated to a common linker, and various types of transition metals in the polymer's main-chain. Using this approach, polymers with molecular weights up to 10⁶ Da were prepared and cast into robust thin films. Using four-point probe technique, the inherent conductivities of these materials were found to be on the order of 10⁻³ S/cm. Secondly, the dynamics of these polymers were probed in solution using gel permeation chromatography. At specific cross-linker loadings, thermally-responsive gels were obtained. Collectively, these experiments suggested that the essential features for a thermally-responsive, structurally dynamic, conjugated organometallic polymer were developed. Efforts toward probing their ability to display self-healing characteristics in the solid-state are described. The inherent conductivity of the polymers permitted the healing behavior of thin films to be observed by scanning electron microscopy in the absence of a dopant. Long range goals of implementing and utilizing these materials in electronic circuits and other advanced devices are also described. An additional approach towards a dynamic material utilized functional imidazolium-based ionic liquids. A series of functional ionic liquids were produced by appending N-substituents containing pendant halides, alkynes, azides, furans and maleimides. These functional groups allowed for polymerization and crosslinking. The physical properties of the imidazolium monomers, as well as the resulting polymers, could be tuned by altering the anion. When a trifunctional monomer is used in conjunction with the polymerization of difunctional ionic liquids an insoluble crosslinked material forms. This behavior, combined with NHCs ability to bind transition metals as ligands and catalyze various organic transformations, provides potential for this system to be used as a method for catalyst recovery and ultimately catalyst recycling. / text

Un matériau qui se répare tout seul. Une fissure ou une rayure qui se rebouche elle-même après un impact, comme une blessure pour un être vivant. Le concept d’autoréparation ainsi décrit n’est plus une idée purement fantaisiste issue de l’imagination fertile des chercheurs. De récents travaux prouvent le contraire. Catalyse a choisi de mettre au point un processus d’autoréparation par l’intégration de microparticules contenant un principe actif liquide, libéré lors son l’éclatement. Ce liquide, un monomère, va alors polymériser, rebouchant ainsi la fissure et empêchant sa propagation.L’innovation de Catalyse a été d’imaginer une formulation autoréparante capable de polymériser directement au contact du milieu extérieur. Les éléments alors mis à disposition par l’environnement peuvent être la lumière (rayonnements UV ou visibles), l’oxygène, ou l’humidité. Les monomères envisagés pour l’encapsulation sont alors respectivement un acrylate, TMPTA, ou une époxy (mélangés avec un photoamorceur adapté), l’huile de lin (siccative) et un isocyanate trimère de l’hexamétylène diisocyanate. L’encapsulation des ces quatre composés est étudiée en parallèle et les travaux réalisés sont explicités dans les chapitres 2, 3 et 4 de ce document. Le TMPTA et l’huile de lin sont encapsulés par le procédé sol-gel, l’époxy et l’isocyanate, par polycondensation interfaciale. Les résultats obtenus sont variables d’un monomère à l’autre, mais dans l’ensemble, les résultats sont concluants et montrent d’une part, qu’il est possible d’obtenir des particules contenant un taux de principe actif intéressant et stables dans le temps, et d’autre part que suite à l’éclatement desdites capsules, le monomère polymérise, assurant ainsi le processus d’autoréparation. / A material that could repair itself, a crack that can heal itself after an impact, like a wound on the body. The concept of self-healing described is not science fiction created by the crazy imagination of researchers. Recent studies show otherwise. The French company CATALYSE has developed a process of self-healing through the integration of microparticles containing an active liquid ingredient that is released during a crack in the material. The liquid monomer fills the crack, polymerizes and prevents further spread. The innovation of CATALYSE was to imagine a self-repairing formula, which polymerizes when exposed to the outside of the self-contained environment. This includes light (UV or visible rays), oxygen or humidity. The corresponding monomers to be encapsulated are respectively an acrylate (for example TMPTA), an epoxy (mixed with an adapted photoinitiator), linseed oil or diisocyanate (for example an isocyanine trimer or hexamethylene diisocyanate). The encapsulations of these four compounds were studied in parallel and the results are explained in chapters 2, 3 and 4 of this document. The TMPTA and linseed oil are both encapsulated by the sol-gel process, the epoxy and isocyanate, by interfacial polycondensation. The results vary from one monomer to another but the overall results are conclusive. They show that it is possible to obtain a high percentage of the active ingredient and that the particles stay stable over time. Following the bursting of such capsules, the monomer polymerizes and ensures the self-healing process.

Cybercrime costs a total loss of about $338 billion annually which makes it one of the most profitable criminal activities in the world. Controlled malware (Botnet) is one of the most prominent tools used by cybercriminals to infect, compromise computer networks and steal important information. Infecting a computer is relatively easy nowadays with malware that propagates through social networking in addition to the traditional methods like SPAM messages and email attachments. In fact, more than 1/4 of all computers in the world are infected by malware which makes them viable for botnet use. This thesis proposes, implements and presents the Self-healing framework that takes inspiration from the human immune system. The designed self-healing framework utilises the key characteristics and attributes of the nature’s immune system to reverse botnet infections. It employs its main components to heal the infected nodes. If the healing process was not successful for any reason, it immediately removes the infected node from the Enterprise’s network to a quarantined network to avoid any further botnet propagation and alert the Administrators for human intervention. The designed self-healing framework was tested and validated using different experiments and the results show that it efficiently heals the infected workstations in an Enterprise network.