L’auto-cicatrisation des fissures des matériaux cimentaires présente un intérêt important pour améliorer leur durabilité (propriétés de transfert par exemple). L’impact du laitier de haut-fourneau sur ce phénomène a été peu étudié bien qu’il ait été observé sur des ouvrages du Génie Civil. Dans cette étude, la cinétique et l’amplitude de l’auto-cicatrisation ont été suivies par des essais non destructifs : la tomographie aux rayons X et la perméabilité à l’air, pour une fissuration créée à 7 jours et à 28 jours. Les résultats montrent que le laitier de haut-fourneau possède un potentiel d’auto-cicatrisation intéressant pouvant dépasser les résultats obtenus pour les formulations de référence sans laitier. Ce bon potentiel dépend des caractéristiques physicochimiques des matériaux brutes et du potentiel d’hydratation de la formulation au cours du temps. De plus pour suivre l’auto-cicatrisation, un nouvel essai a été mis en place afin de fissurer les éprouvettes de mortier par retrait gêné et d’étudier l’auto-cicatrisation d’une fissure naturelle. Cet essai s’est avéré efficace sur la formulation de référence. Une caractérisation des produits de cicatrisation par MEB-EDS témoigne de la formation de nouveaux produits dans les fissures et de l’impact important des conditions de stockage sur le type de produits formés: des C-S-H pour un stockage sous eau et des carbonates de calcium pour un stockage en chambre humide (CO2 + eau). Les résultats de migration aux chlorures de nano-indentation montrent que ces produits de cicatrisation possèdent de bonnes propriétés de durabilité et des propriétés mécaniques à l’échelle microscopique intéressantes (pour le carbonate de calcium). Enfin, une modélisation du phénomène d’auto-cicatrisation est proposée au moyen du code de calcul de géochimie PHREEQC. L’étude a révélé le potentiel intéressant de PHREEQC pour modéliser l’auto-cicatrisation et en faire un outil de prédiction du phénomène. / Self-healing of cementitious materials presents great interest to improve the durability of concrete structure (transfer properties for example). The impact of blast-furnace slag on this phenomenon is not yet clear even if the self-healing of concrete with blast-furnace slag was observed in building sites. To understand the blast-furnace slag influence, non-destructive methods were used to follow self-healing: X-ray tomography and gas permeability test. All specimens were cracked at 7 days and 28 days. The results show that the blast furnace slag has an interesting self-healing potential that can exceed the reference formulation results. This good potential depends on the physico-chemical characteristics of the raw materials and the hydration potential of the formulation over time. In addition to follow the self-healing, a new trial was set up to crack mortar specimens by restrained shrinkage and study the self-healing of a natural crack. In addition to follow the self-healing, a new trial was set up to crack mortar specimens by restrained shrinkage and study the self-healing of a natural crack. This test has proven effective over the reference formulation.The SEM with EDS analysis showed the formation of new products in the crack and the impact of storage conditions on these products : C-S-H for specimens stored in water and calcium carbonate for specimens stored in a damp chamber (CO2 + water). Migration chlorures and nano-indentation tests results showed that self-healing products had interesting durability properties and micro-mechanical properties (for calcium carbonate). Finally, self-healing modelling is proposed by means of geochemistry PHREEQC calculation code. The study revealed interesting potential PHREEQC to model self- healing phenomenon and make it a of predictive tool.

Les hydrogels injectables et auto-réparants suscitent un intérêt particulier dans les domaines de l'ingénierie tissulaire et de la médecine régénératrice. En raison de la nature dynamique de leurs réticulations, ces gels peuvent être pré-formés dans des seringues, extrudés sous cisaillement et s’auto-réparer spontanément après arrêt de la déformation mécanique. Au vu du potentiel que peuvent offrir les polymères fonctionnalisés par des acides boroniques pour la fabrication de gels covalents réversibles, nous avons développé des hydrogels injectables d’acide hyaluronique (HA) réticulés par des liaisons esters boronates pour des applications esthétiques et biomédicales. Pour élaborer de tels gels avec des propriétés optimisées, nous avons exploré l’effet de la nature du dérivé d’acide boronique ainsi que du motif saccharidique greffés sur le HA sur les propriétés rhéologiques dynamiques des gels. Parmi les différents dérivés d'acide boronique, le benzoboroxole (BOR) a été choisi en plus de l'acide phénylboronique (PBA) pour complexer différents motifs saccharidiques greffés sur le HA. Comparé au PBA, le dérivé BOR est, en effet, capable de se complexer de manière plus efficace à pH neutre et avec une plus grande variété de composés saccharidiques, en particulier les glycopyranosides. Cette étude a démontré que les propriétés rhéologiques dynamiques des assemblages de HA formés par complexation des unités de BOR ou PBA avec les différents sucres sont étroitement liées à la dynamique des échanges moléculaires et à la thermodynamique des pontages. En outre, nous avons également établi pour la première fois la possibilité d’obtenir des hydrogels de HA auto-réticulants à pH physiologique via des interactions multivalentes entre les unités de BOR greffées sur le HA et des groupements diols se répétant sur la chaîne polysaccharidique. Outre le BOR, la capacité de son homologue cyclique à six chaînons, la benzoxaborine, et d’un nouveau dérivé original similaire à ce composé a été explorée en tant que nouveaux sites de complexation de saccharides pour la formation de réseaux de HA réversibles. Compte-tenu des propriétés injectables, d'auto-réparation et de réponse à différents stimuli démontrées par ces nouveaux hydrogels de HA, ces biomatériaux apparaissent comme des candidats prometteurs pour de nombreuses applications innovantes dans le domaine biomédical, notamment pour l'ingénierie tissulaire et la thérapie cellulaire. / Injectable and self-healing hydrogels have recently drawn great attention in the fields of tissue engineering and regenerative medicine. Such gels can be pre-formed into syringes, be extruded under shear stress and show rapid recovery when the applied stress is removed due to the dynamic nature of their crosslinks. Given the exciting potential benefit of using boronic acid-containing polymers to construct dynamic covalent hydrogels, we explored this attractive strategy to design injectable boronate-crosslinked hydrogels based on hyaluronic acid (HA) for aesthetic and other biomedical applications. To design hydrogels with optimized properties, we investigated the effect of the nature of the boronic acid moiety as well as the sugar molecule grafted onto the HA backbone on the gel properties. Among arylboronic acid derivatives, benzoboroxole (BOR) was selected in addition to phenylboronic acid (PBA) as the binding site for sugar moieties grafted on HA. This choice was based on the efficient binding capability of BOR at neutral pH compared to PBA, and on its ability to complex glycopyranosides. With this study, we demonstrated that the dynamic rheological properties of the HA networks based on BOR- or PBA-saccharide complexation are closely linked to the molecular exchange dynamics and thermodynamics of the small molecule crosslinkers. Besides, we also established for the first time the feasibility of self-crosslinking HA hydrogels with extremely slow dynamics at physiological pH through multivalent interactions between BOR derivatives grafted on HA and diols from the polysaccharide chains. Finally, in addition to BOR, we demonstrated the unprecedented capacity of its six-membered ring homologue, benzoxaborin, and a new original benzoxaborin-like derivative as new carbohydrate binding sites for the formation of reversible HA networks. Taking into account the injectable, self-healing and stimuli-responsive properties showed by these new HA hydrogels, these biomaterials appear as promising injectable scaffolds for many innovative applications in the biomedical field, including in tissue engineering and cell therapy.

Ammonium ionenes are polycations that have quaternary nitrogens in their macromolecular backbone and are synthesized via step-growth polymerization technique. They offer interesting coulombic properties, and the synthetic design provides control over charge density. Non-covalent interactions including nucleobase hydrogen bonding and electrostatics were studied in ammonium ionenes. The non-covalent interactions are expected to increase the effective molecular weight of polymeric precursors and induce microphase separation due to intermolecular associations. The influence of non-covalent interactions on structure-property relationships of ammonium ionenes were studied regarding mechanical (tensile, DMA), thermal (DSC, TGA), and morphological (AFM, SAXS) properties. Hydrogen bonding interaction (10-40 kJ/mol) was introduced using DNA nucleobase pairs such as adenine and thymine. Novel adenine and thymine functionalized segmented and non-segmented ammonium ionenes were successfully synthesized using Michael addition chemistry. In non-segmented systems, we investigated the influence of spacer length on homoassociation and heteroassociation of complementary nucleobase-containing ionenes. Based on DSC analyses, complementary non-segmented ionenes made miscible blends. The Tgs of ionene blends with shorter spacer length (4 bonds between the nucleobase and secondary amine in the polymer backbone) followed the Fox equation, which indicated no intermolecular interactions. The longer alkyl spacer (9 bonds between nucleobase and secondary amine in the polymer backbone) provided efficient flexibility for the self-assembly process to occur. Thus, increasing the spacer length from 4-bonds to 9-bonds, the Tgs of the blends deviated from both Fox and Gordon-Taylor equations and demonstrated the presence of hydrogen bonding interactions. In segmented systems, we investigated the association between nucleobase-containing ionenes and their complementary guest molecules. Job's method revealed a 1:1 stoichiometry for the hydrogen-bonded complexes. These association constants for the 1:1 complexes, based on the Benesi-Hildebrand model were 94 and 130 M-1 respectively, which were in agreement with literature values for adenine and thymine nucleobase pairs (10-100 M-1). DSC thermograms confirmed no macrophase separation for 1:1 [ionene-A/T]:[guest molecule] complexes based on the disappearance of the melting peak of the guest molecule. Morphological studies including atomic force microscopy (AFM) demonstrated a reduced degree of microphase separation for the 1:1 complexes due to the disruption of adenine-adenine or thymine-thymine interactions. Poly(dimethyl siloxane)-based ammonium ionenes having various hard segment contents were synthesized. The charge density or hard segment content was tuned for appropriate application using low molecular weight monomer. The change in hard segment content had a profound effect on thermal, mechanical, rheological, and gas permeability. Microphase separation was confirmed using DSC and DMA in these systems. DMA showed that the rubbery plateau modulus extended to higher temperatures with increasing hard segment content. Tensile analysis demonstrated systematic increase in modulus of PDMS-ionenes with increasing hard segment content. Oxygen transmission rates decreased linearly as the wt% hard segment increased. / Ph. D.

Alkali-Aggregate Reaction (AAR) is one of the most harmful distress mechanisms affecting the serviceability and durability of concrete critical infrastructure worldwide. Over the past decades, several approaches and recommendations have been developed to assess the potential reactivity of aggregates in the laboratory and the efficiency of preventive measures (e.g., supplementary cementing materials – SCMs) to mitigate ASR in the field. Yet, recent findings suggest that the appropriate use of SCMs “only” delayed and does not entirely prevent ASR occurrence. Moreover, once ASR starts in the field, there is no “universal” solution that should be applied in various cases, and each situation should be evaluated as “unique”. Nevertheless, artificially triggering healing agents have been studied in the late years, thus presenting an interesting “physical” solution to reduce the ingress of water and recover damaged concrete elements, which could present an interesting solution for durability-related distress due to ASR. This Ph.D. project focuses on detailed laboratory investigations aiming first to understand the self-healing process of concrete (i.e., by the natural or engineered process). Then, its further influence on ASR-induced expansion and deterioration, either applied internally or externally to the concrete. To achieve this goal, concrete mixtures presenting a wide range of binder compositions, using distinct types of chemical admixtures (e.g., crystalline self-healing), and incorporating five different types/nature of highly reactive aggregates (i.e., coarse and fine) were combined to manufactured concrete specimens in the laboratory. Otherwise, in aging specimens, concrete samples were designed only with GU-cement as the binder material but incorporated two different types/nature of highly reactive aggregates. Then, the samples were exposed to ASR-induced development until they reached pre-determined expansion levels, in which a wide range of sealers and coating materials were applied on the surface of the affected specimens. Mechanical (i.e., stiffness damage test, modulus of elasticity, micro indentation, shear and compressive strengths) and microscopic (damage rating index and scanning electron microscopy) tests were performed on samples at different ages (up to two years of accelerated ASR development). The results show that besides changing AAR-kinetics, the different binder compositions or the chemical admixtures could modify the distress mechanism due to AAR. The addition of crystalline healing agents or their combination with SCMs in concrete not only delayed the development of inner damage but significantly lowered the compressive strength loss at equivalent expansion amplitudes than control specimens. Moreover, the combination of different binder materials modified the chemical and mechanical properties of the ASR-gel, changing its swelling properties and the further damage development in concrete. On the other hand, the wide range of surface treatments used were not able to alter ASR distress mechanism; yet, they changed ASR-kinetics. Moreover, their effectiveness to slower the reaction shows to be significantly influenced by the damage degree to which the surface treatment is applied. Finally, a comprehensive framework enabling the optimized selection of raw materials to prevent or mitigate ASR development is proposed.

Immune-orchestrating biomaterials that precisely modulate the immune reac-tion to the host could lead the way for improving the implantation outcomein the transplantation field, in comparison to passive biomaterials. The lab-oratory of Dr. Thomas Crouzier has shown hydrogels derived from mucinsare capable of orchestrating the immune response mediated by foreign bodyresponse (FBR), as a result of evading fibrosis. Further, a recent study fromhis group showed sialic acid on mucin hydrogels is essential for the immuno-logical activity of those materials. Mucin glycans transiently activated thendampened macrophages, important orchestrators for material-mediated FBR,in a sialic acid-dependent manner for the majority of cytokines followed. Thematerial properties such as rheological properties, self-healing capacity, andstability, can be governed by the crosslinking chemistry used and have a drasticimpact on the functionalities of the materials. In this project, various cross-linking strategies are applied to tune the hydrogel properties. We show thatthe robust cross-linking formed mucin hydrogels having a 1.5% (wt/v) bettersupported insulin-secreting cells form islet-like organoids, compared to 2.5%mucin hydrogels. We then investigate the self-healing properties of the newmucin hydrogels and their interactions with various cell systems. / Immunologiska biomaterial som specifikt modulerar en immunologisk reak-tion hos värden kan vara vägen till att förbättra resultatet av en transplantationi jämförelse med att använda passiva biomaterial. Inom laboratoriet lett av Dr.Thomas Crouzier har det kunnat påvisas att hydrogels erhållna från mucinerär kapabla till att förändra en immunlogisk respons, Foreign Body Respon-se (FBR) vilket resulterat i att kringgå fibrosis. Utöver detta har ytterligareen studie utförts av hans grupp vilken kunde påvisa att sialinsyra på mucinhydrogel är essentiellt för den immunologiska aktiviteten för dessa biomateri-al. Mucin glykaner aktiveras tillfälligt för att dämpa bildandet av makrofager,vilket är viktigt vid biomaterial FBR i ett sialinsyra-beroende för bildandet avmajoriteten av cytokiner. Materialegenskaperna såsom reologiska egenskaper,självläkande kapacitet, och stabilitet kan regleras genom en krosslänkad kemisom har en drastisk impakt för funktionen för biomaterialen. I detta projekt, ärflera krosslänkande strategier tillämpade för att förstå egenskaperna för hyd-rogelerna. Vi har kunnat påvisa att robusta krosslänkande system av mucinhydrogel bestående av 1.5% (wt/v) ger bättre support till insulin sekreterandeceller att bilda islet liknande organider, att jämföra med 2.5% mucin hydrogel.Vi undersöker sedan den självläkande egenskaperna av nya mucin hydrogeleroch deras interaktioner med ett flertal olika cellsystem.

Large scale distributed computing systems have been extensively utilized to host critical applications in the fields of national defense, finance, scientific research, commerce, etc. However, applications in distributed systems face the risk of service outages due to inevitable faults. Without proper fault management methods, faults can lead to significant revenue loss and degradation of Quality of Service (QoS). An ideal fault management solution should guarantee fast and accurate fault diagnosis, scalability in distributed systems, portability for a variety of systems, and the versatility of recovering different types of faults. This dissertation presents a model-based fault management structure which automatically recovers computing systems from faults. This structure can recover a system from common faults while minimizing the impact on the system’s QoS. It covers all stages of fault management including fault detection, identification and recovery. It also has the flexibility to incorporate various fault diagnosis methods. When faults occur, the approach identifies fault types and intensity, and it accordingly computes the optimal recovery plan with minimum performance degradation, based on a cost function that defines performance objectives and a predictive control algorithm. The fault management approach has been verified on a centralized Web application testbed and a distributed big data processing testbed with four types of simulated faults: memory leak, network congestion, CPU hog and disk failure. The feasibility of the fault recovery control algorithm is also verified. Simulation results show that our approach enabled effective automatic recovery from faults. Performance evaluation reveals that CPU and memory overhead of the fault management process is negligible. To let domain engineers conveniently apply the proposed fault management structure on their specific systems, a component-based modeling environment is developed. The meta-model of the fault management structure is developed with Unified Modeling Language as an abstract of a general fault recovery solution for computing systems. It defines the fundamental reusable components that comprise such a system, including the connections among them, attributes of each component and constraints. The meta-model can be interpreted into a userriendly graphic modeling environment for creating application models of practical domain specific systems and generating executable codes on them.

Solid Oxide Fuel Cells (SOFC) are attractive candidates in the search for cleaner and energy efficient production due to their numerous advantages such as fuel flexibility, modularity and exceptional efficiencies when combined heat and power is harnessed. A key element in its design are the interconnects which are mainly manufactured from custom ferritic stainless steels to carry the electricity between two adjacent cells. However, the high operation temperatures increase the chromia scale thickness in those steels, which reduces their conductivity. At the same time, chromium (VI) volatilization due to the wet atmosphere poisons the electrodes and reduces the cell life. Therefore, the narrow of the selection of suitable materials and high production costs have hindered their commercialization. Recent advances in lower temperature SOFC operation have opened a window for new interconnect materials and innovative processes. A Ce/Co nanocoating can be applied in the readily available AISI 441 ferritic steel to form a protective spinel oxide layer that reduces the effect of both degradations in the interconnects. The coating is applied in a continuous roll-to-roll process and then the interconnect shape is pressed in the material, manufactured as Sanergy HT 441 by Sandvik. However, mechanical stresses cause microcracks that expose the substrate material, which can impact the oxidation behaviour negatively. Fortunately, pre-treatments can achieve the spinel to diffuse over short distances and combine with elements in the substrate, homogenizing the protective effect. This phenomenon known as self-healing has not been studied with sufficient depth for the Sanergy HT 441. Thus, different series of temperature and short pre-treatments times were tested, and self-healing properties were observed by means of SEM surface characterization and chemical analysis. The results indicate that self-healing can be obtained within short times using isothermal pre-treatments at temperatures over 750 °C. / Solid Oxide Fuel Cells (SOFC) är attraktiva kandidater i jakten på renare och energieffektiv produktion på grund av deras många fördelar som bränsleflexibilitet, modularitet och exceptionella effektivitet när kombinerad värme och kraft utnyttjas. Ett viktigt element i dess utformning är sammankopplingar som huvudsakligen tillverkas av anpassade ferritiska rostfria stål för att transportera elektricitet mellan två angränsande celler. De höga driftstemperaturerna ökar emellertid tjockleken på kromskalan i dessa stål, vilket minskar deras konduktivitet. Samtidigt förorenar krom (VI) på grund av den våta atmosfären elektroderna och reducerar celllivslängden. Därför har det smala urvalet av lämpliga material och höga produktionskostnader hindrat deras kommersialisering. De senaste framstegen inom SOFC-drift med lägre temperatur har öppnat ett fönster för nya sammankopplingsmaterial och innovativa processer. En Ce / Co-nanocoating kan appliceras i det lättillgängliga AISI 441 ferritstålet för att bilda ett skyddande spinelloxidskikt som minskar effekten av båda nedbrytningarna i sammankopplingarna. Beläggningen appliceras i en kontinuerlig rulle-till-rullningsprocess och sedan pressas sammankopplingsformen in i materialet, tillverkat som Sanergy HT 441 av Sandvik. Mekaniska spänningar orsakar emellertid mikrokrackar som exponerar underlagsmaterialet, vilket kan påverka oxidationsbeteendet negativt.Lyckligtvis kan förbehandlingar uppnå att spinellen diffunderar över korta avstånd och kombineras med element i underlaget och homogeniserar den skyddande effekten. Detta fenomen som kallas självhelande har inte studerats med tillräckligt djup för Sanergy HT 441. Således testades olika serier av temperatur och korta förbehandlingstider, och självhelande egenskaper observerades med hjälp av SEM-ytkarakterisering och kemisk analys. Resultaten indikerar att självläkning kan uppnås inom korta tider med användning av isotermisk förbehandling vid temperaturer över 750 ° C.

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A Sustainable Autonomic Architecture for Organically Reconfigurable Computing System based on SRAM Field Programmable Gate Arrays (FPGAs) is proposed, modeled analytically, simulated, prototyped, and measured. Low-level organic elements are analyzed and designed to achieve novel self-monitoring, self-diagnosis, and self-repair organic properties. The prototype of a 2-D spatial gradient Sobel video edge-detection organic system use-case developed on a XC4VSX35 Xilinx Virtex-4 Video Starter Kit is presented. Experimental results demonstrate the applicability of the proposed architecture and provide the infrastructure to quantify the performance and overcome fault-handling limitations. Dynamic online autonomous functionality restoration after a malfunction or functionality shift due to changing requirements is achieved at a fine granularity by exploiting dynamic Partial Reconfiguration (PR) techniques. A Genetic Algorithm (GA)-based hardware/software platform for intrinsic evolvable hardware is designed and evaluated for digital circuit repair using a variety of well-accepted benchmarks. Dynamic bitstream compilation for enhanced mutation and crossover operators is achieved by directly manipulating the bitstream using a layered toolset. Experimental results on the edge-detector organic system prototype have shown complete organic online refurbishment after a hard fault. In contrast to previous toolsets requiring many milliseconds or seconds, an average of 0.47 microseconds is required to perform the genetic mutation, 4.2 microseconds to perform the single point conventional crossover, 3.1 microseconds to perform Partial Match Crossover (PMX) as well as Order Crossover (OX), 2.8 microseconds to perform Cycle Crossover (CX), and 1.1 milliseconds for one input pattern intrinsic evaluation. These represent a performance advantage of three orders of magnitude over the JBITS software framework and more than seven orders of magnitude over the Xilinx design flow. Combinatorial Group Testing (CGT) technique was combined with the conventional GA in what is called CGT-pruned GA to reduce repair time and increase system availability. Results have shown up to 37.6% convergence advantage using the pruned technique. Lastly, a quantitative stochastic sustainability model for reparable systems is formulated to evaluate the Sustainability of FPGA-based reparable systems. This model computes at design-time the resources required for refurbishment to meet mission availability and lifetime requirements in a given fault-susceptible missions. By applying this model to MCNC benchmark circuits and the Sobel Edge-Detector in a realistic space mission use-case on Xilinx Virtex-4 FPGA, we demonstrate a comprehensive model encompassing the inter-relationships between system sustainability and fault rates, utilized, and redundant hardware resources, repair policy parameters and decaying reparability.