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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
51

Temporal Manipulation of Spatiotemporal Optical Vortex Via Temporal Airy Profile

Wei, Fanli 09 August 2021 (has links)
No description available.
52

Etude de l’élaboration de revêtements autocicatrisants pour le développement de matériaux robustes en condition nucléaire / Elaboration of self-healing coatings for the development of robust materials in nuclear conditions

Ougier, Michaël 09 December 2019 (has links)
Dans le cadre des recherches menées sur l'amélioration de la résistance à l'oxydation des gaines de combustible en conditions accidentelles, des revêtements Cr-Al-C et Cr2AlC ont été développés dans ce travail. Dans la première partie, nous avons étudié le procédé HiPIMS afin de comprendre l'effet de différents paramètres de dépôt sur le plasma et les propriétés des films obtenus. Il en ressort que malgré un bombardement ionique plus intense, un apport supplémentaire d'énergie est requis pour obtenir un revêtement cristallin. Des recuits à partir de 500°C sous argon de systèmes Cr-Al-C tels que déposés permettent ainsi une cristallisation partielle des revêtements en Cr2AlC à une température suffisamment basse pour être compatible avec la métallurgie des alliages de zirconium. Dans un second temps, l'évaluation du comportement à haute température de ces deux types de revêtements, recuits ou non, a révélé un effet protecteur contre l'oxydation rapide du zirconium jusqu'à 1200°C en atmosphère oxydante grâce à la formation d'une couche d'oxyde continue. Cette couche est constituée d'un mélange d'alumine α et de chromine pour le revêtement de Cr-Al-C tandis que seule l'alumine α est présente pour le revêtement Cr2AlC dans les premiers instants de l'oxydation. Ensuite, en raison de l'appauvrissement en Al, les revêtements se dégradent en formant une couche intermédiaire résiduelle de carbure Cr7C3 servant de réservoir de Cr jusqu'à complète oxydation. Ces résultats ont également montré la perte d'une partie du réservoir d'Al par diffusion dans les alliages Zr. Une architecture multicouche a été développée pour limiter cette diffusion et ainsi prolonger la durée de vie du revêtement. L'ajout d'un intercalaire en Mo pour bloquer la diffusion d'Al dans le substrat s'est avéré peu concluant, le molybdène s'évaporant à haute température. Les systèmes base Cr-Al-C revêtus chrome, présentent quant à eux, un comportement amélioré par rapport aux revêtements monocouches. / This study aims to improve oxidation resistance of nuclear fuel claddings in accident conditions. In this context, Cr-Al-C and Cr2AlC coatings deposition and their behavior were studied. Firstly, we investigated the influence of HiPIMS process parameters on the properties of the plasma and the deposited films. Despite more intense ionic fluxes due to the HiPIMS process, coatings do not crystallize without an additional energy supply. Partially crystallized Cr2AlC thin films were obtained by a 500°C annealing of as-deposited Cr-Al-C coatings. This two-step process is a viable solution to protect nuclear claddings with Cr2AlC coating while maintaining the metallurgical properties of the zirconium-based substrates. Secondly, the assessment of the oxidation resistance of as-deposited and annealed coatings revealed significant protective effect against rapid oxidation under dry and wet air at high temperatures (up to 1200°C) owing to the formation of a continuous oxide layer. During the first stages of oxidation, this layer is made of α Al2O3 and Cr2O3 for as-deposited coating while only α-Al2O3 is present for the annealed one. Because of Al depletion, coatings later deteriorate and form a residual and porous intermediate chromium carbide (Cr7C3) layer which further fully oxidizes. It was shown that the inward diffusion of Al with Zr also accelerates the coating deterioration. To improve the oxidation resistance of these coatings, multilayered architectures were developed. Adding a molybdenum interlayer as diffusion barrier globally decreased the oxidation resistance of the coating. In contrast, topping Cr-Al-C and Cr2AlC with a Cr layer improved oxidation behavior over single-layer coatings.
53

Estrutura e propriedades eletroquímicas de revestimentos híbridos PMMA-sílica modificados com íons cério e lítio /

Trentin, Andressa. January 2019 (has links)
Orientador: Peter Hammer / Resumo: Este trabalho relata uma investigação detalhada das propriedades estruturais e eletroquímicas de revestimentos de polimetilmetacrilato (PMMA)-sílica. Espectroscopia Raman e análise térmica mostraram que o ajuste da quantidade de peróxido de benzoíla (BPO), como um parâmetro crítico de síntese, melhora a eficiência de polimerização do metilmetacrilato (MMA), levando a uma estrutura híbrida altamente reticulada. A espectroscopia de impedância eletroquímica (EIS) mostrou para revestimentos depositados sobre aço carbono (A1020) e liga de Al (AA7075) uma resposta de impedância capacitiva quase ideal, mantendo o módulo de impedância de baixa frequência de até 10 GΩ cm2 essencialmente inalterado durante 19 meses de imersão em NaCl 3,5%. Embora revestimentos passivos de alto desempenho tenham sido desenvolvidos, pites de corrosão podem afetar significativamente sua durabilidade. Assim, a inibição da corrosão ativa induzida por íons lítio e cério em revestimentos de sílica sol-gel de PMMA foi investigada. A adição de carbonato de lítio produziu revestimentos com melhor conectividade dos nós de sílica nanométricos e forte adesão ao substrato de alumínio. Os resultados de EIS mostraram que as concentrações de lítio mais altas resultam em um aumento no módulo de impedância e induzem a autorregeneração que aumenta significativamente sua vida útil dos revestimentos. Time-of-flight secondary ion mass spectrometry (ToFSIMS) e a espectroscopia de fotoelétrons excitados por raios-X (XPS) suger... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This work reports on a detailed investigation of the structural and electrochemical properties of poly(methyl methacrylate) (PMMA)-silica coatings. Raman spectroscopy and thermal analysis showed that the fine-tuning of the benzoyl peroxide (BPO) amount, as a critical synthesis parameter, improves the polymerization efficiency of methyl methacrylate (MMA), leading to a highly cross-linked hybrid structure. Electrochemical impedance spectroscopy (EIS) showed for coatings deposited on carbon steel (A1020) and Al alloy (AA7075) a quasi-ideal capacitive impedance response, maintaining the low frequency impedance modulus of up to 10 GΩ cm2 essentially unchanged during 19 months of immersion in 3.5% NaCl. Although high performance passive coatings have been developed, pitting can significantly affect their durability. Hence, active corrosion inhibition induced by lithium and cerium ions in PMMA-silica sol-gel coatings was investigated. The addition of lithium carbonate yielded coatings with improved connectivity of nanometric silica cross-link nodes and stronger adhesion to the aluminum substrate. EIS results showed that higher lithium concentrations result in an increased impedance modulus and induce the self-healing ability, extending significantly the service life of the coatings. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) suggest that the regeneration process occurs by means of lithium ions leaching from the adjacent coat... (Complete abstract click electronic access below) / Doutor
54

Revestimentos de poliuretanos derivados de óleos vegetais com e sem adição de inibidores de corrosão : propriedades químicas, estruturais e de resistência à corrosão /

Nardeli, Jéssica Verger. January 2020 (has links)
Orientador: Assis Vicente Benedetti / Resumo: Os revestimentos de poliuretano (PU) foram preparados a partir de óleos vegetais (crambe e mamona) e modificados pela incorporação de inibidores de corrosão (tanino condensado). A reação foi monitorada caracterizando os produtos intermediários (poliéster e pré-polímero). O poliéster foi caracterizado pela solubilidade em metanol, índice de acidez, grupos hidroxila e espectroscopia no infravermelho por transformada de Fourier com refletância total atenuada (FTIR), e o pré-polímero foi caracterizado por teor de sólido, teor de solvente, isocianato livre (NCO) e FTIR. Os revestimentos de PU foram caracterizados por FTIR e absorção de água. Esses revestimentos foram aplicados sobre as ligas de alumínio com extensômetro. O processo de cura foi conduzido em temperatura ambiente (~25 oC). A espessura dos revestimentos foi determinada por microscopia eletrônica de varredura (SEM) e a adesão foi avaliada pela Norma ASTM D3359. Após a caracterização química e morfológica dos revestimentos foi realizado o estudo eletroquímico. A resistência à corrosão e o processo de degradação do filme (longevidade da ação do revestimento), foram estudadas por medidas de potencial em circuito aberto (EOCP) e espectroscopia de impedância eletroquímica (EIS) em solução aquosa 0,6 mol L-1 NaCl com o tempo de imersão. Foram empregadas técnicas eletroquímicas localizadas como espectroscopia de impedância eletroquímica local (LEIS) em solução aquosa 0,005 mol L-1 NaCl e as técnicas de varredura com eletrodo ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Polyurethane (PU) coatings were prepared from vegetable oils (crambe and castor) and modified by the incorporation of corrosion inhibitors (condensed tannins). The reaction was monitored by characterizing the intermediate products (polyester and prepolymer). Polyester was characterized by solubility in methanol, acidity index, hydroxyl groups and attenuated total reflectance Fourier transform infrared spectroscopy (FTIR), and the prepolymer was characterized by solid content, solvent content, free-isocyanate (NCO) groups and FTIR. PU coatings were characterized by FTIR and water uptake. These coatings were applied on aluminum alloys with an extensometer. The curing process was carried out at room temperature (~25 oC). The thickness of the coatings was determined by scanning electron microscopy (SEM) and the adhesion was assessed using the ASTM D3359 standard. After the chemical and morphological characterization of the coatings, the electrochemical study was carried out. The corrosion resistance and the film degradation process (longevity of the coating action) were studied by open circuit potential measurements (EOCP) and electrochemical impedance spectroscopy (EIS) in 0.6 mol L-1 NaCl aqueous solution with the immersion time. Localized electrochemical techniques were also used, such as local electrochemical impedance spectroscopy (LEIS) in 0.005 mol L-1 NaCl aqueous solution and scanning techniques with vibrating electrode (SVET) and with ion-selective electrode (SIET), in ... (Complete abstract click electronic access below) / Doutor
55

Autonomic test case generation of failing code using AOP

Murguia, Giovanni 02 September 2020 (has links)
As software systems have grown in size and complexity, the costs of maintaining such systems increases steadily. In the early 2000's, IBM launched the autonomic computing initiative to mitigate this problem by injecting feedback control mechanisms into software systems to enable them to observe their health and self-heal without human intervention and thereby cope with certain changes in their requirements and environments. Self-healing is one of several fundamental challenges addressed and includes software systems that are able to recover from failure conditions. There has been considerable research on software architectures with feedback loops that allow a multi-component system to adjust certain parameters automatically in response to changes in its environment. However, modifying the components' source code in response to failures remains an open and formidable challenge. Automatic program repair techniques aim to create and apply source code patches autonomously. These techniques have evolved over the years to take advantage of advancements in programming languages, such as reflection. However, these techniques require mechanisms to evaluate if a candidate patch solves the failure condition. Some rely on test cases that capture the context under which the program failed---the patch applied can then be considered as a successful patch if the test result changes from failing to passing. Although test cases are an effective mechanism to govern the applicability of potential patches, the automatic generation of test cases for a given scenario has not received much attention. ReCrash represents the only known implementation to generate test cases automatically with promising results through the use of low-level instrumentation libraries. The work reported in this thesis aims to explore this area further and under a different light. It proposes the use of Aspect-Oriented Programming (AOP)---and in particular of AspectJ---as a higher-level paradigm to express the code elements on which monitoring actions can be interleaved with the source code, to create a representation of the context at the most relevant moments of the execution, so that if the code fails, the contextual representation is retained and used at a later time to automatically write a test case. By doing this, the author intends to contribute to fill the gap that prevents the use of automatic program repair techniques in a self-healing architecture. The prototype implementation engineered as part of this research was evaluated along three dimensions: memory usage, execution time and binary size. The evaluation results suggest that (1) AspectJ introduces significant overhead with respect to execution time, (2) the implementation algorithm causes a tremendous strain on garbage collection, and (3) AspectJ incorporates tens of additional lines of code, which account for a mean size increase to every binary file of a factor of ten compared to the original size. The comparative analysis with ReCrash shows that the algorithm and data structures developed in this thesis produce more thorough test cases than ReCrash. Most notably, the solution presented here mitigates ReCrash's current inability to reproduce environment-specific failure conditions derived from on-demand instantiation. This work can potentially be extended to apply in less-intrusive frameworks that operate at the same level as AOP to address the shortcomings identified in this analysis. / Graduate
56

Étude expérimentale et modélisation de l'auto-cicatrisation des matériaux cimentaires avec additions minérales / Experimental study and modelisation of self-healing cementitious materials with mineral additions

Olivier, Kelly 14 January 2016 (has links)
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.
57

Hydrogels injectables et auto-réparants à base de polysaccharides réticulés par des liaisons ester boronate : relations entre le mode de complexation acide boronique-saccharide et les propriétés mécaniques / Injectable and self-healing polysaccharide hydrogels via boronate ester bonds : relationships between the binding mode of boronic acids to saccharide moieties and the macroscopic mechanical properties

Figueiredo, Tamiris Vilas Boas 05 December 2018 (has links)
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.
58

Synthesis and characterization of ammonium ionenes containing hydrogen bonding functionalities

Tamami, Mana 16 January 2013 (has links)
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.
59

Avoiding & Mitigating Alkali-Aggregate Reaction (AAR) in Concrete Structures

De Souza, Diego Jesus 21 January 2022 (has links)
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.
60

Tuning the crosslinking chemistry for self-healable mucin hydrogel synthesis and application / Justering av kemiska tvärbindningar för mucin hydrogels-syntes och applikation

Pacella, Francesca January 2020 (has links)
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.

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