Tesis sobre el tema "Multi-Scale Material Characterization"

Avec le développement des matériaux fonctionnels (multi-matériaux, multicouches,…), la caractérisation du comportement mécanique par des moyens macroscopiques conventionnels est devenue de plus en plus difficile. Ces méthodes conventionnelles sont donc substituées progressivement par des moyens de caractérisation multi-échelles. Parmi ces moyens, la nanoindentation, qui peut résoudre certains défis de la micro-caractérisation tels que la présence de phases indissociables, les systèmes multicouches, les revêtements ultra-minces, etc. Cet outil est devenu une technique de haute précision capable de solliciter des volumes de matière très faibles et fournir des informations riches pour la caractérisation des matériaux. Cependant, cet outil est utilisé majoritairement pour identifier les propriétés élastiques et qualitativement certains paramètres tels que la dureté, la ductilité et les contraintes internes.Ce travail de thèse s’intéresse à la caractérisation du comportement élastoplastique par nanoindentation à deux échelles : l’échelle macroscopique et l’échelle du cristal.Le premier défi de ce travail est expérimental. Il s’agit de générer des surfaces avec des propriétés représentatives de la microstructure étudiée. Ce défi est d’autant plus relevé que le matériau utilisé comme modèle est l’acier 316L très ductile et dont la surface est sensible au moindre changement. Un protocole expérimentale a été mis en place, à l’issu de ce travail, et les erreurs et dispersions de la réponse en nanoindentation introduites par les différentes étapes de génération de surface ont été quantifiés.Une base de données étendue a été mise en place, par la suite. Différentes géométries d’indent ont été appliquées à plusieurs profondeurs. Cette base de données va alimenter des stratégies d’identification inverse basée sur un couplage entre des algorithmes d’optimisation et une modélisation éléments finis de l’essai. Deux types d’algorithme ont été appliqués : Levenberg-Marquardt et l’algorithme génétique. Ce dernier est très consommateur en temps de calcul. Différents modèles EF axisymétrique et 3D ont été utilisés. Ces modèles ont été soigneusement optimisés par rapport au temps de calcul.Plusieurs stratégies d’identification ont été employées en se basant sur différentes données expérimentales issues de l’essai de nanoindentation telles que la courbe de charge-décharge, la forme de l’empreinte résiduelle et l’association de plusieurs géométries d’indent. Plusieurs modèles d’écrouissage isotrope ont été identifiés. À l’échelle macroscopique, les modèles d’écrouissage isotrope classiques ont été déterminés. À l’échelle du grain, la loi cristalline de Méric et Cailletaud a été identifiée. Les résultats obtenus ont été confrontés, à l’échelle macroscopique, à des identifications réalisées sur le même matériau à partir des essais de traction et de compression et ont montré que l’association de multiples géométries d’indentation permet de reproduire le comportement volumique du 316L avec une précision acceptable. Pour le comportement du cristal, des essais de compression de micropilliers ont été utilisé pour se procurer des données de référence à cette échelle. La comparaison montre beaucoup de dispersion dans les deux cas. En effet, certains phénomènes liés à la densité de dislocation très variables d’un grain à l’autre sont responsables de cette dispersion. Cette densité de dislocation n’est pas prise en compte, en tant que variable, dans le modèle cristallin utilisé. L’utilisation d’un modèle plus physique intégrant la densité de dislocation et son évolution permet d’améliorer ces résultats. Enfin, une nouvelle méthode d’identification a été proposée. Cette méthode est basée sur l’estimation et l’introduction de la géométrie réelle de l’indent dans le modèle EF utilisé pour l’identification. La méthode a été validée dans le cas de la pointe Berkovich et elle montre des résultats très prometteurs
With the development of functional materials (multi-materials, multilayers, ...), the mechanical behavior characterization by conventional macroscopic methods has become progressively difficult. These conventional methods are therefore gradually substituted by multiscale characterization processes. Among these methods, the nanoindentation, this can solve certain challenges of micro-characterization such as the presence of indissociable phases, multilayer systems, ultra-thin coatings, etc. This tool has become a high-precision technique capable of testing very small volumes of matter and providing rich information for material characterization. However, this tool is used mainly to identify the elastic properties and, qualitatively, some parameters such as hardness, ductility and internal stresses.This thesis work focuses on the characterization of elastoplastic behavior by nanoindentation at two scales: the macroscopic scale and the crystal scale.The first challenge of this work is experimental. It involves generating surfaces with properties representative of the studied microstructure. This challenge is important because the material used as a model is 316L steel which is very ductile and whose surface is sensitive to small perturbations. An experimental protocol was implemented at the end of this work, and the errors and dispersions of the nanoindentation response introduced by the different surface generation steps were quantified. Then, a wide database was implemented with different indenter geometries and several depths. This database will feed inverse identification strategies based on a coupling between optimization algorithms and finite element modeling of this test. Two types of algorithm have been applied: Levenberg-Marquardt and genetic algorithms. The latter is very consumer in computing time. Different axisymmetric and 3D FE models have been used. These models have been carefully optimized with respect to computation time.Several identification strategies were employed based on various experimental databases from the nanoindentation test such as the loading-unloading curve, the residual imprint shape and the association of several indent geometries. Some models of isotropic hardening have been identified. On the macroscopic scale, classical isotropic hardening models have been determined. At the grain scale, the crystal plasticity constitutive model of Méric and Cailletaud has been identified. The results obtained were compared on the macroscopic scale with identifications carried out on the same material from the tensile and compression tests. The comparison showed that the combination of multiple indentation geometries makes it possible to reproduce the volume behavior of the 316L with acceptable accuracy. For crystal behavior, micropillar compression tests were used to obtain reference data at this scale. The comparison shows a lot of dispersion in both cases. Indeed, some phenomena related to the density of dislocation very variable from one grain to another are responsible of this dispersion. This dislocation density is not taken into account, as a variable, in the used crystal constitutive model. The use of a more physical law integrating the dislocation density and its evolution makes it possible to improve these results. Finally, a new identification method has been proposed. This method is based on estimating and introducing the real indent geometry in the FE model used for identification. The method has been validated in the case of Berkovich tip and shows very promising results

Cette thèse présente une étude expérimentale pour améliorer le moulage par compression et transfert de résine thermoplastique (CRTM), axée sur l'efficacité industrielle, la durabilité et la recyclabilité, conformément aux objectifs de développement durable pour l’industrie, l’innovation et l’action climatique. En abordant la complexité de l'écoulement de la résine à plusieurs échelles dans le CRTM, cette recherche étudie l'écoulement transversal (à travers l’épaisseur) et la porosité induite par le processus à l'échelle méso des faisceaux de fibres de verre afin d'améliorer l'uniformité de l'imprégnation et le contrôle du compactage, en faisant le lien entre les cadres théoriques et les applications évolutives. L’étude est conduite sur une préforme, constituées de 6 couches de fibres de verre UD ([0/90]3) et d’une matrice thermoplastique en polypropylene (PP) mise en forme par un procédé CRTM . Un procédé « CRTM simplifié » permettant de contrôler la direction du front de matière est développé sur une presse industrielle, pilotée en déplacement. Trois configurations de procédé sont analysées : Configuration 1 (Référence) : configuration de type « film stacking » comme base de comparaison de la distribution de la résine et de la structure des fibres. Configuration 2 (CRTM simplifié) : Compression contrôlée par déplacement, les films de polymères formant initialement une couche unique en surface de la préforme. Configuration 3 (CRTM simplifié avec scellement des bords) : Compression améliorée avec un dispositif d’étanchéité limitant les fuites de résine en périphérie de la préforme et assurant un écoulement transversal. Un protocole d’analyse d'imagerie 2D est proposé, incluant l’analyse en lumière polarisée, la microscopie à fluorescence et la microscopie électronique à balayage pour caractériser qualitativement et quantitativement les taux de porosités au niveau des mèches et des plis de tissus. Un processus original de polissage en deux étapes permet de préserver l'intégrité de la surface. L'étude est complétée par une évaluation fine des mécanismes d'imprégnation à l'aide de la technique d'inspection hélicoïdale en microtomographie à rayon-X (micro-CT). Les résultats démontrent que les paramètres de compaction influencent directement le niveau d'imprégnation, atteignant une limite d'imprégnation. Cette thèse établit une démarche d’analyse du procédé CRTM pour des composites thermoplastiques haute performance, en vue d’une maitrise et d’une optimisation du procédé. Elle offre des perspectives sur des protocoles d’analyse précis basés sur l’étude à différentes échelles, améliorant la compréhension de l'interaction entre l'imprégnation et la perméabilité. Ces résultats répondent aux exigences de précision dans des secteurs tels que l'automobile et l'aérospatiale, où les composites CRTM sont essentiels pour les applications structurelles
This thesis presents an experimental study to advance thermoplastic Compression Resin Transfer Molding (CRTM), focusing on industrial efficiency, sustainability, and recyclability goals aligned with the Sustainable Development Goals for Industry, Innovation, and Climate Action. By addressing multi-scale resin flow complexity in CRTM, this research investigates transverse flow and process-induced porosity at the meso scale of glass fiber bundles to improve impregnation uniformity and compaction control, bridging theoretical frameworks with scalable applications. The study focuses on a thermoplastic polypropylene matrix reinforced with six layers of bidirectional UD woven glass fibers ([0/90]3) consolidated on a CRTM setup. The “Simplified CRTM” method is developed on an industrial press, using displacement-controlled compaction ratios. This method omits active resin injection, relying on a uniformly distributed viscous polymer pool beneath the unsaturated preform to drive resin flow uniformly with a unidirectional flow path. Controlled displacement and pressure optimize resin paths, manage fiber volume fraction, and reduce porosity. Three multi-step compaction configurations are evaluated: Configuration 1 (Reference): Uses force compaction as a baseline for comparing resin distribution and fiber structure. Configuration 2 (simplified CRTM): Displacement-controlled compaction enhances resin infiltration but faces challenges like edge race-tracking and fiber volume fraction (Vf) variability, affecting impregnation. Configuration 3 (simplified CRTM with Edge Sealing): Introduces high-temperature sealant tape at mold edges, limiting resin escape, maintaining transverse flow, and reducing porosity and race-tracking. Configuration 3 edge-sealing technique establishes a reproducible process for high quality CRTM composites. An advanced 2D multi-modal imaging protocol, tailored for partially impregnated samples produced via simplified CRTM with unfilled spaces and fragile microstructures, includes polarized light microscopy, fluorescence microscopy, and scanning electron microscopy for qualitative and quantitative characterization. An original two-step polishing process preserves surface integrity, and image post-processing workflows quantify impregnation quality and void distribution. The study is completed with a fine evaluation of the impregnation mechanisms using X-ray micro computed tomography technique (micro-CT) relying on helicoidal inspection method. Results demonstrate that compaction parameters directly impact impregnation level, reaching an impregnation limit. This thesis establishes a scalable, data-driven CRTM framework bridging laboratory experimentation with industrial requirements for high-performance thermoplastic composites. It offers insights into streamlined protocols and microstructure-based analysis, enhancing understanding of the interplay between impregnation and permeability in CRTM. These findings align with precision demands in sectors like automotive and aerospace, where CRTM composites are crucial for structural applications

With industries aiming at higher efficiencies, lightweight parts, and easier manufacturability there has been a recent trend of replacing the metallic materials with polymeric materials and its composites. Particularly in the automotive industry, there is a demand of replacing metallic material of bushes and bearings with polymer based materials (PBM). For these heavy performance requirements (as in automobiles), the commonly used industrial polymers like Acetal and Nylon fail to provide good mechanical and tribological performance. High-performance polymer like Polyphenylene Sulfide (PPS) is a relatively newer material and shows a potential of being a PBM alternative for metallic bearings in automobiles if their tribological performance can be improved.  One of the ways of improving the tribological performance of the polymer is by the addition of filler material, hence making a polymer composite. In this study, we used Short Carbon Fibre as micro-reinforcement material and Nano-diamonds and Graphene Oxide as nano-reinforcement material to make PPS composites. The varying mechanical and tribological behaviour of PPS composites with different weight percentage of reinforcement materials was investigated. The optimum composition of the reinforcement materials was identified, which resulted in significant improvement in mechanical and tribological properties of the base material.

Le travail présenté dans cette thèse porte sur la synthèse, la caractérisation des propriétés structurelles et électroniques du sulfure de cuivre Cu22Fe8Ge4S32, un matériau dérivé de la germanite ayants des propriétés thermoélectriques prometteuses. Les deux premiers chapitres sont consacrés à l'optimisation des propriétés thermoélectriques par différentes approches. Le dernier chapitre est une étude structurelle approfondie de la germanite Cu22Fe8Ge4S32. Premièrement, les conditions spécifiques de la synthèse permettant de produire un échantillon ‘‘pure’’ de germanite par tube scellé sont examinées par le biais de réactions in situ. Ensuite, deux approches différentes de synthèse sont comparées, à savoir l’alliage mécanique et la synthèse en tube scellé, combinées à deux méthodes de densification différentes: le frittage SPS et le pressage à chaud. Deuxièmement, les séries de composés Cu22-xZnxFe8Ge4S32 (0 ≤ x ≤ 2) et Cu22Fe8Ge4-xSnxS32 (0 ≤ x ≤ 4) ont été étudiées dans l’espoir d’améliorer les propriétés thermoélectriques en augmentant la diffusions des phonons. En plus de la diminution de la κ_Latt, l'augmentation de la concentration en Zn dans le réseau de cuivre entraîne une diminution de la concentration en trous. De plus, l’incorporation de Sn diminue la κ_Latt en augmentant la diffusion des phonons par des défauts ponctuels due à des disparités de masse, de taille et de force de liaison. Enfin, un nouvelle structure crystalline pour la germanite synthétique a été proposé en conservant le groupe d'espace et le paramètre de maille du matériau minéral (P4 ̅3n and a ≈ 10.595 Å). La détermination de la structure cristalline a été possible par la complémentarité des techniques de DRX sur poudre et monocristal, de spectroscopie Mössbauer 57Fe et de diffusion résonante. L’originalité de ce travail réside dans l’approche expérimentale développée pour surmonter la complexité inhérente à la distribution cationique de germanite
The work presented in this Ph.D. thesis deals with the synthesis, the structural and electronic properties characterization of the Cu22Fe8Ge4S32 copper sulfide, a material derived of the germanite mineral with promising thermoelectric properties. The first two chapters are dedicated to the optimization of the thermoelectric properties. The last chapter is an in-depth structural study of Cu22Fe8Ge4S32. First, the specific synthesis conditions to yield a ‘‘pure’’ germanite sample by sealed tube are investigated by the means of in situ reactions. Then, two different powder synthesis approaches are compared, namely mechanical alloying and conventional sealed tube synthesis, combined with two different densification methods: spark plasma sintering and hot pressing. This study drags attention to the process impact on the transport properties of complex Cu-based sulfides. Second, the series of compounds Cu22-xZnxFe8Ge4S32 (0 ≤ x ≤ 2) and Cu22Fe8Ge4-xSnxS32 (0 ≤ x ≤ 4) were investigated in the hope to enhance the TE properties through enhanced phonon scattering due to differences in atomic mass. In fact, in addition to lowering the κ_Latt, the Cu by Zn substitution in Cu22-xZnxFe8Ge4S32 leads to a decrease in the concentration of hole carriers. In addition, a reduction of κ_Lattis observed with the Sn-incorporation due to point defect scattering enhancement of the heat carrying phonons as a result of mass, size, and bonding strength disparities. Finally, a new structural model for synthetic germanite was proposed with respect to the space group and lattice parameter of the mineral material, P4 ̅3n and a ≈ 10.595 Å. The crystal structure is proposed based on the complementarity from powder and single crystal XRD, 57Fe Mössbauer spectroscopy and resonant scattering. The originality of this work lies in the experimental approach that was developed to overcome the inherent complexity of germanite cationic distribution

Thesis (Ph. D.) -- University of Maryland, College Park, 2009.
Thesis research directed by: Dept. of Mechanical Engineering. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.

L’objectif de cette thèse est d’établir le scénario multi-échelles de déformation du PEEK lorsqu’il est sollicité en traction uniaxiale. Préalablement à la mise en oeuvre d’échantillons de deux grades commerciaux de PEEK, les propriétés thermiques et mécaniques de ces matériaux ont été caractérisées. La température d’oubli thermodynamique ainsi que la sensibilité aux vitesses de refroidissement ont été établies. Des éprouvettes de traction ont été obtenues à partir de plaques thermocompressées, procédé choisi pour obtenir des morphologies les plus isotropes possibles. Les propriétés mécaniques en traction ont ensuite été caractérisées au-dessus et au-dessous de la transition vitreuse de la phase amorphe (Tg). Grâce à un dispositif expérimental fabriqué sur mesure, des essais de traction à deux températures distinctes au-dessous et au-dessus de Tg ont été suivis par diffusion des rayons X aux petits (SAXS) et grands angles (WAXS) pour caractériser les déformations à l’échelle des empilements lamellaires et à l’échelle de la maille cristalline. Simultanément, le champ de déformation a été mesurée par corrélation d’images (DIC) afin de comparer la déformation macroscopique et microscopique. Pour les deux températures, les lamelles tendent à s’orienter perpendiculairement à la direction de traction (TD). Ce mécanisme d’orientation local (que nous appelons « modèle de réseau de chaînes ») est induit par la transmission des contraintes par les chaînes amorphes reliant les lamelles cristallines adjacentes. Au-dessus de Tg, l’allongement local est plus faible que l’allongement macroscopique dans les lamelles perpendiculaire à TD, ce qui implique que les lamelles inclinées doivent être cisaillées. L’évolution de la distribution d’orientation des lamelles appuie ce résultat. Une morphologie fortement orientée est finalement obtenue quelle que soit la température. Cependant, le profil d’endommagement est différent. En-dessous de Tg, le profil de diffusion centrale indique l’existence de petites entités (lamelles ou crystallites) orientées aléatoirement. A hautes température, le matériau est fibrillaire et présente des cavités
The aim of this PhD work is accessing the microscopic deformation mechanisms of bulk poly-ether-ether-ketone (PEEK) under tensile stretching. Beforehand, the thermal and mechanical properties of two commercial grades of PEEK were characterized. Tensile specimens were then compression-molded to obtain morphologies as isotropic as possible and characterized below and above the glass transition temperature. Deformations at the scales of lamellar stacks and of the crystalline unit cell have been characterized by small and wide-angle X-ray scattering (SAXS and WAXS) performed in-situ during tensile tests. Simultaneously, the strain field within the samples was followed by digital image correlation (DIC) in order to compare microscopic and macroscopic strains. At both temperatures, lamellae tend to orient perpendicular to the tensile direction (TD). This orientation mechanism (which we denote as ‘Chain Network model’) is driven by the amorphous chains which transmit the stress between adjacent lamellae. The tensile strain in lamellar stacks perpendicular to TD is lower than the macroscopic tensile strain, which must be compensated by increased shear in inclined stacks. Some differences of behavior have been observed depending on the test temperature, especially at high deformation. A highly oriented morphology is ultimately obtained in all cases. However, the central scattering profiles changes with testing temperatures. Below Tg, the presence of small entities randomly oriented is indicated. Above Tg, the material is fibrillar and contains cavities

Les préoccupations environnementales de l'industrie et les stratégies visant à développer un système économique plus durable suscitent un intérêt croissant pour la recherche dans le domaine des biocomposites. Le fort caractère polaire et hydrophile des fibres végétales entraîne, lors de leur utilisation comme renfort, une complexité de mise en œuvre et des limites en termes de transfert de charge à l’interface fibre/matrice. Ces verrous pour le développement des biocomposites sont les lignes directrices de ce travail de thèse s'inspirant de la présence des interfaces au sein des tiges de chanvre. L’évolution progressive de la microstructure et des propriétés mécaniques est cruciale pour l'intégrité et le fonctionnement de la tige à travers des régions de transition. Ces interfaces, potentiels maillons faibles de la structure, sont étudiées en appliquant un processus de rouissage impactant la microstructure interne et la cohésion tissulaire. Des tiges aux fibres élémentaires, l'étude du comportement mécanique des systèmes naturels est une source d’inspiration pour un transfert des principes fondamentaux des biocomposites. Visant à accroître la compréhension de l'effet de l'humidité présente dans l’environnement lors des utilisations composites, l’analyse des propriétés hygro-mécanique permet de mettre en évidence des performances optimales de composites unidirectionnels de part un effet bénéfique de la sorption d’eau. Des études à l'échelle microscopique ont permis d’attribuer une contribution importante du comportement hygroscopique aux performances de l'interface fibre/matrice par la création de contraintes résiduelles et de mécanismes d'adhésion capillaire. Généralement décrite comme un inconvénient, ce travail de recherche montre que la sensibilité à l'eau des fibres végétales ainsi que la sorption de vapeur d’eau dans un biocomposite pourraient favoriser le transfert de charge et être bénéfiques pour leurs performances mécaniques
Industry environmental concerns and strategies to become part of a more sustainable economic system, leads to a growing interest in research on biocomposite. The strong polar and hydrophilic nature of plant fibers leads, when used as a reinforcement, to a complexity of biocomposite manufacturing and limits in terms of load transfer at the fiber/matrix interface. These major locks (fiber polarity and moisture sensitivity) for biocomposites development are the guidelines of this thesis work taking its inspiration in the design of hemp stem tissue interfaces. The multi-scale evolution of gradient microstructure and internal mechanics is crucial for the integrity and functioning of the stem through smooth transitions regions. These potential weak interfaces are investigated by applying a retting process that affect the stem internal microstructure and tissue cohesion. From the stems of agricultural crops to the hierarchical elementary fibers, studying the mechanical behavior of natural systems may serve as inspiration for a biomimetic transfer of the fundamental principles to fiber-reinforced composites. Aimed at increasing the understanding of the effect of moisture present during composite use, hygro-mechanical coupling highlights an optimum in hemp fibre-based unidirectional composites performances from a beneficial effect of moisture sorption. Deeper analysis at the micro-scale attributed a significant contribution of this hygroscopic behavior to fiber/matrix interface performances through the creation of residual stresses and capillary adhesion mechanisms. Generally described in the literature as a drawback, this research demonstrates that water sensitivity of plant fibers and moisture sorption in biocomposite could promote load transfer and be beneficial for their performance

En raison de leur capacité de prise, les liants hydrauliques sont utilisés à des fins très variées (e.g., matériaux de construction, substituts osseux, ...). La réaction de prise est toujours initiée par le mélange d'une ou plusieurs poudres fines avec une solution aqueuse. La dissolution des poudres réactives initiales entraîne la formation d'une pâte visqueuse, dont les propriétés évoluent avec le temps pour former une céramique poreuse monolithique par la nucléation et la précipitation de phase(s) plus stable(s). Dans le cadre de cette thèse, le plâtre CaSO4·2H2O obtenu par la réaction d'hydratation du sulfate de calcium hémihydraté CaSO4·0,5H2O est étudié dans des conditions standards (e.g., rapport massique liquide/solide, température et pression), afin de développer des techniques de caractérisation multi-physiques et multi-échelles in-situ et ex-situ pour suivre l'évolution de:- la composition des phases (réaction de dissolution et de précipitation) à l'aide de mesures calorimétriques, de la de la diffractométrie des rayons X et de la spectrophotométrie infrarouge à transformée de Fourier;- la microstructure à l'aide de la microscopie électronique à balayage et de la microtomographie aux rayons X;- les propriétés mécaniques en utilisant la mesure de vitesse de propagation des ultrasons, l'analyse mécanique dynamique en cisaillement et en compression et le test de résistance en compression. Ce panel de techniques a permis de suivre et de corréler les différentes transitions physiques survenant au cours de la réaction de prise et ainsi de dresser un portrait global des phénomènes physiques mis en jeu
Because of their setting ability, hydraulic binders are used for a wide variety of applications (e.g., construction materials, bone substitutes, ...). The setting reaction is always initiated by mixing one or several fine powders with an aqueous solution. The dissolution of the initial reactive powders results in the formation of a viscous paste, whose properties evolve with time to form a porous monolithic ceramic through the nucleation and precipitation of more stable phase(s). In this thesis, gypsum plaster CaSO4·2H2O obtained by the hydration reaction of calcium sulfate hemihydrate CaSO4·0,5H2O is studied under standard conditions (e.g., liquid/solid mass ratio, temperature and pressure), in order to develop multi-physic and multi-scale characterization techniques in-situ and ex-situ to monitor the evolution of:- the phase composition (rate of dissolution and precipitation) using calorimetric measurements, X-ray diffraction and Fourier-transform infrared spectrophotometry techniques;- the microstructure using scanning electron microscopy and X-ray microtomography;- the mechanical properties using ultrasonic propagation velocity measurement, shear and compressive dynamic mechanical analysis and compressive strength testing. This panel of techniques enabled to monitor and to correlate the various physical transitions occurring during the setting reaction, and thus to draw a global picture of the on-going phenomena

abstract: Being a remarkably versatile and inexpensive building material, concrete has found tremendous use in development of modern infrastructure and is the most widely used material in the world. Extensive research in the field of concrete has led to the development of a wide array of concretes with applications ranging from building of skyscrapers to paving of highways. These varied applications require special cementitious composites which can satisfy the demand for enhanced functionalities such as high strength, high durability and improved thermal characteristics among others. The current study focuses on the fundamental understanding of such functional composites, from their microstructural design to macro-scale application. More specifically, this study investigates three different categories of functional cementitious composites. First, it discusses the differences between cementitious systems containing interground and blended limestone with and without alumina. The interground systems are found to outperform the blended systems due to differential grinding of limestone. A novel approach to deduce the particle size distribution of limestone and cement in the interground systems is proposed. Secondly, the study delves into the realm of ultra-high performance concrete, a novel material which possesses extremely high compressive-, tensile- and flexural-strength and service life as compared to regular concrete. The study presents a novel first principles-based paradigm to design economical ultra-high performance concretes using locally available materials. In the final part, the study addresses the thermal benefits of a novel type of concrete containing phase change materials. A software package was designed to perform numerical simulations to analyze temperature profiles and thermal stresses in concrete structures containing PCMs. The design of these materials is accompanied by material characterization of cementitious binders. This has been accomplished using techniques that involve measurement of heat evolution (isothermal calorimetry), determination and quantification of reaction products (thermo-gravimetric analysis, x-ray diffraction, micro-indentation, scanning electron microscopy, energy-dispersive x-ray spectroscopy) and evaluation of pore-size distribution (mercury intrusion porosimetry). In addition, macro-scale testing has been carried out to determine compression, flexure and durability response. Numerical simulations have been carried out to understand hydration of cementitious composites, determine optimum particle packing and determine the thermal performance of these composites.
Dissertation/Thesis
Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2018

abstract: This research is a comprehensive study of the sustainable modifiers for asphalt binder. It is a common practice to use modifiers to impart certain properties to asphalt binder; however, in order to facilitate the synthesis and design of highly effective sustainable modifiers, it is critical to thoroughly understand their underlying molecular level mechanisms in combination with micro and macro-level behavior. Therefore, this study incorporates a multi-scale approach using computational modeling and laboratory experiments to provide an in-depth understanding of the mechanisms of interaction between selected modifiers and the constituents of asphalt binder, at aged and unaged conditions. This study investigated the effect of paraffinic wax as a modifier for virgin binder in warm-mix asphalt that can reduce the environmental burden of asphalt pavements. The addition of wax was shown to reduce the viscosity of bitumen by reducing the self-interaction of asphaltene molecules and penetrating the existing nano agglomerates of asphaltenes. This study further examined how the interplay of various modifiers affects the modified binder’s thermomechanical properties. It was found that the presence of wax-based modifiers has a disrupting effect on the role of polyphosphoric acid that is another modifier of bitumen and its interactions with resin-type molecules. This study was further extended to using nanozeolite as a mineral carrier for wax to better disperse wax in bitumen and reduce the wax's adverse effects such as physical hardening at low service temperatures and rutting at high service temperatures. This novel technique showed that using a different method of adding a modifier can help reduce the modifier's unwanted effects. It further showed that nanozeolite could carry wax-based modifiers and release them in bitumen, then acting as a scavenger for acidic compounds in the binder. This, in turn, could promote the resistance of asphalt binder to moisture damage by reducing the quantity of acidic compounds at the interface between the binder and the stone aggregates. Furthermore, this study shows that iso-paraffin wax can reduce oxidized asphaltene molecules self-interaction and therefore, reduce the viscosity of aged bitumen while cause brittleness at low temperatures. Additionally, a cradle to gate life-cycle assessment was performed for a new bio-modifier obtained from swine manure. This study showed that by partially replacing the bitumen with bio-binder from swine manure, the carbon footprint of the binder can be reduced by 10% in conjunction with reducing the cost and environmental impact of storing the manure in lagoons.
Dissertation/Thesis
Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2020

The epoxy resins are organic matrices with excellent heat, moisture, and chemical resistance and good adhesion to many substrates, therefore they are mostly applied in the field of coatings, adhesives, casting, composites, laminates and encapsulation of semiconductor devises. However, due to their low mechanical properties and high coefficient of thermal expansion value compared with inorganic materials, the epoxy resins cannot meet all the requirements, especially for the electrical and structural applications such as epoxy molding compounds. Thus organic/inorganic materials are frequently employed in order to overcome this limitation. Two separated routes can be followed in order to prepare these hybrid/nanocomposite materials, either the addition of preformed inorganic particles, i.e. layered silicates montmorillonite (MMT), or the in situ growth of siloxane clusters, since both MMT and silica particles are commonly used for the reinforcement of epoxy matrix to lower shrinkage on curing, to decrease coefficient of thermal expansion, to improve thermal conductivity and barrier properties, and to meet mechanical requirements. In order to prepare epoxy based hybrids/nanocomposites materials, the sol-gel method is widely used either to modify preformed nanoparticles (i.e. MMT) or to synthesize siloxane clusters. Therefore, in this study, both organo-siloxane clusters and silylated MMT by sol-gel method were used to prepare epoxy-based hybrids/(nano)composites. Considerable attention was given to the use of coupling agents to make compatible the organic matrix and the inorganic particles and improve the interfacial interactions providing chemical bonds between them. In details the surface modification of Na-MMT was done by the silylation reaction with three different aminosilanes, namely 3-aminopropyltriethoxysilane (A1100), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (A1120) and 3-[2-(2-aminoethylamino)ethylamino]-propyl-trimethoxysilane (A1130). The effects on the Na-MMT d-spacing of three aminosilanes with different chain length were studied in details by combining experimental and computational techniques. Additionally, different routes in terms of reaction temperature and aminosilane concentration was followed to the aim to correlate the final d-spacing between silicates layers and the process parameters. Therefore, with silylated A1100 and A1120 MMT several epoxy-based composites were prepared employing two different dispersion methods, namely the sonication (S) and a combination of sonication and high energy ball-milling (SB). The effect of both the silylation reaction parameters and the dispersion method on the mechanical and thermal properties of composites was evaluated. It was found that the silylation reaction of Na-MMT with aminosilanes is a valuable approach to enhance the interactions between the epoxy matrix and the fillers by means of both the covalent bonds due to the cross-linking reaction and the hydrogen bonding with the hydroxyl groups of opened oxirane rings. In fact, the silylated MMTs provide composites with improved mechanical properties with respect the pristine Na-MMT in terms of increased Tg and elastic modulus in the rubbery region. This improvements is more evident in the sonicated composites since the combination of sonication and ball milling makes compact the interlayer spacing and partially destroys the original layers structures. Additionally the silylated clay composites highlighted an increased fire resistance compared to the pristine epoxy resin as well as to the Na-MMT composite. The effect of both the coupling agent and sol-gel process parameters on the organo-siloxane domains morphology and mechanical properties of epoxy-based hybrids was evaluated. It was found that the use of large amount of γ-Glycidoxypropyltrimethoxysilane (GOTMS) as coupling agent represents an available route to tailor the mechanical and thermal properties of epoxy-based hybrids samples. In details, we demonstrated that a suitable choice of functionalized siloxane monomers, amine hardener and reaction conditions leads to the formation of nano-heterogeneous networks with well-organized cage-like structures, up to nearly homogeneous bicontinuous systems. In fact under particular process parameters GOTMS molecules are able to spontaneously arrange to form structures similar to polyhedral oligomeric silsesquioxane POSS units with well established architecture. Therefore, as the siloxane amount increases the number of cages become high enough to make them bonded with the amine hardener Jeffamine D230. Thus the distance between two neighbouring cages will be determined only by the length of the amine hardener which links them. This ordered arrangement highlighted as distance correlation peak in the SAXS patterns profile of hybrids samples at high siloxane content becomes responsible of the improved thermal and mechanical properties of hybrids samples. In particular, the co-continuous organic-inorganic structure is demonstrated with the achievement of films instead of powders in the pyrolysis experiments. It also affects the viscous-elastic behaviour causing both the Tg and the elastic modulus to increase. Moreover the symmetric shape of the loss factor peak speaks in favour of siloxane structure homogenously dispersed throughout the organic matrix. Whereas the increase of the Tg’s value highlights the strong evidence of hindrance the polymeric chains movements during the glass transition. Hence, only the high siloxane content assures the clusters to be bonded highlighting the improved mechanical properties. To the best of our knowledge it is the first time such cage-like clusters bonded by Jeffamine D230 molecules could be detected assuring the Tg to increase without any phase separation. Moreover, the effect of two amine hardeners, namely MXDA and Jeffamine D230 on the inorganic network morphology and then on the mechanical and thermal properties of hybrid samples was also evaluated. It was found that MXDA is an organic cross-linker faster than the Jeffamine D230, therefore in the MXDA-based hybrids the organic grows more rapidly than the inorganic network, leaving out the GOTMS siloxanes monomers, as the high content of T0 units in MXDA-based hybrids proved. The presence of T0 units is detrimental in the cured hybrids samples, since it causes a dramatic reduction in Tg values. On the contrary, in the Jeffamine-based samples the Tg is markedly increased with respect to the neat epoxy due to their particular organic-inorganic morphology. In fact the Jeffamine is able to bond two neighbouring siloxane cages building up a co-continuous organic-inorganic structure, as the siloxane amount increases.