Polymer Nanocomposites (PNC) are a new class of materials characterized by their large interfacial areas between the host polymer and nanofiller. This unique feature, due to the size of the nanofiller, is understood to be the cause of enhanced mechanical, electrical, optical, and barrier properties observed of PNCs, relative to the properties of the unfilled polymer. This interface can determine the miscibility of the nanofiller in the polymer, which, in turn, influences the PNC's properties. In addition, this interface alters the polymer's structure near the surface of the nanofiller resulting in heterogeneity of local properties that can be expressed at the macroscopic level. Considering the polymer-nanoparticle interface significantly influences PNC properties, it is apparent that some atomistic level of detail is required to accurately predict the behavior of PNCs. Though an all-atom simulation of a PNC would be able to accomplish the latter, it is an impractical approach to pursue even with the most advanced computational resources currently available. In this contribution, we develop (1) an equilibrium coarse-graining method to predict nanoparticle dispersion in a polymer melt, (2) a dynamic coarse-graining method to predict rheological properties of polymer-nanoparticle melt mixtures, and (3) a numerical approach that includes interfacial layer effects and polymer rigidity when predicting barrier properties of PNCs. In addition to the above, we study how particle and polymer characteristics affect the interfacial layer thickness as well as how the polymer-nanoparticle interface may influence the entanglement network in a polymer melt. More specifically, we use a mean-field theory approach to discern how the concentration of a semiflexible polymer, its rigidity and the particle's size determine the interfacial layer thickness, and the scaling laws to describe this dependency. We also utilize molecular dynamics and simulation techniques on a model PNC to determine if the polymer-nanoparticle interaction can influence the entanglement network of a polymer melt. / text

Le procédé sol-gel permet la réalisation de matériaux optiquement performants et la possibilité d'intégrer diverses molécules dans ces systèmes ouvre les portes à des applications dans de nombreux domaines. Nous nous sommes intéressés en particulier à la réalisation de matériaux sol-gel monolithiques, fortement dopés avec des molécules actives, dans le cadre de la réalisation de limiteurs optiques performants dans le visible et dans l'infrarouge.La mise au point de procédés et de matrices sol-gel compatibles avec divers types de chromophores a tout d'abord été effectuée. Une investigation des paramètres expérimentaux et de la nature des précurseurs influençant la microstructure des matériaux a été réalisée, ainsi que la mise au point de méthodes de gélification accélérée capables de piéger efficacement les chromophores dans les matrices sol-gel même à de très hautes concentrations.Le dopage des matrices obtenues avec différents chromophores pour la limitation optique dans le visible et dans l'infrarouge s'en est suivi, avec une étude de l'impact des matrices sur les propriétés optiques des dopants. L'évaluation des performances en limitation a révélé les performances exceptionnelles des systèmes étudiés dans le visible, et des résultats prometteurs pour l'infrarouge.Enfin, la synthèse de nanoparticules d'or isotropes et anisotropes et leur incorporation dans les matériaux préparés a permis de mettre en évidence des effets d'exaltation importants sur les propriétés non-linéaires des chromophores au sein des matrices sol-gel et permettent d'améliorer les performances en limitation de manière considérable.

<p>The fascinating optical properties of metallic nanostructures, dominated by collective oscillations of free electrons known as plasmons, open new opportunities for the development of devices fabrication based on noble metal nanoparticle composite materials. This thesis demonstrates a low-cost and versatile technique to produce stimuli-responsive ultrafast plasmonic nanostructures with reversible tunable optical properties. Albeit challenging, further control using thermal external stimuli to tune the local environment of gold nanoparticles embedded in VO2 host matrix would be ideal for the design of responsive functional nanocomposites. We prepared Au-VO2 nanocomposite thin films by the inverted cylindrical reactive magnetron sputtering (ICMS) known as hollow cathode magnetron sputtering for the first time and report the reversible tuning of surface plasmon resonance of Au nanoparticles by only adjusting the external temperature stimuli. The structural, morphological, interfacial analysis and optical properties of the optimized nanostructures have been studied. ICMS has been attracting much attention for its enclosed geometry and its ability to deposit on large area, uniform coating of smart nanocomposites at high deposition rate. Before achieving the aforementioned goals, a systematic study and optimization process of VO2 host matrix has been done by studying the influence of deposition parameters on the structural, morphological and optical switching properties of VO2 thin films. A reversible thermal tunability of the optical/dielectric constants of VO2 thin films by spectroscopic ellipsometry has been intensively also studied in order to bring more insights about the shift of the plasmon of gold nanoparticles imbedded in VO2 host matrix.</p>

Mixed matrix membranes (MMMs) consisting of a polymer bulk phase and an inorganic dispersed phase have the potential to provide a more selective membrane because they incorporate the selectivity of a zeolite dispersed phase while maintaining the ease of use of a polymer membrane. A critical problem in MMM applications is control over the polymer-zeolite interface adhesion during fabrication which can detrimentally impact membrane performance. In this work, MgOxHy (1≤x≤2, 0≤y≤2) nanostructures have been grown on pure-silica MFI and aluminosilicate LTA zeolites through four surface deposition techniques: Grignard decomposition reactions, solvothermal and modified solvothermal depositions, and ion-exchange induced surface crystallization. The structural properties of the surface nanostructures produced by each of the four methods were thoroughly characterized for their morphology, crystallinity, porosity, surface area, elemental composition, and these properties were used to predict the method’s suitability for use in composite membranes. The nanostructured zeolites were used in mixed matrix membranes (MMMs) at two MMMs weight loadings. The dispersion, mechanical properties, and CO₂/CH₄ gas separation properties were measured MMMs made with each method of functionalized LTA. All functionalization methods improve adhesion with the polymer observable by microscopy, the dispersion of particles, and the elastic modulus and hardness of the membrane. Gas permeation measurements prove the quality and effectiveness of the Ion Exchange membrane for CO₂/CH₄ separation by its significant increase in selectivity over the pure polymer. Lastly, the interface between the two materials was studied by probing the interfacial polymer mobility using NMR spin-spin relaxation measurements and mechanical mapping of membrane cross sections. It was shown that the nanostructures have both steric and chemical interactions with the polymer. Mapping of the elastic modulus indicated that functionalization methods that resulted in poorer zeolite coverage also disrupted the mechanical properties of the membrane at the interface of the materials. The investigations in this thesis provide detailed structure-property relationships of surface-modified molecular sieves and nanocomposite membranes fabricated using these materials, allowing a rational approach to the design of such materials and membranes.

This thesis is divided into two parts, experimental part presenting the synthesis of exchange spring magnets and theoretical part showing the magnetization dynamics of exchange spring magnets. For the synthesis, ferrite and metal alloy based magnets using mechanical milling and ultrasonic mixing are studied. This part discusses the difficulty in controlling the microstructure during synthesis. Several samples with varying volume fractions of the soft phase are synthesized. It is found that mechanical milling initiates a reaction and this leads to disintegration of the ferrite phase into its intermediate phases. Samples prepared using ultrasonic mixing however show presence of the ferrite phase up to very large volume fraction of the soft alloy phase which provides better perspective for the synthesis. Dynamics of the exchange spring system is studied theoretically using micromagnetic theory. Microwave assisted magnetization reversal are studied in the bulk bilayer exchange coupled system. We investigate the nonlinear magnetization reversal dynamics in a perpendicular exchange spring media using the Landau-Lifshitz equation. In the limit of the infinite thickness of the system, the propagation field leads the reversal of the system. The reduction of the switching field and the magnetization profile in the extended system are studied numerically. The possibility to study the dynamics analytically is discussed and an approximation where two P-modes are coupled by an interaction field is presented. The ansatz used for the interaction field is validated by comparison with the numerical results. This approach is shown to be equivalent to two exchange coupled macrospins.

The exceptional properties of carbon nanomaterials make them ideal reinforcements for polymers. However, the main challenges in utilizing their unique properties are their tendency to form agglomerates, their non-controlled orientation, non-homogeneous distribution and finally the change in their shape/size due to processing. All the above are the result of the nanomaterial/polymer interfacial interactions which dictate the overall performance of the composites including the mechanical properties. The aforementioned uncertainties are the reason for the deviation observed between the experimentally determined properties and the theoretically expected ones. The focus of this study is to understand the reinforcing efficiency of carbon nanomaterials in polymers through finite element modeling that captures the effect of the interfacial interactions on the tensile modulus of polymer nanocomposites (PNCs). The novelty of this work is that the probability distribution functions of nanomaterials dispersion, distribution, orientation and waviness, determined through image analysis by extracting 3-D information from 2-D scanning electron micrographs, are incorporated into the finite element model allowing thus for fundamental understanding of how the nanostructure parameters affect the tensile modulus of the PNCs. The nanocomposites are made using melt mixing followed by either injections molding or melt spinning of fibers. Polypropylene (PP) is used as the polymer and carbon nanotubes (CNT) or exfoliated graphite nanoplatelets (xGnP) are used as nanoreinforcements. The presence of interphase, confirmed and characterized in terms of stiffness and width using atomic force microscopy, is also accounted for in the model. The dispersion and distribution of CNT within the polymer is experimentally altered by using a surfactant and by forcing the molten material to flow through a narrow orifice (melt spinning) that promotes alignment of CNT and even of the polymer chains along the flow/drawing direction. The effect of nanomaterials' geometry on the mechanical behavior of PNCs is also studied by comparing the properties of CNT/PP to those of xGnP/PP composites. Finally the reinforcing efficiency of CNT is determined independently of the viscoelastic behavior of the polymer by conducting tensile testing at temperatures below the glass transition temperature of PP. The finite element model with the incorporated image analysis subroutine has sufficient resolution to distinguish among the different cases (dispersion, distribution, geometry and alignment of nanomaterials) and the predicted tensile modulus is in agreement with the experimentally determined one. In conclusion, this study provides a tool, that integrates finite element modeling and thorough experiments that enables design of polymer nanocomposites with engineered mechanical properties.

Certains problèmes d'audition trouvent leur origine dans des anomalies de transmission de l'énergie des vibrations acoustique par la chaîne des osselets de l'oreille moyenne. Il se pratique aujourd'hui des opérations chirurgicales visant à la reconstruire. Un outil permettant d'évaluer la qualité de transmission des vibrations par de la chaîne ossiculaire pendant l'opération apporterait une aide substantielle au praticien afin dans le but d'optimiser la configuration des osselets. Les travaux présentés dans ce manuscrit traitent de la conception d'un capteur microsystème adapté à la mesure de l'amplitude de vibrations des osselets. Nous y avons particulièrement développé les travaux de modélisation de la structure mécanique du capteur. Il s'agit d'une structure communément employée pour les capteurs tactiles dont nous modélisons le comportement en régime harmonique. Dans une la deuxième partie nous présentons une étude d'optimisation du capteur en vue de son utilisation " tenu en main " par le chirurgien. Celle-ci repose notamment sur l'utilisation d'un modèle électrique équivalent de l'oreille moyenne et d'un logiciel d'optimisation multicritères. Nous présentons dans cette partie un concept de filtre mécanique des basses fréquences par l'utilisation des propriétés viscoélastiques des matériaux polymères. La dernière partie traite des travaux de réalisation des différents composants d'un capteur basé sur les matériaux polymères. Les travaux de réalisation et de test de membranes en résine SU8 y sont présentés ainsi que l'intégration de jauges en matériaux électroactifs chargés en nanoparticules. L'utilisation d'une technique de moule perdu pour réaliser la structure mécanique du capteur est discutée.

Ce mémoire est essentiellement consacré à la synthèse électrochimique et à la caractérisation structurale de matériaux composites d'électrode nanostructurés du type polymère fonctionnalisé contenant une dispersion homogène de nanoparticules d'oxydes de ruthénium ou d'iridium, ainsi qu'à l'étude de leurs propriétés électrocatalytiques vis-à-vis de l'oxydation en milieu aqueux de l'arsenic(III) en arsenic(V). La combinaison de l'oxydation électrocatalytique de l'arsenic(III) avec la technique d'ultrafiltration LPR (Liquid phase Polymer-assisted Retention) nous a permis de confirmer tout l'intérêt de cette approche combinée pour éliminer l'arsenic. Dans ce processus, les matériaux nanocomposites à base d'oxyde d'iridium ont montré les propriétés les plus intéressantes, car ils sont capables de catalyser l'oxydation de l'arsénite en milieu neutre et à des potentiels peu positifs. Enfin, les matériaux d'électrode nanostructurés à base d'oxyde d'iridium sont également efficaces pour l'oxydation catalytique à 4 électrons de l'eau en dioxygène et présentent donc un fort intérêt potentiel dans le contexte de la réaction de dissociation de l'eau. Mots clés : oxyde de ruthénium, oxyde d'iridium, nanocomposite, électrocatalyse, arsenic, ultrafiltration, oxydation de l'eau

Liées de façon covalente à des chaînes polymères, les nanoparticules POSS (polysilses-quioxanes polyédriques) permettent l'obtention de matériaux nanocomposites hybrides orga-nique/inorganique. Ces nanoparticules présentent deux intérêts majeurs: des dimensions bien définies (cœur inorganique: 0.5 nm), ainsi que leur caractère hybride ( groupements organiques entourant les cages inorganiques). Les nanocomposites polymère/POSS peuvent présenter un renfort important des propriétés mécaniques et de la stabilité thermique de la matrice polymère. Cependant, l'origine moléculaire de ce renfort reste mal comprise. Aussi, afin de mieux comprendre le renfort des propriétés mécaniques de la matrice, nous avons étudié l'effet des particules POSS sur l'organisation à l'état solide et la dynamique des chaînes po-lymères au sein d'une matrice semi-cristalline. Pour cela, nous avons considéré une série de copolymères polyéthylène-POSS, caractérisés par une large gamme de concentration en POSS. Le polyéthylène et le POSS ayant intrinsèquement tendance à cristalliser, les copolymères présentent des organisations à l'état solide complexes que nous avons caractérisés par l'utilisation combinée de la calorimétrie différentielle à balayage (DSC), de la diffraction des rayons X aux grands angles (DRX) et de la résonance magnétique nucléaire en phase solide (RMN). Dans un second volet de cette étude, nous nous sommes intéressés à la dynamique des chaînes de polyéthylène en phase amorphe et à l'évolution de celle-ci avec le taux de charge des nanocomposites. Enfin, nous avons également étudié, de façon sélective, la dynamique des segments de chaînes de polyéthylène situés au voisinage de la charge

Nanoemulsions are templates that have the potential to fill the gap between micellar systems and latex particles in the preparation of porous materials. A nanoemulsion can also be used as a carrier for uploading the desired materials inside the pore formed after the removal of the template. In this research, oil-in-water (O/W) nanoemulsions were prepared by means of a low-energy method based on a phase inversion composition (PIC) technique, using two nonionic surfactants (Tween 80 and Span 80), which can be mixed in order to adjust the hydrophilic-lipophilic balance (HLB). The influence of a number of parameters on the tunability and stability of such nanoemulsions was also studied. The effect of the simultaneous intercrossing of multifactors on droplet size was explored using a process- mixture design, and the size of the nanoemulsion oil droplets was measured by means of dynamic light scattering (DLS). The nanoemulsions were combined with sol-gel method in order to prepare porous silica with a macroporosity in the 50 nm to 400 nm range. The results demonstrate that a precise synergy between the silica source and the nanoemulsions is essential for effective interactions and homogeneous structures. Depending on the nature of such interactions, a variety of materials were observed, from hollow particles to continuous gels. Changing the size of the oil droplet and the volume of the nanoemulsions produced silica with differing pore sizes and varying total pore volumes. The obtained hierarchical porous silica (HPS) were characterized using mercury porosimetry, small angle X-ray scattering (SAXS), nitrogen isotherms, Fourier transform infrared (FTIR) analysis, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The parallel use of the oil vesicles as containers for the further synthesis of metal oxide is a novel method of internally functionalizing the silica. When hydrophobic metal precursors are dissolved into the oil phase before the preparation of the nanoemulsion, they are confined within the globular cavities of the silica. The thermal treatment applied to the material to burn the organics then leads to the final formation of metal oxide nanoparticles, which are larger than the porosity of the silica matrix but entrapped within the large cavities, producing a "rattle-like" structure. This method was demonstrated through the synthesis of Fe2O3, Fe3O4, and Co3O4 nanoparticles, and the results showed that a rather large amount of metal oxide (up to a 60 wt.% of metal oxide in nanocomposites) be generated while still maintaining the nanometric size observed at lower concentrations. This method allows control of the type of metal oxide, the concentration of the metal oxide, and the pore size, which enables the creation of different types of nanocomposites. Metal oxide hierarchical porous silica (MHPS) nanocomposites were characterized based on nitrogen isotherms, TEM and SEM observations, FTIR analysis, X-ray diffraction (XRD), and Mossbauer spectroscopy. Magnetic measurements were also taken. This new method, using the new templating objects, is a perfect illustration of the concept of "integrative synthesis,??? whereby the combination of building units and reactional mechanisms leads to complex structures as a result of true synergy among the elements during the reaction. In this case, the size of the nanoemulsion and the total water volume both contribute to the generation of distinctive architectures. In addition, the reaction of the metal oxide precursors within the cavities limits the extension of the final crystal size, but the surrounding solid matrix plays a role as well by keeping the particles apart. The final factor is that the reactive materials cannot leak from the silica because of the rattle-like structure, but the reagents can reach those particles through the porosity of the silica framework.