Disertační práce se zabývá studiem povrchových vlastností jedno a vícevrstvých filmů deponovaných z vinyltriethoxysilanových a tetravinylsilanových monomerů. Zabývá se také charakterizací adheze jednovrstvých filmů z tetravinylsilanu. Plazmaticky polymerizované tenké vrstvy byly připraveny na leštěných křemíkových substrátech pomocí plazmové depozice z plynné fáze za ustálených podmínek. Povrchové vlastnosti vrstev byly charakterizovány pomocí různých metod rastrovací sondové mikroskopie a nanoindentačních technik jako je konvenční a cyklická nanoindentace. Vrypový test byl použit pro charakterizaci vlastností adheze vrstev. Jednovrstvé filmy připravené za různých depozičních podmínek byly charakterizovány s ohledem na povrchové morfologie a mechanické vlastností (modul pružnosti, tvrdost). Výsledky morfologie povrchu, analýzy zrn, nanoindentace, analýzy konečných prvků a modulů mapování pomohly rozlišit hybridní charakter filmů, které byly deponovány při vyšších výkonech RF-výboje. Nový přístup byl použit v povrchové charakterizaci vícevrstvého filmu pomocí rastrovací sondové mikroskopie a nanoindentace. Adhezívní chování plazmaticky polymerizovaných vrstev různých mechanických vlastností a tloušťek bylo analyzováno pomocí normálních a laterálních síl, koeficientu tření, a snímků vrypů získaných pomocí mikroskopie atomárních sil.

Les revêtements composites métal/céramique s'imposent aujourd'hui comme une réponse au fort besoin industriel d'amélioration de la fiabilité des pièces sous sollicitations multiples. Le procédé de projection plasma est envisagé pour la réalisation de tels revêtements avec d'excellentes propriétés tribologiques. Du fait de leur mode d'élaboration, la microstructure des revêtements projetés plasma est complexe et les propriétés en dépendant hétérogènes. Afin d'optimiser le comportement tribologique de ces dépôts, l'objectif de cette étude est d'établir des relations entre microstructure et propriétés tribologiques.<br />Utilisant la souplesse du procédé de projection plasma, notamment celui de projection réactive particulièrement développé pour cette étude, des dépôts composites présentant une large gamme de microstructures ont été obtenus. Pour cela, divers paramètres ont été étudiés : la nature des poudres métalliques projetées (alliages de titane ou de cuivre), la nature du renfort céramique (exogène et/ou endogène), le mode de projection (projection plasma réactive, mode RPS et en surpression, mode HPPS ou co-projection) et les conditions de projection propres à chaque procédé. Une caractérisation des dépôts a été menée, jusqu'à une échelle fine. Le niveau de renforcement de ces microstructures composites fines a été, en particulier, étudié par nanoindentation. Pour chaque mode de projection, deux dépôts composites ont été sélectionnés pour étudier leur comportement tribologique à l'aide d'un essai de frottement de type « pion-disque ». Cet essai a montré une sensibilité élevée à la microstructure et a ainsi permis de déterminer le rôle de certaines caractéristiques microstructurales des dépôts composites sur leurs propriétés tribologiques.<br />A partir d'observations métallographiques et d'analyses des faciès d'usure, un mécanisme d'usure commun aux deux types de dépôts, élaborés par co-projection et par projection réactive, a été mis en évidence. L'influence de la microstructure caractéristique de ces dépôts sur leur comportement tribologique a également été examinée.

Le procédé sol-gel permet l'élaboration aisée de films minces hybrides organiquesinorganiques. Les propriétés mécaniques des matériaux hybrides étudiés sont fixées d'une part par la composition du revêtement et d'autre part par la nature de l'interface entre les composantes organique et inorganique.<br /><br />Cette étude a permis de valider la reproductibilité des mesures de module d'élasticité et de dureté effectuées par nanoindentation sur des matériaux hybrides PMMA–SiO2 par un contrôle efficace des phénomènes viscoélastiques induits par la présence du polymère.<br /><br />Nous avons également étudié l'influence de la morphologie du matériau (c'est-à-dire le rôle de l'interface hybride) sur la réponse mécanique obtenue par nanoindentation ; pour cela, nous avons modifié la nature des interactions établies entre les composantes organique et inorganique. Puis, nous avons modifié la taille de l'interface en modifiant la nature de la composante inorganique.

The enhancement of strength of nanoscale materials such as face-centered cubic metal nanowires is well known and arises largely from processes mediated by high energy surface atoms. This leads to strong size effects in nanoscale plasticity; ,smaller is stronger. Yet, other factors, such as crystalline defects also contribute greatly to the mechanical properties. In particular, twin boundaries, which are pervasive and energetically favorable defects in face-centered cubic metal nanowires, have been shown to greatly enhance the strength, furthermore this increase in strength has been shown to be directly influenced by the twin density. However, attempts to control the introduction of beneficial defects remains challenging. Additionally, even minor local variations in the crystalline structure or size of metal nanowires may have drastic effects on the yielding of metal nanowires, which are difficult to measure through tensile and bending tests. In this study, atomic force microscopy based nanoindentation techniques are used to measure the local plasticity of Ni-Au bimetallic as well as Cu and Ag metallic nanowires. In the first part of the thesis the hardness of bimetallic nanowires synthesized through template-assisted electrodeposition is measured and found to show significant size-effects. It was found that the nanoindentation hardness was governed by materials properties, the observed indentation size effects were dependent on geometrical factors. The second part of this thesis presents a methodology to control the crystal structure of Ag and Cu nanowires through direct electrodeposition techniques, which were tested directly as grown on the substrate to limit effects of pre-straining. Ag nanowires showed marked size-effects as well as two distinct modes of deformation which we attribute to the defects that arise during crystalline growth. We also show control of the surface microstructure in Cu nanowires which leads to strengths that are more than doubled compared to single crystalline Cu nanowires. Finally, we present support from classic crystal growth theory to justify that the observed plasticity in Ag and Cu nanowires is largely dependent on defects that are nucleated through changes in the growth environment.

The surface response of a polymer substrate to external stimuli such as initial wetting is controlled by the outermost molecular layer. Thus, changes on the nanoscale may be engaged to control macroscale wetting behavior. Our work has predominantly focused on surface modification of conventional polyurethane coatings (HMDI-BD-PTMO). Studies on network constrained phase separation and facile polydimethylsiloxane surface functionalization led to the discovery of a simpler one-step and more general approach to functional polymer surfaces that we have designated as “Bottle-Brush Nanoglass” (BB-NG) after the two principle components: (a) a polyoxetane soft block “spine” with side chain “A” bristles and triethoxysilyl chain ends and (b) an alkoxysilane that together with BB chain ends comprise precursors to a “nanoglass”, NG phase. This paper focuses on the extent of modification for a conventional aliphatic polyurethane using a range of fluoropolyoxetane (poly(trifluoroethoxymethyl-methyl oxetane) diol) or 3F diol based modifier concentrations. Upon generating a blend of the polyurethane with the modifier, the BB-NG which is a minor constituent of the blend, phase separates to provide the topmost layer of the coating. Initial results demonstrate that the modified polymer coatings exhibit an expected increase in contact angles with water. Wetting behavior was characterized using the sessile drop technique as well as Dynamic Contact Analysis (DCA, Wilhelmy Plate). Surface composition as well as near surface topology and morphology are characterized by X-ray Photoelectron Spectroscopy (XPS) and Tapping Mode Atomic Force Microscopy (TM-AFM) respectively. Contrast in phase images reflect the surface modulus and viscoelasticity, from which physical form or compositional differences may be deduced. These characteristics have also been explored in our study by hardness tests via nanoindentation.

O presente estudo teve como objetivo realizar uma revisão da literatura para verificar se os novos compostos bioativos presentes no mercado, como CPP-ACP, fosfosilicato de cálcio e sódio e o nitrato de potássio são eficazes na remineralização do esmalte dental clareado. As alterações ocorridas na superfície dental devido ao clareamento são diversas. Dentre elas, pode-se citar a rugosidade, dureza, perda de conteúdo mineral e alterações morfológicas como as mais estudadas. Muitas formas de análises tem sido utilizadas para essas avaliações, porém duas novas técnicas demonstram-se promissoras: o QLF e a nanoidentação. O QLF relaciona-se com a auto fluorescência dental, possuindo vantagens relacionadas a sua especificidade, simples manuseio e preservação do espécime. Já a nanoidentação é capaz de mensurar a dureza em sítios específicos, em uma escala nanométrica, permitindo uma criteriosa seleção da área a ser analisada. Os resultados obtidos não necessitam da mensuração visual da área demarcada pelo identador, o que se torna mais uma vantagem da técnica. Foi conclusivo que a literatura diverge quanto aos resultados apresentados até o momento relacionados aos efeitos do clareamento dental na superfície dental, e os estudos que avaliaram os diversos compostos bioativos apresentam diferentes metodologias que não permitem o estabelecimento de um protocolo de aplicação dos mesmos. Sendo assim, faz-se necessária a realização de novos estudos para avaliar os possíveis efeitos dos diferentes compostos quando da utilização destes como dentifrícios de uso terapêutico após o tratamento clareador. / This study aimed to review the literature and verify if the new bioactive compounds, like CPP-ACP, calcium sodium phosphosilicate and potassium nitrate are effective on the remineralization of the bleached dental enamel. There are several alterations occurred on the dental surface owing to the bleaching procedure. Among them: roughness, microhardness, mineral content loss and morphologic alterations are the most evaluated. Many different analysis have been used to assess the changes in the dental structure, however two of them have shown to be promising: the QLF and the nanoindentation. The QLF is related with the auto fluorescence of the teeth and has advantages related to its specificity, simple manipulation and it is not a destructive technique. On the other hand, the nanoindentation is capable to measure the surface hardness in very specific sites, in a nanometric scale, enabling a criterious selection of the area which will be analyzed. The results obtained by this equipment do not require the visual measure of the impressed area of the indentation, which is one advantage of the methodology. It was conclusive that the literature disagrees of the results presented about the effects of dental bleaching on the enamel surface and the researches that evaluated the bioactive compounds have demonstrated differences in their methodologies. These inconclusive findings interfere on the establishment of an application protocol to those new dentifrices. Thus, it is necessary to develop new researches to better understand the possible effects of the bioactive compounds when the use of these dentifrices are related to a therapeutic use after treatment with bleaching agents.

<p>Li-ion batteries is a system that dynamically couples electrochemistry and mechanics. The electrochemical processes occurring during battery operation induces a wealth of elemental mechanics such as deformation, plasticity, and fracture. Likewise, mechanics influences the electrochemical processes via modulating the thermodynamics of Li reactions and kinetics of ionic transport. These complex interrelated phenomena are far from being well understood and need to be further explored. This thesis studies the couplings between the mechanical phenomena and electrochemical processes in Li-ion batteries using integrated theories and experiments. </p> <p>A continuum model coupling the kinetics of Li diffusion and kinematics of large elasto-plastic deformation is established to investigate the coupling between Li transport and stress evolution in electrodes of Li-ion batteries. Co-evolutions of Li distribution, stress field and deformation in the electrodes with multiple components are obtained. It is found that the Li profile and stress state in a composite electrode are significantly different from <a></a><a>that </a>in a free-standing configuration, mainly due to the regulation from the mechanical interactions between different components. Chemomechanical behaviors of the heterogeneous electrodes in real batteries are further explored. Three-dimensional reconstructed models are employed to investigate the mechanical interactions of the constituents and their influence on the accessible capacity of batteries. </p> <p>Structural disintegration of the state-of-art cathode materials LiNi_xMn_yCo_zO₂ (x+y+z=1, NMC) during electrochemical cycling is experimentally revealed. Microstructural evolution of different marked regimes in electrodes are tracked before and after lithiation cycles. It is found that the decohesion of primary particles constitutes the major mechanical degradation in the NMC materials. Electrochemical impedance spectroscopy (EIS) measurement confirms that the mechanical disintegration of NMC secondary particle causes the electrochemical degradation of the battery. To reveal the reasons for particle disintegration, the dynamic evolution of mechanical properties of NMC during electrochemical cycling is explored by using instrumented nanoindentation. It is found that the elastic modulus, hardness, and interfacial fracture strength of NMC secondary particle significantly depend on the lithiation state and degrade as the electrochemical cycles proceed, which may cause the damage accumulation during battery cycling.</p> <p>Corrosive fracture of electrodes in Li-ion batteries is investigated. Li reaction causes embrittlement of the host material and typically results in a decrease of fracture toughness. The dynamics of crack growth depends on the chemomechanical load, kinetics of Li transport, and the Li embrittlement effect. A theory of coupled diffusion, large deformation, and crack growth is implemented into finite element program and the corrosive fracture of electrodes under concurrent mechanical and chemical load is simulated. The competition between energy release rate and fracture resistance as crack grows during both Li insertion and extraction is examined in detail, and it is found that the corrosive fracture behaviors of the electrodes rely on the chemomechanical load and the supply of Li to the crack tip. The theory is further applied to model corrosive behavior of intergranular cracks in NMC upon Li cycles. The evolving interfacial strength at different states of charge and different cycle numbers measured by in-situ nanoindentation is implemented in the numerical simulation.</p>

The fast progress in the exploration of 2D materials such as graphene became possible due to development of fabrication techniques that allowed these materials to be protected from e.g. undesirable doping and gave rise to new functionalities realized within van der Waals heterostructures. Attracted by van der Waals interaction the constituent layers of such heterostructures preserve their exceptional electronic quality and for example in graphene allow for high electron mobility to be achieved. However, the studies of atomically thin layers such as NbSe2 that exhibit metallic behavior have been impeded by their reactivity and hence oxidation during exposure to ambient or oxidizing agents such as solvents. In this thesis, the existing heterostructure assembly technique was improved by the introduction of exfoliation and re-stacking by a fully motorized system placed in an inert atmosphere. This approach allowed us to overcome the problem of environmental degradation and create Hall bars and planar tunnel junctions from atomically thin superconducting NbSe2. Furthermore, this versatile approach allowed us to study the thickness dependence of the normal and superconducting state transport properties of NbSe2, uncovering the reduction of the superconducting energy gap and transition temperature in the thinnest samples. On the other hand, 2D materials being just 1-3 atoms thick represent an ultimate example of a membrane - thin but laterally extended object. Consisting of such atomically thin membranes the van der Waals heterostructures can be used for purposes other than the studies of electronic transport. In this work, ubiquitous bubbles occurring during van der Waals heterostructure assembly are employed as a tool to explore 2D materials' mechanical properties and mutual adhesion. This allowed us to measure Young's modulus of graphene and other 2D materials under 1-2% strain and deduce the internal pressure that can reach up to 1 GPa in sub-nanometer size bubbles.

Zirconium alloys (zircaloy) have been widely used in light water reactors due to their good thermomechanical properties, corrosion resistance, and low thermal neutron absorption rate. As one of the most important safety barriers, cladding is not only used to encapsulate nuclear fuel, but also to prevent the nuclear fission products from leaking into the coolant. During the operation of nuclear reactors, hydride will form in zircaloy and significantly degrade the tensile strength, ductility, fracture toughness, and creep behavior of the cladding, and eventually leading to the failure of cladding. Therefore, understanding the material properties of zircaloy and its hydrides is crucial to the safety of power plants. In this study, the mechanical Raman spectroscopy and nano-mechancial testing techniques were used to perform thermomechanical measurements and damage analysis of zircaloy-4. The Raman thermometry method was used to measure localized spatially resolved thermal conductivity and establish the potential linkage of microstructure to thermal and mechanical properties of zircaloy-4. The local thermal conductivity values showed to increase with increase in grain size. Nanoindentation and nano-scale impact techniques were used to obtain the viscoplastic constitutive relation of hydrides at elevated temperatures. Based on the obtained viscoplastic model, fracture strength of hydrides was predicted by using finite element method (FEM) simulations. An extended Gurson-Tvergaard-Needleman (GTN) model was used to study the macro-scale fracture behavior of hydrided zircaloy-4 structures. Good agreement between calculated and experimental results was obtained for various boundary conditions.

Mechanical surface treatments using an elastic-plastic cold working process can develop residual stresses on the surface of a workpiece. Compressive residual stresses on the surface increase resistance against surface crack propagation, so the overall mechanical performance can be improved by this technique. Compressive residual stresses can be created by different methods such as hammering, rolling, and shot peening. Shot peening is a well-established method to induce compressive residual stresses in the metallic components using cold working, and often ascribed to being beneficial to fatigue life in the aerospace and automobile industries. In this method, the surface is bombarded by high-velocity spherical balls which cause plastic deformation of the substrate, leading to a residual compressive stress after shot peening on the surface of the part. Computational modeling is an appropriate and effective way which can predict the amount of produced residual stresses and plastic deformation to obtain surface roughness after shot peening simulation. Finally, an experimental method to measure the magnitude of the residual stress using a nanoindentation technique was developed. The experimental indentation method was compared to both computational predictions (in aluminum) and with x-ray diffraction measurements of stress (in an alloy steel). The current study validates the relation between the nanoindentation method and numerical simulation for assessing the surface residual stresses resulting from single or multiple shot peening processes.