Les microcantileviers fonctionnalisés offrent une plateforme idéale pour la nano- et micro-mécanique et pour le développement de (bio-) capteurs tres sensible. Le principe d’opération consiste dans des évènements physicochimiques qui se passent du côté fonctionnalisé du microcantilevier induisant une différence de stress de surface entre les deux côtés du cantilevier qui cause une déflexion verticale du levier. Par contre, les facteurs et les phénomènes interfacials qui régissent la nature et l'intensité du stress de surface sont encore méconnus. Pour éclaircir ce phénomène, la première partie de cette thèse porte sur l'étude des réactions de microcantileviers qui sont recouverts d'or et fonctionnalisés par une monocouche auto-assemblée (MAA) électroactive. La formation d'une MAA de ferrocènylundécanethiol (FcC11SH) à la surface d'or d'un microcantilevier est le modèle utilisé pour mieux comprendre le stress de surface induit par l’électrochimie. Les résultats obtenus démontrent qu'une transformation rédox de la MAA de FcC11SH crée un stress de surface qui résulte dans une déflexion verticale du microcantilevier. Dépendamment de la flexibilité du microcantilevier, cette déflexion peut varier de quelques nanomètres à quelques micromètres. L’oxydation de cette MAA de FcC11SH dans un environnement d'ions perchlorate génère un changement de stress de surface compressive. Les résultats indiquent que la déflexion du microcantilevier est due à une tension latérale provenant d'une réorientation et d'une expansion moléculaire lors du transfért de charge et de pairage d’anions. Pour vérifier cette hypothèse, les mêmes expériences ont été répéteés avec des microcantileviers qui ont été couverts d'une MAA mixte, où les groupements électroactifs de ferrocène sont isolés par des alkylthiols inactifs. Lorsqu’un potentiel est appliqué, un courant est détecté mais le microcantilevier ne signale aucune déflexion. Ces résultats confirment que la déflexion du microcantilevier est due à une pression latérale provenant du ferrocènium qui se réorganise et qui crée une pression sur ses pairs avoisinants plutôt que du couplage d’anions. L’amplitude de la déflexion verticale du microcantilevier dépend de la structure moléculaire de la MAA et du le type d’anion utilisés lors de la réaction électrochimique. Dans la prochaine partie de la thèse, l’électrochimie et la spectroscopie de résonance de plasmon en surface ont été combinées pour arriver à une description de l’adsorption et de l’agrégation des n-alkyl sulfates à l’interface FcC11SAu/électrolyte. À toutes les concentrations de solution, les molécules d'agent tensio-actif sont empilées perpendiculairement à la surface d'électrode sous forme de monocouche condensé entrecroisé. Cependant, la densité du film spécifiquement adsorbé s'est avérée être affectée par l'état d'organisation des agents tensio-actifs en solution. À faible concentration, où les molécules d'agent tensio-actif sont présentes en tant que monomères solvatés, les monomères peuvent facilement s'adapter à l’évolution de la concentration en surface du ferrocènium lors du balayage du potential. Cependant, lorsque les molécules sont présentes en solution en tant que micelles une densité plus faible d'agent tensio-actif a été trouvée en raison de l'incapacité de répondre effectivement à la surface de ferrocenium générée dynamiquement. / Surface-functionalized microcantilevers provide an ideal platform for nano- and micro-mechanical actuation and highly sensitive sensing technologies. The basic principle of operation is that a chemical or physical event occurring at the functionalized surface of one side of the cantilever generates a surface stress difference (between the active functionalized and passive non-functionalized sides) that causes the cantilever to bend away from its resting position. However, the factors and phenomena contributing to both the nature and magnitude of the surface stress are not well understood. To this end, the first part of this thesis focused on investigating the potential-controlled actuation and surface stress properties of free-standing gold-coated microcantilevers functionalized with a redox-active self-assembled monolayer (SAM). A ferrocenylundecanethiolate (FcC11SAu) SAM on a gold-coated cantilever was used as a model system to investigate the surface stress generated by faradaic chemistry. The data obtained clearly demonstrates that the electrochemical transformation of a ferrocene moiety in a monomolecular organic film can generate a surface stress change of sufficient magnitude to deflect a microcantilever. In fact, depending on the flexibility of the microcantilever, the mechanical deflection resulting from the redox transformation of the surface-tethered ferrocene can range on the order of nanometers to micrometers. The oxidation of the FcC11SAu SAM in perchlorate electrolyte generates a compressive surface stress change. The microcantilever deflection is driven by the lateral tension resulting from molecular reorientation/volume expansion accompanying the charge-transfer and ion-pairing events. To verify this hypothesis, mixed SAM-modified microcantilevers, in which the electroactive ferrocenes are isolated from one another by an inert n-alkylthiolate matrix, were investigated. Under an applied potential, a Faradaic current was measured, but no microcantilever beam deflection was observed. This finding confirms that the cantilever responds to the lateral pressure exerted by an ensemble of re-orienting ferrocenium-bearing alkylthiolates upon each other rather than to individual anion pairing events. Changes in molecular structure and anion type can also be used to modulate the extent of micromechanical motion. In the next part of the dissertation, electrochemical measurements and surface plasmon resonance spectroscopy were combined to present a description of the adsorption and aggregation of n-alkyl sulfates at the FcC11SAu/electrolyte interface. At all bulk solution concentrations, the surfactant moieties packed perpendicular to the electrode surface in the form of an interdigitated condensed film. However, the density of the specifically adsorbed film was found to be affected by the organizational state of the surfactants in solution. At low concentrations, where the surfactant molecules are present as solvated monomers, the monomers can readily adapt to the changing ferrocenium concentration with the potential potential scan. However, when the molecules are present as micellar structures in solution, a lower surfactant packing density was found because of the inability to respond effectively to the dynamically generated surface ferroceniums. This research demonstrates the potential utility of charge-transfer interactions for organizing materials at solid interfaces and effecting micromechanical actuation using an electrifical stimulus.

This thesis presents a numerical exploration of the dynamics governing rotating flow driven by a surface stress in the " sliced cylinder " model of Pedlosky & Greenspan (1967) and Beardsley (1969), and its close relative, the " sliced cone " model introduced by Griffiths & Veronis (1997). The sliced cylinder model simulates the barotropic wind-driven circulation in a circular basin with vertical sidewalls, using a depth gradient to mimic the effects of a gradient in Coriolis parameter. In the sliced cone the vertical sidewalls are replaced by an azimuthally uniform slope around the perimeter of the basin to simulate a continental slope. Since these models can be implemented in the laboratory, their dynamics can be explored by a complementary interplay of analysis and numerical and laboratory experiments. ¶ In this thesis a derivation is presented of a generalised quasigeostrophic formulation which is valid for linear and moderately nonlinear barotropic flows over large-amplitude topography on an f-plane, yet retains the simplicity and conservation properties of the standard quasigeostrophic vorticity equation (which is valid only for small depth variations). This formulation is implemented in a numerical model based on a code developed by Page (1982) and Becker & Page (1990). ¶ The accuracy of the formulation and its implementation are confirmed by detailed comparisons with the laboratory sliced cylinder and sliced cone results of Griffiths (Griffiths & Kiss, 1999) and Griffiths & Veronis (1997), respectively. The numerical model is then used to provide insight into the dynamics responsible for the observed laboratory flows. In the linear limit the numerical model reveals shortcomings in the sliced cone analysis by Griffiths & Veronis (1998) in the region where the slope and interior join, and shows that the potential vorticity is dissipated in an extended region at the bottom of the slope rather than a localised region at the east as suggested by Griffiths & Veronis (1997, 1998). Welander's thermal analogy (Welander, 1968) is used to explain the linear circulation pattern, and demonstrates that the broadly distributed potential vorticity dissipation is due to the closure of geostrophic contours in this geometry. ¶ The numerical results also provide insight into features of the flow at finite Rossby number. It is demonstrated that separation of the western boundary current in the sliced cylinder is closely associated with a " crisis " due to excessive potential vorticity dissipation in the viscous sublayer, rather than insufficient dissipation in the outer western boundary current as suggested by Holland & Lin (1975) and Pedlosky (1987). The stability boundaries in both models are refined using the numerical results, clarifying in particular the way in which the western boundary current instability in the sliced cone disappears at large Rossby and/or Ekman number. A flow regime is also revealed in the sliced cylinder in which the boundary current separates without reversed flow, consistent with the potential vorticity " crisis " mechanism. In addition the location of the stability boundary is determined as a function of the aspect ratio of the sliced cylinder, which demonstrates that the flow is stabilised in narrow basins such as those used by Beardsley (1969, 1972, 1973) and Becker & Page (1990) relative to the much wider basin used by Griffiths & Kiss (1999). ¶ Laboratory studies of the sliced cone by Griffiths & Veronis (1997) showed that the flow became unstable only under anticyclonic forcing. It is shown in this thesis that the contrast between flow under cyclonic and anticyclonic forcing is due to the combined effects of the relative vorticity and topography in determining the shape of the potential vorticity contours. The vorticity at the bottom of the sidewall smooths out the potential vorticity contours under cyclonic forcing, but distorts them into highly contorted shapes under anticyclonic forcing. In addition, the flow is dominated by inertial boundary layers under cyclonic forcing and by standing Rossby waves under anticyclonic forcing due to the differing flow direction relative to the direction of Rossby wave phase propagation. The changes to the potential vorticity structure under strong cyclonic forcing reduce the potential vorticity changes experienced by fluid columns, and the flow approaches a steady free inertial circulation. In contrast, the complexity of the flow structure under anticyclonic forcing results in strong potential vorticity changes and also leads to barotropic instability under strong forcing. ¶ The numerical results indicate that the instabilities in both models arise through supercritical Hopf bifurcations. The two types of instability observed by Griffiths & Veronis (1997) in the sliced cone are shown to be related to the western boundary current instability and " interior instability " identified by Meacham & Berloff (1997). The western boundary current instability is trapped at the western side of the interior because its northward phase speed exceeds that of the fastest interior Rossby wave with the same meridional wavenumber, as discussed by Ierley & Young (1991). ¶ Numerical experiments with different lateral boundary conditions are also undertaken. These show that the flow in the sliced cylinder is dramatically altered when the free-slip boundary condition is used instead of the no-slip condition, as expected from the work of Blandford (1971). There is no separated jet, because the flow cannot experience a potential vorticity " crisis " with this boundary condition, so the western boundary current overshoots and enters the interior from the east. In contrast, the flow in the sliced cone is identical whether no-slip, free-slip or super-slip boundary conditions are applied to the horizontal flow at the top of the sloping sidewall, except in the immediate vicinity of this region. This insensitivity results from the extremely strong topographic steering near the edge of the basin due to the vanishing depth, which demands a balance between wind forcing and Ekman pumping on the upper slope, regardless of the lateral boundary condition. The sensitivity to the lateral boundary condition is related to the importance of lateral friction in the global vorticity balance. The integrated vorticity must vanish under the no-slip condition, so in the sliced cylinder the overall vorticity budget is dominated by lateral viscosity and Ekman friction is negligible. Under the free-slip condition the Ekman friction assumes a dominant role in the dissipation, leading to a dramatic change in the flow structure. In contrast, the much larger depth variation in the sliced cone leads to a global vorticity balance in which Ekman friction is always dominant, regardless of the boundary condition.

The demand for flat glass is high and increasing significantly in the building industry as a direct result of architectural requirements for lightness, transparency and natural light. Current architectural trends require glass in curvilinear forms for smooth free-form façades. Two principal challenges arise from this: to cost-effectively produce the desired curvature and; to ensure its safe performance after exposure to ageing. The recent availability of high strength glass provides an opportunity to address the first challenge by developing cold bent glass. Cold bending involves the straining of relatively thin glass components, at ambient temperatures, and is a low energy and cost effective manner of creating curvilinear forms. However, cold bending is not yet widely established as a reliable method. The aim of this thesis is to develop the understanding of cold bent glass during the bending process and to evaluate its post-ageing performance. This thesis, firstly, investigates the mechanical response of monolithic glass plates during the cold bending process. The stability of cold bent glass is investigated experimentally by bending it in double curved anticlastic shapes. A parametric numerical analysis involves different boundary conditions, geometrical plate characteristics and bending parameters. The principal outcome is that a local instability, now termed cold bending distortion, occurs when certain displacement limits are exceeded and could degrade the optical quality of the glass. An evaluation procedure is also formulated to set limits and aid designers/manufacturers to predict the mechanical response and the optical quality of the glass. Cold bent glass is subjected to permanent bending stresses throughout its service life and therefore, its strength degradation after ageing needs to be quantified. Analytical, experimental and numerical investigations are undertaken in this thesis to identify the most effective method for estimating glass strength (evaluation of destructive tests, required number of specimens, statistical analysis methods and sub-critical crack growth). The limited availability of naturally aged toughened glass and the absence of a reliable ageing standard impede the evaluation of its aged performance. Therefore, a parametric experimental investigation of artificial ageing methods on glass is undertaken in this thesis. A procedure for the evaluation of the strength of aged glass is finally, formulated to allow the selection of artificial ageing parameters that correspond to a target level of erosion. The knowledge on artificial ageing and strength prediction acquired above is finally implemented on different types of glass to determine their strength after ageing and assess their safe use in cold bending / load bearing applications. The investigation showed that fully toughened glass has a superior performance to chemically toughened or annealed glass. Overall, the research presented in this thesis demonstrates that high quality cold bent toughened glass can be created when certain applied displacement limits are respected. These can be used as a safe, cost-effective and energy efficient replacement to the more conventional hot bent glass. However, cold bending / load bearing applications in which the stressed glass surface is exposed to ageing, require glass with a relatively high case depth such as fully toughened or bi-tempered glass.