Une nouvelle méthode de détection sans marquage des interactions biomoléculaires a été développée. Elle est basée sur la conception d’une couche sensible supportée innovante réalisée par la technique de Langmuir‐Blodgett. Cette couche est composée d'un lipide à tête polaire immobilisant un cation métallique divalent capable (i) de chélater une molécule possédant une affinité pour ce type de cation et (ii) de catalyser la réaction de chimiluminescence du luminol. L'intensité du signal chimiluminescent est modulée par la présence de biomolécules fixées en surface de la couche sensible, qui modifient l'environnement immédiat du cation métallique. La variation du signal chimiluminescent (issu de la catalyse par le cation immobilisé) a pu être quantifiée et corrélée à une gamme de concentration d’histamine et d’anticorps. Les potentialités de cette approche ont finalement été exploitées pour développer une puce de PMMA de type macropuce immobilisant la monocouche de lipides. / A new label‐free detection method for biomolecular interactions was developed. It is based on the development of an original sensitive layer performed with the Langmuir‐ Blodgett technique. This layer is composed of a lipid which immobilized a bivalent metallic cation on his polar head, able (i) to chelate a molecule which has an affinity for this cation and (ii) to catalyze the luminol chemiluminescent reaction. The chemiluminescent signal intensity is modulated by the presence of immobilized biomolecules on the sensitive layer surface, which modifies the immediate environmentof the metallic cation. The chemiluminescent signal variation (from catalysis by the metallic cation) has been quantified and correlated to a histamine and antibody concentration range. The potentialities of this approach have finally been employed to achieve a PMMA chip (macroarray type), immobilizing the lipid monolayer.

Sub-surface modification using a frequency doubled Ti: Sapphire femtosecond (fs) laser at 1kHz repetition rate, producing 100-fs pulse duration at 400nm, is studied in order to fabricate optical components within non-photosensitised polymethyl methacrylate (PMMA). This thesis explores the feasibility of producing three-dimensional optical devices in bulk polymers and polymer optical fibre (POF) using fs laser direct-writing techniques. For effective and optimal structuring, the laser writing parameters and focusing conditions, such as focusing depth, translation speed, and accumulated fluence are investigated by means of photo-modification thresholds; structural changes in dimensions and morphologies; and the magnitude of the refractive index modulation. The highest refractive index change is 3.2x10^(-3) achieved by using a dry (non-immersion) 0.45-NA objective for a single laser scan. Variations in damage threshold with focusing depths are attributed to a combination of material absorption or surface scattering of light due to contamination or surface imperfections, as well as oxygen diffusion and spherical aberration. Distortion of the laser-induced feature size and shape due to spherical aberrations is controlled and compensated by adjusting the laser power near the damage threshold. Permanent refractive index structures with cross-sectional dimensions of 2μm by 0.9μm and 3μm by 1.4μm are demonstrated at depths of 300μm and 500μm below the surface, resulting in the axial/ lateral ratio of 2.2 and 2.1, respectively. A novel phenomenon relevant to effects of translation speed on the fs laser modification is observed for the first time. As translation speeds reduce from 1.2 to 0.6mm/s, the optical damage threshold power decreases by 6μW, whilst other writing conditions remain constant. However, the damage threshold increases by 74μW with decreasing speeds from 0.6 to 0.35mm/s. This significant increase in threshold power enables inscription of refractive index gratings <5μm below the surface, because irradiation on the surface or near the surface initiates ablation rather than refractive index changes, and this forms a limit for writing useful structures. Compensating for this limit by using appropriate writing parameters highlights the potential of fabricating three-dimensional integrated optical circuits in thin (100μm) polymer substrates. Finally, highly localised fabrication of long period gratings into step-index single mode polymer fibres is demonstrated by removing distortion effects due to the curved surface. The distortion is compensated by sandwiching the fibre with two flat PMMA sheets, between which index-matching oil (n=1.5) is injected. This arrangement enables precise laser micro-structuring with flat interfaces and continuous inner material. The first demonstration of a 250-μm-period fibre grating, resulting in attenuation bands in the visible spectral region at 613, 633, 728, 816, 853, 877 and 900nm, is presented.

Indentation hardness, H, has been widely used to characterize the mechanical properties of materials for more than a century because of the following advantages of this technique; (1) it requires small sample and (2) the test is non destructive in nature. Recent technological advances helped in the development of instrumented indentation machines which can record the load, P, vs. displacement, h, data continuously during indentation with excellent load and displacement resolutions. From these, H and the elastic modulus, E, of the indented material can be obtained on the basis of the ‘contact area’ of the indentation at the maximum load. The estimation of true contact area becomes difficult during ‘pile-up’ and ‘sink-in’, commonly observed phenomena while indentation of a low and high strain hardened materials. In order for the better understanding of these phenomena it is important to understand the plastic flow distribution under indenters. It is also important for the prediction of elastic-plastic properties from the P-h data. Recently, there have been considerable theoretical and simulation efforts on this front with a combination of dimensional analysis and finite element simulations. One of the important input parameter for the dimensional analysis is the ‘representative strain’ under the indenter, which is a strong function of the indenter geometry. However there is no comprehensive understanding of the representative strain under the indenter despite several studies till date. One objective of the present thesis is to conduct an experimental analysis of the plastic flow during the sharp indentation. The plastic zone size and shape under conical indenters of different apex angles in a pure and annealed copper were examined by employing the subsurface indentation technique to generate the hardness map. From these isostrain contours are constructed joining the data having similar strain values. The following are the key observations. (1) The plastic strain contours are elliptical in nature, spreading more along the direction of the indenter axis than the lateral direction. (2) The magnitude of the plastic strain in the contact region decreases with increasing the indenter angle. (3) The strain decay in the indentation direction follow a power-law relation with the distance. The estimated representative strains under the indenters, computed as the volume average strain within the elastic-plastic boundary, decreases with increasing indenter angle. We also performed finite element simulations to generate plastic flow distribution under the indenter geometries and compared with the experimental results. The results suggest that the experimental and computed average strains match well. However, the plastic strain contours do not, suggesting that further detailed understanding of the elasto-plastic deformation underneath the sharp indenter is essential before reliable estimates of plastic properties from the P-h curves can be made routinely. The second objective of this thesis is to understand plastic flow in amorphous alloys. It is now well established that plastic deformation in metallic glasses is pressure sensitive, owing to the fundamentally different mechanisms vis-à-vis the dislocation mediated plastic flow in crystalline metals alloys. Early work has shown that the pressure sensitivity of amorphous alloys gets reflected as high constraint factor, C (hardness to yield stress ratio), which sometimes exceed 3.0. In this thesis, we study the temperature dependence of pressure sensitive plastic flow in bulk metallic glasses (BMGs) using C as the proxy for the pressure sensitivity. Experiments on three different BMGs show that C increases with temperature hence the pressure sensitivity. In addition we have carried out finite element simulations to generate P-h curves for different levels of pressure sensitivities and match them with the experimental curves that are obtained at different temperatures. Simulations predict that higher pressure sensitivity index values are required to match the experimental curves at high temperatures confirming that the pressure sensitivity increases with increasing temperature. The fundamental mechanisms responsible for the increase in pressure sensitivity are discussed in detail. Finally we pose a question, is the increase in pressure sensitivity with temperature is common to other amorphous materials such as strong amorphous polymers? In order to answer this question we have chosen PMMA, a strong amorphous polymer. In this study also we have taken C as a proxy to index the pressure sensitivity. Indentation stress-strain curves are constructed at different temperature using spherical indentation experiments. The C values corresponding to different temperatures are determined and plotted as a function of temperature. It is found that C increases with temperature implying that the pressure sensitivity of amorphous polymers also increases with temperature. The micro-mechanisms responsible for the increase in pressure sensitivity are sought.