<p>The newfound capability of creating moisture sensitive interference multilayered thin films (MLTFs) comprising microfibrillated cellulose and polymers has not previously been possible to implement on surfaces other than silicon wafer strips. Being able to incorporate interference MLTFs on fibre-based materials would introduce the possibility for new applications within authentication, sensing and customer attraction for the paper and packaging industry. By using trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane we were able to hydrophobically modify silicon substrates, enabling interference MLTF lift-off and thus the creation of free-standing MLTFs of approximately 400 nm thickness. Contact dried MLTFs approximately 250 nm thick, were successfully transferred to copy- and filter paper as well as to cellulose-based dialysis membranes. We can also report on the successful synthesis of interference MLTFs directly on a fibre composite material and on aluminium. Initial tests of a method to quantify the pull-off conditions of the MLTFs from the fluorinated surfaces using the Micro Adhesion Measurement Apparatus showed promising results.</p>

The newfound capability of creating moisture sensitive interference multilayered thin films (MLTFs) comprising microfibrillated cellulose and polymers has not previously been possible to implement on surfaces other than silicon wafer strips. Being able to incorporate interference MLTFs on fibre-based materials would introduce the possibility for new applications within authentication, sensing and customer attraction for the paper and packaging industry. By using trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane we were able to hydrophobically modify silicon substrates, enabling interference MLTF lift-off and thus the creation of free-standing MLTFs of approximately 400 nm thickness. Contact dried MLTFs approximately 250 nm thick, were successfully transferred to copy- and filter paper as well as to cellulose-based dialysis membranes. We can also report on the successful synthesis of interference MLTFs directly on a fibre composite material and on aluminium. Initial tests of a method to quantify the pull-off conditions of the MLTFs from the fluorinated surfaces using the Micro Adhesion Measurement Apparatus showed promising results.

L’environnement réactif du plasma constitue un outil puissant dans la science des matériaux, permettant la création de matériaux innovatifs et l'amélioration de matériaux existants qui ne serait autrement pas possible.Le plasma fournit simultanément des fluxes de particules chargées, des molécules chimiquement actives, des radicaux, de la chaleur, des photons, qui peuvent fortement influencer les voies d'assemblage à différentes échelles temporelles et spatiales, y compris à l’échelle atomique.Dans cette thèse de doctorat, des méthodes tenant pour base des plasmas micro-ondes ont été utilisées pour la synthèse de nanomatériaux de carbone, y compris graphène, graphène dopé à l'azote (N-graphène) et structures de type diamant.À cette fin, ce travail est lié à optimisation de la synthèse de nanostructures 2D du carbone, comme graphène et N-graphène par la poursuite de l'élaboration et du raffinement de la méthode développée en Plasma Engineering Laboratory (PEL). La synthèse de graphène de haute qualité et en grandes quantités a été accomplie avec succès en utilisant des plasmas d'Ar-éthanol à ondes de surface dans des conditions de pression ambiante. De plus, le N-graphène a été synthétisé par un procédé en une seule étape, de l'azote a été ajouté au mélange d’Ar-éthanol, et par un procédé en deux étapes, en soumettant des feuilles de graphène préalablement synthétisées ont été exposées à un traitement plasma argon-azote à basse pression. Les atomes d'azote ont été incorporés avec succès dans le réseau de graphène hexagonal, formant principalement liaisons pyrroliques, pyridiniques et quaternaires. Un niveau de dopage de 25 at.% a été atteint.Différents types de nanostructures de carbone, y compris du graphène et des structures de type diamant, ont été synthétisées au moyen d'un plasma d’argon en utilisant du méthane et du dioxyde de carbone comme précurseurs du carbone.De plus, des plasmas à couplage capacitif ont également été utilisés pour la fonctionnalisation du graphène et pour la synthèse de nanocomposites, tels que les composites de Polyaniline (PANI)-graphène. Les utilisations potentielles de ces matériaux ont été étudiées et les deux structures ont démontré avoir des attributs remarquables pour leur application aux biocapteurs. / Plasma environments constitute powerful tools in materials science by allowing the creation of innovative materials and the enhancement of long existing materials that would not otherwise be achievable. The remarkable plasma potential derives from its ability to simultaneously provide dense fluxes of charged particles, chemically active molecules, radicals, heat and photons which may strongly influence the assembly pathways across different temporal and space scales, including the atomic one.In this thesis, microwave plasma-based methods have been applied to the synthesis of advanced carbon nanomaterials including graphene, nitrogen-doped graphene (N-graphene) and diamond-like structures. To this end, the focus was placed on the optimization of the production processes of two-dimensional (2D) carbon nanostructures, such as graphene and N-graphene, by further elaboration and refinement of the microwave plasma-based method developed at the Plasma Engineering Laboratory (PEL). The scaling up of the synthesis process for high-quality graphene using surface-wave plasmas operating at atmospheric pressure and argon-ethanol mixtures was successfully achieved. Moreover, N-graphene was synthetized via a single-step process, by adding nitrogen to the argon-ethanol mixture, and via two-step process, by submitting previously synthetized graphene to the remote region of a low-pressure argon-nitrogen plasma. Nitrogen atoms were usefully incorporated into the hexagonal graphene lattice, mainly as pyrrolic, pyridinic and quaternary bonds. A doping level of 25% was attained.Different types of carbon nanostructures, including graphene and diamond-like nanostructures, were also produced by using methane and carbon dioxide as carbon precursors in an argon plasma.Additionally, capacitively-coupled radio-frequency plasmas have been employed in the functionalization of graphene and in the synthesis of Polyaniline (PANI)-graphene composites. The potential uses of these materials were studied, with both showing favourable characteristics for their applicability in biosensing applications.

An alternative indirect integration regime of porous low-k materials was investigated. Based on a single Damascene structure the intra level dielectric SiO2 or damaged ULK was removed by using HF:H2O solutions to create free standing metal lines. The free spaces between the metal lines were refilled with a spin-on process of a low-k material. The persistence of barrier materials and copper against HF solutions, the gap fill behavior of the used spin on glass on different structure sizes and the main challenges which have to solve in the future are shown in this study.

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Ces travaux concernent l’étude expérimentale des textures se développant dans les ménisques de films smectiques de cristaux liquides thermotropes. Ces fluides complexes nous servent de système modèle pour l’étude des couplages élasto-capillaires qui se manifestent dans certaines conditions par des déformations périodiques de l’interface cristal liquide-air. Dans un premier temps, à partir de l’étude détaillée de la topographie de l’interface par une méthode interférométrique, nous caractérisons les différents types de structures, puis, identifions les principaux paramètres impliqués dans le processus d'apparition des défauts dans le ménisque de films libres suspendus. Ces résultats nous servent de base pour discuter des mécanismes physiques qui génèrent les différents types de défauts observés. Nous regardons en particulier, comment la diminution d’épaisseur de couche associée à une transition de phase va induire une instabilité mécanique responsable de l’apparition des ondulations de l’interface. Dans un deuxième temps, afin d’aller plus loin dans la compréhension des mécanismes, nous avons utilisé des films minces de cristaux liquides déposés sur des substrats solides microstructurés par des plots fabriqués par des techniques photolitographiques. Une telle géométrie permet de générer un ménisque autour de chaque plot et surtout de faire varier un plus grand nombre de paramètres comme par exemple l’ancrage sur le substrat via un traitement chimique de surface. L’ensemble de nos résultats apportent un éclairage nouveau sur la caractérisation et la compréhension des déformations spécifiques aux ménisques de fluides complexes. / The present work is an experimental study of the textures that appear in the meniscus of free standing smectic films with thermotropic liquid crystals. These complex fluids serve as model systems to investigate elasto-capillary phenomena which, under certain conditions, manifest themselves through periodic deformations of the liquid crystalair interface. In the first part of the thesis, we focus our attention on meniscus structures whose interfacial topographies are thoroughly characterized thanks to an in-house optical interferometry technique. Our study allows us to identify the main parameters involved in the development of meniscus structures and to discuss the physical mechanisms that are likely to be responsible for their formation. In particular, we show how a phase transition-induced layer shrinkage triggers a mechanical instability leading to interfacial undulations of the smectic free surface. In the second part of the manuscript, we address the case of thin liquid crystal films deposited on solid patterned solid substrates. The latter consist of regular arrays of microposts fabricated through photolithographic techniques. Such a geometry allows a meniscus to be formed around each micropost and makes it possible to examine the influence of other parameters such as the anchoring conditions on the solid substrate. The results gathered so far are able to shed some light on the characterization and the understanding of the specific deformations and textures that appear in the menisci of complex fluids.

Liquid crystals exhibit a great variety of phases which differ one from another by their structure and physical properties. Near a phase transition, these mesoscopic phases are very sensitive to the surface interactions showing interfacial phenomena which are extraordinarily variable and interesting. The interaction between boundary surfaces and liquid crystal molecules results in surface layers with properties strongly different from the interior ones. For example, it is observed experimentally the unusual phenomenon of layer thinning upon heating. Above the bulk Smetic A - Isotropic transition temperature, the film is thinned to a low number of layers as the temperature increases. The temperature of these layer thinning transitions are related to the film thickness by means of a simple power-law. The characteristic exponent, &#956;, measured from experiments using distinct compounds, varies slightly in the range 0.6 < &#956; < 0.8. In this work, we investigate how surface effects modify the order parameter profiles in the vicinity of the Smectic-A-Isotropic (Sm A - I) transition in freestanding liquid crystal films using an extended mean-field approach which allows to incorporate explicitly the anchoring of the surface layers in the effective potential. We observed the contribution of the surface anchoring to the film stability. We found that there is a characteristic surface anchoring above which the bulk layers are less ordered than the surface ones. We also determine the characteristic exponent which governs the transition temperature dependence with the film thickness. We show that the different values of the exponents are related with the ratio between the size of the central rigid portion of the molecules and the typical layer spacing, as well as to the range of film thicknesses investigated. Our results qualitatively reproduce the main experimental findings concerning the layer thinning transitions in free-standing smectic films. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Cristais líquidos exibem uma grande variedade de fases que diferem umas das outras por suas propriedades físicas e estruturais. Próximo a uma transição de fase, estes compostos são bastante sensíveis às interações superficiais apresentando fenômenos interfaciais que são extraodinariamente variados e interessantes. A interação entre as surperfícies limitantes e as moléculas de cristal líquido produz camadas superficiais com propriedades muito diferentes das camadas interiores do filme. Por exemplo, observa-se experimentalmente o fenômeno não-usual da redução de camadas ocasionado pelo aquecimento do filme. Acima da temperatura de transição esmética-A - Isotrópica da porção interior do filme, a amostra é reduzida para um número menor de camadas com o aumento da temperatura. A temperatura dessas transições por redução de camadas se relaciona com a espessura do filme por meio de uma lei de potência simples. O expoente característico, &#956;, medido experimentalmente usando compostos distintos, varia ligeiramente no intervalo 0.6 < &#956; < 0.8. Neste trabalho, investigamos como os efeitos de superfície modificam os perfis dos parâmetros de ordem na vizinhan¸ca da transição Esmética-A-Isotrópica (EsmA- I) em filmes de cristal líquido livremente suspensos, usando uma aproximação de campo médio estendida que permite incorporar explicitamente o ancoramento das camadas superficiais no potencial efetivo. Observamos a contribuição do ancoramento das superfícies para a estabilidade do filme. Encontramos que há um ancoramento superficial característico acima do qual as camadas da porção central do filme são menos ordenadas que as camadas da superfície. Também determinamos o expoente característico que governa a dependência da temperatura de transição com a espessura do filme. Mostramos que os diferentes valores dos expoentes estão relacionados com a razão entre o comprimento da porção central (rígida) das moléculas e o espaçamento típico entre as camadas, bem como com a espessura dos filmes estudados. Nossos resultados reproduzem qualitativamente os principais dados experimentais relacionados com as transições por redução de camadas em filmes esméticos livremente suspensos.

La mousse est un matériau fascinant nous accompagnant au quotidien depuis des siècles, mais sa complexité fait qu’il est difficile de comprendre et contrôler ses propriétés. L’objet de cette thèse expérimentale est de montrer par deux exemples que si l’on contrôle les écoulements ayant lieu lors de la génération de la mousse et pendant sa vie on peut alors avoir un très bon contrôle de ses propriétés structurelles et sa stabilité. Dans la première partie j’étudie la génération de mousse constituée de bulles micrométriques par un écoulement diphasique cyclique dans un tuyau connectant deux seringues. Cette technique permet de varier la fraction liquide sans affecter les distributions de tailles de bulle. Je montre que ces distributions sont essentiellement contrôlées par la présence de constrictions dans le tuyau connectant les seringues et par les propriétés physico-chimiques de la solution moussante. Mes résultats montrent que ce n’est pas le vieillissement de la mousse mais bien les instabilités hydrodynamiques qui contrôlent la taille caractéristique des bulles. Avec diverses expériences modèles de millifluidique en régime inertiel je mets en évidence ce qui semble être un nouveau processus de fragmentation de bulles. L’accélération et la décélération des bulles lors de leur passage dans une constriction seraient le moteur de cette fragmentation. Le lien précis reste à quantifier dans de futurs travaux. Dans un second temps je montre qu’il est possible de faire des films minces, libres et d’une grande stabilité avec un fondu de copolymère en peigne de PDMS-g-PEG-PPG à température ambiante, sans ajout d’agents stabilisants. Les expériences de caractérisation indiquent que c’est un liquide newtonien ayant une faible tension de surface ne présentant pas de transition de phase à température ambiante. J’ai étudié de manière approfondie le drainage de films verticaux et horizontaux, qui se fait par un écoulement laminaire du liquide confiné entre les deux interfaces liquide/air. A l’aide d’une balance à film mince microfluidique développée pour l’étude des liquides visqueux je rapporte l’apparition de stratifications dans les films très minces. Celles-ci ont la même taille que la longueur caractéristique du fondu, lié soit à la taille du polymère, soit à une micro-séparation de phase. Le drainage et la stabilité sont donc potentiellement contrôlés par cet écoulement stratifié, mais il reste à comprendre si la stratification est la conséquence d’un simple effet de confinement ou d’une micro-séparation de phase près de l’interface. / Foam is a fascinating matter which has been broadly used for centuries, but its complexity makes it difficult to understand and control its properties. The subject of this experimental thesis is to show through two examples that by controlling the flows during the generation and lifetime of the foam its stability and structural properties may be better controlled. In the first part I study the generation of foams made of microscopic bubbles by a cyclic diphasic flow in a tube connecting two syringes. With this technique one can vary the liquid fractions without changing the bubble size distributions. I show that these distributions are mainly controlled by the presence of constrictions in the tubing connecting the syringes and by the physico-chemical properties of the foaming solution. My results show that the characteristic bubble size is not fixed by foam ageing effects but by hydrodynamic instabilities. With various millifluidic model experiments in the inertial regime I highlight what seems to be a new mechanism of bubble fragmentation. The acceleration and deceleration of the bubbles when going through a constriction would be the driving effect of this process. The precise link still has to be established. In the second part I show that it is possible to make highly stable free-standing films made of a comb-copolymer melt of PDMS-g-PEG-PPG, at room temperature, and without stabilising agents. The characterisation of this melt reveals that it is a newtonian liquid with a low surface tension and not subject to phase transitions at room temperature. I studied intensively the drainage of vertical and horizontal films, which is a laminar flow of the liquid confined between its two liquid/air interfaces. Using a millifluidic thin film pressure balance, developed for the study of viscous liquids, I report the formation of stratifications in very thin films. Theses stratifications have the same step hight than the characteristic length of the melt which we measured for the bulk, linked either to the size of the macromolecules or to micro-phase separation. The drainage and stability might be controlled by this stratified flow, but we still have to understand if it results from a simple confinement effect or from an interfacially driven micro-phase separation.

Les canaux ioniques sont des protéines membranaires permettant le transport ionique au travers des membranes biologiques. Du fait de leur omniprésence dans l'organisme, ils représentent une classe de cibles thérapeutiques encore actuellement peu exploitée du fait de limitations expérimentales dans leur étude. La mesure électrique de l'activité des canaux ioniques au sein de bicouches biomimétiques reconstituées in vitro permettrait de répondre à ces limitations. Cependant, il n'existe actuellement pas de système satisfaisant au cahier des charges complet pour de telles analyses : stabilité et pureté de la bicouche, faible niveau de bruit, insertion rapide des canaux ioniques, intégration dans un dispositif fluidique, possibilité de mener une caractérisation optique simultanée. L'objectif de ces travaux de thèse était d'évaluer dans quelle mesure l'utilisation d'un substrat SOI (Silicon On Insulator) comprenant des nanopores pourrait permettre de répondre à tous ces critères. Des nanopores de diamètre compris entre 10 nm et 160 nm ont été réalisés à partir d'un substrat SOI. Une cellule fluidique transparente est utilisée pour l'adressage fluidique. Cette cellule permet d'autre part la double caractérisation électrique et optique. Les propriétés électriques en milieu liquide du dispositif ont été étudiées et permettent de dégager des perspectives d'amélioration. La double caractérisation électrique et optique est démontrée au moyen d'expériences de capture de nanoparticules fluorescentes sur les nanopores. Enfin, des premiers résultats prometteurs d'obtention d'une bicouche lipidique suspendue sont présentés. / Ion channels are membrane proteins responsible for ion transport across biological membranes. Due to their ubiquity, they are promising drug targets but are not yet fully exploited as such due to experimental restrictions in their study. Electrical measurement of ion channels activity within in vitro artificial lipid bilayers would enable to overcome these restrictions. However, there is not yet a system satisfying all the requirements for ion channels studies: stability and purity of the lipid bilayer, low noise level, fast insertion of ion channels, fluidic integration, ability to perform simultaneous optical characterization. The aim of this phD was to assess in which extent the use of an SOI (Silicon On Insulator) substrate bearing nanopores could satisfy all these requirements. 10 nm to 160 nm diameter nanopores were fabricated in an SOI substrate and characterized. A transparent fluidic cell was used for fluidic addressing. This transparent cell allows combined electrical and optical characterization. Electrical properties of the device in aqueous environment were studied, allowing to bring out improvement prospects. The combined electrical and optical characterization was demonstrated with fluorescent nanoparticle trapping experiments on the nanopores. Finally, promising results about the formation of a free-standing lipid bilayer are presented.

BACKGROUND: Despite large investments in maternity care services, perinatal health outcomes in the U.S. are among the worst compared to other industrialized countries, with documented perinatal health disparities disproportionately impacting racial and ethnic minorities. Midwifery-led freestanding birth centers (FSBC) have emerged as an underutilized model for the safe and cost-effective care of women with low-risk pregnancies. Despite approximately 85% of all US pregnancies being considered low-risk, only 0.5% of all US births occurred in a FSBC in 2016. The goal of the study is to elucidate strategies used to develop and sustain freestanding birth centers (FSBCs) that are seeking to serve high proportions of publicly-insured women and women of color. METHODS: I conducted an embedded unit case study, including semi-structured in-depth interviews and focus groups with 49 stakeholders from three exemplary FSBCs. Supplemental interviews were led with five key informants from three additional FSBCs and a relevant national membership organization. Additional data sources used to complete this case study include, where relevant and permitted, observations of maternity care settings, patient-provider encounters, management meetings, community events, and review of pertinent documents. Qualitative analysis methods were used to identify common themes and variations. FINDINGS: Midwifery-led birth center care can improve the experience and outcomes of maternity care among publicly insured women of color. The study revealed persistent multi-level challenges, as well as the use of common approaches to overcome these organizational, financial, and cultural barriers, resulting in greater, yet still fragile, access to family-centered intrapartum care within the communities in which these FSBCs operate. CONCLUSIONS: The careful integration of FSBCs into health systems such as a Federally Qualified Health Center (FQHC) may contribute to the broad scale-up of this underutilized model of care. While integrating FSBCs into FQHCs may be helpful in expanding equitable access to birth center care, it is not necessary, and also not sufficient. Expansion efforts should include additional deliberate processes and strategies to ensure equitable uptake and sustainability of birth center care. / 2020-10-23T00:00:00Z