Dans le cadre de la séparation sélective pour le traitement et la valorisation des combustibles nucléaires usés, l’extraction liquide/liquide est largement utilisée au niveau industriel. Néanmoins, ce procédé est encore mal compris en ce qui concerne les phénomènes physico-chimiques qui se produisent à l’interface liquide/liquide. Ce travail porte sur la compréhension de la dynamique de l’interface liquide nanométrique durant le transfert d’une espèce entre une phase aqueuse et une phase organique. Deux techniques expérimentales ont principalement été utilisées: la mesure de tension interfaciale et l’optique non linéaire. Ce travail a également donné lieu au développement d’un modèle numérique de dynamique de transfert de phase prenant en compte à la fois des phénomènes de transport diffusif proche de l’interface et une cinétique chimique sur l’interface décrivant les processus d’adsorption/désorption. Des systèmes modèles constitués de molécules surfactantes et/ou chromophores et/ou complexantes ont été étudiés aux interfaces air/liquide et liquide/liquide. L’adsorption/désorption, l’agrégation en surface, la complexation d’ion à une interface liquide et la structuration des systèmes ont ainsi pu être étudiées tant d’un point de vue des états d’équilibre que de la dynamique. Enfin, ces études ont été appliquées à un système d’intérêt industriel utilisé dans le procédé de dépollution DIAMEX / Liquid-liquid extraction processes are widely used in the industrial fields of selective separation. Despites its numerous applications, the microscopic mechanisms which occur during a liquid liquid extraction processes are really unknown specially at the liquid/liquid interface. Thus, this work deals on the understanding of the phenomena which drive the mass transfer across a liquid/liquid interface. Two experimental techniques were used in this work: dynamic interfacial tension measurement and non-linear optical experiments. Along with the use of this experimental approach, a numerical model describing the mass transfer dynamic has been developed. This model works under the assumption that both diffusion and a chemical step describing adsorption and desorption processes contribute to the global transfer kinetics. Model systems of surfactant molecules, chromophore molecules and complexing molecule were investigated at liquid/liquid and air/liquid interface. Interfacial phenomena like adsorption, surface aggregation and ion complexing were studied. Finally, the methodology developed in this work was applied to studied an extractant molecule with potential industrial application

Doctor of Philosophy / Department of Grain Science and Industry / Finlay I. MacRitchie / Expansion of dough and hence breadmaking performance is postulated to depend on a dual mechanism for stabilization of inflating gas bubbles. Two flours were used in this study, one from the wheat variety Jagger (Jagger) and the other from a composite of soft wheat varieties (soft). The primary stabilizing mechanism is due to the gluten-starch matrix surrounding the bubble. The secondary mechanism operates when gas bubbles come into close contact during later proofing and early baking. When discontinuities occur in the gluten-starch matrix surrounding gas bubbles, thin liquid lamellae stabilized by adsorbed surface active compounds, provide a secondary stabilization. A key parameter in the primary stabilizing dough film is thought to be the property of strain hardening. Jagger flour gave higher test-bake loaf volume than soft wheat flour and higher strain hardening index for dough. Rheological properties of doughs were varied by addition of protein fractions prepared by pH fractionation. Fractions were characterized by SE-HPLC and MALLS. The molecular weight distribution (MWD) of fractions progressively shifted to higher values as the pH of fractionations decreased. Mixograph peak development time paralleled the MWD. However, the strain hardening index and the test-bake loaf volume increased with increasing MWD up to a point (optimum), after which they declined. At a given strain rate the behavior at the optimum appeared to result from slippage of the maximum number of statistical segments between entanglements, without disrupting the entangled network of polymeric proteins. Shift of MWD to MW higher than the optimum results in a stronger network with reduced slippage through entanglement nodes, whereas a shift to lower MWs will decrease the strength of the network due to less number of entanglements per chain. In order to study the secondary stabilizing mechanism, different lipid fractions were added incrementally to the defatted flours. No effects were observed on the rheological properties of the dough. However, large effects on the loaf volume were measured. The additives used were the total flour lipid and its polar and non polar fractions and the fatty acids palmitic, linoleic and myristic. Polar lipids and palmitic acid had positive or little effect on loaf volume respectively. Non polar lipid, linoleic and myristic acids had negative effects on loaf volume. 1 The different effects of the lipid fractions are thought to be related to the type of monolayer that is formed. Polar lipid and palmitic acid form condensed monolayers at the air/water interface whereas non polar lipid, linoleic and myristic acids form expanded monolayers.

L’augmentation de la prévalence mondiale des pathologies respiratoires et allergiques depuis la seconde moitié du 20ème siècle ainsi que l’émergence de symptômes spécifiques liés à des environnements clos dans les années soixante-dix, ont contribué à incriminer l’exposition à la pollution de l’air intérieur, en particulier aux composés organiques volatils (COV), comme facteur de risque dans l’apparition de ces pathologies. Les différentes approches épidémiologiques et expérimentales existantes ont permis de renseigner la composition, les sources, les déterminants et les effets de cette pollution en particulier sur l’appareil respiratoire humain, première voie d’exposition. A l’heure actuelle, les politiques expérimentales visent à substituer les expérimentations animales par le développement de méthodes alternatives, dont les méthodes in vitro, pour des raisons économiques et éthiques. Cependant, les modèles in vitro permettant l’étude des polluants environnementaux sur les cellules de l’arbre respiratoire sont encore peu développés. L’objectif de cette thèse est donc de proposer une approche expérimentale in vitro adaptée à l’étude d’impact des expositions de cellules épithéliales nasales humaines à des polluants environnementaux, en particulier les COV. La force de ce travail est d’avoir mis en place des méthodologies approchant les conditions réelles d’exposition, et de les avoir appliquées à des atmosphères d’environnement intérieur. Au terme de ces travaux, les acquis méthodologiques ont porté sur le modèle de cellules épithéliales nasales évoluant de la culture primaire à l’épithélium reconstitué, constitué de plusieurs types cellulaires, proche de l’épithélium respiratoire humain ; la génération d’atmosphère chargée en mono (formaldéhyde) ou multi-polluants (COV issus de peinture du commerce), et surtout son contrôle analytique, étape essentielle pour valider notre démarche expérimentale ; l’exposition répétée (jusqu’à 3 par semaine, de durée allant jusqu’à 2 heures, sur une période totale d’au moins un mois) en interface air-liquide, sans perte d’intégrité cellulaire, dynamique (sous flux d’air) pour les polluants gazeux, ou statique (sans flux) pour dépôt des particules ; l’étude morphologique et histologique de l’épithélium, développée comme marqueur d’effet complétant l’approche biologique centrée sur la réponse inflammatoire. L’exposition au formaldéhyde gazeux à une concentration proche des niveaux environnementaux intérieur, n’a pas eu d’effet sur les marqueurs de l’inflammation. Lors de l’exposition de l’épithélium reconstitué choisi (MucilAirTM, Société Epithelix) aux COV, une inhibition de la production spécifique d’IL-8 dépendant de la dose et du nombre d’exposition est observée, alors que l’intégrité tissulaire de l’épithélium n’est pas altérée. Le mécanisme de cette inhibition demande à être exploré plus avant. Pour autant, la réactivité du modèle, en matière de réaction inflammatoire et de changement de structure de l’épithélium a été validée lors d’expositions à un mélange environnemental complexe (particules de fumée de tabac). Notre approche in vitro innovante peut être élargie à l’étude d’autres atmosphères multi-polluants (chimiques, physiques et biologiques) afin d’être au plus proche des conditions réelles d’expositions, mais aussi à d’autres organes cibles. / Increase of respiratory diseases since the second half of the 20th century and emergence of specific symptoms related to closed environments contributed to suspect indoor air pollution, in particular volatile organic compounds (VOC), as a risk factor in the onset of these diseases. Epidemiological and experimental approaches are useful to determine its sources, determinants and effects on the human respiratory tract. Current experimental policies favor replacing animal experiments by alternative methods like in vitro methodologies, for economic and ethical reasons. Until now, in vitro models have been poorly developed to study environmental pollutants on respiratory cells. The objective of our work was to propose an experimental approach adapted to the study of the impact of environmental pollutants, particularly VOC, on human nasal epithelial cells. The strength of this work is to set up a methodology close to actual conditions of exposure, and apply them to indoor environment atmospheres. The methodology developed aimed to study reconstituted epithelium coming from primary culture of nasal cells, composed of several cell types, close to human respiratory epithelium; generate atmosphere charged with mono (formaldehyde) or multi-pollutant (VOC paint), and especially its analytical control (an essential step to validate our experimental approach); and repeated exposure (3 per week, until to two hours, over a total period of one month) at air-liquid interface without loss of cellular integrity, in dynamic conditions (under airflow) for gaseous pollutants, or static (without airflow) for particles. The setup of a morphological and histological approach allowed to complete biological effect (inflammatory response). Gaseous formaldehyde exposure at low concentration had no effect on inflammatory markers. VOC exposures on selected reconstituted epithelium (MucilAirTM, Epithelix Company) showed a decreased release of IL-8 depending on the dose and the number of exposure, without tissue damage. The mechanism of this effect needs to be further investigated. Responsiveness of the model, in terms of inflammation and structural changes of the epithelium was validated by assessing complex environmental mixture (tobacco smoke particles). Our innovative in vitro approach can be extended to the study of other multi-pollutant atmospheres (chemical, physical and biological) in order to get close to the actual conditions of exposure, but also by using other target organs.

Les décharges en phase gazeuse couplées avec les liquides est une branche relativement nouvelle de la physique des plasmas. Le développement des applications technologiques basées sur les plasmas-liquides dans des domaines tels que la médecine, le traitement de matériaux, la remédiation environnementale, etc., est très prometteur. Cependant, la compréhension de la nature de l’interaction plasma-liquide est indispensable pour pouvoir développer les applications. Dans ce mémoire, composé de trois sections, nous avons étudié l’interaction d’un plasma d’air, généré par une décharge à courant alternatif (AC), et couplé directement avec l’eau. Tout d’abord, une présentation générale des systèmes plasmas-liquides et ses applications pour le traitement des eaux est faite dans le Chapitre 1. Chapitre 2, un article publié dans Journal of Physics D: Applied Physics, est une étude de la dynamique spatio-temporelle d’un plasma d’air produit par une décharge AC entre une électrode pointe et la surface de l’eau. Chapitre 3, un article publié dans Plasma Chemistry and Plasma Processing, représente une investigation sur les différents modes de décharges AC en contact avec l’eau et sur l’efficacité de chaque mode pour dégrader un polluant organique modèle (bleue de méthylène). / Gas phase discharges in contact with liquids is a relatively novel research field in plasma physics. Plasma-liquid systems are very promising for various technological applications, such as medicine, solid-state physics, and environmental remediation. However, further development of the applications requires understanding of plasma-liquid interactions. In this thesis, interaction between an air plasma directly coupled in contact with water is studied. This thesis includes three chapters. Chapter 1 presents a general introduction of the plasma-liquid interactions and their applications in water treatment. Chapter 2, an article published in Journal of Physics D: Applied Physics, is an investigation of the spatial and temporal dynamics of an air plasma produced by AC discharge between a pin electrode and water. Chapter 3, an article published in Plasma Chemistry and Plasma Processing, is an investigation of the various modes produced by an AC-driven air discharge in contact with water. The electrical characteristics of each discharge mode are presented in detail, and variations in water properties (namely water acidity and conductivity) are also discussed. The efficiency of each discharge mode on the degradation rate of methylene blue, a standard pollutant, is also reported.

[pt] O deslocamento de um líquido em um tubo capilar pela injeção de um gás ocorre em muitas situações, tais como na recuperação avançada de petróleo, no revestimento de conversores catalíticos e na moldagem assistida por injeção de gás. Geralmente o líquido deslocado é uma solução polimérica ou uma dispersão, que é não Newtoniana. Forças viscoelásticas alteram o balanço de forças em várias partes do escoamento e, conseqüentemente, alteram a eficiência do deslocamento, isto é, mudam a quantidade de líquido deixada na parede do capilar. Modelos de tais escoamentos devem se basear em teorias que levem em consideração o comportamento diferenciado de líquidos com microestrutura complexa, tanto no cisalhamento quanto na extensão. Além do mais, escoamentos de deslocamento envolvem uma superfície livre, e o domínio no qual as equações diferenciais são resolvidas é desconhecido a priori, fazendo parte da solução. Estas duas características tornam o problema extremamente complexo. Este problema foi estudado aqui tanto experimentalmente quanto teoricamente. Os experimentos consistiram da visualização do escoamento e medição da massa deslocada pela passagem de uma bolha de gás através de um tubo capilar preenchido por um líquido viscoelástico. Várias soluções de baixo peso molecular de Polietileno Glicol (PEG) e de alto peso molecular de Óxido de Polietileno (PEO) em água foram usadas a fim de avaliar os efeitos do comportamento viscoelástico no escoamento. As propriedades reológicas das soluções foram avaliadas tanto em cisalhamento quanto em extensão. Na análise teórica, o escoamento com superfície livre bidimensional próximo µa interface gás- líquido foi modelado usando três equações diferenciais constitutivas distintas que aproximam o comportamento viscoelástico de soluções poliméricas diluídas, as quais são os modelos Oldroyd-B, FENE-P e FENE-CR, juntamente com as equações de conservação de massa e de quantidade de movimento linear. O sistema de equações foi resolvido pelo Método dos Elementos Finitos. O sistema de equações algébricas não-lineares resultante foi resolvido pelo método de Newton. Os resultados mostram o efeito do caráter viscoelástico do líquido na forma da superfície livre e a espessura do filme líquido deixado na parede. / [en] Displacement of a liquid in a capillary tube by gas injection occurs in many situations, like enhanced oil recovery, coating of catalytic converters and gas-assisted injection molding. Generally the liquid being displaced is a polymeric solution or dispersion, which is not Newtonian. Viscoelastic forces alter the force balance in various parts of the flow and consequently change the amount of liquid left attached to the capillary wall. Models of such flows must rely on theories that can account for the different behavior of microstructured liquids in simple shear and extensional flow. Moreover, displacement flows involve a free surface, and the domain where the differential equations are posed is unknown a priori being part of the solution. These two characteristics make the problem extremely complex. This problem was analyzed here both by experiments and theory. The experiments consisted of flow visualization and measurement of mass displaced by a gas bubble in a capillary tube filled with a viscoelastic liquid. Various solutions of low molecular weight Polyethylene Glycol (PEG) and high molecular weight Polyethylene Oxide (PEO) in water were used in order to evaluate the effect of viscoelastic behavior on the flow. The rheological properties of the solutions were evaluated both in simple shear and predominantly extensional flows. In the theoretical analysis, the two- dimensional free surface flow near the gas-liquid interface was modelled using three different differential constitutive equations that approximate viscoelastic behavior of dilute polymer solutions, namely Oldroyd-B, FENE-P and FENE-CR, together with momentum and continuity equations. The equation system was solved with the Finite Element Method. The resulting non- linear system of algebraic equations was solved by Newton`s method. The results show the effect of the viscoelastic character of the liquid on the free surface shape and the film thickness attached to the capillary wall.

In dieser Arbeit werden verschiedene Aspekte des Designs und der Funktionsweise von in Flüssigkeit betriebenen Graphen-basierten Sensoren untersucht, wodurch neue Einblicke in grundlegende Prozesse an der Graphen-Flüssigkeits-Grenzfläche gewonnen werden. Zunächst wird die Wirkung redoxaktiver Moleküle in der Elektrolytlösung in elektrochemisch gesteuerten Graphen-FETs untersucht. Während des Betriebs kann ein heterogener Elektronentransfer stattfinden, der zu Faradayschen Strömen am Graphenkanal führt. Diese führen zu Verschiebungen der Transferkurve von Graphen, da die Graphen-Flüssigkeits-Grenzfläche eine nur teilweise polarisierbare Elektrode darstellt. Dies wird als „Faradayscher Effekt“ bezeichnet. Er unterscheidet sich grundlegend von typischen Transduktionsmechanismen. Parameter, die den Faradayschen Effekts beeinflussen, werden detailliert untersucht. So sind die Verschiebungen z.B. abhängig von der Graphenkanalfläche. Der zweite Abschnitt konzentriert sich auf die Kante von Graphen, die einen nanoskopischen eindimensionalen Defekt des zweidimensionalen Materials darstellt. In dieser Arbeit wird ein neuer Graphen-FET vorgestellt, der auf der Steuerung von Graphen nur über die elektrochemische Doppelschicht an der Kante basiert. Um dies zu erreichen, wird der basale Teil des Graphens durch eine Passivierung vollständig von der Elektrolytlösung abgeschirmt. Des Weiteren wird gezeigt, dass die Kante des Graphens durch elektrochemische Modifizierung kovalent funktionalisiert werden kann, wodurch die Ladungsdichte an der Graphenkanten-Flüssigkeits-Grenzfläche effektiv verändert wird. Dabei bleiben die vorteilhaften Eigenschaften der Devices erhalten. Schließlich wird ein neuartiger Ansatz zu Untersuchungen an der Graphenkante in Form von mit hexagonalem Bornitrid-verkapseltem Graphen-Elektroden verfolgt. Die elektroanalytische Detektion von Ferrocenmethanol und Dopamin an der Graphenkante mittels zyklischer Voltammetrie wird an diesen Elektroden gezeigt. / Several aspects of the design and function of sensors based on graphene operated in liquid have been investigated in this thesis, providing new insight into fundamental processes at the graphene-liquid-interface. First, the effect of the presence of redox active molecules in the analyte solution of electrochemically gated graphene FETs is explored. During operation, heterogeneous electron transfer may occur at relevant potentials leading to Faradaic currents at the graphene channel. These lead to doping-like shifts of the transfer curve of graphene, as the graphene-liquid-interface represents a partially polarizable electrode. Due to the origin of the shifts, this observation is termed “Faradaic effect”. It is fundamentally different from typically discussed transduction mechanisms. Parameters influencing the direction and magnitude of the Faradaic effect are discussed in detail, e.g. the shifts are the stronger, the larger the area of the graphene channel. The second part focuses on the edge of graphene, which represents a nanoscopic one-dimensional defect of the two-dimensional material. Here, a new type of graphene FET is introduced based on electrochemical gating of graphene exclusively via the electrical double layer at its edge. To achieve edge-gating, the basal part of graphene is passivated by a photoresist and shielded entirely from interaction with the solution. It is demonstrated that the edge of graphene can be functionalized covalently via electrografting. This changes the charge density at the graphene edge-liquid-interface effectively, while maintaining the favorable transfer characteristics of the devices. Finally, a novel approach towards graphene edge devices was pursued in the form of hexagonal boron nitride encapsulated graphene. The electrochemical detection of ferrocene methanol and dopamine was demonstrated in standard and fastscan cyclic voltammetry at the edge of graphene in these devices.

No description available.

This thesis presents a research project in the field of oxygen system fire safety relating to the heterogeneous burning of iron in normal gravity and reduced gravity. Fires involving metallic components in oxygen systems often occur, with devastating and costly results, motivating continued research to improve the safety of these devices through a better understanding of the burning phenomena. Metallic materials typically burn in the liquid phase, referred to as heterogeneous burning. A review of the literature indicates that there is a need to improve the overall understanding of heterogeneous burning and better understand the factors that influence metal flammability in normal gravity and reduced gravity. Melting rates for metals burning in reduced gravity have been shown to be higher than those observed under similar conditions in normal gravity, indicating that there is a need for further insight into heterogeneous burning, especially in regard to the rate-limiting mechanism. The objective of the current research is to determine the cause of the higher melting rates observed for metals burning in reduced gravity to (a) identify the rate-limiting mechanism during heterogeneous burning and thus contribute to an improved fundamental understanding of the system, and (b) contribute to improved oxygen system fire safety for both ground-based and space-based applications. In support of the work, a 2-s duration ground-based drop tower reduced-gravity facility was commissioned and a reduced-gravity metals combustion test system was designed, constructed, commissioned and utilised. These experimental systems were used to conduct tests involving burning 3.2-mm diameter cylindrical iron rods in high-pressure oxygen in normal gravity and reduced gravity. Experimental results demonstrate that at the onset of reduced gravity, the burning liquid droplet rapidly attains a spherical shape and engulfs the solid rod, and that this is associated with a rapid increase in the observed melting rate. This link between the geometry of the solid/liquid interface and melting rate during heterogeneous burning is of particular interest in the current research. Heat transfer analysis was performed and shows that a proportional relationship exists between the surface area of the solid/liquid interface and the observed melting rate. This is confirmed through detailed microanalysis of quenched samples that shows excellent agreement between the proportional change in interfacial surface area and the observed melting rate. Thus, it is concluded that the increased melting rates observed for metals burning in reduced gravity are due to altered interfacial geometry, which increases the contact area for heat transfer between the liquid and solid phases. This leads to the conclusion that heat transfer across the solid/liquid interface is the rate-limiting mechanism for melting and burning, limited by the interfacial surface area. This is a fundamental result that applies in normal gravity and reduced gravity and clarifies that oxygen availability, as postulated in the literature, is not rate limiting. It is also established that, except for geometric changes at the solid/liquid interface, the heterogeneous burning phenomenon is the same at each gravity level. A conceptual framework for understanding and discussing the many factors that influence heterogeneous burning is proposed, which is relevant to the study of burning metals and to oxygen system fire safety in both normal-gravity and reduced-gravity applications.

Βασικός στόχος της παρούσας διατριβής είναι η αποσαφήνιση του τρόπου της διεπιφανειακής εναπόθεσης του νικελίου στην επιφάνεια της τιτάνιας, η οποία λαμβάνει χώρα στη διεπιφάνεια “τιτάνιας / ηλεκτρολυτικού διαλύματος”. Ο στόχος αυτός επιτεύχθηκε μέσω μιας κατάλληλης θεωρητικής και υπολογιστικής επεξεργασίας δεδομένων, που προέρχονται από την εφαρμογή ηλεκτροχημικών και φασματοσκοπικών τεχνικών, την εκτέλεση πειραμάτων προσρόφησης, καθώς επίσης και σε ab – initio υπολογισμούς για την εξακρίβωση της δομής των συμπλόκων εσωτερικής σφαίρας τα οποία σχηματίζονται και των συγκεντρώσεών τους στη διεπιφάνεια. Δείγματα βιομηχανικής τιτάνιας (Degussa, P 25) πλούσιας σε ανατάση χρησιμοποιήθηκαν για το σκοπό αυτό. Η μελέτη πραγματοποιήθηκε για μια ευρεία περιοχή παραμέτρων εμποτισμού και πιο συγκεκριμένα τιμές pH, ιονικής ισχύος και συγκέντρωσης του υδατικού συμπλόκου [Ni(H2O)6]2+ στο διάλυμα. Μεταβάλλοντας τις παραμέτρους αυτές ρυθμίστηκε η επιφανειακή συγκέντρωση των ιόντων Ni(II). Χρησιμοποιήθηκε μια πληθώρα μεθοδολογιών στηριγμένες σε δεδομένα εναπόθεσης, μετρήσεις τιμών pH, ποτενσιομετρικές τιτλοδοτήσεις μάζας και πειράματα μικροηλεκτροφόρησης σε συνδυασμό με φασματοσκοπία διάχυτης ανάκλασης (DRS). Ο συνδυασμός όλων των παραπάνω φαίνεται πως υποδεικνύει το σχηματισμό μονοπυρηνικών / ολιγοπυρηνικών συμπλόκων εσωτερικής σφαίρας κατά την εναπόθεση των ιόντων [Ni(H2O)6]2+ στη διεπιφάνεια “τιτάνιας / ηλεκτρολυτικού διαλύματος”. Η μοντελοποίηση της διαδικασίας εναπόθεσης η οποία βασίστηκε στα προαναφερθέντα πειραματικά αποτελέσματα, αποκάλυψε την ακριβή δομή αυτών των επιφανειακών συμπλόκων και κατέστησε δυνατό τον προσδιορισμό της κατανομής των εναποτιθέμενων ειδών και ειδικότερα των σχετικών τους συγκεντρώσεων για διάφορες τιμές της επιφανειακής συγκέντρωσης Ni(II). Στο συμπαγές τμήμα της διεπιφάνειας “τιτάνιας / ηλεκτρολυτικού διαλύματος” σχηματίζονται τρία μονοπυρηνικά σύμπλοκα εσωτερικής σφαίρας: ένα μονο - υποκατεστημένο, δι - υδρολυμένο σύμπλοκο πάνω από τις ακραίες οξο - ομάδες ανταλλάσοντας ένα υδατικό υποκαταστάτη με ένα επιφανειακό άτομο οξυγόνου (διαμόρφωση TiO), ένα δι - υποκατεστημένο, δι - υδρολυμένο σύμπλοκο πάνω από δύο ακραίες γειτονικές οξο - ομάδες ανταλλάσοντας δύο υδατικούς υποκαταστάτες με δύο επιφανειακά άτομα οξυγόνου (διαμόρφωση TiO - TiO) και ένα δι - υποκατεστημένο μη υδρολυμένο σύμπλοκο πάνω από μία ακραία και μία γεφυρωμένη οξο - ομάδα (διαμόρφωση Ti2O - TiO). Επιπρόσθετα, σχηματίζονται ένα διπυρηνικό και ένα τριπυρηνικό σύμπλοκο εσωτερικής σφαίρας κατά την εναπόθεση των ιόντων [Ni(H2O)6]2+ στο συμπαγές τμήμα της διεπιφάνειας “τιτάνιας / ηλεκτρολυτικού διαλύματος”. Στην πρώτη περίπτωση η θέση υποδοχής συμπεριλαμβάνει μία γεφυρωμένη και δύο ακραίες οξο - ομάδες (διαμόρφωση Ti2O-TiO—TiO), ενώ στη δεύτερη περίπτωση δύο γεφυρωμένες και τρεις ακραίες οξο - ομάδες (διαμόρφωση Ti2O-TiO—TiO—TiO-Ti2O). Η διαμόρφωση TiO κυριαρχεί σε όλο το εύρος της περιοχής επιφανειακών συγκεντρώσεων το οποίο μελετήθηκε. Η συνεισφορά των διαμορφώσεων TiO - TiO και Ti2O - TiO είναι επίσης σημαντική σε πολύ χαμηλές τιμές επιφανειακής συγκέντρωσης Ni(II), μειώνεται όμως σε μεγάλο βαθμό καθώς αυτή αυξάνεται. Οι σχετικές επιφανειακές συγκεντρώσεις των διαμορφώσεων Ti2O-TiO--TiO και Ti2O-TiO—TiO--TiO-Ti2O αρχικά αυξάνουν με την επιφανειακή συγκέντρωση Ni(II) και μετά μένουν πρακτικά σταθερές. Η προαναφερθείσα κατανομή των εναποτιθέμενων ειδών στη διεπιφάνεια εξηγήθηκε με τη χρήση στερεοχημικών όρων. Επιπρόσθετα, η δομή των επιφανειακών συμπλόκων εσωτερικής σφαίρας και η κατανομή αυτή είναι σε γενική συμφωνία με εκείνες οι οποίες προβλέφθηκαν με την εκτέλεση ημιεμπειρικών κβαντομηχανικών υπολογισμών για την εναπόθεση του Ni στο TiO2. Το μοντέλο εναπόθεσης το οποίο αναπτύχθηκε περιέγραψε πολύ καλά τις adsorption edges, τις τιτλοδοτήσεις “πρωτονίου - ιόντος” και τις ισόθερμες εναπόθεσης, ενισχύοντας επιπλέον την αξιοπιστία και ορθότητά του. / The main goal of this work is the elucidation of the mode of interfacial deposition of nickel on the surface of titania, which takes place in the “titania / electrolytic solution” interface. This goal was achieved through the use of several methodologies combined with spectroscopic techniques, as well as ab – initio calculations in order to determine the structure of the inner sphere complexes formed as well as their relative interfacial concentrations. Samples of titania (Degussa, P 25) rich in anatase were used for this purpose. The study was performed over a quite wide range of impregnation parameters namely pH, ionic strength and concentration of the [Ni(H2O)6]2+ aqua complex in the solution. By changing these parameters, the Ni(II) surface concentration was regulated. Several methodologies based on deposition data, pH measurements, potentiometric mass titrations and microelectrophoresis have been used in conjunction with diffuse reflectance spectroscopy. These suggested the formation of mono - nuclear / oligo - nuclear inner sphere complexes upon deposition of the [Ni(H2O)6]+2 ions at the “titania / electrolytic solution” interface. The modelling of the deposition process based on the aforementioned experimental results revealed the exact structure of these surface complexes and allowed the determination of their relative concentrations at various values of Ni(II) surface concentration (interfacial speciation). Three mono-nuclear inner sphere complexes are formed at the compact layer of the “titania / electolytic solution” interface; one mono - substituted, di - hydrolyzed complex above the terminal oxo - groups by exchanging one water ligand with a surface oxygen atom (TiO configuration), a di - substituted, di - hydrolyzed complex above two terminal adjacent oxo - groups by exchanging two water ligands with the two surface oxygen atoms (TiO-TiO configuration) and one di - substituted, non - hydrolyzed complex above one terminal and one bridging adjacent oxo - groups ( Ti2O-TiO configuration). One binuclear and one three - nuclear complex are formed, in addition, at the compact layer. In the first case the receptor site involves one bridging and two terminal oxo- groups (Ti2O-TiO--TiO configuration) whereas in the second case the receptor site involves two bridging and three terminal oxo - groups (Ti2O-TiO--TiO--TiO-Ti2O configuration). The TiO configuration predominates in the whole range of the surface concentration studied. The contribution of the TiO-TiO and Ti2O-TiO configurations is also important at very low Ni(II) surface concentration, but this contribution is rapidly decreased as the Ni(II) surface concentration increases. The relative surface concentrations of the Ti2O-TiO--TiO and Ti2O-TiO--TiO--TiO-Ti2O configurations initially increase with the Ni(II) surface concentration and then remain practically constant. The aforementioned interfacial speciation was explained in stereochemical terms. Moreover, the structure of the inner sphere surface complexes and the interfacial speciation are in general agreement with those predicted by performing semi-empirical quantum chemical calculations of the deposition process. The deposition model developed has described the ‘adsorption edges’, the ‘proton–ion titration curves’ and the deposition isotherms well, further corroborating its validity.

Ce travail combine l'électrochimie à l'interface liquide - liquide avec le procédé sol - gel pour la modification interfaciale avec de la silice mésoporeuse. Dans la première partie de ce travail, l’interface liquide – liquide macroscopique a été utilisée pour séparer la solution aqueuse de l'espèce de précurseur de silice hydrolysées (tétraéthoxysilane (TEOS)) de l'agent tensioactif cationique (cethyltrimethylammonium (CTA+) qui a agi comme un template et a été dissous dans le dichloroéthane. Le dépôt de matériau de silice a été déclenchée par le transfert du CTA+ à partir de la phase organique vers la phase aqueuse. CTA+ qui a transféré à la phase aqueuse a catalysé la réaction de condensation de la silice sur l’interface liquide – liquide. Le dépôt de silice à des interfaces liquide – liquide miniaturisées était la deuxième partie de ce travail. Les dépôts stables sur le côté de l'interface ont été synthétisés in situ par voie électrochimique. La stabilité mécanique des dépôts de silice permis un traitement thermique de la silice. Basé sur les techniques d’imagerie (par exemple SEM) il a été constaté que les dépôts forment des hémisphères pour des temps plus long. La réaction interfaciale a également été suivie in situ par spectroscopie Raman confocale. Caractéristiques moléculaires de l'interface ont été modifiées de manière spectaculaire une fois les espèces CTA+ ont été transférés à la phase aqueuse. Les interfaces liquide – liquide miniaturisés et modifiés ont également été évaluée avec le transfert voltampérométrique / This work combines the electrochemistry at the interface between two immiscible electrolyte solutions (ITIES) with the Sol – Gel process of silica leading to an interfacial modification with mesoporous silica using soft template. In the first part of this work the macroscopic liquid – liquid interface was employed to separate the aqueous solution of the hydrolyzed silica precursor species (tetraethoxysilane (TEOS)) from the cationic surfactant (cethyltrimethylammonium (CTA+)) dissolved in the dichloroethane. The silica material deposition was controlled by the electrochemical CTA+ transfer from the organic to the aqueous phase. Template transferred to the aqueous phase catalyzed the condensation reaction and self-assembly resulting in silica deposition at the interface. Silica deposition at the miniaturized ITIES (membranes supporting array of micrometer in diameter pores were used in this regard) was the second part of this work. Silica interfacial synthesis performed in situ resulted in stable deposits growing on the aqueous side of the interface. Mechanical stability of the supported silica deposits allowed further processing – silica material was cured. Based on imaginary techniques (e.g. SEM) it was found that deposits forms hemispheres for longer experimental time scales. Interfacial reaction was also followed with in situ confocal Raman spectroscopy. Molecular characteristics of the interface were changed dramatically once CTA+ species were transferred to the aqueous phase. Array of microITIES modified with silica was also assessed by ion transfer voltammetry