An optical fiber humidity sensor has been devised using a porous sol-gel silica (PSGS) coating as a transducer. Evanescent wave scattering (EWS) in the PSGS coating. PSGS particles are highly hydrophilic and have a strong tendency to absorb water molecules from the surrounding environment. The absorbed water molecules form a thin layer on the inner surface of the pores inside the porous silica and enhance EWS, from which an indicatory signal can be obtained. The humidity sensor presented in this thesis has a fast response, is reversible, low cost, and has a broad dynamic relative humidity range from 3.6?0-6% to 100% or humidity range from 1.2ppm to 30000ppm. Because of its multiple advantages, including immunity to electromagnetic interference, resistance to corrosive environments, and high sensitivity, this humidity sensor has various applications. In soil moisture sensing, this humidity sensor can avoid the interference caused by compounds in soil water. For electrical transformer moisture sensing, this humidity sensor can avoid the effect of electromagnetic fields.

Modeling the competition between drying and curing processes in polymerizing films is of great importance to many existing and developing materials synthesis processes. These processes involve multiple length and time scales ranging from molecular to macroscopic, and are challenging to fully model in situations where the polymerization is non-ideal, such as sol-gel silica thin film formation. A comprehensive model of sol-gel silica film formation should link macroscopic flow and drying (controlled by process parameters) to film microstructure (which dictates the properties of the films). This dissertation describes a multiscale model in which dynamic Monte Carlo (DMC) polymerization simulations are coupled to a continuum model of drying. Unlike statistical methods, DMC simulations track the entire molecular structure distribution to allow the calculation not only of molecular weight but also of cycle ranks and topological indices related to molecular size and shape. The entire DMC simulation (containing 106 monomers) is treated as a particle of sol whose position and composition are tracked in the continuum mass transport model of drying. The validity of the multiscale model is verified by the good agreement of the conversion evolution of DMC and continuum simulations for ideal polycondensation and first shell substitution effect (FSSE) cases. Because our model allows cyclic and cage-like siloxanes to form, it is better able to predict the silica gelation conversion than other reported kinetic models. By studying the competition between molecular growth and cyclization, and the competition between mass transfer (drying) and reaction (gelation) on the drying process of the sol-gel silica film, we observe that cyclization delays gelation, shrinks the molecular size, increases the likelihood of skin formation, and leads to a molecular structure gradient inside the film. We also find that compared with a model with only 3-membered rings, the molecular structure is more complicated and the structure gradients in the films are larger with 4- membered rings. We expect that our simulation will allow better prediction of the formation of structure gradients in sol-gel derived ceramics and other nonideal multifunctional polycondensation products, and that this will help in developing procedures to reduce coating defects.

Le travail de thèse est consacré au développement d'électrodes composites à base d'argiles naturelles et à leur caractérisation électrochimique à des fins analytiques, notamment pour le dosage de cations métalliques (Cu2+) et de quelques substances à visée thérapeutique. Le premier chapitre expérimental est consacré à une étude comparée des caractéristiques chimiques, structurales et physico-chimiques de deux argiles naturelles extraites sur deux sites en Roumanie. Il apparaît que l'argile de Valea Chioarului, de type montmorillonite, présente les propriétés les plus intéressantes avec une surface spécifique importante (190 m2/g). Le deuxième chapitre fait état d'une analyse prospective des deux argiles comme matériaux d'électrodes en utilisant un film composite argile/poly-électrolyte. Trois molécules d'intérêt pharmaceutique ont été choisies pour cible, l'acide ascorbique, la riboflavine et l'acétaminophène. Cette dernière molécule peut être détectée soit par oxydation directe, soit via une réaction électro-enzymatique avec la peroxydase de raifort. Les troisième et quatrième chapitres sont consacrés à l'utilisation d'argiles échangées par des cations ammonium pour la détection du cuivre. Ainsi, l'argile de Valea Chioarului a été échangée partiellement avec du tétrabutylammumium. La perméabilité des films d'organo-argile recouverts d'un film de cellulose a été étudiée en utilisant différentes sondes électro-actives de charge différentes, Ru(NH3)63+, [Fe(CN)6]3-, Fc(MeOH)2. Les conditions expérimentales ont été ensuite optimisées pour la détection du Cu(II) et Cd(II) avec ces électrodes modifiées en voltammétrie à vague carrée. Dans le dernier chapitre, une configuration originale d'électrode modifiée a été mise au point. Il s'agit d'électrodes composites argile-silice mésoporeuse préparée par électrodéposition en présence ou non d'un tensioactif, le cétyltriméthylammonium. La perméabilité des films a également été étudiée avec les mêmes molécules que précédemment. Il apparait que l'extraction du tensio-actif conduit à des films homogènes très poreux et stables qui présentent des propriétés d'accumulation du Cu(II) / The thesis is devoted to the development of composite electrodes based on natural clays and their electrochemical characterization for analytical purposes, in particular for the determination of metal cations (Cu2+) and some therapeutic substances. The first experimental chapter is devoted to a comparative study of the chemical, structural and physico-chemical properties of two natural clays extracted from two sites in Romania. It appears that Valea Chioarului clay, of montmorillonite type, has the most interesting properties with a high specific surface area (190 m2/g). The second chapter presents a prospective analysis of the two clays as electrode materials using a clay/polyelectrolyte composite film. Three target molecules of pharmaceutical interest have been selected: ascorbic acid, riboflavin, and acetaminophen. This last molecule can be detected either by direct oxidation or through an electro-enzymatic reaction with horseradish peroxidase. The third and fourth chapters are devoted to the use of clays exchanged by ammonium cations for copper detection. Thus, Valea Chioarului clay was partially exchanged with tétrabutylammumium. The permeability of the organoclay films coated with a cellulose membrane was studied by using different electroactive probes of different charging, Ru(NH3)63+, [Fe(CN)6]3-, Fc(MeOH)2. The experimental conditions were then optimized for the detection of Cu (II) and Cd (II) with the modified electrodes by square wave voltammetry. In the last chapter, an original modified electrode configuration was developed. This implies composite mesoporous silica-clay electrodes prepared by electrodeposition in the presence or absence of a surfactant, like cetyltrimethylammonium. The permeability of the films was also investigated with the above mentioned molecules. It appears that the extraction of the surfactant leads to very stable and homogeneous porous films that show Cu (II) accumulation properties