Alors que le procédé sol-gel a été fortement étudié il existe peu d’études concernant le procédé sol-gel photoinduit. Le principe repose sur la libération in situ d’espèces acides ou basiques photogénérées capables d’amorcer les réactions d’hydrolyse et de condensation caractéristiques du procédé sol-gel. L’alternative photoinduite est particulièrement adaptée pour préparer des films minces et possède de nombreux avantages tel qu’une formulation de départ stable, sans solvant et photolatente ainsi que des vitesses de réactions plus importantes. À partir de précurseurs inorganiques simples, nous avons dans un premier temps réalisé une étude mécanistique et cinétique de ce procédé en catalyse acide. Puis l’influence de différents paramètres physiques, chimiques et photochimiques sur les vitesses de réactions a été évaluée. Une comparaison avec un système similaire en catalyse basique a aussi été réalisée.Dans un second temps, nous nous sommes intéressés à appliquer ce procédé photoinduit pour la préparation de films de silice mésoporeuse. Un tensioactif de type copolymère tribloc a été ajouté au précurseur inorganique de départ. La faisabilité d’une approche photochimique à partir de formulation sans eau ni solvant a d’abord été étudiée, des films mésoporeux ont été obtenus. Puis, nous nous sommes intéressés à la compréhension des 2 mécanismes interdépendants : le mécanisme d’assemblage du tensioactif et la condensation du réseau inorganique. Par la suite, le système a été optimisé pour aboutir à un contrôle précis de la structure et de la taille des pores. Enfin, une dernière étape a consisté à éliminer la partie organique (pour libérer la porosité) grâce à l’UV. / Whereas sol-gel process has been extensively studied almost no papers concerning photoinduced sol-gel process subsists. This later is based on in situ generation of acids or basics species able of initiating hydrolysis and condensation reactions happening on sol-gel process. This photoinduced alternative is particularly adapted for preparation of thin films and has lots of advantages such as photolatent, stable, solvent and water free initial formulation along with faster reaction rates. In one hand, from simple inorganic precursors, a kinetic and mechanistic study of the photoacid-catalyzed sol-gel reactions was realized. Then, we attempt to define what chemical, physical and photochemical parameters determine the precise sequence, kinetics and advancement of these reactions under different processing conditions Furthermore, an equivalent photobase-catalyzed sol-gel process has been also studied thoroughly. In a second hand, we focus on application of this photoinduced process for the preparation of mesoporous silica films. A triblock copolymer surfactant was added to the initial inorganic precursor. Feasibility of this photochemical approach from water and solvent free formulation was first investigated and mesoporous films were obtained. Then, we work on understanding the two interdependent mechanisms: surfactant self-assembly and inorganic network condensation. The system was after that optimized in order to have a precise control of pore size and structure. Finally, the last point involves organic photodegradation in order to liberate porosity.

Chapter one reviewed the development of sol-gel stationary phase for gas chromatograph (GC). Inorganic sol-gel precursor creates the substrate support for stationary phase bind to silica surface through the condensation of silanol groups, the rough surface with enhanced surface area enlarger the capacity of the sol-gel stationary phase, the porosity of sol-gel structure decreases the mass transferring coefficient, the term C in Van Deemter equation, which makes sol-gel stationary phase thicker coating up to 1 um but keeps the high resolution for gas chromatography. Chemical bound stationary phase significantly improve GC column with better thermal stability and solvent stability. Partial derivatizations of known polymers have not increased the column performance but remained at the same level of 3200 plates per meter. The sol-gel chemistry with essential structure rebuilding will make sol-gel stationary phase to a new level. The chapter two reported the non-silica-based metal alkoxide oxide as the new building block, cooperated with known polymer poly(dimethyldiphenylsilanoxan), developed the original nonpolar feature of the stationary phase to broad the polarity from the nonpolar to extreme polar, overcome the thermal stability for other types of polar column. The theoretical plate number reached the 3200 plates per meter, and the optimized plate number arrived at the top level at 3800 plates per meter. The basic recipe and preparation of sol-gel process were verified by tungsten alkoxide incorporated with poly(dimethyldiphenylsilanoxan) as the stationary phase which arrived the same plate number level at 3800 per meter. Chapter three demonstrated the preparation of core-shell particle for HPLC. Conventional silica core particles were prepared with stÖbe methods. The extended layer of germanium oxide coating was made with acid and alkaline as a catalyst. EDS characterize the extended layers of germanium oxide has been coated at ratio 12/1(Ge/Si). Then the carbon loading with C 18 for surface derivatization were also confirmed with EDS testing. 2 um core-shell particles were successfully prepared from the external composition (1.7 um core, 0.3 um shell). The function of the core-shell particles was slurry packed with 5cm regular steel column and the capillary column with sol-gel frit. The preliminary HPLC testing showed the core-shell particles had more retention ability compare with 4 um commercial core particles. The backpressure of the short steel column and capillary both were beyond the pressure limit of conventional HPLC pump. Chapter three demonstrates the new ideal of the surface sol-gel process for GC stationary phase. Without the catalyst, the sol solution has constant viscosity and gelation time is much longer, the sol-gel reaction was taking on the silica surface only, to accomplish the thinner coating for sol-gel stationary phase. From the retention time of the grob mixture, the surface sol-gel coated 2 meters of column acquired the half retention time, grob mixture analytes were eluted within 7 minutes, compared with conventional sol-gel coated column eluted within 14 minutes. Without the TFA as the catalyst, the sol-gel matrix may not form effective surface area and porosity to support the functional polymer for separation, the column performances were two third of the protocol column, at 1500-2500 plate number per meter. The coating results proved the sol-gel stationary phase could be fulfilled with diluted sol solution by static coating. Basic parameters for dynamic coating and static coating with conventional coating and surface sol-gel were acquired for further development. The germania and niobium precursor is highly active, the water amount in the solvents used as received without drying process can meet the surface sol-gel coating without precipitates and gelation formed before finishing coat. For germania -PDMDPS column, thermal stability is very important because of the temperature for remaining the low residual OH- group in silica and germania film at 350 °C.

La mise en forme de matériaux fonctionnels et leur texturation contrôlée à toutes les échelles sont des conditions sine qua non pour l’amélioration des systèmes existants. Ce projet de thèse consiste en la création de structures solides complexes en utilisant des méthodes interdisciplinaires telles que la chimie sol-gel et la physique des fluides complexes. Ainsi, il est possible d’obtenir des fibres ou des films de dioxyde de Titane poreux présentant des pores de différentes tailles organisés hiérarchiquement. Cette organisation texturale optimise le transport de matière (gaz / liquides) pour des applications telles que la dépollution d’air (photocatalyse) ou les cellules solaires à colorant. Par ailleurs, nous avons contrôlé l’alignement de nano-bâtonnets d’oxyde de Zinc au sein d’une fibre macroscopique générant ainsi des propriétés collectives d’émission de lumière (photoluminescence)anisotrope, spécificité d’utilité pour l’électronique à permutation. Enfin, nous avons synthétisé des nano objets anisotropiques et des nano-lamelles de polypyrrole afin de générer des films minces lisses avec des propriétés électriques permettant leur utilisation comme électrode ou électrolyte solide dans des cellules solaires à colorant. / The shaping of functional materials and the control of their texture at all length scales are sine qua non conditions for the improvement of current systems. This PhD project consists in creating complex solid architectures using interdisciplinary methods such as sol-gel chemistry or complex fluids physics. Therefore, it is possible to synthesize Titanium Dioxide macroscopic fibers orfilms which possess a hierarchical porosity. This organization allows the optimization of the matter transport (liquid/gaz) for air depollution application (photocatalysis) or dye-sensitizedsolar cells. In another project, we were able to control the alignment of zinc oxide nanorods within a macroscopic fiber. This alignment provides to the fiber an anisotropic photoluminescence behavior which can be useful for switching devices application. Finally, we synthesized anisotropic particles and nano-sheets of polypyrrole (conducting polymer) in order to obtain smooth thin films presenting interesting electrical properties. The objective was to use them as electrolyte and/or electrode in dye-sensitized solar cells.

Ces travaux sont consacrés à la synthèse d'un nouveau type de métamatériaux acoustiques dans le domaine ultrasonore. L'étude porte sur les résonances de cavité, elles peuvent influer sur les différentes grandeurs physiques impliquées dans la propagation des ondes acoustiques. Pour amplifier les résonances, la stratégie a été de mettre en place un contraste de vitesse de phase entre la matrice et les inclusions résonantes. Pour travailler dans le domaine ultrasonore, les techniques de mise en oeuvre sont issues de la microfluidique. Les premiers échantillons sont élaborés par émulsification micrométrique assistée par robotique. Cela permet d'obtenir des polydispersités de l'ordre de 1%. Différents modes de résonances acoustiques ont ainsi été observés. Les recherches ont été poussées jusqu'à l'étude de la polydispersité (1 à 12 %) et l'analyse de systèmes comprenant deux populations de gouttes. Le reste du travail s'est fait en millifluidique avec la mise en forme de dispersions de billes de xérogel de silice avec de plus importants contrastes de vitesse. La synthèse utilisée est une réaction de type sol-gel en milieu basique salin. Le montage millifluidique a été mis en place et calibré pour cette synthèse. La réaction chimique et les particules obtenues ont été caractérisées de nombreuses manières (Raman, rhéologie, mesure de compression, de densité, BET, MEB...). Les mesures acoustiques sur de tels systèmes ont permis de mettre en évidence des gammes de fréquence pour lesquelles l'indice de réfraction acoustique était négatif les plus fortes fractions volumiques (≈ 20%). / This work is dedicated to the synthesis of a new kind of acoustic metamaterials working in the ultrasonic range. The study is based on cavity resonance which can influence physical quantities involved in acoustic wave propagation. For amplifying these resonances, a large phase velocity contrast is required between the matrix and the inclusions.For the ultrasonic range and because of size requirements, the implementation is achieved using microfluidics. First, samples are generated using robotic-assisted emulsification which leads to a very small size polydispersity, around 1%. For these calibrated emulsions, different modes of acoustic resonance are clearly identified. We then generated polydisperse samples on purpose (up to 12%) and correlated the quality factor of the resonances to the size dispersity. Then, in order to enhance the resonance magnitude, silica-based xerogels are synthesized and templated using digital millifluidics. The chemical reaction along with the final xerogel micro-beads (≈ 100 μm radius) are characterized with a large variety of techniques (Raman, rheology, compression and density measurement, BET, SEM...). Acoustic measurements on these systems show that there is a frequency range with a negative acoustic refractive index for a at high enough volume fraction of xerogel particles (20%).

Les piles à combustibles à électrolyte solide de type SOFC permettent de transformer directement l’énergie de la réaction chimique de formation de l’eau à partir de l’hydrogène et de l’oxygène, en énergie électrique. De nos jours, les apatites de type silicates de terres rares présentent beaucoup d’intérêt comme électrolyte solide en raison de leurs propriétés de transport élevées avec une forte conductivité ionique et une faible énergie d'activation. Ils peuvent fonctionner de manière stable à une température intermédiaire sur une large plage de pression partielle d'oxygène en maintenant d'excellentes performances. Ils sont ainsi considérés comme de bons candidats pour les électrolytes de piles de type IT-SOFC. Parmi cette série de conducteurs, le type La-Si-O possède une conductivité plus élevée et leur performance serait modifiée par différents éléments dopants.L'objectif de cette thèse est d'étudier les effets des éléments de substitution / dopage ainsi que les méthodes de synthèse sur les propriétés structurales ainsi que sur la conductivité des apatites de type silicates de lanthane. Dans cette étude, nous utilisons une double approche: une approche de simulation et une approche expérimentale pour optimiser la pureté et les performances des matériaux d'électrolyte.Dans l'approche de simulation, le calcul basé sur la DFT (Théorie de la fonctionnelle de la densité) a été réalisée en vue d’étudier l'effet des positions de dopage: dopant Sr à La position de La et dopant Ge à la position de Si. Les résultats obtenus par le calcul concernant la conductivité ionique confirment ceux obtenus par l’expérience.Avec l’approche expérimentale, nous présentons la synthèse et la caractérisation de La10Si6O27 (LSO) dopé par Sr et élaboré par des procédés sol-gel. Les résultats montrent que la conductivité ionique est activé thermiquement et que les valeurs se situent entre 4,5 × 10-2 et 1 x 10-6 S·cm-1 à 873 K et dépend des conditions d’élaboration et de la composition de la poudre. / The Solid Oxide Fuel Cell (SOFC) defined by its ceramic and oxide electrolyte, is an electrochemical energy conversion device that produces electricity directly from the chemical reaction of fuel. Nowadays, apatite type rare earths silicates and germaniums attract many interests as the solid electrolyte due to the superior transport properties with high ionic conductivity and low activation energy. They can operate stably at intermediate temperature over a wide oxygen partial pressure range and maintain excellent performances, being considered as a candidate for IT-SOFC electrolytes. Among this series of conductors, the La-Si-O type has a higher conductivity and the performance would be modified by different doping elements.The objective of this thesis is to study the effects of element substitution/doping and synthesis methods on the structural and conductivity properties of apatite type lanthanum silicates. In this study, we use a double approach: a simulation approach and an experimental approach to optimize the electrolyte materials purity and performance.Using simulation approach, a first principle calculation based on DFT (Density Functional Theory) was carried out to investigate the effect on doping positions: Sr dopant at La position and Ge dopant at Si position. The calculation results give a connection to the ionic conductivity obtained by experiments.With experimental approach, we present the synthesis and characterization of Sr-doped La10Si6O27 (LSO) prepared through an optimized water-based sol-gel process. The results show that the ionic conductivity is thermally activated and values lies between 4.5×10-2 and 1×10-6 Scm-1 at 873 K as a function of the composition and powder preparation conditions.

The present work provides an insight in the development of silica films prepared by water-based sol-gel process. The weaknesses of the coating technology are identified, also solutions are discussed. The silica film is applied on aluminium alloy 6082-T6 and magnesium alloy AZ31. The development of the coating properties such as cost-efficiency, crack-free, self-healing and long-term corrosion protection is the main topic of this work. Cracking is the major drawback of silica films; the cracks are generated due to shrinkage of the film during the heat treatment, nanoparticles-doped silica film is successfully reduced the shrinkage which leads to crack-free silica films. The self-healing of the coated aluminium and magnesium samples is generated by corrosion inhibitors-doped silica film. When a defect appears in the film, the corrosion inhibitors leach out of the silica film to the defect area to heal the corroded surface. The long-term corrosion protection is realized by means of a mixture of corrosion inhibitors-doped silica film. / Die vorliegende Arbeit liefert einen Einblick in die Entwicklung von Silikafilmen, die mittels Sol-Gel-Prozess auf Wasserbasis hergestellt wurden. Die Schwächen der Beschichtungstechnologie werden dargestellt und Lösungen diskutiert. Der Silikafilm wird auf Aluminiumlegierung 6082-T6 und Magnesium-legierung AZ31 aufgebracht. Schwerpunkt dieser Arbeit ist die Entwicklung der Schichteigenschaften, wie Kosteneffizienz, Rissfreiheit, Selbstheilung so wie langfristiger Korrosionsschutz. Rissbildung ist ein wesentlicher Nachteil von Silikafilmen; rissfreie Filme wurden mittels nanopartikeldotierter Silikafilme hergestellt. Die Selbstheilung von Aluminium-und Magnesiumsubstraten mit Silikafilm wird durch den Effekt der wasserlöslichen Korrosionsinhibitoren generiert. Die Experimente haben gezeigt, dass die Proben mit inhibitordotierter Beschichtung selbst gegen Korrosion geschützt sind. Ein langfristiger Korrosionsschutz wird durch eine Mischung aus Korrosionsinhibitor-dotierten Silika-Film realisiert.

The Ni-base superalloy, IN-718, has been coated with alumina sols. Coated surfaces, carrying alumina layers having thicknesses between 0.6 μm and 3.6 μm show a significantly reduced oxidation rate when compared with uncoated reference surfaces, even if heating temperature is increased up to 900 °C and heating time is extended to 800 h. Alumina layers were prepared via sol-gel processing using a modified Yoldas procedure to obtain alumina sols. No change in rheological sol behavior was observed for more than 1 year of aging under static conditions at room temperature. Depending on pH value, modified Yoldas sols contain a manifold of Al species, among them Al13 polycations. Thermal evolution of sol derived alumina powders depends on Al speciation of parent sols. Depending on sol composition, both gamma-Al2O3 and eta-Al2O3 occur as intermediate transition aluminas. Phase composition and gas phase velocity influence oxygen permeability of thin layers prepared with modified Yoldas sols.

Novel on-line methods are presented for the extraction, preconcentration and analysis of zwitterionic biomolecules using sol-gel-coated columns coupled to a conventional UV/visible detector. The presented approaches do not require any additional modification of the commercially available standard CE instrument. Extraction, stacking, and focusing techniques were used in the preconcentration procedures. The positively charged sol-gel coatings were created using N-octadecyldimethyl[3-(trimethoxysilyl) proply]ammonium chloride (C18-TMS) in the coating sol solutions. Due to the presence of a positively charged quaternary ammonium moiety in C18-TMS, the resulting sol-gel coating carried a positive charge. The negatively charged sol-gel coatings were due to the presence of sulfonate groups, which was formed from the oxidation of thiol groups in precursor mercaptopropyltrimethoxysilane (MPTMS) by hydrogen peroxide. Besides MPTMS, tetramethoxysilane (TMOS) and n-octadecyltriethoxysilane (C18-TEOS) were also used to prepare the sol solution for the creation of the negatively charged coatings. For extraction, the pH of the samples was properly adjusted to impart a net charge opposite to the sol-gel coatings. When a long plug of the sample was passed through the sol-gel-coated capillary, extraction was achieved via electrostatic interaction between the charged sol-gel coating and the charged sample molecules. The extracted analytes were then desorbed and focused via local pH change and stacking. The local pH change was accomplished by passing buffer solutions with proper pH values, while a dynamic pH junction between the sample solution and the background electrolyte was utilized to facilitate solute focusing. The developed methods showed excellent extraction and preconcentration effects on both positively and negatively charged sol-gel-coated columns. On-line preconcentration and analysis results obtained on the sol-gel coated columns were compared with those obtained on an uncoated fused silica capillary of identical dimensions using conventional sample injections. The described procedure provided a 150 000-fold enrichment effect for alanine on the positively charged sol-gel-coated column. On the negatively charged sol-gel-coated column, the presented sample preconcentration technique provided a sensitivity enhancement factor (SEF) on the order of 3 x 103 for myoglobin, and 7 x 103 for asparagines. The developed methods provided acceptable repeatability in terms of both peak height and migration time.

The discovery of superconductivity in ceramic materials by Bednorz and Müller [2, 3] in early 1987, immediately followed by Wu et al. [4, 5] who showed that YBa2Cu3O7−x (YBCO) becomes superconducting (92K) well above the boiling point of nitrogen (77K) created a great excitement in superconductivity research. Potential applications of high Tc-superconductors require large critical currents and high-applied magnetic fields. Effective ways to increase the critical current density at high magnetic fields in YBCO are the introduction of nanoparticles and chemical substitution of yttrium by other rare earth elements. Since low costs and environmental compatibility are essential conditions for the preparation of long length YBCO films, the cost effective chemical solution deposition (CSD) procedure was selected, given that no vacuum technology is required. To reveal the flexibility and the good optimization possibilities of the CSD approach two main processes were chosen for comparison: a fluorine-free method, namely the polymer-metal precursor technique, and a fluorine-based method, the metalorganic deposition (MOD) using the trifluoroacetates (TFA) technique. Sharp transition temperature widths DTc of 1.1K for the polymer metal method, 0.8K for TFA method and critical current densities Jc of _3.5MA/cm2 shows that high quality YBCO thin films can be produced using both techniques. Especially interesting is the magnetic field dependence of the critical current density Jc(B) of the Y(Dy)BCO (80 %) films showing that for the lower magnetic fields the critical current density Jc(B) is higher for a standard YBCO film, but at fields higher than 4.5T the critical current density Jc(B) of Y(Dy)BCO is larger than that for the YBCO. Above 8T, Jc(B) of the Y(Dy)BCO film is more than one order of magnitude higher than in pure YBCO film. / Die Entdeckung der Supraleitung in keramischen Materialien durch Bednorz und Müller 1987 und die kurz darauf folgende Beobachtung von Wu et al., dass YBa2Cu3O7−x (YBCO) supraleitende Eigenschaften deutlich oberhalb (92K) des Siedepunktes von Stickstoff (77K) aufweist, führten zu einer enormen Intensivierung der Forschung hinsichtlich neuer supraleitender Materialien sowie deren Eigenschaften und möglichen Einsatzgebieten. Potentielle Anwendungsgebiete für diese neuen Hochtemperatur-Supraleiter erfordern hohe kritische Stromdichten und hohe kritische Feldstärken. Effektive Wege zur Erhöhung der kritischen Stromdichte in starken Magnetfeldern in YBCO sind der Einbau von Nanoteilchen oder die chemische Substitution von Yttrium durch ein anderes Seltenerd-Element. Da niedrige Kosten und gute Umweltverträglichkeit wichtige Voraussetzungen für die Herstellung von YBCO-Schichten großer Länge darstellen, werden in dieser Arbeit die Vorteile und Einsatzmöglichkeiten der Chemischen Lösungsabscheidung (chemical solution deposition - CSD) untersucht. CSD Prozesse sind besonders gut geeignet, weil sie keine Vakuum-Technologie erfordern und einen hohen Grad an Flexibilität garantieren. Zur Demonstration der guten Optimierbarkeit werden zwei wichtige CSD-Verfahren miteinander verglichen: die Polymer-Metall Precursor Technik - eine Fluor-freie Methode - und die metallorganische Abscheidung mittels Trifluoroacetat (TFA-MOD), bei der Fluor zum Einsatz kommt. Scharfe supraleitende Übergänge (Polymer-Metall Precursor Technik: DTc = 1.1K; TFA -MOD: DTc = 0.8K) sowie hohe kritische Stromdichten von ca. 3.5MA/cm2 (B= 0 T) zeigen, dass mit beiden Verfahren dünne YBCO-Schichten hoher Qualität hergestellt werden können. Außerdem bieten CSD-Verfahren durch die hervorragende Kontrollierbarkeit der Stöchiometrie des Precursors die Möglichkeit Yttrium teilweise oder vollständig durch andere Seltenerd-Metalle zu ersetzen und damit die kritische Stromdichte in hohen Magnetfeldern deutlich zu erhöhen. In dieser Arbeit wird gezeigt, dass besonders die TFA-Methode besonders geeignet ist, um (RE)BCO-Schichten (RE: rare earth) herzustellen. Untersucht wurden verschiedene Zusammensetzungen mit Sm, Dy und Ho. Außerordentlich interessant sind dabei die Ergebnisse für Y(Dy)BCO-Schichten. Schichten mit einem Dy-Gehalt von 80 % zeigen oberhalb von 4.5T deutlich höhere kritische Stromdichten als reine YBCO Schichten. Bei Magnetfeldern größer als 8T beträgt der Unterschied mehr als eine Größenordnung.

A custom-built surface sol-gel pumping system was built for applying conformal sol-gel based coatings with controlled thicknesses on three-dimensional (3-D) nanostructured templates. The 3-D templates utilized in this work were derived from biological species, such as diatoms and butterfly wings, as well as a synthetic photoresist polymer (SU-8). Tin oxide coatings were applied on silica-based diatom frustules using the automated surface sol-gel pumping system. An organic dendrimer method was developed for amplifying hydroxyl groups on the silica-based frustule surfaces to enhance the surface sol-gel deposition process. Conformal tin oxide coatings with controlled thicknesses were obtained on the hydroxyl amplified frustule surfaces; however, little if any deposition was observed on the frustules that were not subjected to the hydroxyl amplification process. The automated surface sol-gel system was also utilized to apply multicomponent tin oxide-doped titania alkoxide chemistries on the wing scales of a blue Morpho butterfly. The alkoxide solutions reacted directly with the OH functionalities provided by the native chitin chemistry of the scales. The tin oxide served as a rutile nucleating agent which allowed the titania to completely crystallize in the high refractive index rutile titania phase with doping concentrations of tin oxide as low as 7 mol % after annealing at 450oC. The tin oxide-doped titania coatings were both nanocrystalline and nanothick and replicated the nanostructured scales with a high degree of precision. Undoped titania coatings applied on the scales required a heat treatment of 900oC to crystallize the coating in the rutile titania phase which led to adverse coarsening effects which destroyed the nanostructed features of the scales. Tin oxide-doped titania coatings were also deposited on 3-D SU-8 photonic crystal structures. The coating was crystallized in an acidic solution at 80oC which led to the formation of rutile titania inverse opal photonic crystal structures which maintained the overall structure and ordering of the template. Barium titanate and europium-doped barium titanate coatings were applied on diatom frustules using a conventional reflux/evaporation deposition process. The silica-based diatom frustules had to first be converted into magnesia/silicon composite replicas using a gas/solid displacement reaction to render the template chemically compatible with the barium titanate-based coating. Conformal titanate-based coatings were obtained on the magnesia frustule replicas possessing uncontrolled thicknesses and excess inorganic particles using the reflux/evaporation deposition process. The europium-doped barium titanate coated frustules exhibited bright red photoluminescent properties upon stimulation with an ultraviolet light source.