Surfactant-templated, sol-gel based methodologies for the synthesis of tailored, nanostructured, hybrid inorganic–organic materials are incredibly powerful and versatile. Although growth in this field has been explosive in recent decades, a lot of room remains to contribute to the design and synthesis of new materials, as well as the development of advanced applications. In the work described herein, we firstly explored the synthesis of thick, mesoporous organosilica films and their application as functional coatings for solution-based, fibre-optic heavy metal sensors. Notably, sub-ppm level detection was observed for the detection of Pb(II) in mixed aqueous–organic media in short timeframes, and progress has been made toward synthesizing organotitania films that would allow for heavy metal sensing in purely aqueous solution. Furthermore, the utility of these types of surfactant-templated, organically-functionalized, mesostructured coatings has been preliminarily extended to other types of optical devices for heavy metal sensing. We have also explored the use of designer amphiphilic, alkyl oligosiloxane precursors for the tightly-controlled formation of thin, self-templated, hybrid nanostructured films. Moreover, films bearing uniaxial 2D hexagonal alignment over macroscopic length scales were obtained using polymer-treated substrates to control the interfacial interactions between the film precursors and the substrate surface. In addition, a relatively mild UV / ozone treatment was employed to remove the alkyl moieties from the films to yield porous materials without catastrophic loss of the as-synthesized, mesostructural order. Lastly, novel chiral, binaphthylene-based, periodic mesoporous organosilica (PMO) materials have been prepared. With the aim of demonstrating chiral recognition with such materials, porous, co-continuous capillary monoliths have been synthesized and applied as chiral stationary phases in nano-HPLC and CEC. Notably, enantioselective interactions between our materials and a chiral acetal-based analyte have been observed. Quantification of these enantioselective interactions in chiral PMOs by isothermal titration microcalorimetry is also being pursued. It has thus been demonstrated that a wide array of different functional materials may be accessed through template-based synthetic strategies. By varying parameters such the starting monomers, the sol composition, and the interfacial interactions between reacting species and a given substrate (to name a few), the resulting materials may be tailored to meet the demands of new and emerging technologies. / Thesis (Ph.D, Chemistry) -- Queen's University, 2011-05-24 19:50:17.478

The potential use of 3D aluminium nanorod structures as current collectors and negative electrodes for 3D Li-ion micro-batteries was studied based on the use of relatively simple and cost-effective electrochemical and sol-gel deposition techniques. Aluminium rod structures were synthesised by galvanostatic electrodeposition using commercial porous membranes as templates. It was shown that the use of a short (i.e., 50 ms long) potential pulse (i.e., -0.9 V vs. Al3+/Al) applied prior to a pulsed current electrochemical deposition gave rise to homogeneous deposits with more even rod heights.  Electrophoretic and sol-gel deposition of TiO2 on the same substrates were also studied. The use of the sol-gel technique successfully resulted in a thin coating of amorphous TiO2 on the Al nanorod current collector, but with relatively small discharge capacities due to the amorphous character of the deposits. Electrophoretic deposition was, however, successful only on 2D substrates. Anodisation of titanium was used to prepare 3D TiO2 nanotube electrodes, with a nanotube length of 9 um and wall thickness of 50 nm. The electrodes displayed high and stable discharge capacities of 460 µAh/cm2 at a 0.1 C rate upon prolonged cycling with good rate capability. The 3D aluminium nanorod structures were tested as negative electrodes for Li-ion cells and the observed capacity fading was assigned to trapping of LiAl alloy inside the aluminium electrode caused by the diffusion of lithium into the electrode, rather than to pulverisation of the aluminium rods. The capacity fading effect could, however, be eliminated by decreasing the oxidation potential limit from 3.0 to 1.0 V vs. Li+/Li. A model for the alloying and dealloying of lithium with aluminium was also proposed. Finally, a proof-of-concept for a full 3D Li-ion micro-battery with electrodes of different geometries was demonstrated. The cell comprised a positive electrode, based on LiFePO4 deposited on a carbon foam current collector, with an area gain factor an order of magnitude larger than that for the Al nanorod negative electrode. This concept facilitates the balancing of 3D Li-ion cells as the positive electrode materials generally have significant lower specific energy densities than the negative electrodes.

The thin films of oxide xerogels and bronzes and molecular oxide xerogels and bronzes of vanadium compounds were synthesized by sol-gel technology method. The chemical composition of mentioned compounds was investigated using XPS method in order to determine the valence of metal ions. It is shown that it is possible to produce the thin films of vanadium oxide bronzes using simple methods. The possibility to use vanadium-ammonium oxide hydrated compounds as materials for producing the ammonium sensors is shown in the dissertation. / Šiame darbe panaudojant zolis-gelis technologiją, susintetinti vanadžio junginių oksidinių kserogelių ir bronzos bei molekulinių oksidinių kserogelių ir bronzų plonieji sluoksniai. Visų minėtų medžiagų cheminė sudėtis ištirta Rentgeno fotoelektronų spektroskopijos metodu, siekiant nustatyti metalų jonų valentines būsenas. Panaudojant zolis-gelis technologiją, galima gana paprastais metodais, nenaudojant sudėtingos technologinės įrangos, gaminti vanadžio oksidinių bronzų plonuosius sluoksnius. Vanadžio amonio hidratuoti oksidiniai junginiai gali būti naudojami kaip medžiagos amoniako dujų jutikliams gaminti.

Atlikta istorinių kobalto pigmentų analogų Rentgeno spindulių difrakcinė analizė parodė, kad metodas efektyvus, nustatant kobalto šviesiai violetinį CoNH4PO4•H2O, kobalto mėlynąjį šviesų, ceruleumą ir kobalto žalsvai mėlyną CoO·ZnO, jų švino glazūrose, bet netinka aureolino [K3(Co(NO2)6]•3H2O, kobalto tamsiai violetinio Co3(PO4)2, kobalto mėlynojo tamsus, kobalto melsvai žalio ir smaltos CoO•nSiO2 nustatymui. IR spektroskopiniai tyrimai parodė, kad šis metodas efektyvus, kokybiškai nustatant neoksidinius kobalto pigmentus aureoliną, kobalto šviesiai violetinį, kobalto tamsiai violetinį jų švino glazūrose. Paprastu nusodinimo metodu susintetintas kobalto pigmentas violetinis šviesusis CoNH4PO4, pasižymintis analogiškomis fizikinėmis savybėmis, kaip ir komercinis Kremer Pigmente pigmentas. Sukurtas naujas, patogus ir pakankamai tikslus IR spektroskopinis SiO2 kiekio CoO ir SiO2 mišiniuose (ribose tarp 9,1-50 mol%) ir kobalto pigmente smaltoje CoO×nSiO2 (ribose tarp 20 iki 50 mol%) nustatymo metodas. Zolių-gelių metodu susintetinti ir visapusiškai ištirti nauji kobalto pigmentai: špinelio struktūros kobalto aliuminatas CoAl2O4 ir chromatas CoCr2O4 bei kobalto, aliuminio ir neodimio oksidų mišiniai (CoAl1,75Nd0,25O4, CoAl1,5Nd0,5O4, CoAlNdO4), pasižymintys spalvinėmis keraminių pigmentų savybėmis. Pirmą kartą zolių-gelių metodu susintetinti ir visapusiškai ištirti nauji kobalto pigmentai: vienfazis perovskito struktūros neodimio kobaltatas NdCoO3, mišrūs perovskitiniai neodimio... [toliau žr. visą tekstą] / X-ray diffraction analysis (XRD), infrared (IR) spectroscopy and scanning electron microscopy have been used for the characterization of cobalt-based pigments (Kremer Pigmente) and their lead-based glazes. It was also demonstrated that XRD analysis could be successfully used for the identification of cobalt pigments cobalt violet brilliant light CoNH4PO4•H2O, cobalt blue light, cerulean blue, cobalt green bluish CoO·ZnO in their glazes. However, only non-oxide cobalt pigments cobalt yellow [K3(Co(NO2)6]•3H2O, cobalt violet brilliant light and cobalt violet dark Co3(PO4)2 could be determined in their glazes using IR spectroscopy. The similarity of all SEM images of cobalt-based glazes let us to conclude, that the main morphological features of glazes are not dependent on the nature of cobalt pigment. The single phase cobalt violet light brilliant pigment has been synthesized using a simple co-precipitation approach. The characteristics of the obtained product were compared with those of a commercial sample purchased from Kremer Pigmente. For the first time to our knowledge, it was demonstrated that the characteristic Si-O absorption band at 812 cm-1 could be successfully used as indicator in the evaluation of molar ratio of CoO and SiO2 in their mixture. The novel method for the determination of SiO2 in physical mixtures of CoO ir SiO2 (in the range 9,1-50 %) or blue cobalt smalt pigment (CoO×nSiO2) (in the range 20-50 %) by FTIR spectroscopy is suggested. New cobalt-based... [to full text]

Cette thèse présente l'écriture de motifs périodiques 1D ou 2D, sur des films sol-gel réalisés par lithographie interférométrique dynamique. Elle a pour objectif la fabrication d'éléments optiques diffractifs dont les propriétés sont utilisées dans le traitement de la lumière visible et du proche infrarouge. Les outils technologiques compatibles nécessaires à l'obtention de ces éléments optiques ont été développés durant la thèse en combinant des matériaux fonctionnels, comme le TiO2, apportés par la voie sol-gel à une technique de lithographie permettant une microstructuration directe sur de grande surface. Ces deux technologies ont été transférées du laboratoire à un équipement semi-industriel avec succès. Cette étude a été guidée par une application des réseaux de diffraction aux modules solaires photovoltaïques. Un démonstrateur de module à déflecteurs diffractant, permettant d'augmenter le rendement global du module, a été produit et testé durant la thèse : les résultats ont été comparés aux simulations effectuées en amont

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 or films which possess a hierarchical porosity. This organization allows the optimization of the matter transport (liquid/gaz) for air depollution application (photocatalysis) or dye-sensitized solar 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.

Sample preparation has a critical role as a first step in analytical processes, especially in bioanalysis and environmental analysis. A good sample preparation technique should be robust and stable, regardless of the sample matrix. The aim of this thesis is to design and synthesize molecularly imprinted polymers that can be used in various sample preparation techniques, such as on-line MEPS, on-line SPE and on-line monolithic pre-columns used for the extraction of drugs, hormones, and cancer biomarkers from human plasma and urine samples. Additional aim was to provide full automation, on-line coupling, short sample preparation time and high-throughput. In this thesis MIP in MEPS was used on-line with liquid chromatography-tandem mass spectrometry (LC/MS/MS) for the determination of sarcosine in human urine and plasma samples. The method was fully automated and the packed sorbent could be used for about hundred extractions. In additional work a coated needle with MIP-Sol-Gel as thin layer was prepared and used for the microextraction of bilirubin from human plasma and urine. Small sample volumes could be handled and the validation of the method showed that the method was robust and selective. In a further work MIP-SPE on-line with HPLC was used for the extraction and determination of dextromethorphan in human plasma samples. MIP-SPE showed a good selectivity and high recovery (87% - 92%). On-line MIP monolithic pre-column was prepared and used in a coupled system for the extraction of tramadol in human plasma and urine samples. The MIP monolithic pre-column showed good selectivity and high extraction recovery was obtained (91-96%). The extraction and analysis of human insulin in plasma and pharmaceutical formulation solutions were carried out using MIP-SPE on-line with HPLC. The validation of the method showed that the method was accurate and robust. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Submitted.</p>

Zirconium- and tantalum-based diborides, and diboride/carbide composites are of interest for ultra-high temperature applications requiring improved thermomechanical and thermochemical stability. This thesis focuses on the synthesis, processing and sintering of nanocrystalline powders with Zr- and Ta-based diboride/carbide/silicide compositions. A solution-based processing method was developed to prepare reactive mixtures that were precursors for ZrB₂-based powders. The precursors reacted to form the ceramic powders after suitable pyrolysis and borothermal/carbothermal reduction heat treatments. Single-phase ZrB₂ powders were prepared with initial composition of C/Zr = 4.8 and B/Zr = 3.0. ZrB₂-based composite powders with ZrC, ZrO₂, TaB₂, TaC, SiC, TaSi₂ and B₄C were prepared with particle sizes of 10-500 nm for different phases based SEM micrographs. The composite powders were highly sinterable with proper processing methods developed to avoid and remove oxide impurities. The relative densities of ZrB₂/B₄C, ZrB₂/TaB₂, ZrB₂/TaB₂/B4C, ZrB₂/TaSi₂ were in the range of 91%-97% after pressureless sintering at 2020 ℃ for 1 h or 30 min.

In our study, the superhydrophobic surface based on biomimetic lotus leave is explored to maintain the desired properties for self-cleaning. In controlling bead-up and roll-off characteristics of water droplets the contact angle and contact angle hysteresis were very important and we investigated the determining conditions on different model surfaces with micro- and nanostructures. Two governing equations were proposed, one for contact angle based on Laplace pressure and one for contact angle hysteresis based on Young-Dupré equation. Based on these understanding on superhydrophobicity, possible applications of the superhydrophobicity for self-cleaning and water repellency were explored and application related technical issues were addressed. Based on our understanding of the roughness effect on superhydrophobicity (both contact angle and hysteresis), structured surfaces from polybutadiene, polyurethane, silica, and Si etc were successfully prepared. For engineering applications of superhydrophobic surfaces, stability issues regarding UV, mechanical robustness and humid environment need to be investigated. Among these factors, UV stability is the first one to be studied. Silica surfaces with excellent UV stability were prepared. UV stability on the surface currently is 5,500 h according the standard test method of ASTM D 4329. No degradation on surface superhydrophobicity was observed. New methods for preparing superhydrophobic and transparent silica surfaces were investigated using urea-choline chloride eutectic liquid to generate fine roughness and reduce the cost for preparation of surface structures. Another possible application for self-cleaning in photovoltaic panels was investigated on Si surfaces by construction of the two-scale rough structures followed by fluoroalkyl silane treatment. Regarding the mechanical robustness, epoxy-silica superhydrophobic surfaces were prepared by O2 plasma etching to generate enough surface roughness of silica spheres followed by fluoroalkyl silane treatment. A robustness test method was proposed and the test results showed that the surface is among the most robust surfaces for the superhydrophobic surfaces we prepared and currently reported in literature.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23732号 / 理博第4822号 / 新制||理||1690(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 吉村 一良, 教授 竹腰 清乃理 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM