Barium Strontium Titanate (BST) based ferroelectric thin film devices have been popular over the last decade due to their versatile applications in tunable microwave devices such as delay lines, resonators, phase shifters, and varactors. BST thin films are promising candidates due to their high dielectric constant, tunability and low dielectric loss. Dielectric-tunable properties of BST films deposited by different deposition techniques have been reported which study the effects of factors, such as oxygen vacancies, film thickness, grain size, Ba/Sr ratio, etc. Researchers have also studied doping concentrations, high temperature annealing and multilayer structures to attain higher tunability and lower loss. The aim of this investigation was to study material properties of Barium Strontium Titanate from a comprehensive point of view to establish relations between various growth techniques and the film physical and electrical properties. The primary goal of this investigation was to synthesize and characterize RF magnetron sputtered Barium Strontium Titanate (Ba1-xSrxTiO3), thin film structures and compare their properties with BST thin films deposited by sol-gel method with the aim of determining relationships between the oxide deposition parameters, the film structure, and the electric field dependence. In order to achieve higher thickness and ease of fabrication, and faster turn around time, a `stacked' deposition process was adopted, wherein a thin film (around 200nm) of BST was first deposited by RF magnetron sputtering process followed by a sol-gel deposition process to achieve higher thickness. The investigation intends to bridge the knowledge gap associated with the dependence of thickness variation with respect to the tunability of the films. The film structures obtained using the three different deposition methods were also compared with respect to their analytical and electrical properties. The interfacial effect on these `stacked' films that enhance the properties, before and after annealing these structures was also studied. There has been significant attention given to Graphene-based supercapacitors in the last few years. Even though, supercapacitors are known to have excellent energy storage capability, they suffer from limitations pertaining to both cost and performance. Carbon (CNTs), graphene (G) and carbon-based nanocomposites, conducting polymers (polyaniline (PANI), polypyrrole (PPy), etc.) have been the fore-runners for the manufacture of supercapacitor electrodes. In an attempt to better understand the leakage behavior of Graphene Polyaniline (GPANI) electrodes, BST and BST thin films were incorporated as constituents in the process of making supercapacitor electrodes resulting in improved leakage behavior of the electrochemical cells. A detailed physical, chemical and electrochemical study of these electrochemical cells was performed. The BST thin films deposited were structurally characterized using Veeco Dektek thickness profilometer, X-ray diffraction (XRD), Scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. The interfacial structural characterization was carried out using high-resolution transmission electron microscopy (HRTEM). This investigation, also presents noncontact electrical characterization of BST films using Corona Kelvin metrology (C-KM). The `stacked' BST thin films and devices, which were electrically tested using Corona Kelvin metrology, showed marked improvement in their leakage characteristics over both, the sputtered and the sol-gel deposited counterparts. The `stacked' BST thin film samples were able to withstand voltages up to 30V positive and negative whereas, the sol-gel and sputtered samples could hold only up to a few volts without charge leaking to reduce the overall potential. High frequency, 1GHz, studies carried out on BST thin film interdigitated capacitors yielded tunability near 43%. Leakage barrier studies demonstrated improvement in the charging discharging response of the GPANI electrochemical electrodes by 40% due to the addition of BST layer.

Στην παρούσα εργασία η ενασχόλησή μας αφορούσε τη σύνθεση και τον χαρακτηρισμό βιοενεργών γυαλιών. Οι συνθέσεις που πραγματοποιήθηκαν ήταν καθαρής SiO2, μικτών γυαλιών SiO2–ΜΟ (Μ=Ca, Mg) αλλά επίσης και γυαλιών σύστασης SiO2 –CaΟ–P2O5. Πραγματοποιήθηκαν παρασκευές με διάφορα ποσοστά τροποποιητών (Ca, Mg). Μετά την παρασκευή των υλικών ακολούθησε ο φυσικοχημικός χαρακτηρισμός τους με διάφορες τεχνικές όπως: προσδιορισμός ειδικής επιφάνειας και όγκου πόρων (ΒΕΤ), ηλεκτρονική μικροσκοπία σάρωσης (SEM), θερμοσταθμική ανάλυση (TGA), περίθλαση ακτίνων Χ (XRD) και φασματοσκοπία απορρόφησης υπερύθρου (IR). Μετά ακολούθησε μελέτη της βιοενεργότητας με εμβάπτιση σε διάλυμα SBF. Τα αποτελέσματα έδειξαν ότι τα γυαλιά που παρασκευάστηκαν είχαν μεσοπορώδη δομή ενώ όσον αφορά τη βιοενεργότητα τα γυαλιά σύστασης SiO2–CaO and SiO2–CaΟ–P2O5 προκάλεσαν σχηματισμό απατίτη στην επιφάνειά τους. / In the present thesis our work was focused on the study of the synthesis and characterization of bioactive glasses. Pure SiO2 and mixed glasses composed of SiO2–ΜΟ (Μ=Ca, Mg) and SiO2–CaΟ–P2O5 were prepared using different amounts of modifiers (Ca, Mg). Next the prepared materials were characterized by using various techniques such as: BET, SEM, TGA, XRD and IR. Finally their bioactivity was studied in vitro after immersion in SBF solution. It was found that the prepared materials showed a mesoporous structure. Regarding the bioactivity glasses with compositions of SiO2–CaO and SiO2–CaΟ–P2O5 induced the formation of apatite layer on their surface.

Šiame darbe vienfazis perovskito struktūros gadolinio aliuminatas GdAlO3 zolių-gelių metodu buvo gautas 1000 oC temperatūroje, gadolinio jonų šaltiniu naudojant Gd2O3, kompleksus sudarančiu reagentu – 1,2 etandiolį, natūralią vyno rūgštį, citrinų rūgštį arba citrinų rūgšties ir etanolamino mišinį. Sintetinant GdAlO3, gautų tyrimų rezultatai parodė, kaip yra svarbu zolių gelių procese pasirinkti tinkamas pradines medžiagas bei kompleksus su metalais sudarančius reagentus: gadolinio jonų šaltiniu naudojant Gd2O3 buvo gauti geresni rezultatai nei naudojant Gd(NO3)3•6H2O, vienfazis GdAlO3 gali būti sėkmingai susintetintas kompleksus sudarančiu reagentu naudojant tiek natūralią vyno rūgštį, tiek 1,2 etandiolį, tiek citrinų rūgštį, tiek citrinų rūgšties ir etanolamino mišinį. Nustatyta, kad sintetinant stronciu pakeistus gadolinio aliuminatus Gd1–xSrxAlO3– (x = 0,10, 0,25, 0,50, 0,75), tinkamesnis gadolinio jonų šaltinis yra gadolinio oksidas nei gadolinio nitratas heksahidratas, kompleksus sudarantis reagentas – EDTA nei natūrali vyno rūgštis. Vienfazis perovskito struktūros stronciu pakeistas gadolinio aliuminatas Gd0,90Sr0,10AlO3– buvo susintetintas zolių-gelių metodu 1000 oC temperatūroje, gadolinio jonų šaltiniu naudojant Gd2O3, stroncio jonų šaltiniu – Sr(NO3)2, kompleksus sudarančiu reagentu – EDTA. Be to, 800 ºC iškaitinimo temperatūra yra per maža šiems junginiams sintetinti. Pirmą kartą pasiūlytas vandeninis zolių gelių metodas lantano ir gadolinio kobaltatams... [toliau žr. visą tekstą] / In the present thesis the reported results let us to conclude that the developed aqueous sol–gel procedure could be successfully used for the low-temperature synthesis of monophasic perovskite gadolinium aluminate ceramics. It was also demonstrated that the selection of raw materials for the sol–gel processing should be done with care. Monophasic perovskite structure gadolinium aluminate GdAlO3 has been synthesized by sol gel synthesis method at 1000 oC, using gadolinium oxide as gadolinium raw material and 1.2 ethanediol, natural tartaric acid, citric acid or mixture of citric acid and ethanolamine as complexing agent. According to the XRD results, the Gd2O3 instead of Gd(NO3)36H2O preferably should be used as starting material for the preparation of GdAlO3. Monophasic perovskite structure strontium substituted gadolinium aluminate Gd0.90Sr0.10AlO3– was synthesized by the same sol gel synthesis method at 1000 oC, using gadolinium oxide as gadolinium raw material, strontium nitrate as strontium ion source and EDTA as complexing agent. It was proved that better gadolinium ion source is gadolinium oxide than gadolinium nitate hexahydrate, better complexing agent – EDTA than natural tartaric acid in the synthesis of GdAlO3 and strontium substituted Gd1–xSrxAlO3– (x = 0.10, 0.25, 0.50, 0.75) samples. According to the XRD results, increasing amount of strontium reduces amount of peaks of perovskite structure gadolinium aluminate. Besides, 800 ºC temperature is too low for the... [to full text]

In the present thesis the reported results let us to conclude that the developed aqueous sol–gel procedure could be successfully used for the low-temperature synthesis of monophasic perovskite gadolinium aluminate ceramics. It was also demonstrated that the selection of raw materials for the sol–gel processing should be done with care. Monophasic perovskite structure gadolinium aluminate GdAlO3 has been synthesized by sol gel synthesis method at 1000 oC, using gadolinium oxide as gadolinium raw material and 1.2 ethanediol, natural tartaric acid, citric acid or mixture of citric acid and ethanolamine as complexing agent. According to the XRD results, the Gd2O3 instead of Gd(NO3)36H2O preferably should be used as starting material for the preparation of GdAlO3. Monophasic perovskite structure strontium substituted gadolinium aluminate Gd0.90Sr0.10AlO3– was synthesized by the same sol gel synthesis method at 1000 oC, using gadolinium oxide as gadolinium raw material, strontium nitrate as strontium ion source and EDTA as complexing agent. It was proved that better gadolinium ion source is gadolinium oxide than gadolinium nitate hexahydrate, better complexing agent – EDTA than natural tartaric acid in the synthesis of GdAlO3 and strontium substituted Gd1–xSrxAlO3– (x = 0.10, 0.25, 0.50, 0.75) samples. According to the XRD results, increasing amount of strontium reduces amount of peaks of perovskite structure gadolinium aluminate. Besides, 800 ºC temperature is too low for the... [to full text] / Šiame darbe vienfazis perovskito struktūros gadolinio aliuminatas GdAlO3 zolių-gelių metodu buvo gautas 1000 oC temperatūroje, gadolinio jonų šaltiniu naudojant Gd2O3, kompleksus sudarančiu reagentu – 1,2 etandiolį, natūralią vyno rūgštį, citrinų rūgštį arba citrinų rūgšties ir etanolamino mišinį. Sintetinant GdAlO3, gautų tyrimų rezultatai parodė, kaip yra svarbu zolių gelių procese pasirinkti tinkamas pradines medžiagas bei kompleksus su metalais sudarančius reagentus: gadolinio jonų šaltiniu naudojant Gd2O3 buvo gauti geresni rezultatai nei naudojant Gd(NO3)3•6H2O, vienfazis GdAlO3 gali būti sėkmingai susintetintas kompleksus sudarančiu reagentu naudojant tiek natūralią vyno rūgštį, tiek 1,2 etandiolį, tiek citrinų rūgštį, tiek citrinų rūgšties ir etanolamino mišinį. Nustatyta, kad sintetinant stronciu pakeistus gadolinio aliuminatus Gd1–xSrxAlO3– (x = 0,10, 0,25, 0,50, 0,75), tinkamesnis gadolinio jonų šaltinis yra gadolinio oksidas nei gadolinio nitratas heksahidratas, kompleksus sudarantis reagentas – EDTA nei natūrali vyno rūgštis. Vienfazis perovskito struktūros stronciu pakeistas gadolinio aliuminatas Gd0,90Sr0,10AlO3– buvo susintetintas zolių-gelių metodu 1000 oC temperatūroje, gadolinio jonų šaltiniu naudojant Gd2O3, stroncio jonų šaltiniu – Sr(NO3)2, kompleksus sudarančiu reagentu – EDTA. Be to, 800 ºC iškaitinimo temperatūra yra per maža šiems junginiams sintetinti. Pirmą kartą pasiūlytas vandeninis zolių gelių metodas lantano ir gadolinio kobaltatams... [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] / 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]

Le premier chapitre de ce manuscrit expose les différentes voies d'élaboration de films poreux par le procédé sol-gel et montre les avantages apportés par l'utilisation de couches mésoporeuses structurées par des tensioactifs. Ainsi, tout au long de ce travail, nous nous sommes attachés à préparer des films les mieux ordonnés possible. Par ailleurs, nous avons choisi des procédés d'élaboration compatibles avec la faible stabilité thermique des substrats ophtalmiques organiques. La partie suivante décrit la synthèse de films de silice mésoporeuse présentant des morphologies poreuses variées et le choix, parmi l'ensemble de ces structures, de celles dont la robustesse et la porosité finale conviennent pour l'élaboration de couches à bas indice de réfraction. Le troisième chapitre a pour objectif la préparation de couches dont le vieillissement est limité. Cet objectif s'inscrit dans le cadre plus général de la synthèse de couches mésoporeuses les plus hydrophobes et les mieux organisées possible. Cette étude aboutit sur l'élaboration d'un anti-reflets intégrant une couche mésoporeuse, déposée sur un empilement ophtalmique réel. Le système ainsi réalisé est caractérisé en termes de performances optiques et de tenue mécanique.

The high-temperature superconductor Sr1-xCaxCuO2 was synthesized using sol-gel, solid-state reaction and co-precipitation methods. The analysis of its formation was made and the structure of the products was determined with the help of the X-ray diffraction. The termal processes, that take place during the synthesis, were analyzed with the help of differential-termal analysis. The experiment has showed that the SrCuO2 formes in the the process of heating the citrats precursors at the temperature of 800oC. And the S0,5Ca0,5CuO2 formes at 900oC by sol-gel, solid-state reaction methods. The best results are achieved using citric gel precursor at the temperature of 900oC. The increase of heating duration up to 36 hours, made no considerable diference in the qualitative composition, however this has changed the quantitative composition.

Darbo tikslas yra ištirti atkaitintų prie aukštų temperatūrų vakuume La2O3 sluoksnių Rentgeno fotoelektronų spektrus. Darbe aprašyti Rentgeno fotoelektronų spektroskopijos (RFS) (XPS - X-ray photoelectron spectroscopy) metodo, naudojamo įvairių medžiagų paviršių cheminei sudėčiai nustatyti, pagrindai. Pirmame skyriuje aprašyti: La2O3 oksidiniai junginiai ir jų tyrimų metodika, plonų nanostruktūrizuotų medžiagų sluoksnių nusodinimo iš dujų fazės (plazmos) metodas- magnetroninis dulkinimas (magnetron sputtering), aparatūra ir zolis – gelis metodas. Antrajame skyriuje aprašytas Rentgeno fotoelektroninės spektroskopijos metodas, pagrindinė RFS aparatūra bei teorinė dalis. Trečiasis skyrius yra skirtas Rentgeno fotoelektroninių spektrų matavimų, naudojant spektrometrą XSAM 800 (Kratos Analytical, Didžioji Britanija) ypatumams ir bandinių gamybos metodikai aptarti. Pateiktas išsamus La2O3 sintezės zolių-gelių metodu technologijos aprašymas. Ketvirtajame skyriuje pateikiami eksperimentiniai rezultatai gauti, matuojant La2O3 Rentgeno fotoelektronų spektrus. Darbo pabaigoje yra pateikiamos išvados, kurios galėtų būti naudingos, tobulinant La2O3 bandinių gamybos technologiją. Gautas rezultatas: nustatyta, kad zolių – gelių technologija leidžia paprastais metodais, nenaudojant sudėtingos aparatūros, susintetinti La2O3. / The aim of presented work was to synthesis by using sol-gel technology and investigate the X-ray photoelectron spectra (XPS) of La2O3 thin films in the annealed high temperature vacuum. In the present work we described the essentials of the method of X-ray photoelectron spectroscopy, used to determine chemical composition of various materials. In the first part are described: La2O3 oxide compounds and the methods of the their production from the gas phase – magnetron sputtering and sol – gel method. The second part describes the X- ray photo-electronic spectroscopy method, basic XPS equipment and theoretical part. In the third part we discussed the peculiarities and methodology of spectrometer XSAM 800 (Kratos Analytical, Great Britain) samples production while measuring X-ray photoelectron spectra. The thorough description of the technology by synthesis of La2O3 sol-gel method was provided. The fourth part presents the experimental results obtained by measuring the La2O3 X-ray photoelectron spectra. In the end of the work conclusions are produced that could be useful in improving production technology of La2O3 samples. Obtained results: we identified that sol-gel technology allows to synthesize La2O3 by simple methods, without using sophisticated equipment.

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.