Le dioxyde de titane (TiO2) est un matériau polyvalent qui présente des propriétés intéressantes allant de la catalyse au stockage et conversion d'énergie. Afin d'améliorer ses propriétés physico-chimiques, plusieurs approches ont été appliquées telles que, la réduction de la taille des particules, modification de la morphologie, le dopage par d'autres éléments. Dans cette thèse, une nouvelle méthode de synthèse basée sur la chimie de sol-gel est développée en milieu fluoré. Les anions divalents de O2- dans TiO2 anatase sont substitués par anions monovalents de F- et OH-, le déficit de charge négative est compensée par la création simultanée de lacunes cationiques dont la concentration peut être réglés par la température de réaction. La nouvelle famille de matériaux polyanioniques a la composition générale de Ti1-x-y•x+yO2-4(x+y)F4x(OH)4y avec de lacune cationique jusqu’à 22 %. Le matériau considérablement dopé maintient son réseau cristallin original et montre une structure locale unique. Son mécanisme de formation est étudié à l'échelle atomique. Les effets des paramètres de synthèse sur la structure, la morphologie et la composition chimique de la phase obtenue sont étudiés en détail. Lorsqu'il est utilisé comme anode pour batteries aux ions lithium, l'anatase fluorée lacunaire montre des performances supérieures pour le stockage de lithium, surtout à haute régime de charge/décharge. La présence de lacune modifie le mécanisme d'insertion du lithium par rapport à TiO2 anatase stœchiométrique: une réaction de solution solide a été trouvé à la place une réaction diphasique, soulignant l'impact de la modification de la structure sur les propriétés électrochimiques vis-à-vis au Li+. Enfin, le mécanisme d'insertion de sodium dans anatase stœchiométrique et lacunaire est étudié. Des aperçus sans précédent sont acquis pour la réaction d’insertion de Na+. / Titanium dioxide (TiO2) is a multifunctional material and presents promising properties ranging from catalysis to energy storage and conversion. In order to obtain enhanced physico-chemical properties, several approaches were applied such as, reducing particle sizes, modifying morphology, doping with other elements. In this thesis, a new synthesis method based on sol-gel chemistry is developed in fluorinated medium. The divalent O2- in TiO2 anatase is substituted by monovalent F- and OH- anions, the deficiency of negative charge is counterbalanced by the simultaneous formation of cationic Ti4+ vacancies (•) which can be tuned by the reaction temperature. The new family of polyanionic materials has the general composition of Ti1-x-y•x+yO2-4(x+y)F4x(OH)4y with up to 22 % of cationic vacancies. The drastically doped material keeps its original crystalline network and shows unique local structure. Its formation mechanism is investigated at atomic scale. The effects of synthesis parameters on structure, morphology and chemical composition of the resulting phase are studied in details. When used as anode for lithium-ion batteries, the cation-defected fluorinated anatase shows superior lithium storage performance, especially at high charge/discharge rate. The presence of vacancy modifies lithium insertion mechanism compared to stoichiometric TiO2 anatase: a solid solution reaction was found instead a well-known two-phase reaction, highlighting the impact of structure modification on the electrochemical properties vs. Li+. Sodium insertion mechanism into stoichiometric and defective anatase are studied at the last. Unprecedented insights into Na+ insertion reaction are gained.

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This work is focused on the study of perovskite ferroelectric materials group and monitoring changes their dielectric parameters in temperature and frequency dependence Is described scrystallographic systems of barium titanate and their influence on material properties. The measured values are mathematically interpreted using the Curie – Weiss law and discussed about the influence of strontium titanite on important dielectric parameters.

Diplomová práce je zaměřena na studium degradace kontrastních látek pro magnetickou rezonanci. Tyto látky se dnes ve velké míře používají v oblastech s rozvinutým zdravotnictvím. Můžeme je najít v odtocích z čistíren odpadních vod, což svědčí o tom, že běžné stupně čištění odpadních vod nejsou dostatečně efektivní pro jejich odstranění. O degradaci kontrastních látek na bázi gadolinia je jen málo informací. Fotokatalytický rozklad za pomoci oxidu titaničitého a také ozonace vybrané kontrastní látky gadobutrolu, byl sledován pomocí měření celkového organického uhlíku, mikroskopie termálních čoček a spektrofotometrie.

<p>U poslednjih nekoliko decenija, feroelektrici su prepoznati kao dobri kandidati<br />za &scaron;irok spektar primene. Barijum titanat je jedan od najče&scaron;će istraživanih<br />perovskitnih materijala usled tipičnog feroelektričnog pona&scaron;anja na sobnoj<br />temperaturi, sa histerezisnom zavisnosti između polarizacije i električnog polja.<br />Specifična svojstva BaTiO₃ čine ovaj materijal veoma korisnim u proizvodnji<br />kondenzatora, memorija, senzora i dr. Pored toga, paraelektrična faza BaTiO₃<br />ima primenu u proizvodnji mikrotalasnih tunabilnih uređaja. BaTiO₃ pokazuje<br />paralaketrično pona&scaron;anje iznad Kirijeve temperature (120&deg;C) i veliki je izazov<br />modifikovati materijal da bude paraelektričan na sobnoj temperaturi. Delimičnom<br />supstitucijom Ba²⁺ ili Ti⁴⁺ jona, jonima Sr²⁺ ili Zr⁴⁺, respektivno, snižava<br />se Kirijeva temperatura i dolazi do pomeranja fazne transformacije feroelektri<br />čno/paraelektrično na niže temperature. Monolitna keramika na bazi bazi<br />BaTiO₃ je često istraživana kako bi se ispitale promene u strukturi i svojstvima<br />uzrokovane dodatkom dopanata, međutim ne postoji praktična primena ovih<br />materijala u mikrotalasnim tunabilnim tehnologijama. S druge strane, u trendu<br />sveop&scaron;te minijaturizacije elektronskih komponenti, tanki filmovi su prepoznati<br />kao dobri kandidati za proizvodnju tunabilnih uređaja. Jedan od ciljeva ovog<br />istraživanja bio je ispitivanje strukturnih i funkcinalnih svojstava tankih filmova na<br />bazi barijum titanata, BaTiO₃, Ba_1-xSr_xTiO₃ (x=0,1, 0,2, 0,3 i 0,4) i BaTi_1-xZr_xO₃<br />(x=0,1 i 0,2), pripremljenih hemijskom depozicijom iz tečne faze. Metalne<br />soli BaCO₃, C₄H₆O₄Sr i ZrOCl₂ H₂O i Ti(OCH₂CH₂CH₂CH₃)₄ rastvorene su<br />odvojeno u kiseloj sredini i pome&scaron;ane u transparentne solove. Inkdžet &scaron;tampa<br />i spin tehnika kor&scaron;ćene su za depoziciju funkcionalnih filmova na bazi BaTiO₃.<br />Nakon deponovanja, pripremljeni filmovi su termički tretirani na različitim<br />temperaturama do 1000&deg;C. U zavisnosti od koncentracije pripremljeni su filmovi<br />debljine od 100 do 700 nm,sa veličinom zrna od nekoliko desetina nanometara. Strukturna karakterizacija potvrdila je promene u strukturi BaTiO₃ tankih filmova<br />sa dodatkom Sr²⁺ i Zr⁴⁺. Tetragonalna (feroelektrična) faza BaTiO₃ je potvrđena<br />rentgenostrukturnom analizom i Ramanovom spektroskopijom. S druge strane,<br />smanjenje tetragonalnosti je primećeno kod dopiranih uzoraka. Promene u<br />funkcionalnosti dopiranih BaTiO₃ filmova analizirane su na osnovu dielektričnih<br />i feroelektričnih merenja. Izvr&scaron;ene analize su potvrdile feroelektrično pona&scaron;anje<br />kod BaTiO₃, dok se feroelektrični odgovor u tankim filmovima smanjuje sa<br />dopiranjem. Priprema elektroda specifičnih geometrija pogodnih za tunabilna<br />merenja različitim tehnikama depozicije bio je drugi cilj istraživanja. Tehnika spaterovanja u kombinaciji sa laserskim uklanjanjem, inkdžet &scaron;tampa i fotolitografija<br />su kori&scaron;ćene za pripremu kružnih i koplanarnih elektroda na povr&scaron;ini barijum<br />titanatnih tankih filmova. Uticaj procesnih parametara svake od pomenutih<br />metoda na dimenzionalnu preciznost pripremljenih elektroda je bio predmet istraživanja<br />u okviru teze. Odabrani laser se pokazao kao neprikladan za pripremu<br />elektroda na pripremljenim barijum titanatnim tankim filmovima. Inkdžet &scaron;tampa<br />se pokazala kao korisna u pripremi elektroda mikrometarskih fimenzija, dok je za<br />pripremu sofisticiranijih geometrija fotolitografija pokazala najbolje performanse.</p> / <p>In past few decades, ferroelectrics are recognized as good candidates for wide<br />range of applications. Barium titanate is one of the most investigated perovskite<br />materials due to typical ferroelectric behavior at room temperature, with hysteresis<br />dependence of the polarization and electric field. Specified properties<br />of BaTiO₃ make this material useful in production of capacitors, memories,<br />sensors, etc. Nevertheless, paraelectric phase of BaTiO₃ may have application<br />in production of microwave tunable devices. Barium titanate shows paraelectric<br />behavior at temperatures above the Currie temperature (120 &deg;C) and it is great<br />challenge to make material paraelectric at room temperature. Partial substitution<br />of Ba²⁺ or Ti⁴⁺ ions, by Sr²⁺ or Zr⁴⁺, respectively, decreases the Currie temperature<br />of barium titanate and moves phase transition ferroelectric/paraelectric<br />to lower temperatures. Bulk BaTiO₃was often investigated in order to improve<br />structure and functionality by addition of dopant, but do not have practical<br />application in microwave tunable technologies. On the other hand, with the<br />trend of overall miniaturization of electronic devices, thin films are recognized<br />as good candidates for production of tunable devices. One of the aims in this<br />research was investigation of structural and functional properties of barium<br />titanate based thin films, BaTiO₃, Ba_1-xSrxTiO₃ (x=0,1, 0,2, 0,3 i 0,4) and<br />BaTi_1-xZrxO₃ (x=0,1 i 0,2), prepared by chemical solution deposition. Metal<br />salts of BaCO₃, C₄H₆O₄Sr and ZrOCl₂ H₂O and Ti(OCH₂CH₂CH₂CH₃)₄were<br />separetly disolved in acetic environment and mixed in clear transparent sols.<br />Inkjet printing and spin coating were used for deposition of functional BaTiO3<br />based fims. After deposition prepared films were thermally treated at different<br />temperatures up to 1000 &deg;C. In dependence of sol concentration thickness of<br />obtained films is from 100 to 700 nm and grain size is few tens of nanometers. Structural characterization confirmed changes in structure of barium titanate thin<br />films by addition of Sr^₂₊ i Zr⁴⁺. Tetragonal (ferroelectric) phase of BaTiO₃ is<br />confirmed by X-ray diffraction and Raman spectroscopy. On the other hand, decreasing<br />of tetragonality was noticed in doped samples. Changes in functionality<br />of doped BaTiO₃ thin films were analyzed by dielectric and ferroelectric measurements.<br />Performed analysis confirmed ferroelectric behavior of barium titanate<br />thin films, and decrease in ferroelectric answer of doped films. Investigation of<br />possibility of complex shaped electrodes preparation,suitable for tunability measurements, by different deposition techniques was the second goal of this research.<br />Sputtering technique in combination with laser removal, inkjet printing and photolithography were used for preparation of complex circular and coplanar electrodes<br />on the surface of barium titanate based thin films. Influence of processing<br />parameters for the each of mentioned technique on dimensional precision of prepared<br />electrodes was investigated. Selected laser was not appropriate for production<br />of electrodes on prepared barium titanate based thin films. Inkjet printing<br />was useful for production of electrodes in micrometer range, but for more sophisticated<br />geometries photolithography shows the best performance.</p>

Als Modellsystem für Oxide mit Perowskitstruktur ist Strontiumtitanat besonders geeignet, um generalisierbare Erkenntnisse über die Auswirkungen von Defekten zu gewinnen und ausgehend davon Struktur-Eigenschafts-Korrelationen zu diskutieren. Durch den Einsatz verschiedener oberflächensensitiver Methoden lässt sich im Ausgangszustand eine erhöhte Konzentration von Liniendefekten an der Oberfläche nachweisen, die sich durch Temperaturbehandlung verkleinert. Die Defektchemie bei hohen Temperaturen wird zur Simulation der elektrischen Leitfähigkeit in Abhängigkeit vom umgebenden Sauerstoff-Partialdruck genutzt. Die Dotierung des oxidischen Halbleitermaterials ist von Eigendefekten abhängig, wobei Sauerstoff-Leerstellen Donatorniveaus bilden und Strontium-Leerstellen Akzeptorcharakter besitzen. Neben der Diffusionsbewegung dieser Eigendefekte bei hohen Temperaturen kann bei niedrigen Temperaturen ein elektrisches Feld deren Umverteilung bewirken. Damit zeigt sich die Leitfähigkeit abhängig von externen elektrischen Feldern, aber auch weitere Eigenschaften sind auf diesem Wege modifizierbar. Im Rahmen der Arbeit werden strukturelle Änderungen, Valenz-Änderungen und veränderte mechanische Eigenschaften nachgewiesen, die jeweils abhängig vom elektrischen Feld schaltbar sind. Schließlich wird das gezielte Ausnutzen struktureller Defekte für Speicherzellen, die den schaltbaren Widerstand von Metall-SrTiO3-Kontakten zur Grundlage haben, vorgestellt. Die Anwendbarkeit des oxidischen Halbleiters als resistives Speicherelement beruht wiederum auf der Kopplung von Sauerstoff-Leerstellen an das elektrische Feld. / Being a model system for oxides with pervovskite-type of structure, strontium titanate can be used to gain generalizable insights into the consequences of defects and to discuss resulting structure-property relationships. By employing different surface sensitive methods, an increased concentration of line defects is found at the surface that reduces on temperature treatment. The defect chemistry at elevated temperatures is used to simulate the electric conductivity depending on the oxygen partial pressure during annealing. Doping of the oxidic semiconductor depends on intrinsic defects, whereby oxygen vacancies form donor states and strontium vacancies have acceptor character. Beside the diffusion movement of these intrinsic defects at elevated temperatures, at low temperatures an electric field may cause their redistribution. Hence, the conductivity becomes dependent on external electric fields but also other properties can be altered in this way. Within this work, structural changes, valence changes and changing mechanical properties are shown to be switchable by the electric field. Finally, the dedicated usage of structural defects is demonstrated on memory cells that employ the switchable resistance of metal-SrTiO3 junctions. The applicability of the oxidic semiconductor as a resistive memory element is again based on the coupling between oxygen vacancies and the electric field.

The implementation of polymer membranes in gas separation applications has been investigated to a great extent. Nevertheless, only a few types of polymers are used in commercial applications, disclosing the need for new materials with superior membrane performance to make membrane processes a more competitive technology over the conventional ones. Based on this context, this work focuses on the development of new polymeric membranes. Polyaniline (PANI), a multifaceted polymer that can change its structural properties upon various modification procedures, was chosen as membrane material. PANI membranes possess attractive O2/N2 selectivities, wherefore it is an interesting candidate for the use in gas separation applications, such as generation of oxygen-enriched air or inert gas generation. However, membranes made from neat PANI are suffering from brittleness and thus create leak paths through the membrane. Therefore PANI was blended with polybenzimidazole (PBI), a temperature stable polymer with good film-forming properties facilitating the preparation of thin, stable polymer films. Furthermore, several techniques were investigated including acid-doping, thermal treatment, and addition of titanate nanotubes (TiNTs) to enhance the separation properties. The materials that have been prepared are: 1)...

京都大学 / 新制・課程博士 / 博士(人間・環境学) / 甲第23265号 / 人博第980号 / 新制||人||232(附属図書館) / 2020||人博||980(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 吉田 寿雄, 教授 田部 勢津久, 教授 中村 敏浩 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

A literature review on the topic of ferroic and multiferroic solid solutions of BaTiO3, SrTiO3 and EuTiO3 forms the first part of this master thesis. The second part describes the experimental preparation and evaluation of the properties of samples of europium strontium titanates - EuxSr1-xTiO3. First, the high temperature solid state synthesis was carried out and relative density and open porosity of the sintered samples were evaluated. The sintered samples showed open porosity higher than 10%. The reasons for this behavior were evaluated and described from the point of view of experimental conditions and thermodynamical calculations. Finally, electric and dielectric properties of selected samples were measured. These results show that these samples are insulators and their residual conductivity is caused probably by oxygen vacancies, arising from the synthesis in a strongly reducing atmosphere of pure hydrogen.

京都大学 / 0048 / 新制・論文博士 / 博士(工学) / 乙第13015号 / 論工博第4140号 / 新制||工||1650(附属図書館) / 32943 / (主査)教授 斧 髙一, 教授 木村 健二, 教授 立花 明知 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM