The stability of glass is linked to its composition and the atmosphere controls its alteration. The organic pollutants emitted by wooden showcases play a role in the alteration of historic glasses. This study examines the effects of acetic acid, formic acid and formaldehyde on objects from the National Museums of Scotland and on replica glasses aged artificially, all with a soda silicate composition. Composition was determined by electron microprobe and analytical decomposition of the Raman spectra was used to establish correlations between glass structure and composition. This allowed interpretation of the structural variations between bulk and altered glass. The structure of the glasses altered by pollutants is characteristic of an alteration by selective leaching, with transformation of the silicates linked to alkali into silanols, which subsequently underwent condensation reactions to form a more polymerised structure. The SIMS concentration profiles of glass aged in artificial and real atmospheres were used to follow the alteration evolution as a function of time, humidity and pollutant concentration. The water film formed by the humidity at the surface and its acidity control the alteration by leaching of alkali and hydration of the glass. Formaldehyde does not act on the leaching reaction while acids accelerate and amplify it. In mixed polluted atmosphere, formates compounds always predominate in the film even at low formic acid concentration. The humidity and temperature fluctuations in museums maintain the leaching reaction. Knowledge of the harmful effect of organic acid pollutants in the alteration of soda silicate glasses will help improve their conservation.

Indiana University-Purdue University Indianapolis (IUPUI) / Observations of heterogeneities in Earth’s mantle motivate studies of mantle phase assemblages with variable composition. As samples cannot be directly collected from these regions, synthetic glasses can act as analogues for mantle melt and starting materials for high-pressure synthesis of stable mantle minerals in experiments. Here, I develop a specific methodology to produce homogeneous glasses that accurately span the composition space from enstatite (MgSiO3) to forsterite (Mg2SiO4), as well as Fe-bearing enstatite ((Mg0.1Fe0.9)SiO3 and ((Mg0.95Fe0.05)(Si0.95Fe0.05)O3) with variable oxidation states. This study systematically tests and iterates upon glass synthesis methods using an aerodynamic levitation laser furnace, in which a spherical glass sample levitates on a gas stream flowing vertically through a conical nozzle, while being heated from above with a 400 W CO2 laser. With sample diameters of 0.6-2.0 mm, shutting off the laser results in supercooling of levitated spheres at rates between 350 and 1350 °C/s. Sample preparation begins with grinding and mixing pure oxide powders in an agate mortar and pestle, followed by heating in a high temperature oven to devolatilize the mixture. Powders (0.5-7 mg aliquots) are fused into spheres in a copper hearth plate. To tune Fe valency and vitrify each sphere, samples are then levitated on flows of Ar, O2, 5% CO in Ar, 5% CO2 in Ar, or combinations of two of these gases, while being heated with the laser to temperatures above the liquidus for each composition for ~10 s before quenching. After x-ray diffraction (XRD) analyses confirm vitrification, a dual polish is applied, exposing parallel flat polished surfaces for scanning electron microscope (SEM) and electron probe microanalyzer analyses (EPMA). Back-scattered electron images and energy-dispersive x-ray spectroscopy (EDS) analyses of the spheres are obtained first on the SEM to gauge compositional accuracy and homogeneity, then EPMA analyses determine quantitatively the samples’ compositions. Once fully characterized, these glasses can be used in diamond anvil cell experiments, where they can act as proxies for an otherwise inaccessible area of the Earth. In addition to the development of this methodology, two web applications produced during this research aid in visualization of both data logs and analytical results.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24902号 / 工博第5182号 / 新制||工||1989(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 三浦 清貴, 教授 田中 勝久, 教授 藤田 晃司 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

No description available.

Le comportement mécanique du verre silico-sodo-calcique soumis à un contact ponctuel peut être amélioré par trempe. Les effets de trempe se manifestent par des gradients de propriétés sur le comportement du verre rendant la modélisation plus complexe. Ce travail a porté sur la modélisation et la simulation des verres non trempés et trempés soumis aux essais de nano-indentation et de nano-rayage. Les outils de simulation par éléments finis ont été développé et validés sur le verre métallique, choisi en raison de son comportement plastique connu. En comparant avec les données expérimentales, nous avons observé que les paramètres du matériau et les conditions expérimentales pouvaient donner la même réponse sur la courbe force-déplacement et l'empreinte. L’identification des propriétés du matériau doit être basée sur des comparaisons avec des simulations considérant la géométrie réelle de l'indenteur, la souplesse de la machine et le tilt de surface de l'échantillon. Les stratégies développées permettent de faire des identifications sur le comportement du verre silico-sodo-calcique. Dans la famille du verre silicaté, le verre silico-sodo-calcique a un comportement plastique semblable au verre de silice qui est affecté non seulement par le mécanisme de cisaillement mais aussi par la densification. Il est essentiel donc d'étudier le comportement densification/cisaillement du verre de silice car il est largement discuté dans la littérature. La comparaison des résultats de simulation par plusieurs modèles avec les courbes force-déplacement et les images d'empreinte a montré que la modélisation de la densification, en prenant en compte l'écrouissage et la modification des modules élastiques, est suffisante pour décrire le comportement des verres silicatés. Enfin, les connaissances sur les simulations des essais à chargement ponctuel et la modélisation du comportement du verre ont guidé une étude sur les effets du gradient de propriétés dans les verres trempées thermiquement et chimiquement. / The mechanical behavior of soda-lime-silica glass subjected to contact damage can be improved by tempering. The effects of tempering created tailor properties and the glass behavior more complicated. Therefore, this work studied the modeling and simulation of non-tempered and tempered glasses subjected to the nano-indentation and nano-scratch tests. The finite element simulation tools have been primarily validated and the metallic glass was chosen for the studies because of its known plastic behavior. By comparing with the experimental data, we have observed that the parameters of material model and the experimental conditions could give the same response on load displacement curve and imprint. The evaluation of material properties must be based on the comparisons with fully modeled simulation considering the real geometry of the indenter, the compliance of the instrument and the tilting of the sample surface. The developed strategies allow identification of soda-lime-silica glass behavior. Similar to that of silica glass, the plastic behavior of soda-lime-silica glass is not only affected by the shear mechanism but also the densification. Hence, it is essential to study the shear/densification behavior of silica glass as it is widely discussed in the literature. The comparison of simulation results by several models with the load displacement data and the images of imprint showed that the modeling of densification by taking into account the hardening and the change in elastic moduli is sufficient for describing the behavior of silicate glasses. Finally, the knowledge about the simulation of the contact loading tests and the modeling of glass behavior guided a study on the coupling of tailored properties effects in the thermally and chemically tempered glasses.

本研究では分子の構造を系統的に変化させて合成したポルフィリン発色団をもつ種々のアルコールを用いて、シリケートガラス表面にポルフィリンの単分子膜を作製し、縮合反応やシリルエステル結合の化学的安定性を検討し、安定な有機/無機界面の構築に必要な分子設計の指針を示すことに成功した。また、リニアテトラピロールであるビリンジオンのソルバトクロミズムについても述べている。 / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University

Le nouvel essor industriel du marché des applications mobiles telles que les smartphones ou les tablettes tactiles nécessite de nombreuses recherches afin de concevoir des écrans en verres encore plus résistant. Le procédé d’échange ionique au potassium permet d’améliorer la résistance mécanique des verres grâce à la substitution des ions Na⁺ par des ions K⁺, de plus gros rayon ionique. Elle permet ainsi de bloquer les fissures superficielles du verre et de réduire la casse du matériau. Ce travail est consacré à comprendre le principe de diffusion des ions K⁺ au sein de la structure silicatée de différents verres. Les paramètres, temps, température et composition verrière, influent sur la cinétique de l’échange ionique. Dans les mêmes conditions de trempe, la réduction de la composition à un formateur et à l’ion mobile permet d’améliorer la diffusion et la propagation des ions au sein du matériau. Les conditions de trempe, thermique et temporelle, agissent sur la cinétique de diffusion des ions. Elles réduisent la facilité de déplacement des ions à travers la structure silicaté du matériau avec un changement de comportement au-delà de 8h d’immersion dans les sels fondus. La substitution des Na⁺ par les ions K⁺ et leur différence de taille modifient l’environnement des sites laissés vacants par les ions Na⁺ et modifie la structure silicatée du verre. La spectroscopie IR permet de mettre en évidence les modifications structurales des verres soumis à ce procédé d’échange ionique. Lors de l’introduction des ions K⁺, la structure du verre se dépolymérise et crée des oxygènes non pontants. Ceci permet de montrer que l’échange ionique conduit à l’amélioration du renforcement mécanique des verres. / The new industrial boom of the market for mobile applications such as smartphones or tablets requires much research in order to touch-screens design more resistant. The potassium ion exchange process improves the mechanical strength of glass by Na⁺ ions substitution with K⁺ ions, of larger ionic radius. It thus helps to block surface cracks in glass and reduce breakage of the material. This work is devoted to understand the principle of K⁺ diffusion in the silicate structure of different glasses. The parameters: time, temperature and glass composition affect the kinetic of ion exchange process. In the same quenching conditions, the limitation of the composition just to a former network and a mobile ion can improve the diffusion and the penetration ions inside the material. The quenching conditions, temperature and time, act on the kinetic diffusion. They reduce the mobility of the ions through the structure of the silicate material with a change of behaviour above 8h immersion in molten salts. Substitution of Na⁺ by K⁺ ions having different size affect the environment of the sites left vacant by the Na⁺ ions and modifies the silicate structure of the glass. IR spectroscopy allows highlighting the structural modifications of the glass submitted to this ion exchange process. During the introduction of the K⁺ ions inside the glass, the silicate structure is depolymerized and creates no-bridging oxygens. This allows to demonstrate that the ion exchange lead to the mechanical improvement of the glass.

No description available.