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The grades of steel used for automotive bodies are interstitial free steel grades and titanium stabilized ultra-low carbon steel grades. During the manufacturing of these grades, the addition of titanium in liquid steel is achieved in the steel refining units and may cause processing problems. Titanium reacts with the dissolved aluminum and oxygen to form complex solid aluminum titanate type micro-particles (inclusions). During the flow of titanium alloyed steel grades containing solid inclusions (such as aluminum titanate and alumina type inclusions), the clog accompanied by steel skull can be formed at the submerged entry nozzle between the tundish and the mold. To reduce the effects of aluminum titanate type inclusions, they can be either modified or removed. The current study focused on the removal of Al2O3, TiO2, and Al2TiO5 inclusions by dissolving them in slag in the temperature range of 1430 – 1600 °C using a high-temperature confocal scanning laser microscope. In this technique, a single particle (inclusion) is placed on the surface of a solid slag, and the inclusion-slag system is heated to steelmaking temperatures. The dynamic changes in inclusion size are measured to determine dissolution kinetics and mechanism. This work has developed a complex oxide particle synthesis technique and provides the first-ever kinetic data for removal of aluminum titanate inclusions into steelmaking slags. It is found that Al2O3 inclusions have a slower dissolution rate than that of Al2TiO5 inclusions followed by TiO2 inclusions. The rate-controlling steps are investigated using a shrinking core model. It is shown that the rate-controlling step for dissolution of both Al2O3 and Al2TiO5 inclusion types is the mass transfer of alumina. Evidence in support of this finding is the particle-slag interface characterization by line scan analysis and calculated diffusivity values being inversely proportional to the viscosity of slag. The dissolution path of aluminum titanate is proposed in the following steps. First, aluminum titanate dissociates into alumina, titanium oxide and oxygen while slag penetrates through the particle. In the next step, the alumina and titanium oxide dissolves in slag, and the oxygen leaves the system. The existence of gas bubbles enhances the overall rate of Al2TiO5 dissolution. The current work establishes a detailed understanding of the dissolution of Al-Ti-O type inclusions in steelmaking slags. This knowledge will inform steelmakers on which inclusions of different chemistry can be removed preferably and develop strategies on better slag design to produce superior quality steel with reduced operational downtime. / Thesis / Doctor of Philosophy (PhD)

京都大学 / 新制・課程博士 / 博士(工学) / 甲第25287号 / 工博第5246号 / 新制||工||1999(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 杉村 博之, 教授 邑瀬 邦明, 准教授 小林 圭 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

The corrosion resistance of two commercially available SiC filter materials coated with Mg-doped Al₂ TiO₅ and (Ca _0.6.6' Mg_0.52) Zr₄P₆O₂₄ (CMZP) was investigated in high-temperature high pressure (HTHP) alkali-steam environments. Coated specimen properties, including cold and hot compressive strengths, bulk density, apparent porosity, permeability, and weight change, detected after exposure to 92% air-S% steam 10 ppm Na at 8OO°C and 1.8 MPs for 500 h were compared with those of uncoated specimens. Procedures for applying homogeneous coatings of Mg-doped Al₂ TiO₅ and CMZP to porous SiC filters were established and coating of the materials was successfully accomplished. Efforts to stabilize the Al₂ TiO₅ coating composition at elevated temperature were successful. Coatings show promise for providing improved corrosion resistance of the materials in pressurized fluidized bed combustion (PFBC) environments as evidenced by higher compressive strengths exhibited by coated SiC specimens than by uncoated SiC specimens following HTHP alkali-steam exposure. / Master of Science

The coupling of magnetic and electric order parameters, i.e., the magnetoelectric effect, has been widely studied for its intriguing physical principles and potentially broad industrial applications. The important interactions between ferroic orderings -- ferromagnetism, ferroelectricity and ferroelasticity -- will enable the manipulation of one order through the other in miniaturized materials, and in so doing stimulate emerging technologies such as spintronics, magnetic sensors, quantum electromagnets and information storage. By growing ferromagnetic-ferroelectric heterostructures that are able to magneto-electrically couple via interface elastic strain, the various challenges associated with the lack of single-phase multiferroic materials can be overcome and the magnetoelectric (ME) coupling effect can be substantially enhanced. Compared with magnetic field-controlled electric phenomena (i.e., the direct magnetoelectric coupling effect), the converse magnetoelectric effect (CME), whereby an electric field manipulates magnetization, is more exciting due to easier implementation and handling of electric fields or voltages. CME also affords the possibility of fabricating highly-efficient electric-write/magnetic-read memories. This study involved two avenues of inquiry: (a) exploring the strain-mediated electric field manipulation of magnetization in ferroelectric-ferromagnetic heterostructures, and (b) investigating coupling and switching behaviors at the nanoscale. Accordingly, a series of magnetoelectric heterostructures were prepared and characterized, and their electric field tunability of magnetic properties was explored by various techniques and custom-designed experiments. Firstly, the relevant properties of the individual components in the heterostructures were systematically investigated, including the piezoelectricity and ferroelectric/ferroelastic phase transformations of the ferroelectric substrates, lead magnesium niobate-lead titanate, or Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT). This investigation revealed significant information on the structure-property relationships in crystals oriented at <110>, as well as shed light on the effect of ferroelectric phase transformation on magnetoelectric coupling. This investigation of electric field controlled strain, in contrast to many prior studies, enables a more rational and detailed understanding of the magnetoelectric effect in complex ferroelectric-ferromagnetic heterostructures. The magnetoelectric thin film heterostructures were fabricated by depositing ferromagnetic iron-gallium (Fe-Ga) or cobalt ferrite (CoFe2o4 or CFO) films on top of differently-oriented ferroelectric PMN-PT substrates. Through significant electric field-induced strain in the piezoelectric substrate, the magnetic remanence and coercive field, as well as the magnetization direction of the ferromagnetic overlayer, can be substantially tuned. These goals were achieved by the interfacial strain modification of the magnetic anisotropy energy profile. The observation and analysis of the electric field tunability of magnetization and the establishment of novel controlling schemes provide valuable directions for both theoretical development and future application endeavors. / Master of Science

Diese Arbeit beschäftigt sich mit den elektrischen Eigenschaften der resistiven Schaltmaterialien SrTiO3 und NbO2. Im ersten Teil werden NbO2 (001)-Dünnschichten untersucht. Bisher sind die für NbO2-Dünnschichten in der isolierenden Phase gemessenen spezifische Widerstände um einen Faktor von 200 niedriger als der in NbO2-Einkristallen gemessene 10 kΩ cm Widerstand. In dieser Arbeit wird der spezifische Widerstand von NbO2-Dünnschichten auf 945 Ω cm erhöht. Es wird gezeigt, dass leitfähige Perkolationspfade entlang der Korngrenzen für die Abnahme des spezifischen Widerstandes verantwortlich sind. Durch temperaturabhängige Leitfähigkeitsmessungen wurden Defektzustände identifiziert, die für die Verringerung des spezifischen Widerstandes gegenüber dem theoretischen Wert verantwortlich sind. Im zweiten Teil wird der Einfluss des Ti-Antisite Defekts auf das resistive Schalten in SrTiO3 Dünnschichten untersucht, welche mit metallorganischer Dampfphasenepitaxie gezüchtet wurden. Dabei werden sowohl stoichiometrische als auch Strontium defizitäre Schichten untersucht. Es wird über temperaturabhängige Permittivitätsmessungen gezeigt, dass durch Kristalldefekte die weiche Phononenmode gestört wird und bei stark strontiumverarmten Schichten polare Nanoregionen gebildet werden, was auf die Bildung des TiSr Defekts zurückgeführt wurde. Darüber hinaus wird gezeigt, dass stark strontiumdefiziente SrTiO3 -Schichten ein stabiles resistives Schalten mit einem Ein-Aus-Verhältnis von 2e7 bei 10 K aufweisen, während stöchiometrische Dünnschichten kein stabiles Schalten zeigen. Es wird ein diodenartiger Transportmechanismus, der im hochohmigen Zustand auf Schottkyemission beruht und ihm niederohmigen Zustand durch defektassistierten Tunnelstrom dominiert wird, identifiziert. Daraus wurde ein neues Modell für das resistive Schalten, basierend auf dem TiSr Defekt und der induzierten Ferroelektrizität, entwickelt. / In this work, the impact of crystal defects on the resistive switching materials SrTiO3 and NbO2 is investigated. The work is divided into two parts. In the first part, NbO2 (001) thin films are studied. So far, resistivities measured for NbO2 thin films in the insulating phase are by a factor of 200 lower than the 10 kΩ cm resistivity measured in NbO2 single crystals. To make this material applicable for resistive switching, the resistivity in the insulating phase has to be increased to effectively block the current in the high resistive state. Throughout the investigations presented in this work, the resistivity of NbO2 thin films is increased to 945 Ω cm. It is shown that conductive percolation paths along the grain boundaries are responsible for the decrease in resistivity. Temperature-dependent conductivity measurements identified defect states responsible for the reduction in resistivity from the theoretical value. In the second part of this work, the influence of the Ti anti-site defect on resistive switching in SrTiO3 thin films grown by metal-organic vapor phase epitaxy is studied. Both stoichiometric and strontium deficient thin films are studied. It is shown via temperature-dependent permittivity measurements that crystal defects harden the soft phonon mode and polar nano regions are formed in highly strontium deficient films, which was attributed to the formation of Ti antisite defects. In addition, highly strontium deficient SrTiO3 films are shown to exhibit stable resistive switching with an on-off ratio of 2e7 at 10 K, whereas stoichiometric thin-films do not show stable switching. A diode-like transport mechanism based on Schottky emission in the high-resistance state and dominated by defect-assisted tunneling current in the low-resistance state is identified. From this, a new model for resistive switching based on the Ti antisite defect and the induced ferroelectricity is developed.

Les principaux objectifs de cette thèse de doctorat ont été de réaliser la synthèse et la caractérisation structurale et dieléctrique des échantillons céramiques ferroélectriques appartenants au système Pb1-xRxZr0,40Ti0,60O3 avec R = Ba et La et x entre 0,00 à 0,50. Ce système a été choisi car il est un matériel ferroélectrique qui a des propriétés physiques intéressantes, comme haute constante diélectrique et piézo-électrique, ce qui les rend candidats potentiels pour des applications telles que les condensateurs à haute densité d'énergie et les actionneurs. Afin d'évaluer le comportement relaxor, les études ont été effectuées avec la variation de la composition, du type de dopage (par des atomes de la même ou différente valence – La ou Ba) et de la taille des particules de céramique, dès l'échelle micrométrique à l'échelle nanométrique. Les échantillons céramiques micrométriques ont été préparées par la méthode de réaction de l'état solide et la frittage dans un four électrique conventionnel. Les données fournies par la technique de diffraction des rayons X de cettes échantillons ont montré une transition de une phase tétragonal pour une phase cubique avec l'augmentation de la concentration de cations substituants. Ces changements ont été attribués à une diminution de distorsion dans le maille cristallographique en raison de l'apparition de défauts causés par l'incorporation de dopage. Les mesures électriques ont été obtenues par spectroscopie d'impédance et ont montré un comportement électrique relaxor à partir de compositions avec plus de 12% at. La et de 30% at. Ba pour les systèmes PLZT et PBZT, respectivement. Les mesures électriques de l'échantillon avec 12%, 13% et 14% at. La et 30% at. Ba présentent un comportement qui, selon la littérature, est liée à une transition de phase spontanée d'un comportement relaxor et au comportement d'un matérial ferroélectrique normal. La technique de diffraction des rayons X a également été utilisé pour surveiller le processus de transition de phase en fonction de la température pour échantillons PLZT et PBZT. Il est possible de voir le changement de structure tétragonal de groupe d'espace P4mm en structure cubique de groupe d'espace Pm-3m. En ce qui concerne la structure locale, nous avons effectué des mesures expérimentales avec la technique de spectroscopie d'absorption des rayons X dans le spectre XANES aux seuils d'absorption de différents éléments pour les échantillons PLZT et PBZT. Dans les cas de seuil d'absorption K du titane, l'intégration de La et Ba atomes de la structure du PZT entraîne une diminution dans le désordre local dans le octaèdre TiO6, vérifié par la réduction du déplacement statique de atome Ti au centre de l'octaèdre TiO6. Cette évolution est plus faible pour les échantillons que montrent le comportement relaxor. Les spectres d'absorption EXAFS au seuil LIII du plomb et seuil K du zirconium ont été effectués aussi et ces mesures indiquent que la structure locale autour des atomes de plomb ou de zirconium est également affectée par l'introduction des atomes de La et Ba dans la structure. Le comportement relaxor a été aussi étudié en fonction de la taille de grain dans une échelle nanométrique. Ainsi les échantillons de compostions PZT, PLZT11 et PBZT10 ont eté préparés en utilisant la méthode de synthèse chimique de polymères précurseurs et le processus de frittage par spark plasma. La caractérisation de ces échantillons par diffraction de rayons X montrent que les paramétres de maille réduisent en comparison avec les échantillons de même composition et taille de grain micrométrique. Pour l'échantillon de composition PLZT11, il est possible de constater le comportement relaxor par les mesures de la constante dieléctrique en fonction de la température. Les changements quand la taille de grain est dans une échelle nanométrique sont attribués à la limitation des frontières de grains, qui provoquent un systéme de tension, responsable de la diminuition des paramétres de maille, et provoquent l'apparition de domaines ferroélectriques nanométriques / The main objectives of this doctoral thesis were the synthesis and structural characterization of Pb1-xRxZr0.40Ti0.60O3 ferroelectric ceramic samples, with R = Ba and La and x between 0.00 to 0.50. This system was chosen because its interesting physical properties such as high dielectric and piezoelectric constant. These characteristics make it potential candidate for applications such as capacitors in high energy density and actuators. To evaluate the relaxor behavior, the studies were carried out with the change in the composition, type of doping (by atoms of the same or different valence – La or Ba) and the particle size of ceramics, from the micrometer to nanometer scale. Micrometric ceramic samples are prepared by the method of reaction of solid state and sintering in a conventional furnace. The characterization with X-ray diffraction technique of these samples showed a transition from tetragonal phase to a cubic phase with increase of the dopping cation concentration. These changes have been attributed to the appearance of defects caused by the incorporation of La or Ba cations. Electrical measurements were obtained by impedance spectroscopy and showed a electric relaxor behavior from compositions with more than 12 at. % of La and the 30 at. % of Ba for PLZT and PBZT systems, respectively. These measurements for the samples with 12 at. %, 13 at. % and 14 at. % of La and 30 at. % of Ba exhibit a behavior that, according to the literature, is related to a spontaneous phase transition from a relaxor behavior to a normal ferroelectric behsvior. The technique of X-ray diffraction also been used to monitor the phse transition phase as a function of the temperature for PLZT and PBZT samples. It is possible to note the change in a tetragonal structure with P4mm space group to a cubic structure with Pm-3m space group. Concerning the local structure, XANES spectra in the absorption edge of various elements in PLZT and PBZT samples were performed. In the cases of Ti K-edge absorption, the dopping of La and Ba atoms in the PZT structure leads to a decrease of the local disorder in the TiO6 octahedron and it is verified the reduction of static displacement of Ti atom in the center of the TiO6 octahedron. This displacement is lower for samples that show relaxor behavior. The EXAFS measurements in Pb LIII-edge and Zr K-edge were performed and also indicate that local structure around lead or zirconium atoms is also affected by the introduction of La and Ba atoms in the PZT structure. The relaxor behavior was also studied depending on the size of particle size in a nanometer scale. Thus samples PZT, PLZT11 and PBZT10 compositions were prepared using the synthesis method of precursor polymers and the process of sintering by spark plasma. Characterization of these samples by X-ray diffraction shows that the lattice parameters are reduced in comparison with samples of the same composition and micrometer particle size. For PLZT11 composition, it is possible to observe a relaxor behavior by measurement of the dielectric permittivity as a function of the temperature. These changes when the grain size is in a nanoscale are attributed to the grain boundaries, that are responsible for the decrease in the lattice parameters and the appearance of ferroelectric nanodomains