Processing of Bulk Metastable Oxide Ceramics Oxide ceramic materials are extensively used in various modern application domains which require properties such as high temperature stability or creep resistance, wear resistance, chemical stability, useful electronic, optical and magnetic properties. In the diverse arena of materials technology that interlinks processing, structure, properties and performance, the advancement of new processing techniques to develop oxide ceramics facilitates the extension and refinement of their desirable properties and also mitigate their limitation in terms of application. Progress in processing science/technology offers a real impetus to the development of metastable ceramics with novel, non-equilibrium structures that exhibit scientifically interesting properties and have the potential to cater to the requirements of modern application areas. In the absence of the equilibrium state of a material system, metastable states can be formed with amorphous phases, extended solid solutions, metastable crystal structures and nanocrystallinity. Such metastable states can be retained by imposing kinetic constraints, which means that under the conditions of temperature and pressure, atomic mobilities are inadequate for the transformation. Metastable ceramics that are produced using non-equilibrium processing routes, such as rapid solidification, vapour deposition, spray pyrolysis, sol-gel technique etc., have been known to possess potentially useful properties, such as hard and soft magnetic characteristics, semiconductivity, varistor action, optical transmittivity and superconductivity. Apart from possessing attractive properties, a metastable phase may also serve as a precursor to a desired microstructure; for instance, controlled crystallization of an amorphous phase is a possible way enroute to nanocrystalline structure. It was well recognized that the comprehensive study and use of nanostructured and other metastable ceramics requires consolidation of the fine discontinuous forms (powders or flakes) produced from non-equilibrium processing routes, into bulk shapes with greater control on the fine scale of the structure. Such efforts have not been entirely successful. Non-equilibrium processing techniques do not produce the metastable materials in bulk form. Consolidation of metastable ceramics into dense forms needs high temperatures, mechanical activation (in the form of static pressures or shock waves), or a combination of both. Such activation may trigger the transformation of the desired metastable phase into a more stable phase with concurrent grain growth. Conversely, conditions that allow the desired metastable phase to be retained may not be adequate for complete densification. The subject of the present thesis is two-fold: (i) processing of dense amorphous Al2O3-Y2O3 materials through a novel densification route involving hot pressing of amorphous powders, produced by co-precipitation, at low temperatures and moderately high pressures, (ii) detail study of possible deformation mechanisms of the amorphous phase from mechanical testing at elevated temperatures. Unusual deformation behavior of the bulk amorphous material has been related to the densification process. Development of Pressure Consolidation Technique Amorphous powder of composition Al2O3-15 mol% Y2O3 (A15Y) was synthesized by co-precipitating a hydroxide from metal nitrate precursor’s solution by using ammonium hydroxide. Chemical homogeneity was ensured by a molecular level mixing of precursors of aluminium and yttrium at room temperature. The as-precipitated powder undergoes thermal decomposition (pyrolysis) to an amorphous oxide by ~770-800o C. The crystallization temperature was found from thermal analysis to be ~900o C, with γ-Al2O3 as the initial product of crystallization. The true density of the amorphous A15Y phase was measured to be only 2.69 g cm-3 by pycnometry, which is ~2/3 of the assemblage of equilibrium crystalline phases consisted of Al2O3 and YAG. Uniaxial hot pressing was performed with decomposed, classified powders (large agglomerates with sizes more than 10 µm were removed by sedimentation technique) at low temperature of about 630-640o C and moderately high pressure of 710-750 MPa. Pressure was held constant for 30-45 minutes. Cold compaction at pressures of 50-65 MPa for 8-10 minutes was carried out prior to hot pressing to ensure green strength of the compacts. All hot-pressed compacts revealed significant densification (95-96% relative densities) with uniformly distributed fine porosity. X-ray diffraction, electron microscopy analysis, Raman spectroscopy and differential thermal analysis established the amorphous nature of the dense, hot-pressed pellets. The amorphous phase displays an elastic modulus of ~ 50-60 GPa and a hardness of 4-5 GPa, which are considerably lower than those of the crystalline counterpart. Deformation Behavior of Amorphous Al2O3-Y2O3 The experiments described above clearly demonstrated the feasibility of producing bulk metastable ceramics in the Al2O3-Y2O3 system by a novel consolidation (viz., low temperature-high pressure) route of amorphous powders. This section of the thesis concentrates on studying the deformation mechanisms of the amorphous phase, which are found to be characteristic of the temperature domain of the experiment. Uniaxial compression tests at temperatures of 650-850o C with constant engineering strain rates of ~3-4 X 10-4 s-1 were conducted on dense amorphous samples made from the hot-pressed compacts. At a temperature of 850o C, i.e., close to the crystallization temperature, the amorphous phase was characterized by homogeneous deformation with continuous work hardening after yielding, accompanied by an increase in the true density of this glass by 10-12%. X-ray and electron microscopy analysis confirmed that the density increase was not due to the formation of nano-crystals at this high temperature. Raman spectroscopy and differential thermal analysis further corroborates that the glass was amorphous even after deformation. No shear instabilities were formed at the side surfaces due to the deformation. Significantly large compressive longitudinal strains up to about 28% were observed before unloading. Moreover, an interrupted loading-unloading test established that the bulk density increase was monotonic with the existence of multiple amorphous states enroute to a succession of denser structures. A simultaneous increase in both hardness (H) and modulus (E) of the amorphous phase of up to 100% after deformation bolstered this experimental observation of bulk density increment at constant porosity. The above evidence clearly points towards significant structural changes of the amorphous phase during high temperature deformation process and therefore a phenomenon of molecular densification of the amorphous structure through a hierarchy of dense amorphous phases was hypothesized, analogous to density or entropy driven amorphous-to-amorphous phase transitions (polyamorphism). Note that the densification described here does not refer to the conventional removal of porosity in a ceramics. At an intermediate temperature of 725o C, which is significantly (~200o C) below the crystallization temperature, plastic deformation commences at a stress (yield stress) of 700-780 MPa (considerably higher compared to the yield stress at 850o C) and continued to deform plastically with a slowly decreasing flow stress before reaching a plateau. Thus, the glass exhibited flow softening, in contrast to flow hardening observed at 850oC. Plastic deformation of this glass is largely non-viscous through shear instabilities (akin to the low temperature deformation behavior of metallic glass) and resulted in 8% increment in bulk density after deformation. Once again, the amorphous nature of the glass after deformation was confirmed by X-ray and electron microscopy analysis. Therefore, this intermediate temperature domain was characterized by both densification and shear. Deformation at even lower temperature, viz., at the temperature of hot pressing (650o C), was also characterized by elastic-plastic behavior (similar to flow softening described above), with immediate yield drop after yielding and resulted in a fairly large amount of plasticity of about 17% before unloading. The bulk density was found to be increased only by 2%. Another very interesting experimental finding from the present investigation is the time-dependent deformation (viz., creep densification) exhibited by this glass. It was established from the result of longer term creep experiment at 850o C that the glass revealed large uniaxial compression of about 15% with 5.5% densification to a density of 3.02 g cm-3. Strain rate sensitivity of the A15Y glass was revealed by another stress jump test. To summarize, the present thesis elucidates the discovery of a new class of ceramics with unusual physical properties in an amorphous mixture of Al2O3-Y2O3, which is in contrast to the conventional brittle ceramics. This new class of ceramics deforms plastically without any hydrostatic containment, like ductile metal, at temperatures about 1000o C below those at which their crystalline counterpart would deform. The behavior of this amorphous ceramics under stress that leads to unusually large change in shape, density, hardness and modulus with hierarchies of amorphous structures is demonstrated in detail with experimental evidence.

Estudamos um sistema de dois níveis acoplados como um modelo que imita o comportamento de líquidos super-resfriados. Em equilíbrio o modelo apresenta uma fase líquida e uma fase cristalina com diversos estados fundamentais. O modelo é definido numa rede quadrada e a cada sítio é associada uma variável estocástica de Ising. A característica que torna este modelo particularmente interessante é que ele apresenta estados metaestáveis duráveis que podem desaparecer dentro do tempo acessível para as simulações numéricas. Para imitar o processo de formação dos vidros, realizamos simulações de Monte Carlo a taxas de resfriamento constante. Apresentamos também simulações para resfriamentos súbitos a temperatura abaixo da temperatura de fusão. / We study a coupled two level systems as a model that imitate the behavior of supercooled liquids that become structural glasses under cooling. In the equilibrium the model shows a liquid phase and a crystalline phase with many grouond states. The model is defined on a square lattice and to each site a stochastic Ising variable is associated. The feature that makes this model particularly interesting is that it display durable metastables states which can vanish within the time available for numerical simulations. In order to imitate the glass former process, we perform Monte Carlo simulations at constant cooling rate. We present also simulations for quenchs to temperatures below the melting temperature.

La nécessité de synchroniser les différentes étapes des protocoles d’information et de communication quantiques implique l’utilisation de mémoires quantiques. Différents systèmes physiques sont aujourd’hui explorés, parmi lesquels les ions en matrice cristalline, les atomes froids et les vapeurs atomiques. Le protocole de stockage le plus couramment utilisé se fonde sur le phénomène de Transparence Electromagnétiquement Induite (EIT) : une impulsion lumineuse est gravée dans la cohérence Raman entre les deux états fondamentaux d’un système atomique à trois niveaux en Lambda. Bien qu’elle ouvre des perspectives prometteuses, en termes d’efficacité, de fidélité et de temps de stockage, cette technique est néanmoins sensible aux effets déphasants, tels que des gradients de champs magnétiques.Dans ce mémoire, j’étudie tout d’abord le stockage d’impulsions lumineuses classiques par EIT dans une vapeur d’hélium métastable à température ambiante. Les résultats expérimentaux obtenus sont en accord avec les simulations numériques des équations de Maxwell-Bloch complètes du système et montrent notamment l’existence d’une phase supplémentaire acquise par l’impulsion restituée en configuration désaccordée. Cette phase s’explique par la propagation du faisceau sonde dans un milieu dispersif. Dans une deuxième partie, je mets expérimentalement en évidence, dans le même système, une nouvelle forme de stockage basée sur le phénomène d’Oscillations Cohérentes de Population (CPO), par nature plus robuste aux effets déphasants que l’EIT. Les simulations numériques permettent d’analyser plus précisément les mécanismes à l’œuvre dans une mémoire CPO et, notamment, l’influence de la phase relative entre les faisceaux signal et de couplage sur les efficacités de stockage. / The need to synchronise quantum information and communication protocols implies the use of quantum memories. Different physical systems are investigated nowadays, among which ions in crystals, cold atoms and atomic vapours. The most common protocol is based on the Electromagnetically Induced Transparency (EIT) phenomenon: a light pulse is engraved in the Raman coherence of both ground states of an atomic Lambda–type three-level system. Though it opens promising perspectives, with respect to efficiency, fidelity and storage time, this technique is, however, sensitive to dephasing effects such as magnetic field gradients.In this thesis, I first study the storage of classical light pulses via EIT in a room- temperature metastable helium vapor. The obtained experimental results agree with the numerical simulation of the complete Maxwell-Bloch equations of the system. In particular, the existence of an extra phase acquired by the retrieved pulse is demonstrated in the detuned configuration, which can be explained by the propagation of the signal beam in the medium. In the second part, I experimentally isolate, in the same system, a new storage protocol based on the Coherent Population Oscillation (CPO) phenomenon, which is by nature more robust than EIT to dephasing effects. The numerical simulations allow us to precisely analyse the mechanisms involved in a CPO memory and, in particular, the influence of the relative phase between the signal and coupling beams on the storage efficiencies.

In this work, an in-depth analysis of crystalline characteristics has been performed for a unique set of strictly monodisperse poly-ε-caprolactone (PCL) oligomers. The molecules have different sets of end groups with various degrees of bulkiness and hydrogen bonding potential, affecting their aptitude to pack in ordered crystal structures. The oligomers also have different numbers of repeating units (n = 2-64), affecting the degree to which end groups influence overall molecular characteristics. The presence of bulky end groups leads to an innate confinement effect on crystallisation which in turn makes it possible to utilize the set of PCL oligomers to study confined space crystallisation. Confined space crystallisation is explored as a route to gain further understanding about the early metastable phases in crystal formation.   The monodisperse nature of the samples made it possible to collect very precise small-angle and wide-angle X-ray scattering data (SAXS and WAXS) as well as calorimetric data. Computer modeling studies were performed to support experimental findings. It was shown that end groups strongly affected crystallisation features for the shorter oligomers (n ≤ 8) but to a lesser extend for the longer oligomers (n ≥ 16). The presence of a bulky end group at one end of an oligomer could inhibit the formation of hydrogen bonds on the other end. Short oligomers (n = 8) with OH-end groups exhibited novel packing characteristics. At one isothermal crystallisation temperature the molecules exhibited not only lamellar ordering but also an additional, likely rectangular or slanted, ordering. The sample was packed in a unique structure with molecular chains lying parallel but not aligned head to head with each other. At a higher crystallisation temperature the molecules packed in a double layered structure and at an even higher temperature in a typical non-folded but tilted single-molecular layer pattern.   Unit cell determination was performed for a short oligomer with two bulky end groups, showing the existence of a tetragonal unit cell with different dimensions than the orthorhombic unit cells previously reported for linear PCL without end groups. To gain greater insight into the earliest stages of molecular packing, in situ WAXS measurements were performed using a synchrotron radiation beam and measuring data each 12 s whilst very slowly going from melt to isothermal crystallisation. It was shown that the crystal unit cell was distorted during the first minutes of slow crystallisation, which might either represent a metastable phase or else a highly distorted orthorhombic phase. / QC 20101105

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第18088号 / 理博第3966号 / 新制||理||1572(附属図書館) / 30946 / 京都大学大学院理学研究科地球惑星科学専攻 / (主査)教授 下林 典正, 教授 土`山 明, 准教授 三宅 亮 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20161号 / 理博第4246号 / 新制||理||1611(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)教授 高橋 義朗, 教授 田中 耕一郎, 教授 川上 則雄 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21756号 / 工博第4573号 / 新制||工||1713(附属図書館) / 京都大学大学院工学研究科機械理工学専攻 / (主査)教授 蓮尾 昌裕, 教授 木村 健二, 教授 江利口 浩二 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The complex behavior of systems like spin glasses, proteins or neural networks is typically explained in terms of a rugged energy or fitness landscape. Within the high dimensional conformation space of these systems one finds features like barriers, saddle points, and metastable states whose number – at least in the case of spin glasses – grows exponentially with the size of the system. We propose a novel Monte Carlo sampling algorithm that employs an ensemble of short Markovian chains in order to visit all metastable states with equal probability. We apply this algorithm in order to measure the number of metastable states for the two dimensional and the three-dimensional Edwards-Anderson model and compare with theoretical predictions.

<p>The primary focus of this thesis pertains to R&D results associated with deploying tensioned</p> <p>metastable fluid detector (TMFD) technology for monitoring of spent nuclear fuel</p> <p>(SNF) for actinide content from their neutron emissions while under extreme photon backgrounds</p> <p>(> 150 Gy/h), as may be expected within a hotcell. Traditional state-of-the-art</p> <p>neutron detectors such as 3He and BF3 based systems are well-known to be dysfunctional</p> <p>under such conditions, despite having pulse-shaped discrimination capabilities that allow</p> <p>them to differentiate photons vs. neutrons. The aim of this thesis was to test the ‘gamma</p> <p>blind’ ability of the centrifugally tensioned metastable fluid detector (CTMFD) based system,</p> <p>to monitor for actinide generated neutrons despite the anticipated high intensity gamma</p> <p>background, a goal which was successfully accomplished. Methods, designs, and experimental</p> <p>procedures are discussed for successful neutron monitoring from an Americium-Beryllium</p> <p>neutron source, as well as results showing no hindrance to neutron detection capability at</p> <p>modest negative pressure states through 150 Gy (15 kRad) accumulated gamma dose.</p> <p>A secondary focus was the ability of the TMFD based systems to perform alpha spectroscopy</p> <p>on closely separated (<10 keV) alpha particle emissions from 239Pu and 240Pu</p> <p>isotopes. Due to the closely spearated alpha decay energies, this feat could previously only</p> <p>be perfromed by tedious and expensive mass-spectrometry based systems. Instead, a wet</p> <p>chemistry apporach for detecting trace (? 10−3 Bq/mL) quantity alpha radiation with high</p> <p>alpha energy resolution (<10 keV) was developed and validated using the CTMFD system.</p> <p>Using this technique, mixtures containing samples of 239Pu:240Pu with activity concentrations</p> <p>ranging in ratio from 1:0 to 0:1 were able to be identified within ±12% accuracy.</p> <p>Lastly, successful assessments were conducted for detecting neutron emissions from a 1</p> <p>Ci Plutonium-Beryllium source under a variety of shielded configurations using a CTMFD</p> <p>and a 3He based Ludlum 42-49BTM detector. Concrete, lead, and water shielding materials</p> <p>of thicknesses ranging from 0 to ?30 cm were placed as shielding material, with the</p> <p>CTMFD configured only for fast energy neutron detection. Monte Carlo N-Particle Transport</p> <p>(MCNP) code-based simulations were performed for derivation of the neutron energy</p> <p>spectrum incident on the detectors to compute sensitivity estimates. At 0.6 MPa (6 bar) negative pressure, the CTMFD was determined to offer up to 7 times higher sensitivity vs the</p> <p>Ludlum 42-49B, though further increasing the negative pressure state to 1.1 MPA (11 bar)</p> <p>exponentially increases the sensitivity to offer 100+ times higher sensitivity for the CTMFD</p> <p>vs the Ludlum 42-49B.</p>

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21549号 / 理博第4456号 / 新制||理||1640(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)教授 高橋 義朗, 教授 田中 耕一郎, 教授 前野 悦輝 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM