Dissertations / Theses on the topic 'Solid state polymorphic transformations'

The main purposes of this study were; (i) to apply the theory of martensite crystallography to martensitic transformations in low-symmetry materials, (ii) to investigate, using the computer simulation method, the microscopic structure of complex interphase boundaries which are not yet fully understood in terms of the martensitic mechanism. Although the unique symmetry of a twin boundary makes it a rather exceptional kind of interface, it is clearly a particularly appropriate starting point especially due to the role which twinning plays in martensitic transformations. The accuracy of twinning modes is vital for their use as lattice-invariant shears in theories of martensite crystallography. Potential twinning modes for zirconia were determined using the analysis due to Bilby and Crocker (1965) and the associated atomic shuffling was also considered. Twinning orientation relationships involving a screw axis and a glide plane have been established. The theory of martensite crystallography (Acton et al. 1970) was then applied to the tetragonal to monoclinic martensitic transformation in zirconia. The predictions for the habit plane, shape strain and the direction of the shape deformation were obtained and compared with available experimental observations. The application of the theory was also extended to the face-centred cubic to monocline martensitic transformation in plutonium alloys. The predictions of the crystallographic features for this transformation are reported. The computer simulation method was applied to investigate the relaxed atomic structure and energies of the complex interphase boundaries. The (100)b//(100)f and the (011)b /(111)f interphase boundaries were investigated using interatomic potential. Special consideration was given to the misfit dislocations at the interface which can accomplish the lattice-invariant shear of the phenomenological theories of martensite crystallography. A new equilibrium interatomic potential for iron was developed to study the relaxed structure of the (225)f b. c. c. /f. c. c. interphase boundary. These results are also compared with experimental information. Finally the general results of the thesis are discussed and main conclusions summarized.

Thèse Ecole polytechnique fédérale de Lausanne EPFL, no 4336 (2009), Faculté des sciences et techniques de l'ingénieur STI, Programme doctoral Sciences et Génie des matériaux, Institut des matériaux IMX (Laboratoire de simulation des matériaux LSMX). Dir.: Alain Jacot.

O presente trabalho teve como objetivo o estudo do estado sólido do ganciclovir (GCV) e suas diferentes formas polimórficas. O GCV é um fármaco antiviral útil no tratamento de infecções por citomegalovírus (CMV). Embora seja um fármaco amplamente usado, poucos estudos têm sido realizados sobre seu estado sólido. Atualmente, o GCV é conhecido por apresentar quatro formas cristalinas, duas anidras (Forma I e II) e duas hidratas (III e IV). Neste trabalho, nós reportamos a solução da estrutura cristalográfica da Forma I do GCV, que foi encontrado durante o screening de cristalização do fármaco, em que nove ensaios de cristalização (GCV-1, GCV-A, GCV-B, GCV-C, GCV-D, GCV-E, GCV-F, GCV-G e GCV-H) foram realizados e os materiais resultantes foram caracterizados por Difratometria de raios X (DRX), análise térmica (DTA/TG) e Hot Stage Microscopy. De todas as cristalizações realizadas foram obtidas quatro formas sólidas, denominadas como Forma I (GCV-1, GCV-B e GCV-H), Forma III (GCV-C, GCV-D, GCV-F e GCV-G), Forma IV (GCV-A) e Forma V (GCV-E). Esta última está sendo descrita pela primeira vez na literatura e indica a presença de outra forma hidratada de GCV. As Formas I, III e IV corresponderam a forma anidra e as duas formas hidratadas do fármaco, respectivamente. Além disso, foi evidenciado por experimentos de conversão de slurry e análise térmica que o cristalizado de GCV-1 (Forma I) foi o mais estável entre os materiais obtidos, e este deu origem ao monocristal da Forma I de GCV, estrutura cristalina anidra do fármaco. Neste trabalho, pela primeira vez, a estrutura cristalina deste composto foi definida por cristalografia de raios X de monocristal. A análise estrutural mostrou que a Forma I do fármaco cristaliza no grupo espacial monoclínico P21/c e está composta por quatro moléculas de GCV na sua unidade assimétrica. Cada molécula está unida intermolecularmente por ligações de hidrogênio, que dão lugar à formação de cadeias infinitas e estas por sua vez se arranjam de maneira a formar uma estrutura tridimensional.
This presented work aims to study the solid state of ganciclovir (GCV) and its different polymorphic forms. GCV is an antiviral drug useful in the treatment of cytomegalovirus (CMV) infections. Although it is a widely-used drug, few studies have been conducted on its solid state. Currently, GCV is known to have four crystalline forms, two anhydrous (Form I and II) and two hydrates (III and IV). In this investigation, we report a successful preparation of GCV Form I and its crystallographic structure, which was found during the crystallization of the drug, in which nine crystallization tests (GCV-1, GCV-A, GCV-B, GCV- D, GCV-E, GCV-F, GCV-G and GCV-H) were performed and the resulting materials were characterized by X-ray diffractometry (XRD), thermal analysis (DTA/TG) and Hot Stage Microscopy. Of all the crystallizations performed, four solid forms were obtained, denoted as Form I (GCV-1, GCV-B and GCV- H), Form III (GCV-C, GCV-D, GCV-F and GCV-G), Form IV (GCV-A) and Form V (GCV-E). The latter is being described for the first time in the literature and indicates the presence of another hydrated form of GCV. Forms I, III and IV corresponded to the anhydrous form and the two hydrated forms of the drug, respectively. In addition, it was evident by both the slurry conversion and the thermal analysis methods that the GCV-1 crystallized (Form I) was indeed the most stable amongst the materials obtained. This gave rise to GCV Form I monocrystal, anhydrous crystalline structure of the drug. The compound was characterized by monocrystal X-ray crystallography. The structural analysis showed that Form I of the drug crystallized in the monoclinic system space group P21/c is composed of four molecules of GCV in its asymmetric unit. Each molecule is linked intermolecularly by hydrogen bonds, which give rise to the formation of infinite chains arranged in a way that form a three-dimensional structure.

Calcium uranyl(VI) oxyhydrates and uranates are structurally related U(VI)-phases featuring uranium oxo-polyhedral sheets, with calcium ions occupying the interlayer. Both coordination environments appear throughout the nuclear fuel-cycle as alteration products, colloids, and sorption complexes. However, concerted studies spanning the aqueous precipitation mechanisms of uranyl(VI) oxyhydrates, their solid-state transformations, and structural relationships with uranates, have hitherto remained largely unexplored. A series of calcium-based uranyl(VI) oxyhydrates were precipitated via alkalisation of aqueous precursor solutions in titration and batch reactions. The bulk stoichiometric ratio of calcium to uranium (Ca/U) of precipitates was varied by modifying precursor stoichiometry, reaction temperature, or extraction pH. The rate of precipitation and its dependency on temperature was quantified in-situ using a quartz crystal microbalance. Novel insight was revealed on the mechanisms influencing nucleation and growth, by determining associated kinetic barriers as a function of precursor-Ca/U. Remarkably, as the bulk precipitate Ca/U increased from ~⅛ to unity, there was a transition from crystalline Becquerelite to primary or secondary amorphous phases, with uranate-like coordination environments. Formation of the latter was driven by solution alkalinity, and comprises a poorly-ordered matrix with occlusions of Ca2+-rich nano-clusters. A congruency limit lies Ca/U of ~1.5 Ca/U, whereupon discrete Portlandite crystallises. Solid-state transformation of all Ca2+-U(VI)-phases studied involved dehydration, dehydroxylation-decarbonation, and desorption processes. Associated kinetic barriers were catalysed by higher Ca2+-contents, and was reflected by reaction enthalpies for dehydration and desorption. Crystalline Becquerelite (~⅛ Ca/U) underwent amorphisation-crystallisation via partial egress of interlayer calcium, followed by reduction of β-UO3 to form a novel intercalation compound Ca0.18.α-U3O8. The endmember uranates Ca3U11O36, CaU2O7, Ca2U3O11, and CaUO4 crystallised from amorphous precursors with higher bulk Ca/U (~⅓, ~½, ~⅔, ~1), where Ca3U11O36 is a novel compound that is isostructural to (Pb/Sr)3U11O36. Nucleation and growth became predominant in the presence of Ca2+-rich occlusions. A higher Ca2+-loading facilitated the progressive ingress of interlayer-Ca2+, inducing a concerted axial compression in uranyl(VI) oxo-polyhedra towards the uranate-like coordination environment.

Orientador: Heloise de Oliveira Pastore
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica
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Mestrado
Quimica Inorganica
Mestre em Química

Le développement des bioraffineries lignocellulosiques représente une alternative durable aux ressources fossiles pour produire des biocarburants et constitue un enjeu majeur dans le contexte énergétique et environnemental mondial actuel. La production de bioénergies de deuxième génération nécessite obligatoirement un prétraitement physique, chimique, physicochimique ou biologique de la biomasse végétale. Cette première étape a pour objectif de déstructurer la matrice lignocellulosique afin d’améliorer les étapes suivantes d’hydrolyse enzymatique, tant pour la production de méthane que de sucres simples fermentescibles, issus à la fois des fractions cellulosiques et hémicellulosiques, pour la production de bioéthanol. Les travaux réalisés dans le cadre de cette thèse ont eu pour objectif d’explorer la biodiversité des champignons filamenteux afin de sélectionner des souches performantes pour la Fermentation en Milieu Solide (FMS) de deux biomasses lignocellulosiques modèles (paille de blé et miscanthus) afin de faciliter leur conversion énergétique. Dans un premier temps, une nouvelle procédure originale de criblage moyen débit en FMS en microplaques « deep-well » a été mise au point et a permis de cribler 176 souches fongiques issues de la collection du Centre de Ressources CIRM-CF pour leur efficacité à prétraiter de la paille de blé. Les meilleures d’entre elles, 63 souches, ont également été criblées sur de la paille de miscanthus. Ce crible a permis de mettre en évidence plusieurs champignons d’intérêt dont les plus prometteurs ont été étudiés dans un second temps à l’échelle de bioréacteurs en colonnes de 250 ml
The development of lignocellulosic biorefineries represents a sustainable alternative to fossil fuels and constitutes a major challenge in the energy context and current global environment. Second generation bioenergy production necessarily requires a physical pre-treatment of plant biomass either chemical, physicochemical or biological. This first step aims at deconstructing the lignocellulosic matrix to improve the subsequent step of enzymatic hydrolysis, even for the production of methane or simple fermentable sugars from both cellulosic and hemicellulosic fractions for bioethanol production. The work carried out during this thesis aimed to explore the biodiversity of filamentous fungi to select efficient strains for the solid state fermentation (SSF) of two lignocellulosic biomass models (miscanthus and wheat straw) to facilitate their conversion to bioenergy.In a first part, a new original procedure of SSF screening using "deep-well" microplates was developed and was used to screen 176 fungal strains from the collection of the CIRM-CF Resource Centre for their effectiveness in wheat straw pretreatment. The best of them, 63 strains were also screened on miscanthus straw. This screening has enabled to highlight several fungi of interest, among them, the five most promising on wheat straw were studied in a second time to 250 ml bioreactor columns (three of these strains were also performing on miscanthus). The performances of the strains have been analyzed more finely considering critical criteria for evaluating the whole bioprocess such as the mass yields, the holocellulose preservation and the net yields of carbohydrates conversion

Le gypse (CaSO4·2H2O) est la matière première du plâtre. Il est chauffé entre 100 et 200 °C pour obtenir par déshydratation partielle l'hémihydrate (CaSO4 · 1 2H2O) qui, mélangé à de l'eau, se dissout tandis que des cristaux de gypse précipitent pour former une matrice résistante. Ce cycle qui paraît simple est compliqué par l'existence d'autres phases dans le système, en particulier deux formes de l'anhydrite (CaSO4). Les microstructures, encore mal comprises, affectent de plus la solubilité et la stabilité en température des produits de déshydratation ainsi que la cinétique des transitions. Le suivi in-situ de la déshydratation par microtomographie de rayons X synchrotron sur des monocristaux de gypse a mis en évidence l'anisotropie de la réaction. L'influence de la pression partielle de vapeur d'eau et de la température sur la cinétique a été mesurée, ainsi que leurs effets sur la microstructure. Celle-ci, organisée sur plusieurs ordres d'échelle, montre une rémanence de la structure du gypse malgré la fracturation microcristalline. La diffraction des rayons X et la microscopie électronique à balayage ont montré que la modification des symétries lors de la transition de l'anhydrite III vers l'anhydrite II donne lieu à un maclage très dense résultant de l'existence de deux variantes symétriques dont l'alternance limite les contraintes mécaniques. Enfin, une méthodologie a été développée pour mesurer a posteriori le taux de gâchage et la morphologie initiale d'échantillons de plâtre grâce à la microtomographie de rayons X synchrotron. Appliquée à une étude de cas portant sur 13 bas-reliefs florentins du XVe siècle, elle a donné des informations inédites sur les pratiques d'atelier
Gypsum(CaSO4·2H2O)istherawmaterialusedinplastermanufacture. Heatedbetween100and200 °C, it partially dehydrates into hemihydrate (CaSO4· 1 2H2O) which, when mixed with water, dissolves while gypsum crystals precipitate and form a tough matrix. This simple cycle is complicated by other phases in the system, including two forms of anhydrite (CaSO4). In addition, microstructures, which are poorly understood, affect the reactivity and stability of the dehydration products as well as the kinetics of transitions. The dehydration of gypsum single crystals, observed by Synchrotron X-ray microtomography, revealed the anisotropy of the reaction. Water vapor pressure and temperature affect the kinetics as well as the microstructures that are organised on several scales and reflect the structure of gypsum in spite of the microcrystalline fragmentation. X-ray powder diffraction and scanning electron microscopy showed that the change in symmetry during the transition from γ-anhydrite to β-anhydrite leads to a high-frequency twinning, resulting from the stacking of two symmetrical variants that minimises mechanical stress. Finally, a methodology was developed to measure the water-to-plaster ratio and the reactive powder morphology in set plaster samples using synchrotron X-ray microtomography. It was applied to a case study of 13 florentine low-relief sculptures from the 15th century, bringing new insights on workshop practices

Solid state materials are candidates to exhibit a large field-driven thermal response in the vicinity of first-order transitions. The strong sensitivity of the transition temperature with the applied field and the latent heat associated with the change of phase can give rise to the giant magneto-, electro-, baro-, and elastocaloric effects. Furthermore, the coupling between structural, magnetic and electronic degrees of freedom at the transition regime enables the thermal response to be driven by multiple fields and, thus, giving rise to the multicaloric effect. In the last years, the interest in understanding and tailoring novel caloric materials has exceptionally grown in view of their potential application to alternative cooling technologies for large scale industry. The present thesis reports the giant caloric effects encompassing the Fe49Rh51 magnetovolumic transition, the magnetostructural martensitic transformation in Ni-Mn based Heusler alloys, and the ferroelectric perovskites BaTiO3 and Pb(Sc0.5Ta0.5)O3. The physical conditions for the optimization of the thermal response which yield to an enlarged magnitude and operation range are explored, as well as the corresponding reproducibility upon field cycling and the potential multicaloric character. This evaluation is achieved by means of a complete caloric characterization in which the calorimetric experimental techniques which have been developed in purpose are crucial.
Els materials d'estat sòlid són susceptibles de mostrar una gran resposta tèrmica induïda per un camp extern a l'entorn de transicions de fase de primer ordre. La forta sensitivitat de la temperatura de transició amb el camp aplicat i la calor latent associada amb el canvi de fase poden donar lloc als efectes magneto-, electro-, baro- i elastocalòric gegants. A més, l'acoblament entre els graus de llibertat estructurals, magnètics i electrònics en el règim de transició possibilita que la resposta tèrmica sigui induïda per múltiples camps, originant així l'efecte multicalòric. En els darrers anys, l'interès en entendre i elaborar materials calòrics ha crescut excepcionalment, amb l'ull posat en les aplicacions potencials en tecnologies de refrigeració alternatives per a la indústria a gran escala. La present tesi reporta els efectes calòrics gegants que acompanyen la transició magnetovolúmica del Fe49Rh51, la transformació martensítica en aliatges Heusler amb base de Ni-Mn, i les perovskites ferroelèctriques de BaTiO3 i de Pb(Sc0.5Ta0.5)O3. S'exploren les condicions físiques propícies per a una optimització de la resposta tèrmica que resulten amb un eixamplament en magnitud i en rang d'operació, així com també la reproducibilitat corresponent sota ciclatge i el potencial caràcter multicalòric. Aquesta avaluació s'aconsegueix per mitjà d'una caracterització calòrica completa en què les tècniques experimentals calorimètriques que s'han desenvolupat amb aquest propòsit són crucials

The aim of this thesis was to find anomalies of elastic properties induced by topological changes of the Fermi surface. The latter are called "Lifshitz transitions". Lifshitz transitions are an interesting subject to study because a topological change of the Fermi surface results in a van Hove singularity of the density of states at the Fermi energy, which again induces an anomaly in the free energy and therefore yield anomalies of observable physical quantities. In all cases the question arose, if the corresponding van Hove singularities are large enough to cause anomalies in the elastic properties, which are measurable by nowadays experimental techniques and computable within the accuracy reachable in nowadays computer calculations. The calculations have been done with the Full-Potential nonorthogonal Local-Orbital minimum-basis band-structure code FPLO. To shift the van Hove singularities through the Fermi energy we used hydrostatic pressure, which is mimicked in the computations by decreasing the volume of the unit cell. The materials under consideration had been YCo5 and LaCo5 as examples for magnetic compounds and the element Osmium as an example for a non-magnetic material. All these materials exhibit hexagonal symmetry. In the case of YCo5 our calculations yield a first order Lifshitz transition. Here, an extraordinarily large peak in the spin-up part of the DOS, which is caused by a nearly dispersionless band in the hexagonal plane, crosses the Fermi level under a pressure of about 21 GPa. Thus, the spin-up 3d states become partly depopulated, which results in a drop of the total magnetic moment of 35%. Therefore the transition can be regarded as a transition from strong to weak ferromagnetism. Further, the transition results in a volume collapse of 1.4%. Though the volume collapse is isomorphic, it exhibits the following anisotropy: while the lattice constant in the hexagonal plane is almost smoothly contracting with increasing pressure, the lattice constant in c-direction collapses at the transition-pressure. This volume collapse has been verified in experiment. Analogous calculations have been performed for the compound LaCo5, which is isoelectronic to YCo5. Here as well we predict a first order Lifshitz transition, taking place at a pressure of about 23 GPa. The mechanism of the transition is the same than in YCo5. Again we find a volume collapse under pressure together with a decrease of the magnetic moment. The relative volume change amounts to 1.3%. Like in YCo5, the unit cell dimensions in the hexagonal plane are decreasing almost smoothly with pressure while in c-direction the lattice constant collapses at the transition-pressure. For LaCo5 there are no such experiments done so far to the best of our knowledge. For Osmium we found, that LDA reproduces the ground state volume very well. Furthermore, we could detect three Lifshitz transitions taking place at very high pressures of about 72 GPa, 81 GPa, and 122 GPa. At first, a hole ellipsoid appears at the Gamma-point (V=24.6Å^3, P=72 GPa), then a neck is created at the symmetry-line LH (V=24.2Å^3, P=81 GPa), and finally a hole ellipsoid appears at the L-point (V=23.2 Å^3, P=122 GPa). Due to a degeneracy in the band structure, the hole ellipsoid at the L-point appears at the same pressure when the necks, situated at the symmetry-lines LH merge at L. The corresponding van Hove singularities in the DOS are very tiny and thus no anomalies in the elastic properties could be detected. Furthermore, we showed that the kink in c/a at 25 GPa and at 27 GPa found by Occelli et al. [Occelli et al., Phys. Rev. Lett. 93, 095502 (2004)] and Ma et al. [Ma et al., Phys. Rev. B 72, 174103 (2005)], respectively, is not statistically significant and that (c/a)(P) can be fitted equally well by a smooth function as by piece-wise linear functions as proposed in these references
Das Ziel dieser Arbeit war es, Anomalien in den elastischen Eigenschaften zu finden, die durch topologische Änderungen der Fermifläche - genannt "Lifschitz Übergänge" - hervorgerufen werden. Lifschitz Übergänge sind ein interessantes Forschungsgebiet, denn die topologische Änderung der Fermifläche führt zu einer van Hove Singularität in der Zustandsdichte, die an der Fermienergie liegt und eine Anomalie in der freien Energie hervorruft und deswegen zu Anomalien in beobachtbaren physikalischen Größen führt. In allen Fällen kam die Frage auf, ob die entsprechenden van Hove Singularitäten groß genug sind, um mit heutigen Methoden meßbare und berechenbare Anomalien in den elastischen Eigenschaften zu verursachen. Die Daten wurden mit dem Computerprogramm FPLO (Full-Potential nonorthogonal Local-Orbital minimum-basis band-structure scheme) berechnet. Um die van Hove Singularitäten durch die Fermienergie zu schieben, verkleinerten wir das Volumen der Einheitszelle, um hydrostatischen Druck zu simulieren. Als zu untersuchende Stoffe wurden YCo5 und LaCo5 als Beispiele für magnetische Verbindungen gewählt und Osmium als Beispiel für ein nicht magnetisches Element. Im Falle von YCo5 fanden wir einen Lifschitz Übergang erster Ordnung. Hier springt ein besonders großer Peak im Spin-auf Teil der Zustandsdichte unter einem Druck von ca. 21 GPa über die Fermienergie. Dadurch werden die Spin-auf 3d Zustände teilweise unbesetzt und das magnetische Moment verringert sich um 35%. Deswegen kann man den Übergang als einen Übergang von starkem Ferromagnetismus zu schwachem Ferromagnetismus bezeichnen. Das Volumen verkleinert sich hierbei um 1.4%. Obwohl dieser Volumenkollaps isomorph ist, zeigt er folgende Anisotropie: während die Gitterkonstante in der hexagonalen Ebene mit zunehmendem Druck mehr oder weniger glatt kontrahiert, kollabiert am Übergangsdruck die Gitterkonstante in c-Richtung. Dieser Volumenkollaps wurde vom Experiment verifiziert. Analoge Rechnungen wurden für die Verbindung LaCo5, die isoelektronisch zu YCo5 ist, durchgeführt. Auch hier sagen wir einen Lifschitz Übergang erster Ordnung voraus, der bei einem Druck von ca. 23 GPa stattfinden wird. Der Mechanismus dieses Übergangs ist der selbe wie in YCo5. Wiederum finden wir einen Volumenkollaps unter Druck zusammen mit einer Verringerung des magnetischen Moments. Die relative Volumenänderung beträgt hier 1.3%. Wie in YCo5 verläuft hier die Kontraktion der Gitterkonstante in der hexagonalen Ebene mehr oder weniger glatt, während die Gitterkonstante in c-Richtung am Übergang kollabiert. Für LaCo5 existieren unseres Wissens hierzu noch keine Experimente. Im Falle von Osmium fanden wir drei Lifschitz Übergänge bei sehr hohen Drücken von ca. 72 GPa, 81 GPa, und 122 GPa. Zuerst bildet sich ein Lochellipsoid am Gamma-Punkt (V=24.6Å^3, P=72 GPa), dann bildet sich ein Hals an der Symmetrielinie LH (V=24.2Å^3, P=81 GPa), und zum Schluß erscheint ein Lochellipsoid am L-Punkt (V=23.2 Å^3, P=122 GPa). Auf Grund einer Entartung in der Bandstruktur taucht das Lochellipsoid am L-Punkt an dem Druck auf, an dem sich auch die Hälse auf der Symmetrielinie LH bei L verbinden. Die entsprechenden van Hove Singularitäten in der Zustandsdichte sind jedoch extrem klein und deswegen können keine Anomalien in den elastischen Eigenschaften detektiert werden. Desweiteren zeigten wir, daß der Knick in c/a, den Occelli et al. [Occelli et al., Phys. Rev. Lett. 93, 095502 (2004)] bei 25 GPa und Ma et al. [Ma et al., Phys. Rev. B 72, 174103 (2005)] bei 27 GPa fanden, statistisch nicht relevant ist und daß (c/a)(P) genauso gut von einer glatten Funktion gefittet wird als von stückweise linearen Funktionen

The aim of this thesis was to find anomalies of elastic properties induced by topological changes of the Fermi surface. The latter are called "Lifshitz transitions". Lifshitz transitions are an interesting subject to study because a topological change of the Fermi surface results in a van Hove singularity of the density of states at the Fermi energy, which again induces an anomaly in the free energy and therefore yield anomalies of observable physical quantities. In all cases the question arose, if the corresponding van Hove singularities are large enough to cause anomalies in the elastic properties, which are measurable by nowadays experimental techniques and computable within the accuracy reachable in nowadays computer calculations. The calculations have been done with the Full-Potential nonorthogonal Local-Orbital minimum-basis band-structure code FPLO. To shift the van Hove singularities through the Fermi energy we used hydrostatic pressure, which is mimicked in the computations by decreasing the volume of the unit cell. The materials under consideration had been YCo5 and LaCo5 as examples for magnetic compounds and the element Osmium as an example for a non-magnetic material. All these materials exhibit hexagonal symmetry. In the case of YCo5 our calculations yield a first order Lifshitz transition. Here, an extraordinarily large peak in the spin-up part of the DOS, which is caused by a nearly dispersionless band in the hexagonal plane, crosses the Fermi level under a pressure of about 21 GPa. Thus, the spin-up 3d states become partly depopulated, which results in a drop of the total magnetic moment of 35%. Therefore the transition can be regarded as a transition from strong to weak ferromagnetism. Further, the transition results in a volume collapse of 1.4%. Though the volume collapse is isomorphic, it exhibits the following anisotropy: while the lattice constant in the hexagonal plane is almost smoothly contracting with increasing pressure, the lattice constant in c-direction collapses at the transition-pressure. This volume collapse has been verified in experiment. Analogous calculations have been performed for the compound LaCo5, which is isoelectronic to YCo5. Here as well we predict a first order Lifshitz transition, taking place at a pressure of about 23 GPa. The mechanism of the transition is the same than in YCo5. Again we find a volume collapse under pressure together with a decrease of the magnetic moment. The relative volume change amounts to 1.3%. Like in YCo5, the unit cell dimensions in the hexagonal plane are decreasing almost smoothly with pressure while in c-direction the lattice constant collapses at the transition-pressure. For LaCo5 there are no such experiments done so far to the best of our knowledge. For Osmium we found, that LDA reproduces the ground state volume very well. Furthermore, we could detect three Lifshitz transitions taking place at very high pressures of about 72 GPa, 81 GPa, and 122 GPa. At first, a hole ellipsoid appears at the Gamma-point (V=24.6Å^3, P=72 GPa), then a neck is created at the symmetry-line LH (V=24.2Å^3, P=81 GPa), and finally a hole ellipsoid appears at the L-point (V=23.2 Å^3, P=122 GPa). Due to a degeneracy in the band structure, the hole ellipsoid at the L-point appears at the same pressure when the necks, situated at the symmetry-lines LH merge at L. The corresponding van Hove singularities in the DOS are very tiny and thus no anomalies in the elastic properties could be detected. Furthermore, we showed that the kink in c/a at 25 GPa and at 27 GPa found by Occelli et al. [Occelli et al., Phys. Rev. Lett. 93, 095502 (2004)] and Ma et al. [Ma et al., Phys. Rev. B 72, 174103 (2005)], respectively, is not statistically significant and that (c/a)(P) can be fitted equally well by a smooth function as by piece-wise linear functions as proposed in these references.
Das Ziel dieser Arbeit war es, Anomalien in den elastischen Eigenschaften zu finden, die durch topologische Änderungen der Fermifläche - genannt "Lifschitz Übergänge" - hervorgerufen werden. Lifschitz Übergänge sind ein interessantes Forschungsgebiet, denn die topologische Änderung der Fermifläche führt zu einer van Hove Singularität in der Zustandsdichte, die an der Fermienergie liegt und eine Anomalie in der freien Energie hervorruft und deswegen zu Anomalien in beobachtbaren physikalischen Größen führt. In allen Fällen kam die Frage auf, ob die entsprechenden van Hove Singularitäten groß genug sind, um mit heutigen Methoden meßbare und berechenbare Anomalien in den elastischen Eigenschaften zu verursachen. Die Daten wurden mit dem Computerprogramm FPLO (Full-Potential nonorthogonal Local-Orbital minimum-basis band-structure scheme) berechnet. Um die van Hove Singularitäten durch die Fermienergie zu schieben, verkleinerten wir das Volumen der Einheitszelle, um hydrostatischen Druck zu simulieren. Als zu untersuchende Stoffe wurden YCo5 und LaCo5 als Beispiele für magnetische Verbindungen gewählt und Osmium als Beispiel für ein nicht magnetisches Element. Im Falle von YCo5 fanden wir einen Lifschitz Übergang erster Ordnung. Hier springt ein besonders großer Peak im Spin-auf Teil der Zustandsdichte unter einem Druck von ca. 21 GPa über die Fermienergie. Dadurch werden die Spin-auf 3d Zustände teilweise unbesetzt und das magnetische Moment verringert sich um 35%. Deswegen kann man den Übergang als einen Übergang von starkem Ferromagnetismus zu schwachem Ferromagnetismus bezeichnen. Das Volumen verkleinert sich hierbei um 1.4%. Obwohl dieser Volumenkollaps isomorph ist, zeigt er folgende Anisotropie: während die Gitterkonstante in der hexagonalen Ebene mit zunehmendem Druck mehr oder weniger glatt kontrahiert, kollabiert am Übergangsdruck die Gitterkonstante in c-Richtung. Dieser Volumenkollaps wurde vom Experiment verifiziert. Analoge Rechnungen wurden für die Verbindung LaCo5, die isoelektronisch zu YCo5 ist, durchgeführt. Auch hier sagen wir einen Lifschitz Übergang erster Ordnung voraus, der bei einem Druck von ca. 23 GPa stattfinden wird. Der Mechanismus dieses Übergangs ist der selbe wie in YCo5. Wiederum finden wir einen Volumenkollaps unter Druck zusammen mit einer Verringerung des magnetischen Moments. Die relative Volumenänderung beträgt hier 1.3%. Wie in YCo5 verläuft hier die Kontraktion der Gitterkonstante in der hexagonalen Ebene mehr oder weniger glatt, während die Gitterkonstante in c-Richtung am Übergang kollabiert. Für LaCo5 existieren unseres Wissens hierzu noch keine Experimente. Im Falle von Osmium fanden wir drei Lifschitz Übergänge bei sehr hohen Drücken von ca. 72 GPa, 81 GPa, und 122 GPa. Zuerst bildet sich ein Lochellipsoid am Gamma-Punkt (V=24.6Å^3, P=72 GPa), dann bildet sich ein Hals an der Symmetrielinie LH (V=24.2Å^3, P=81 GPa), und zum Schluß erscheint ein Lochellipsoid am L-Punkt (V=23.2 Å^3, P=122 GPa). Auf Grund einer Entartung in der Bandstruktur taucht das Lochellipsoid am L-Punkt an dem Druck auf, an dem sich auch die Hälse auf der Symmetrielinie LH bei L verbinden. Die entsprechenden van Hove Singularitäten in der Zustandsdichte sind jedoch extrem klein und deswegen können keine Anomalien in den elastischen Eigenschaften detektiert werden. Desweiteren zeigten wir, daß der Knick in c/a, den Occelli et al. [Occelli et al., Phys. Rev. Lett. 93, 095502 (2004)] bei 25 GPa und Ma et al. [Ma et al., Phys. Rev. B 72, 174103 (2005)] bei 27 GPa fanden, statistisch nicht relevant ist und daß (c/a)(P) genauso gut von einer glatten Funktion gefittet wird als von stückweise linearen Funktionen.

Uranium-10wt% zirconium (U-10Zr) alloy nuclear fuels have been used for decades and new variations are under consideration ranging from U-5Zr to U-50Zr. As a precursor to understanding the fission gas behavior in U-Zr alloys using ion implantation, a basic study on the U-Zr metallurgy was completed using EPMA, DSC, XRD, Optical microscopy, and TEM with a focus on solid state phase transformations in alloys containing 2, 5, 10, 20, 30, and 50wt% zirconium. Alloys were cast by crucible melting using high temperature furnace under argon atmosphere in yttrium oxide crucibles and various thermal profiles were used to study phase transformations in these alloys. Using TEM, XRD, and DSC data, it was ascertained that athermal-ω, along with martensitic α1, formed in all alloys quenched from γ phase. XRD could detect the presence of athermal-ω only in U-20, 30 and 50wt%Zr alloys. BSE images for as-cast alloys of 2, 5, 10, 20, and 30wt%Zr had lamellar microstructure with lamellae rich in zirconium. All alloy samples clearly showed a heating transformation pertaining to δ → γ in DSC data while XRD could only confirm the presence of δ phase in U-20, 30, and 50wt%Zr alloys. An explanation is offered for the absence of δ phase peaks in uranium-rich alloys based on its formation mechanism. Alloy samples of U-2, 5, and 10wt%Zr were step-cooled from γ phase by annealing in the (α + δ) phase field before cooling to room temperature revealed broad peaks for δ phase indicating incomplete collapse of {111}γ planes. Both as cast and γ- quenched alloys were annealed at 600degreeC, in the (α + δ) phase field for 1, 3, 7, and 30 days. Microstructures of the samples in both cases contained uranium-rich matrix and zirconium-rich precipitates and WDS analyses were consistent with their being α-U and δ phase respectively. However, XRD data for annealed alloys never showed peaks for δ phase even though it’s area fraction was within the detection limits. Moreover, the peaks which were present in U-20wt%Zr vanished after annealing for 7 days. Based on the data obtained, it is suggested that it is more appropriate to consider the presence of metastable diffusional-ω instead of a stable δ in the as-cast alloys and that it is not stable at 600degreeC.

碩士
國立臺灣科技大學
電子工程系
104
Because the capacity of NAND flash memory has increased rapidly, a solid-state drive (SSD) that adopts NAND flash memory has become popular in the market. In particular, an intermediate software called a flash translation layer (FTL) is adopted to hide the characteristics of NAND flash memory and provide efficient management for NAND flash memory. Therefore, an SSD needs a flash translation layer to handle different I/O access patterns. When a software-defined flash translation layer is adopted for users to select different flash translation layers inside an SSD, we will propose transformation of flash translation layers to improve SSD performance in the thesis. We will solve some issues such as space management, data reads/writes, and garbage collection during the transformation. The experimental results show that the proposed method could achieve a good performance for various I/O access patterns.

No
Martensitic transformations are of considerable technological importance, a particularly promising application being the possibility of using martensitic materials, possibly proteins, as tiny machines. For organic crystals, however, a molecular level understanding of such transformations is lacking. We have studied a martensitic-type transformation in crystals of the amino acid DL-norleucine using molecular dynamics simulation. The crystal structures of DL-norleucine comprise stacks of bilayers (formed as a result of strong hydrogen bonding) that translate relative to each other on transformation. The simulations reveal that the transformation occurs by concerted molecular displacements involving entire bilayers rather than on a molecule-by-molecule basis. These observations can be rationalized on the basis that at sufficiently high excess temperatures, the free energy barriers to concerted molecular displacements can be overcome by the available thermal energy. Furthermore, in displacive transformations, the molecular displacements can occur by the propagation of a displacement wave (akin to a kink in a carpet), which requires the molecules to overcome only a local barrier. Concerted molecular displacements are therefore considered to be a significant feature of all displacive transformations. This finding is expected to be of value toward developing strategies for controlling or modulating martensitic-type transformations.

No
Bulk crystallisation of protein therapeutic molecules towards their controlled drug delivery is of interest to the biopharmaceutical industry. The complexity of biotherapeutic molecules is likely to lead to complex material properties of crystals in the solid state and to complex transitions. This complexity is explored using batch crystallised lysozyme as a model. The effects of drying and milling on the solid-state transformations of lysozyme crystals were monitored using differential scanning calorimetry (DSC), X-ray powder diffraction (XRPD), FT-Raman, and enzymatic assay. XRPD was used to characterise crystallinity and these data supported those of crystalline lysozyme which gave a distinctive DSC thermogram. The apparent denaturation temperature (Tm) of the amorphous lysozyme was ∼201 °C, while the Tm of the crystalline form was ∼187 °C. Raman spectra supported a more α-helix rich structure of crystalline lysozyme. This structure is consistent with reduced cooperative unit sizes compared to the amorphous lysozyme and is consistent with a reduction in the Tm of the crystalline form. Evidence was obtained that milling also induced denaturation in the solid-state, with the denatured lysozyme showing no thermal transition. The denaturation of the crystalline lysozyme occurred mainly through its amorphous form. Interestingly, the mechanical denaturation of lysozyme did not affect its biological activity on dissolution. Lysozyme crystals on drying did not become amorphous, while milling-time played a crucial role in the crystalline-amorphous-denatured transformations of lysozyme crystals. DSC is shown to be a key tool to monitor quantitatively these transformations.

by Zhou ping.
Thesis (Ph.D.)--Chinese University of Hong Kong, 1997.
Includes bibliographical references (p. 160-170).
Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Mode of access: World Wide Web.

The past few decades have witnessed an almost exponential increase in interest in the field of metal organic frameworks (MOFs), which can be evidenced from the large number of scientific articles being published routinely in this area. The MOFs are crystalline hybrid materials built via the judicial use of inorganic metal ions and organic linkers, thereby bridging the gap between purely inorganic and organic materials. The structural versatility and the potential tunability of the MOFs imparts unique physicochemical and thermomechanical properties, which have rendered them immensely useful in the branches of chemistry, material science, physics, biology, nanotechnology, medicine as well as environmental engineering. The MOFs have been shown to be promising as materials for gas storage and separation, sensors, ferroelectric and non-linear optical materials, magnetism, catalysis, drug delivery etc and researchers have been devising strategies to utilize the MOFs to tackle a number of global challenges of the twenty-first century. A survey of the literature reveals that the linear organic linkers, 1,4- benzenedicarboxylic acid (BDC) and 4,4’-biphenyldicarboxylic acid (BPDC), have been the organic linkers of choice for the construction of stable, porous and multifunctional MOFs. The aim of this thesis has been to monitor the effect that the presence of a functional group in between the benzene rings of the BPDC would have on the overall structures and the properties of the MOFs. Thus, as part of the investigations, the preparation of the MOF compounds using 4,4’-sulfonyldibenzoic acid (SDBA) and 4,4’- azodibenzoic acid (ABA) have been accomplished. Along with the conventional hydrothermal and solvothermal synthetic techniques, the liquid-liquid biphasic reaction method was also utilized for the synthesis of some of the compounds. The structures of the compounds were ascertained from single crystal X-ray diffraction technique. Proton conductivity studies were performed on Mn based porous MOFs using AC impedance spectroscopy. The ferroelectric behavior in a Co based porous MOF was established using dielectric and polarization vs electric field measurements. The labile nature of the lattice solvent molecules was established utilizing single crystal X-ray diffraction studies and water sorption experiments. In addition, the site selective substitution in a homometallic MOF and the subsequent conversion to a mixed-metal spinel oxide upon thermal decomposition, have also been studied. Chapter 1 of the thesis is a brief overview of the metal organic framework compounds and summarizes the various important structures that have been reported in literature and the interesting properties that they exhibit. In chapter 2, the proton conductivity behavior, solvent mediated single crystal to single crystal (SCSC) and related structural transformations in a family of Mn and Co based porous MOFs with SDBA have been presented. Also presented are the results of the site selective substitution of Mn by Co in a homometallic Mn based MOF and it’s subsequent decomposition to CoMn2O4 spinel oxide nanoparticles. In chapter 3, the syntheses, structures and the magnetic properties of the pentanuclear Mn5 based MOF compounds with SDBA have been presented. The role of the time and the temperature in the formation of the compounds has also been presented. In chapter 4, the dehydration/rehydration mediated switchable room temperature ferroelectric behavior, the single crystal to single crystal solvent exchange studies and selective gas sorption behavior in an anionic Co based MOF with SDBA has been discussed. In chapter 5, the use of the liquid-liquid biphasic synthetic route in the formation of Zn and Cd based MOFs with ABA has been discussed. Structural transformations between the one dimensional Zn based compounds and the heterogeneous catalytic studies using the Cd based compounds have also been presented.