Predicting formation energies of crystals is a common but computationally expensive task. In this work, it is therefore investigated how a neural network can be used as a tool for predicting formation energies with less computational cost compared to conventional methods. The investigated model shows promising results in predicting formation energies, reaching below a mean absolute error of 0.05 eV/atom with less than 4000 training datapoints. The model also shows great transferability, being able to reach below an MAE of 0.1 eV/atom with less than 100 training points when transferring from a pre-trained model. A drawback of the model is however that it is relying on descriptions of the crystal structures that include interatomic distances. Since these are not always accurately known, it is investigated how inaccurate structure descriptions affect the performance of the model. The results show that the quality of the descriptions definitely worsen the accuracy. The less accurate descriptions can however be used to reduce the search space in the creation of phase diagrams, and the proposed workflow which combines conventional density functional theory and machine learning shows a reduction in time consumption of more than 50 \% compared to only using density functional theory for creating a ternary phase diagram.

Spinodal decomposition is a phase separation mechanism within the miscibility gap. Its importance in case of Fe-Cr system, the basis of the whole stainless steel family, stems from a phenomenon known as the “475oC embrittlement” which results in a ruin of mechanical properties of ferritic, martensitic and duplex stainless steels. This work is aimed at a better understanding of the phase separation process in   the Fe-Cr system. Alloys of 10 to 55 wt.% Cr , each five percent, were homogenized to achieve fully ferritic microstructure and then isothermally aged at 400, 500 and 600oC for different periods of time ranging from 30min to 1500 hours. Hardness of both homogenized and aged samples were measured by the Vickers micro-hardness method and then selected samples were studied by means of Transmission Electron Microscopy (TEM).  It was observed that hardness of homogenized samples increased monotonically with increasing Cr content up to 55 wt.% which can be attributed to solution hardening as well as higher hardness of pure chromium compared to pure iron.  At 400oC no significant change in hardness was detected for aging up to 1500h, therefore we believe that phase separation effects at 400oC are very small up to this time. Sluggish kinetics is imputed to lower diffusion rate at lower temperatures. At 500oC even after 10h a noticeable change in hardness, for alloys containing 25 wt.% Cr and higher, was observed which indicates occurrence of phase separation. The alloy with 10 wt.% Cr did not show change in hardness up to 200h which suggests that this composition falls outside the miscibility gap at 500oC. For compositions of 15 and 20 wt.% Cr only a small increase in hardness was detected even after 200h of aging at 500oC, which could be due to the small amounts of α´ formed. However, it means that alloys of 15 wt.% Cr and higher are suffering phase separation. For compositions inside the miscibility gap, hardening effect is a result of phase separation either by nucleation and growth or spinodal decomposition. To distinguish between these two mechanisms, TEM studies were performed and we found evidence that at 500oC the Fe-25 wt.% Cr sample decomposes by nucleation  and growth  while that of 35 wt.% Cr  shows characteristics of the spinodal mechanism. For compositions inside the miscibility gap, with increasing Cr content up to 40% the change in hardness generally increased and for 45% and higher it always decreased. This suggests that the composition range corresponding to the spinodal region at 500oC is biased towards the Fe-rich side of the phase diagram. At 600oC only samples of 25, 30 and 35 wt.% Cr were studied because according to the previous studies, the spinodal boundary is most probably located in this composition range. However, no change in hardness was observed even up to 24h. We believe that this means the miscibility line lies below 600oC for alloys containing 35 wt.% Cr and lower. Further investigations are needed to confirm and explain this result.

Les isotopes de l’Américium sont les principaux contributeurs à la radioactivité des déchets nucléaires. Parmi les scénarios pour diminuer la toxicité des déchets, la transmutation dans les réacteurs à neutrons rapides utilisant des pastilles d’oxyde mixte (U,Am)O2 est une voie prometteuse. Dans ce cadre, la connaissance des propriétés thermodynamiques du système U-Am-O est essentielle pour prédire le comportement des pastilles (U,Am)O2 en conditions nominale et accidentelle. Cette thèse est dédiée à l’étude expérimentale d’oxydes mixtes (U,Am)O2 dans une large gamme de composition (7,5 % at. ≤ Am/(Am+U) ≤ 70 % at.). L’objectif est d’acquérir des données pour développer un modèle thermodynamique avec la méthode semi-empirique CALPHAD. Les résultats peuvent être classés en trois catégories : données structurales, données de diagramme de phase et données thermodynamiques. Pour la modélisation thermodynamique d’un système ternaire, l’optimisation des sous-systèmes binaires est nécessaire. Comme des questions restaient en suspens sur le système Am-O, le diagramme de phase Am-O a tout d’abord été étudié par diffraction des rayons X à haute température. L’existence d’un domaine de composition de la phase bcc AmO1.61 a été mis en évidence et la lacune de miscibilité dans la phase fluorite, proposée dans la littérature, n’a pas été confirmée. Grâce à ces nouveaux résultats, le modèle CALPHAD de Gotcu et al a été modifié. Dans une deuxième étape, des analyses structurales des dioxydes (U,Am)O2±x ont été effectuées par DRX, XAS et spectroscopie RAMAN. La DRX a permis de confirmer que tous les échantillons sont constitués d’une seule phase de structure fluorite. Le rapport O/M (avec M=U+Am) mesuré à température ambiante est inférieur à 2 ; la stabilité de l’Américium trivalent Am3+ a été mise en évidence. Celle-ci induit l’oxydation partielle de l’U4+ en U5+. Cette distribution de charge s’accompagne par la formation de défauts de l’oxygène complexes dans la structure fluorite. Lors de l’étude par DRX HT des oxydes mixtes sous air, il a été montré que la présence d’Am3+ stabilise la phase fluorite par rapport aux oxydes plus riches en oxygène (U4O9, U3O8). De nouvelles données de diagramme de phase ont été obtenues : des conodes dans les domaines biphasés M4O9-M3O8 and MO2+x-M3O8 et la solubilité de l’Américium dans les oxydes M4O9 et M3O8. L’étude du diagramme de phase U-Am-O a été poursuivie par la détermination des températures de solidus/liquidus des oxydes mixtes par une technique de chauffage laser, sous argon et sous air, et par la caractérisation des échantillons après fusion par SEM et XAS. La température de fusion des oxydes mixtes diminue avec une teneur croissante d’Américium (Am/(Am+U)) et d’oxygène (O/(Am+U)). Finalement, les propriétés thermodynamiques des oxydes (U,Am)O2±x ont été mesurées : les incréments enthalpiques par calorimétrie de chute et les pressions partielles des espèces gazeuses par Spectrométrie de Masse couplée à une cellule de Knudsen (KEMS). Une contribution d’excès de la capacité calorifique a été observée à haute température, attribuée à la réduction des oxydes (avec formation de lacunes d’oxygène). Les résultats de KEMS ont permis de déterminer une composition congruente de vaporisation à 2300 K, pour un rapport Am/(Am+U) de 0,6 et un rapport O/(U+Am) inférieur à 1,9. Finalement, la modélisation thermodynamique du système U-Am-O par la méthode CALPHAD a été abordée par la description de la phase fluorite. Un bon accord est obtenu entre le modèle et les données de potentiel d’oxygène pour l’oxyde (U0.5Am0.5)O2±x et de distribution des cations. De plus, le modèle permet de reproduire de façon satisfaisante les données de KEMS. En perspective de ce travail, la modélisation thermodynamique du ternaire sera étendue à la description des équilibres de phase mettant en jeu les oxydes M4O9, M3O8 et la phase liquide. / Americium isotopes are the main contributors to the long-term radiotoxicity of the nuclear wastes, after the plutonium extraction. Among the reprocessing scenarios, the transmutation in fast neutron reactors using uranium-americium mixed oxide (U,Am)O2±x pellets seems promising. In this frame, the knowledge of the thermodynamics of the U-Am-O ternary system is of essential for the prediction of the behavior of (U,Am)O2 pellets and their possible interaction with the cladding, under normal and accidental conditions. This thesis is dedicated to the experimental investigation of U-Am mixed oxides on a wide range of Am contents (7.5 at.% ≤ Am/(Am+U) ≤ 70 at.%), with the aim to collect data for developing a thermodynamic model based on the semi-empirical CALPHAD method. The obtained results can be classified in three categories: structural, phase diagram and thermodynamic data. For the thermodynamic modeling of the ternary system, the assessment of the binary sub-systems is first required. As open questions still existed on the Am-O system, a first part of the work was dedicated to the study of the Am-O phase diagram by high-temperature (HT) XRD. The existence of a composition range of the bcc AmO1.61 phase was highlighted and the miscibility gap in the fluorite phase, proposed in the literature, was not found. Thanks to the new experimental data, the existing CALPHAD model of Gotcu et al. was modified. In a second step, structural investigations were performed on synthesized (U,Am)O2±x dioxides by coupling XRD, XAS and Raman spectroscopy. For all the compositions, the XRD confirmed the formation of a single fluorite structure. The O/M ratio (with M=U+Am) at room temperature was determined to be lower than 2; the stability of trivalent americium Am3+ in the dioxide solid solution was highlighted, which induces a partial oxidation of uranium from U4+ to U5+. This charge distribution, peculiar for a dioxide, is accompanied by the formation of complex oxygen defects in the fluorite structure. By a HT-XRD investigation of the mixed oxides under air combined with XAS characterization of the oxidized samples, it was shown that the presence of Am3+ leads to a stabilization of the dioxide fluorite phase toward the formation of oxides richer in oxygen, in comparison to the U-O system. New phase diagram data were obtained in the oxygen rich region at 1470 K: tie-lines in the M4O9-M3O8 and MO2+x-M3O8 domains were determined and the solubility of americium in the M4O9 and M3O8 oxides was estimated. The investigation of the U-Am-O phase diagram continued at higher temperature with the study of the solidus/liquidus transitions using a laser-heating technique, under argon and air, and post-melting characterizations conducted by SEM and XAS. The melting temperature of Am-U dioxides decreases with the increase of both the Am/(Am+U) and O/M ratios. Finally, thermodynamic properties of the U1-yAmyO2±x oxides were measured: enthalpy increments using drop calorimetry, partial vapor pressures by Knudsen cell effusion mass spectrometry (KEMS). An excess contribution to the heat capacity at high temperature was observed and this was attributed to the reduction of the dioxides at high temperature (formation of oxygen vacancies). The KEMS results lead to determine the congruent vaporization composition at 2300 K, for a Am/(Am+U) ratio of 0.6 and an O/M ratio lower than 1.9. Finally, the CALPHAD thermodynamic assessment of the U-Am-O system was started, by focusing the attention on the modelling of the fluorite phase. A good agreement between the model and the oxygen potential data for (U0.5Am0.5O2±x) and the cation distribution was achieved. Furthermore, the model is able to satisfactorily reproduce the KEMS data and hence the equilibrium between the dioxide and gas phase. For the perspectives of this work, the optimization of the thermodynamic model should be extended to describe the phase equilibria involving the M4O9, M3O8 oxides and the liquid phase.

Comme de nombreux colloïdes, des nanoparticules métalliques recouvertes de ligands en suspension s’organisent au-delà d’une fraction volumique seuil et forment ce que l’on appelle un « supracristal ». Ce sont ainsi des systèmes modèles, déjà largement étudiés à partir de suspensions dans des solvants volatils, qui permettent de mieux comprendre l’auto-assemblage de sphères déformables. Les interactions qui conduisent à l’auto-assemblage sont couramment décrites par une compétition entre une attraction de van der Waals entre les cœurs métalliques et une répulsion entre les ligands qui va dépendre de l’affinité entre les ligands et le solvant. Un effet du solvant a déjà été observé sur l’auto-organisation de nano-objets. En mesurant par diffusion de rayons X aux petits angles le facteur de structure de suspensions de nanoparticules d’or greffées, j’ai pu sonder de façon systématique les interactions entre des nanoparticules en suspension avec plusieurs tailles de cœur, des ligands alcane-thiols de longueur différente et dans différents solvants à la fois volatils et non volatils. J’ai ainsi pu mettre en évidence une interaction attractive inattendue dans des alcanes linéaires flexibles et dont l’intensité augmente avec la longueur de l’alcane. Pour corréler les interactions entre particules à leur diagramme de phase, j’ai suivi le processus de cristallisation dans des suspensions en solvant volatil ou partiellement volatil ainsi qu’en émulsion, techniques qui permettent d’augmenter lentement la concentration en nanoparticules. Les interactions attractives induites par le solvant contribuent ainsi à la formation de supracristaux à de très faibles fractions volumiques. A de fortes concentrations, la structure des supracristaux ne dépend pas du solvant utilisé mais, à forte densité de greffage, du rapport R entre la longueur des ligands et le diamètre du cœur d’or. Pour un rapport R voisin de 0.7, la structure finale observée est cubique centrée, la structure à concentration intermédiaire étant cubique à faces centrées. Pour un rapport R deux fois plus petit, une structure originale a été mise en évidence. Il s’agit d’une structure hexagonale de grand paramètre de maille, analysée comme une phase de Frank et Kasper de type MgZn2 ou C14. C’est la première fois qu’une telle phase à empilement local tétraédrique est observée dans un système de sphères monodisperses molles. L’existence de cette phase ainsi que le rôle du rapport R a pu être interprétée en estimant quantitativement la compétition entre l’attraction de van der Waals forte et l’entropie des ligands. / As many colloids, metallic nanoparticles grafted with hydrophobic ligands self-assemble above a volume fraction threshold and thus build superlattices. These model systems, which are widely studied when suspended in volatile oils, enable a better understanding of soft spheres self-assembly.Interactions which lead to self-assembly are commonly described by the combination of van der Waals attraction with interaction between the ligand shells. The shell behavior is controlled by the ligand affinity with the solvent. An effect of the solvent on the self-assembly of nanoparticles has already been observed. Using a small angle X-ray scattering, I measured, through the structure factor, the interactions between gold nanoparticles grafted with alkanethiols in different oils, at various concentrations, for different lengths of ligands and core diameters. I noticed an attractive interaction when using flexible linear alkanes as solvent. It has also been shown that the attraction intensity increases with the solvent length.In order to correlate the interactions between particles to their phase diagram, I studied the crystallization process by concentrating nanoparticles using evaporation in capillaries or Ostwald ripening in emulsions. I showed that attractive interactions induced by the solvent lead to superlattices formation at very low volume fractions.At high concentrations, the superlattice structure depends on the ratio of the ligand length over the gold core diameter. For a ratio around 0.7, the final structure observed is body centered cubic, whereas at lower concentration, it is face centered cubic. When this ratio is halved, an unexpected structure is observed. It is a hexagonal structure with a large lattice parameter. It has been analyzed as a Frank and Kasper’s phase named MgZn2 or C14. It is the first time that this topologically close-packed structure is observed for monodisperse soft spheres. The existence of this phase and the role of the ratio R have been interpreted by considering quantitatively the competition between ligands entropy and the strong van der Waals attraction.

Chalkopyrit (CuFeS2) stellt den wichtigsten Rohstoff für die Kupfergewinnung dar. Um effiziente hydrometallurgische Gewinnungsverfahren für sulfidische Kupfererze zu entwickeln, sind mechanistische Studien der Redoxchemie von Chalkopyrit erforderlich. Der hierfür als Referenzmaterial erforderliche Chalkopyrit konnte synthetisiert und unter Anwendung der Pulver-Röntgendiffraktometrie und 57Fe-Mößbauer-Spektroskopie analysiert werden. Phasenreiner Chalkopyrit kann unter Verwendung eines Schwefelunterschusses hergestellt werden und ist bis 480 °C thermisch stabil. Mittels elektrochemischer Messungen wurde ein Einblick in die Oxidationsprozesse des Minerals in wässriger, chloridischer Lösung gegeben. Das Lösen der Cu-S- und Fe-S-Bindungen des Minerals ist anhand einer Variation des pH-Wertes der Laugungslösung beeinflussbar. Cu(II)-Ionen sind gegenüber Fe(III)-Ionen das wirksamere Oxidationsmittel bei dem anodischen Lösen des Minerals.

No description available.

This dissertation introduces some new properties of both superfluid phases of fermions with spin-orbit coupling (SOC) and superradiant phases of photons in an optical cavity. The effects of SOC on the phase transition between normal and superfluid phase are revealed; an unconventional crossover driven by SOC from the Bardeen-Cooper-Schrieffer (BCS) state to the Bose-Einstein condensate (BEC) state is verified in three different systems; and two kinds of excitations, a Goldstone mode and a Higgs mode, are demonstrated to occur in a quantum optical system. We investigate the BCS superfluid state of two-component atomic Fermi gases in the presence of three kinds of SOCs. We find that SOC drives a class of BCS to BEC crossover that is different from the conventional one without SOC. Here, we extend the concepts of the coherence length and Cooper-pair size in the absence of SOC to Fermi systems with SOC. We study the dependence of chemical potential, coherence length, and Cooper-pair size on the SOC strength and the scattering length in three dimensions (3D) (or the twobody binding energy in two dimensions (2D)) for three attractively interacting Fermi gases with 3D Rashba, 3D Weyl, and 2D Rashba SOC respectively. By adding a population imbalance to a Fermi gas with Rashba-type SOC, we also map out the finite-temperature phase diagram. Due to a competition between SOC and population imbalance, the finite-temperature phase diagram reveals a large variety of new features, including the expanding of the superfluid state regime and the shrinking of both the phase separation and the normal regimes. We find that the tricritical point moves toward a regime of low temperature, high magnetic field, and high polarization as the SOC strength increases. Besides Fermi fluids, this dissertation also gives a new angle of view on the superradiant phase in the Dicke model. Here, we demonstrate that Goldstone and Higgs modes can be observed in an optical system with only a few atoms inside a cavity. The model we study is the U(1)/Z2 Dicke model with N qubits (two-level atoms) coupled to a single photon mode.

<p>The dissolved concentration of an active pharmaceutical ingredient in biological fluids is of significant importance for establishing a therapeutic effect in patients. However, the current pharmaceutical landscape is abundant in poorly soluble drugs that require solubility enhancing techniques to enable their administration. A promising technique, with increasing commercial success, is to molecularly mix drug and polymer to create an amorphous solid dispersion (ASD). While these mixtures provide enhanced drug solubility and dissolution in aqueous solutions, the mechanistic processes by which they release drug into solution are not well understood. Some unexplained behaviors include rapid drug release even at the maximum supersaturated concentration and spontaneous formation of drug-rich nanoparticles. These are beneficial for rapidly achieving and maintaining a highly supersaturated drug concentration during absorption, if crystallization is inhibited. However, the phenomena occur at typically low drug loading and are abruptly lost above a certain threshold termed the ‘limit of congruency’ (LoC), which has been reported to vary based on the drug-polymer system. In this research, the mechanisms underpinning ASD release at low and high drug loading were studied, and the factors affecting LoC were mechanistically explored by performing dissolution experiments and utilizing imaging, separation, thermal analysis, and spectroscopy methods to characterize the materials in the presence and absence of water. The results show that ASDs developed a gel layer on the surface when exposed to aqueous solution. This water-rich environment was thermodynamically unstable and phase separated into hydrophilic and hydrophobic phases. The morphology of the hydrophobic phase was directly related to the ASD release behavior, where ASDs below the LoC exhibited a dispersed and stable hydrophobic phase morphology, and ASDs above the LoC displayed a continuous or aggregated morphology. In cases where thermodynamic factors were rate limiting, LoC was inferred from features on the ternary phase diagram. Moreover, drug-polymer interactions and polymer molecular weight were demonstrated to affect the morphology of the hydrophobic phase and ultimately the LoC. The conclusions from this work provide the basis of a theoretical framework for rationally designing ASDs and optimizing their release. </p>

Curcumin is the major phenolic diarylheptane derivative in Curcuma longa and has been reported to possess pharmacological activities. Unfortunately this compound suffers from poor bioavailability and rapid neutral-alkaline degradation. Co-crystal of curcumin is one option under exploration, motivated by the fact that a number of active pharmaceutical ingredient (API) co-crystals with improved dissolution have recently been synthesized. Hence, co-crystallization technique highlights an alternative means to improve the performance of curcumin. Within our work evidences for a co-crystal was ascertained from DSC, Kofler hot stage screening and PXRD, and all confirmed a new crystal phase could have been formed between curcumin and a co-crystallizing agent, nicotinamide. We report that re-crystallization step essentially aids the purification of commercial curcumin, a herbal based actives. Otherwise the prevalence of a new crystal phase in solvent-mediated co-crystallization will be significantly reduced. Besides, phase diagram is an effective tool for the study of solubility behaviours in co-crystal system. In order to acquire related techniques, fenbufen, a poorly water soluble drug, was selected. The result showed the huge difference in solubility between fenbufen and nicotinamide lead to difficulty in the construction of phase diagram.

Crystal Engineering is the design of crystalline material using non-covalent synthesis. Co-crystals are multi-component crystals which are constructed from complementary intermolecular interactions, they are also known as supramolecular complexes. Design of such materials utilises the synthon approach, this involves the understanding of common intermolecular interactions which occur in the crystal packing and is used to design new solids with desired physical properties and chemical properties. Primary amides form supramolecular heterosynthons, these synthons represent an opportunity for a design of multi-component crystals in which one molecule contains a primary amide and a second molecule which is complimentary to the primary amide, usually carboxylic acids. The progress with regards to the screening process for the determination of co-crystals is evident in the literature, In particular, high throughput solution growth methods and solvent drop grinding. The comparison of Isonicotinamide and Benzamide as a co-crystal component has been presented. This study was motivated by the observation that the CSD contains 24 Isonicotinamide and 1 Benzamide co-crystal. The interaction with carboxylic acids is the focus of the work, in particular those which form Isonicotinamide co-crystal are being screened with Benzamide. Our work utilises a ReactArray Microvate to carry out the low throughput solution growth on a matrix of carboxylic acid with Benzamide, this study has been coupled with the Kofler hot stage microscope method which visually aids to screen and view co-crystal phase formation. Crystallisation screens have resulted in the identification of known co-crystal phases of Isonicotinamide and Benzamide, additionally new co-crystal phases have also been identified with Fumaric, 3-hydroxybenzoic acid, Mandelic Acid, 4-Nitrobenzoic Acid and Tartaric Acid. Single crystal structures of the Fumaric and 4-Nitrobenzoic acid have been obtained. In order to develop an understanding of co-crystal formation in Isonicotinamide and Benzamide with our supramolecular library, packing landscape analysis is being undertaken using both the CSD and crystal structures we have obtained. This is undertaken as collaboration with Dr Andy Parkin and Professor Gilmore (University of Glasgow), we have identified that the dSNAP analysis is a way forward for the analysis of how co-crystals pack. The analysis highlighted the subtleties that were present in the packing motifs of the Isonicotinamide co-crystals. In particular the cis and trans orientation of the amide and acid carbonyl to each other and the planar and off planar layer assemblies. All of which are required to maximise the hydrogen bond usage of the components comprising the co-crystals. Further investigations have led to the collaborative project with Syngenta Ltd in the design of a co-crystal screen using a high through-put robot, Crissy® -Automation Platform by Zinsser Analytical, using an extended screen of 16 acid coformers with Isonicotinamide, Benzamide and Nicotinamide the sample have been characterised using a reflectance diffraction method, GADDS. Further analysis of this data involves the use of polySNAP, which has led to further collaboration with Professor Gilmore¿s group. / Syngenta