Ammonia and water are major components of many planetary bodies, from comets and icy moons such as Saturn's Titan to the interiors of the planets Neptune and Uranus. Under a range of high pressures and/or low temperatures known to occur in these planetary bodies, ammonia and water form a series of compounds known as ammonia hydrates. Ammonia and water form three stoichiometric compounds, ammonia hemihydrate, ammonia monohydrate and ammonia dihydrate, which have ammonia-to-water ratios of 2:1, 1:1 and 1:2 respectively. Therefore a good understanding of the three stable ammonia hydrates is required for modelling the interiors of these bodies. Additionally, the ammonia hydrates are the simplest systems to incorporate mixed (N-H O and O-H N) hydrogen bonds. Such bonds are important biochemically, and along with O-H O H-bonds, mixed H-bonds are responsible for the second-order structure of DNA, and they are also responsible for the proton transfer reactions in enzymic processes. The understanding of these bonds and processes rests on the knowledge of the relationship between bond strength and geometry, and the ammonia hydrates provide a rich range of geometries against which models of such mixed H-bonds can be tested. X-ray and neutron diffraction techniques have been used to investigate the behaviour of the ammonia-water complex and further the understanding of this system. This includes solving the structure of a phase which was previously thought to be an ammonia monohydrate phase, but has been shown here to be a mixture of an ammonia hemihydrate phase and Ice VII. In addition to this, x-ray and neutron diffraction experiments have been performed to explore how this phase behaves under changing pressure and temperature conditions, and what other implications that this has on the ammonia-water system. It has been found that ammonia hemihydrate can also form a structural phase observed to form in both ammonia monohydrate and ammonia dihydrate within the same pressure and temperature regime, which opens the possibility of a solid solution existing between all three stoichiometric ammonia hydrates.

The alkali elements at ambient conditions are well described by the nearly-free electron (NFE) model, yet show a remarkable departure from this “simple” behaviour with increasing pressure. Low-symmetry complex structures are observed in all, and anomalous melting has been observed in lithium (Li), sodium (Na), rubidium (Rb), and caesium (Cs). In this Thesis, static and dynamic compression techniques have been used to investigate the high-pressure high-temperature behaviour of the alkali elements potassium (K) and Na. Utilising diamond anvil pressure cells and external resistive heating, both in-air and in-vacuum, the melting curve of K has been determined to 24 GPa and 750 K, and is found to be remarkably similar to that of Na, but strikingly different to that reported previously. Furthermore, there is some evidence to suggest that a change in the compressibility of liquid-K occurs at lower pressures than the solid-solid phase transitions, perhaps indicating structural transitions occurring in the liquid phase, similar to those in the underlying solid. This could suggest a mechanism to explain the anomalous melting behaviour observed. Previous ab initio computational studies indicate that the unusual melting curve of Na arises due to structural and electronic transitions occurring in the liquid, mirroring those found in the underlying solid at higher pressures. The discovery that the melting curve of K is very similar to that of Na suggests that the same physical phenomena predicted for Na could be responsible for the high-pressure melting behaviour observed in K. The tI19 phase of K, observed above 20 GPa at 300 K, is a composite incommensurate host-guest structure consisting of 1D chains of guest atoms surrounded by a tetragonal host framework. Along the unique c-axis, the host and guest are incommensurate with each other. During the melting studies described above, it was observed that with increasing temperature, the weaker-bonded guest chains become more disordered while the host structure remains unchanged. To investigate and characterise this order-disorder transition, in situ synchrotron X-ray diffraction studies were conducted on single-crystal and quasi-single crystal samples of tI19-K. An order-disorder phase line has been mapped out to 50 GPa and 650 K. Perhaps the most striking departure from NFE behaviour in the alkali elements is observed in Na at pressures above 200 GPa where it transforms to a transparent electrical insulator. This phase is a so-called elemental “electride”, which may be thought of as being pseudo-ionically bonded. Electrides are predicted to exist in many elements, but at pressures far beyond the current capabilities of static pressure techniques. Utilising laser-driven quasi-isentropic compression techniques, dynamic compression experiments were performed on Na to see if it is possible to observe this electride phase under the timescales of dynamic compression experiment (ns). Optical velocimetry and reflectivity of the sample were measured directly to determine pressure and monitor the on-set of the transparent phase, respectively.

This thesis project has focussed on the experimental study of simple molecular systems at extreme conditions. High-pressure and high-temperature techniques have been used in combination with Raman spectroscopy and X-ray diffraction diagnostics to characterise three simple molecular systems which are unified by the inclusion of nitrogen as a constituent element. The N2 molecule contains the only triple-bond amongst the elemental diatomics and is considered a model system for exploring the changes in structure and bonding induced by tuning pressure and temperature conditions. As such the nitrogen phase-diagram is a focus-point in current extreme conditions research and nitrogen has been found to exhibit a high-degree of polymorphism not observed in other simple molecular systems such as hydrogen or oxygen. Understanding molecular mixtures of nitrogen with other simple molecules at extreme conditions is significant to many scientific fields varying from chemistry to astronomy. The first system presented is the binary mixture of nitrogen and xenon which was studied as a function of pressure. The study constitutes the first comprehensive study of the xenon-nitrogen system at high-pressures. A new van der Waals compound was observed which underwent a phase transition at 14 GPa and was stable up to at least 180 GPa and 3000 K, conditions where pure nitrogen becomes amorphous. Optical measurements suggested possible metallization of the new compound around 120 GPa. The second system presented is the binary mixture of nitrogen and hydrogen which was studied both as a function of pressure and composition. Two known nitrogen-hydrogen structures were confirmed and a pressure-temperature path-dependent formation of hydrazine or ammonia was discovered. Additionally, one mixture was compressed to 242 GPa, the highest pressure investigated in the nitrogen-hydrogen system. The third system presented is the elemental nitrogen phase known as i-nitrogen, an elusive high-temperature polymorph which has hitherto eluded structure determination and proved challenging to access. i-nitrogen was successfully characterised as having an extraordinarily large unit cell containing 48 N2 molecules, making it the most complex molecular nitrogen structure to be determined unambiguously.

L’objet de ce travail est le développement de méthodologies et d’équipements Raman performants, permettant d’accéder aux propriétés des matériaux en conditions extrêmes. Nous décrivons la conception d’un spectromètre Raman portable original, dédié aux mesures in situ dont la sonde versatile permet d’obtenir une caractérisation Raman en conditions extrêmes, offrant une large gamme de longueurs d’ondes d’excitation, et des optiques de collections permettant d’obtenir un signal Raman dans un très grand nombre d’environnements sévères aux accès optiques délicats. De plus, la technique Raman est couplée à des mesures de microluminescence (cathodo/iono/photoluminescence), et ce, au même point de l’échantillon. Le système permet également -via un détecteur CCD intensifié- la caractérisation résolue en temps par spectroscopies Raman et de luminescence, associée à un mode pulsé de l’accélérateur, donnant accès à de nombreuses informations complémentaires sur la structure de l’échantillon. Enfin, ce dispositif donne accès à l’étude des propriétés des matériaux en conditions de haute température et d’irradiation. D’autre part, les systèmes d’analyses ex-situ en conditions extrêmes sont détaillés dans ce travail. Les principaux résultats acquis sont également présentés afin d’illustrer le fonctionnement et la qualité des résultats obtenus. Nous exposons notamment les études décrivant le comportement d’interfaces UO2/H2O sous faisceau He2+, l’évolution in situ des propriétés des matériaux soumis aux irradiations ou à des recuits haute température, ainsi que la caractérisation d’états excités de matériaux. / The aim of this work is the development of efficient Raman methodologies and equipments, giving access to material properties in extremes conditions. We describe the conception of an original portable Raman, dedicated to in situ measurements, whose versatile headprobe allows material characterization in extremes conditions, offering a large range of excitation wavelengths, and whose optical collection system permits to obtain Raman information in a large number of delicate optical access severe environments. Moreover, the Raman technique is coupled to micro-luminescence measurements (cathodo/iono/photo- luminescence) at the same point of the sample. The device also allows – by the mean of an intensified CCD detector – the Raman and luminescence time resolved characterization, combined to a pulsed ion beam accelerator. This setup gives access to hard reachable informations concerning the sample structure. Finally, this device allows studies of materials in both high temperature and irradiation hostile conditions. Besides, extremes conditions ex situ analysis systems are described in this work. We additionally present the main results obtained in order to validate that the system works and to show its performances. More precisely, we report studies describing the behavior of UO2/H2O interfaces under He2+ particles beam, the in situ evolution of material properties under irradiation or high temperature annealing process, and finally the excited states characterization of materials.

L'objectif était de développer un outil individuel de management de la fatigue. Cet outil, dénommé Scextan®, a été conçu sous la forme d'une application informatique. Pour cela, plusieurs étapes de développement et de validation ont été franchies. Dans un premier temps, nous avons choisi d'observer le sommeil des navigateurs à la voile en solitaire qui doivent gérer une forte privation de sommeil. Les résultats ont montré que ces marins sont soumis aux mêmes principes de régulation de sommeil que l'adulte sain. Nous avons retenu ces sujets comme population expérimentale. Dans un deuxième temps, nous avons validé le logiciel Scextan® pour la mesure du rythme veille-sommeil qui s'est révélée plus précise qu'avec un agenda de sommeil manuscrit. Puis, nous avons évalué la pertinence de l'implémentation d'un modèle de prédiction mathématique de performances dans Scextan®. Chez des marins en course, le modèle a su prédire 70% de la variance des mesures. Dans un dernier temps, Scextan® a été proposé aux skippers de la course transatlantique "Route du Rhum". Seul le vainqueur de la course a utilisé de façon quasi systématique le logiciel Scextan® pour gérer son état de forme. L'agenda de Sommeil Interactif Scextan® est toujours en cours de développement, mais a déjà démontré qu'il pouvait être un outil de recherche à part entière, et qu'il tendrait rapidement à devenir un outil pédagogique. / The goal of the thesis was to develop an individual fatigue management tool called Scextan® and designed as a software application. The development of this system involved several research and validation steps. We first describe sleep patterns of single-handed sailors, who have to manage severe sleep deprivation. Results suggested that single-handed sailors are subject to the same principles of sleep regulation as healthy adults and we choose these subjects as our mains test population. In a second step, we developed and validated the Scextan® software application. Results revealed that Scextan® is more accurate than a paper-based sleep diary. The third study was to measure fatigue in single-handed ocean race and compare the results with a mathematical prediction model of performances, which was able to predict 67% of the measured fatigue. Lastly, skippers of the 2010 "Route du Rhum" single-handed transatlantic race were offered use of Scextan®. The race winner was the only sailor to use it intensively to manage and rationallyanticipate his state of alertness. Although Scextan® is still being improved, it has already proved itself to be a valuable research tool and is on the way to becoming an individual management tool.

Inconel 718 has widespread use in critical industries like aerospace, marine, and power generation. However, its challenging machinability, characterized by tool chipping/failure, and poor surface quality, remains a significant concern. Despite numerous efforts to enhance tool performance in machining hard-to-machine materials, the issue of sudden tool failure and chipping persists. This study presents an innovative in-situ tool treatment method, complemented by an optimized recoating strategy, aimed at tackling these challenges. The approach involves the application of a lubricating soft metallic Al-Si alloy coating to the tool’s faces, which can be recoated when needed. During subsequent Inconel machining, the Al-Si layer deposited on the tool melts due to high temperatures. The molten material fills microcracks on the tool surface, preventing their propagation. Moreover, the tool can slide on the beneficial tribo-films Al-Si layer which reduces friction, sticking, seizure, and built-up edge formation, resulting in decreased tool wear and chipping. The newly developed pre-machined recoating method has yielded promising outcomes, reducing cutting force and significantly improving tool lifespan compared to the PVD benchmark and uncoated tools. Additionally, this novel method enhances surface quality and minimizes undesirable microstructural alterations induced by machining. / Thesis / Master of Applied Science (MASc) / Chipping and excessive tool wear pose significant challenges in machining high-strength alloys like Inconel 718, limiting their applicability across various industries. According to research, conventional strategies used to deal with the machining challenges posed by Inconel 718 have not produced the best results. The goal of this research is to overcome the machining issues associated with such a difficult-to-cut material innovatively by depositing soft metallic coatings as a solid lubricant to enhance the machining performance. In this study, a cost-effective novel in-situ deposition technique with recoating capability as an alternative to conventional coatings is presented to achieve this goal. This innovative approach aims to improve tool performance during Inconel 718 machining significantly. This study also provides a thorough insight into the application of solid lubricants in machining, discussing their mechanisms, effectiveness, constraints, and potential to boost productivity and environmental sustainability. Furthermore, comprehensive investigations have been conducted to gain deeper insights into the prevalent wear mechanisms and surface treatments that can lead to improved machining performance for Inconel 718.

Physics at extreme conditions is not a young field; there have been decades of developments that have allowed us to generate high-pressure and high-temperature conditions in a vast array of materials. Conventionally, these extreme conditions were generated using static compression techniques; compressing a material in a diamond anvil cell which could then be heated or cooled, with structural information deduced using synchrotron radiation. These techniques are still invaluable for extreme conditions research although the pressures and temperatures that are accessible to them are limited by the strength of the diamond anvil cells and their ability to withstand extreme temperatures. The necessity for access to pressure-temperature states that are beyond the scope of the conventional diamond anvil cell is driven by the need to characterise extreme environments such as planetary interiors. It was long believed that materials in high pressure-temperature states would exhibit relatively simple, high-symmetry crystal structures, but recent research has proven that, conversely, there is an abundance of complex structural behaviour at these extreme conditions. One means of attaining pressure-temperature states beyond those accessible using static compression techniques is to impart a large amount of energy into a material in a comparatively short period of time (milliseconds to nanoseconds); this is known as dynamic compression. Dynamic compression can be generated using impact techniques or, alternatively, via laser ablation. Access to the most extreme conditions is commonly achieved by generating a shockwave which compresses the sample with the fastest achievable compression wave. Not only does this type of compression facilitate access to the most extreme states, it also allows us to explore the physics of impact phenomena and other such situations involving rapid energy transfer. Dynamic compression occurs on short timescales and, as such, there is a considerable challenge in implementing diagnostics to study the behaviour of compressed materials. Furthermore, because complexity is commonplace in extreme conditions, it is vital that any diagnostics should be able to provide data of high enough quality that this complexity may be resolved. The advent of 4th generation light sources (x-ray free electron lasers) has afforded us the opportunity to obtain extraordinarily high quality data on dynamic compression timescales. In the interest of refining analytical techniques when utilising this novel technology, materials exhibiting complex crystal structures should be investigated. Antimony is an element which is known, under static compression, to transform from a Peierls-distorted rhombohedral phase (R-3m) to an incommensurately modulated host-guest structure (I'4=mcm(00γ)000s), a structure with an incredibly high level of complexity. The complexity of this host-guest phase, and the relatively low pressure at which it forms, makes antimony an ideal candidate for testing the resolution achievable using these 4th generation light sources. Furthermore, it is interesting to observe whether such a complex phase can form on the short timescales of dynamic compression. In this work antimony is both statically and dynamically compressed and the results of both experiments are compared. A static phase diagram is constructed for antimony up to 31 GPa and 835 K, confirming the location of a previously theorised triple point and suggesting the location of an additional triple point. Three solid phases are characterised and data are found to agree with the pre-existing static compression studies. The nature of the host-guest phase is investigated and the guest 'chains' are found to remain intact even at the highest temperatures and pressures, a result which has not previously been observed in high pressure-temperature host-guest structures. Dynamic data from shock-compression experiments at pressures up to 59.3 GPa are plotted alongside the static data and contrasting phase behaviour is discussed. Four solid phases are identified along with one liquid phase. Observation of the host-guest phase in shock-compressed antimony confirms that highly complex crystal structures are able to form on the nanosecond timescale.

La protection des gaines de combustible de réacteur nucléaire contre l’oxydation à haute température en conditions accidentelles est essentielle pour garantir leur intégrité, c’est-à-dire celle de la première barrière de confinement. Celle-ci peut s’effectuer par le dépôt d’un revêtement sur leur paroi interne et ce sont les procédés CVD qui sont les plus à même de le faire. Il s’agit plus précisément du procédé DLI-MOCVD qui a été utilisé ici pour déposer des revêtements à base de chrome (chrome métallique Cr(S) cristallisé) et de carbures de chrome (carbures de chrome CrxCy amorphes non recyclés, recyclés et CrxSizCy dopés au Si), réputés pour leur bonne résistance à l’oxydation. Afin d’améliorer la qualité des revêtements, le procédé de dépôt a été optimisé à l’aide de simulations numériques. Après une réflexion sur le mécanisme chimique, un modèle cinétique réactionnel du dépôt d’un revêtement CrxCy amorphe a pu être ajusté et validé. Il a aussi été montré que la solution utilisée de précurseur organométallique bis(arène)chrome et de solvant toluène pouvait être directement recyclée, augmentant ainsi le potentiel d’industrialisation du procédé. Les propriétés physico-chimiques et structurales des revêtements déposés avec ce procédé ont été caractérisées. Une étude des propriétés mécaniques de ces revêtements a par ailleurs été entreprise. Il en ressort que, comparés à des revêtements apparentés déposés par d’autres procédés, ceux déposés par DLIMOCVD possèdent notamment une dureté élevée (jusqu’à une trentaine de GPa), des contraintes résiduelles en compression, une bonne adhérence avec leur substrat et enfin une résistance à l’usure abrasive différente suivant la température. L’évaluation de leur résistance à l’oxydation à 1200 °C a révélé les excellentes performances des revêtements en carbures de chrome amorphes, qui permettent de retarder l’oxydation catastrophique de plus de deux heures pour une épaisseur de 10 µm. Tous les autres revêtements augmentent la tenue en température des substrats en zircaloy mais ne retardent pas autant l’oxydation catastrophique. / Nuclear fuel cladding tubes resistance against high temperature oxidation during accident conditions is crucial because it means protecting the first containment barrier. This can be done by coating the inner wall of the cladding tube with CVD processes, which are most likely to do so. More specifically, we used DLI-MOCVD to grow chromium based (Cr(S), metallic crystalline chromium) and chromium carbides based (amorphous chromium carbides CrxCy, recycled CrxCy, silicon doped CrxSizCy) coatings, known for their good oxidation resistance. The coating process was optimized using numerical modelling to improve coatings performance. A reaction kinetics model of the deposition process of amorphous CrxCy coatings was adjusted and validated after the identification of the chemical mechanism. It was also shown that the liquid solution containing organometallic precursor (bis(arene)chromium) and solvent (toluene) could be directly recycled, thereby increasing the industrialization potential of such process. Physical, chemical and structural properties of coatings deposited with this process were characterized. A study of the coatings mechanical properties has also been undertaken. It shows that compared to related coatings grown with other processes, those deposited by DLI-MOCVD exhibit a particularly high hardness (up to 30 GPa), compressive residual stresses, good adhesion with the substrate and finally a different abrasive wear resistance depending on the temperature. The assessment of their oxidation resistance at 1200 °C revealed excellent performances of amorphous chromium carbides coatings, which can delay catastrophic oxidation up to two hours with only a 10 µm thickness. All the other coatings only increase the thermal resistance of zircaloy substrates.

This project takes place in the north of Norway, on an Island called Senja. With its beautiful nature and reliable resource of fish it attracts tourists in the summer time and seasonal workers in the fishing industry during the winter.  How can communal housing for tourists and workers act as a hub in the local community? Around this question a cluster of different functions has been developed that serves the whole community as well as the communal housing with private living units.

The recent development of free-electron lasers operating at XUV and X-ray wavelengths are proving vital for the exploration of matter in extreme conditions. The ultra-short pulse length and high peak brightness these light sources provide, combined with a tunable X-ray wavelength range, makes them ideally suited both for creating high energy density samples and for their subsequent study. In this thesis I describe the work done on the XUV free-electron laser FLASH in Hamburg, aimed at creating homogeneous samples of warm dense matter through the process of volumetric XUV photo-absorption, and the theoretical work undertaken to understand the process of high-intensity laser-matter interactions. As a first step, we have successfully demonstrated intensities above 10¹⁷ Wcm-2 at a wavelength of 13.5 nm, by focusing the FEL beam to micron and sub-micron spot sizes by means of a multilayer-coated off-axis parabolic mirror. Using these record high intensities, we have demonstrated for the first time saturable absorption in the XUV. The effect was observed in aluminium and magnesium samples and is due to the bleaching of a core-state absorption channel by the intense radiation field. This result has major implications for the creation of homogeneous high energy density systems, as a saturable absorption channel allows for a more homogeneous heating mechanism than previously thought possible. Further, we have conducted soft X-ray emission spectroscopy measurements which have delivered a wealth of information on the highly photo-excited system under irradiation, immediately after the excitation pulse, yet before the system evolves into the warm dense matter state. Such strongly photo-excited samples have also been studied theoretically, by means of density functional theory coupled to molecular dynamics calculations, yielding detailed electronic structure information. The use of emission spectroscopy as a probe for solid-density and finite-temperature systems is discussed in light of these results. Theoretical efforts have further been made in the study of the free-free absorption of aluminium as the system evolves from the solid state to warm dense matter. We predict an absorption peak in temperature as the system heats and forms a dense plasma. The physical significance of this effect is discussed in terms of intense light-matter interactions on both femtosecond and picosecond time-scales.