Cette thèse porte sur l’étude de la synthèse et des données thermodynamiques des clathrates intermétalliques du système Na-Si, qui sont des matériaux pertinents pour les applications thermoélectriques et qui sont les précurseurs pour de nouvelles formes de Si prometteuses pour des applications photovoltaïques et photoniques. Dans ce travail la formation de clathrates Na-Si a été étudiée in situ et ex situ sous haute pression et haute température. Un nombre de nouvelles formes de silicium a été observé en chauffant des clathrates sous vide. Sous pression inférieure à 3 GPa les clathrates ne se forment pas par l’interaction des éléments. A la place, le siliciure Na4Si4 se forme et reste stable jusqu’à la fusion. Au-dessus de 3 GPa, Na4Si4 formé au début du chauffage, réagit avec l’excès de Si et donne Na30Si136 (structure II) et ensuite, si Na30Si136 réagit avec l’excès de Si pour former Na8Si46 (structure I) au dessous de 7 GPa et le clathrate NaSi6 au-dessus de 7 GPa. Des expériences ont été réalisées en utilisant des cellules standard Paris-Edimbourg (enclumes opposées) jusqu'à 6 GPa et la presse multi-enclumes pour les pressions au-dessus de 6 GPa. La forte sensibilité des produits de cristallisation à la concentration en sodium a été observée. Un schéma de transformations de clathrate pour les pressions entre 0 à 10 GPa et températures entre 300 et 1500 K a été proposé. Le diagramme de phase (concentration – température sous 4 GPa) qui représente les transformations observées et les domaines de stabilité a également été proposé et suggère l’existence de trois équilibres eutectiques : entre Si et structure I, entre structures I et II, et entre structure II et Na4Si4. Pour comprendre la thermodynamique et les interactions dans le système Na-Si, on a également effectué la modélisation du diagramme de phase à pression ambiante, ce que nous a permis de trouver les caractéristiques thermodynamiques de fusion et les équations des liquidus observés. Pour prendre en compte l’impact de la pression sur la thermodynamique, les équations d’état p-V-T de Si à structure diamant, structure I et la forme haute pression de structure II ont été utilisés. / The objective of this thesis is to study the synthesis and thermodynamics of intermetallic clathrates of the Na-Si system, which are the important materials for thermoelectric applications and are the promising precursors for new forms of Si for the photovoltaic and photonic applications. In this work the formation of the Na-Si clathrates have been studied in situ and ex situ at high pressure and high temperature. A number of new forms of silicon have been observed while heating the clathrates under vacuum. Under pressures below 3 GPa the clathrates does not form by the interaction of elements. Instead, the silicide Na4Si4 forms and remains stable up to melting. Above 3 GPa, Na4Si4 formed in the beginning of the heating, react with the excess of Si and gives Na30Si136 (structure II) and after that, if Na30Si136 react with the excess of Si, to form Na8Si46 (structure I) below 7 GPa and the clathrate NaSi6 above 7 GPa. The experiments have been performed by using the standard Paris-Edinburg cell (opposite anvils) up to 6 GPa and multianvil press for pressures above 6 GPa. The strong sensibility of the crystallization product to the concentration of sodium has been observed. The diagram of transformations in clathrates for pressures between 0 and 10 GPa and temperatures between 300 and 1500 K has been proposed. The phase diagram (concentration – temparature at 4 GPa) that represents the observed transformations and stability domains has been also proposed and suggests the existence of three eutetic equilibria: between Si and structure I, between structures I and II, and between structure II and Na4Si4. To understand the thermodynamics and interactions in the system Na-Si, the modelisation of phase diagram at ambient pressure has also been performed that allowed us to establish the thermodynamic characteristics of melting and the equations of observed liquidi. To take into account the impact of pressure on the thermodynamics, the p-V-T equations of state of diamond Si, structure I and high-pressure form of structure II have been used.

<p>  </p> <p>A multidisciplinary study that evaluated Quality Control (QC) laboratory (lab) accreditation, and a salt screen for bedaquiline. Medicines testing facilities always seek to ensure the accuracy of data from their QC labs by attaining accreditation. This research proposed that an understanding of the cross-linkages in the requirements for implementing the 2 most widely used lab standards will facilitate testing efficiencies, and reduce the risks of accreditation failures. For the salt project, the study proposed that new salts of bedaquiline will be formed from acid-base reactions following the pKa rule. Characterizing the salts will provide specifications for the new molecular entities, and form a selection-criteria for a lead candidate.</p> <p>The research reviewed 2 lab standards: the ISO/IEC17025:2017 and the WHO Good Practices for Pharmaceutical QC labs, and identified the areas of overlap in their requirements. It then developed and tested affordable models that mitigate the 3 identified areas of high risks to lab accreditation. Additionally, it mixed<em> equimolar amounts of bedaquiline base with select counterions that have ≥ 2 pKa units in organic solvents, to yield salts</em>. ICHQ6 guidance was used to characterize the new salts.</p> <p>The highest risks to laboratory accreditation were linked to 3 quality system metrics, namely: ‘Proficiency Testing’, ‘Validation’, and ‘Measurement Traceability’. Using the identified areas of overlap in the 2 laboratory standards, this research provided tutorial videos, a competency matrix, and some instrument validation data, to optimize the requirements for lab accreditation. For the salt screen, five new candidates were synthesized as alternatives to the existing fumarate salt of bedaquiline. The results of their physicochemical properties were used for selecting a lead moiety.</p> <p>The research provided evidence that the multipronged models developed will improve efficiencies in QC labs, and increase their chances of attaining international accreditations. It also discovered the best modes for synthesizing the new salts of bedaquiline, and provided critical data to help Pharma make an informed choice for a lead candidate.</p>

Bohemian garnets have been known as a jewellery stone for many centuries. There is still a lot of interest in them, however, the reserves in traditional locations are getting smaller. That is why search for alternative source of similar garnets in gem quality started. Shavaryn Tsaram deposit in Mongolia is considered as one of the potential sources. Pyrope samples from eight Bohemian localities of two areas (České středohoří [The Central Bohemian Uplands] and Podkrkonoší [The Giant Mountains]) and from Shavaryn Tsaram deposit in Mongolia were analysed using electron microprobe, LA-ICP-MS, ICP-OES, Mössbauer spectroscopy and x-ray powder diffraction. The data were compared with the conclusion that the Mongolian garnets from Shavaryn Tsaram deposit are so different from the Bohemian ones that it will not be possible to use them as a gem material of similar qualities. Bohemian garnet can be characterised as a red garnet with refraction index 1.747 (+/- 0.001) with dominant pyrope component of the average composition Py78Alm17Gr5 and Cr2O3 content above 1 wt.%. The data were also evaluated from two classification schemes point of view. The schemes by Schulze (2003) and Grütter (2004) are used in determining source materials and in diamond prospection. According to them source rocks of Bohemian garnets...