No / This communication reports a novel solvent free method to generate and stabilise the triclinic form of artemisinin. We show that the stability of the triclinic form obtained by high temperature extrusion is greater than that of material made using a solvent based technique.

L’objectif de ce travail de thèse est de prendre en compte à la fois l’hétérogénéité, l’anisotropie et des incertitudes dans la simulation 3D de la propagation d’ondes élastiques. Pour ce faire, dans un premier temps, on modélise le champ de propriétés mécaniques, ici le champ de tenseur d’élasticité, par un modèle de champ stochastique 3D des matrices définie-positives. La construction de ce modèle de champ est essentiellement fondée sur celle de Soize [2008]. Notre modèle conserve ainsi les propriétés principales du modèle de Soize comme le paramétrage minimal contrôlant l’amplitude de la fluctuation et la taille caractéristique de la variabilités patiale, le comportement local a priori arbitrairement anisotrope (anisotropie triclinique) et les propriétés mathématiques fondamentales. De plus, un nouveau paramètre est introduit dans ce modèle pour imposer un niveau d’anisotropie moyen souhaité. Dans un deuxième temps, on effectue des adaptations du code de calcul d’éléments finis spectraux, à savoir le code parallèle SPEC3D, afin d’une part de générer les réalisations du champ stochastique du tenseur d’élasticité et d’autre part de prendre en compte l’anisotropie dans la résolution numérique du problème élastodynamique. Des études paramétriques utilisant SPEC3D sont ensuite réalisées mettant en évidence les influences de l’anisotropie et des paramètres d’hétérogénéité sur la propagation d’ondes sismiques. En particulier, elles démontrent une dépendance directe entre la longueur de corrélation du champ de propriétés et le temps caractéristique d’apparition de la diffusion. Ce régime se manifeste par l’équipartition d’énergie entre les mouvements irrotationnels et rotationnels. / The aim of this thesis is to take into account the heterogeneity, the anisotropy and the uncertainties within 3D numerical simulation of elastic waves propagation. Firstly, the elasticity tensor field is modeled by means of a stochastic tensor-valued field. Its construction is generalized from the model of Soize [2008]. Hence, our model preserves principle properties of the former : a small set of parameters controlling the whole dispersion and the characteristic size of spatial variability, a local behavior being a priori arbitrary anisotropic (triclinic anisotropy) andothers essential mathematical properties. Moreover, a new parameter is added in order to impose a desired anisotropy mean level. Secondly, we carry out adaptations of an existing spectral finite elements-based elastic waves simulation software, namely the SPEC3D parallel computing code. On the one hand a sample generator of the elasticity random field model is implemented and on the other hand anisotropic material behavior is introduced in the elastodynamic solver. Finally, numerical parametric studies are performed using SPEC3D highlighting influences of heterogeneity and anisotropy on elastic waves behavior. In particular, it is observed that the characteristic time beyond which a multiple scattering pattern can be approximated by a diffusion regime directly depends on the correlation length of elasticity tensor field model. This time is detected by an energy equipartition between rotational and irrotational movements.

X-ray diffraction experiments have been used to determine the structure of cesium methylsulfonate (CsCH₃SO₃), lithium hydrazinium sulfate (LiN₂H₅SO₄), above 160ºC and triclinic potassium dichromate (K₂Cr₂O₇). The solved CsCH₃SO₃ structure is compared with BaSO₄ and the CsCH₃SO₃⁻¹ ion stereochemistry is dicussed in terms of a current theory of bonding for such groups. The previously known structure of room temperature ferroelectric LiN₂H₅SO₄ has recieved additional refinement and a comparison is made with the structure determined above 160ºC. The symmetry and structure found for K₂Cr₂O₇ are compared with similar compounds and predictions are given for the yet unsolved structures of other K₂Cr₂O₇ phases. The first accurate data for the Cr₂O₇⁻² ion stereochemistry is presented. This ion is compared to similar ones, and the possibility of extending a bonding theory to such ions involving chromium is discussed. / Thesis / Doctor of Philosophy (PhD)

Diploma thesis deals with laboratory preparation of the main clinker mineral - alit. The theoretical part summarizes the existing knowledge and the practical part deals with the methodology of preparation of the alite. The main goal was to prepare and study the monoclinic phases of alite, another goal was to optimize the triclinic alite.

Diploma thesis deals with the methodology of preparation of Alit – the main clinker mineral. The content of this work involves design and optimization of the methodology of preparation of pure Alit polymorphs, analysis of their properties by available analytical methods and evaluation of the change of crystallinity in the process of preparation of these polymorphs by XRD-analysis.

The synthesis and properties of metal phosphonates prepared using piperazine-based bisphosphonic acids have been investigated. The ligands N,N’-piperazinebis(methylenephosphonic acid) (H₄L), and the 2-methyl (H₄L-Me) and 2,5-dimethyl (H₄L 2,5-diMe) derivatives have been prepared using a modified Mannich reaction. Hydrothermal reaction of gels prepared from metal (II) acetates and the bisphosphonic acids results in the synthesis of four structures: STA-12, Ni VSB-5, Co H₂L.H₂O and Mg H₂L. STA-12, synthesised by reaction of Mn, Fe, Co or Ni acetate with H₄L or H₄L-Me, has been investigated further. STA-12 crystallises in the space group R⁻₃, and Ni STA-12 is the most crystalline version. Its structure was solved from synchrotron data (a = b = 27.8342(1) Å, c = 6.2421(3) Å, α = β = 90°, γ = 120°), and it has large 10 Å hexagonal shaped pores. Helical chains of Ni octahedra are coordinated by the ligands, resulting in phosphonate tetrahedra pointing towards the pore space. Water is present, both coordinated to the Ni²⁺ cations and physically adsorbed in the pores. Mixed metal structures based on Ni STA-12, where some Ni is replaced in the gel by another divalent metal (Mg, Mn, Fe or Co) can also be synthesised. Dehydration of STA-12 results in two types of behaviour, depending on the metal present. Rhombohedral symmetry is retained on dehydration of Mn and Fe STA-12, the a cell parameter decreasing compared to the as-prepared structures by 2.42 Å and 1.64 Å respectively. Structure solution of dehydrated Mn STA-12 indicates changes in the torsion angles of the piperazine ring bring the inorganic chains closer together. Fe and Mn STA-12 do not adsorb N₂, which is thought to be due to the formation of an amorphous surface layer. Dehydration of Ni and Co STA-12 causes crystallographic distortion. Three phases were isolated for Ni STA-12: removal of physically adsorbed water results in retention of rhombohedral symmetry, while dehydration at 323 K removes some coordinated water forming a triclinic structure. A fully dehydrated structure (dehydrated at 423 K) was solved from synchrotron data (a = 6.03475(5) Å, b = 14.9156(2) Å, c = 16.1572(7) Å, α = 112.5721(7)°, β = 95.7025(11)°, γ = 96.4950(11)°). The dehydration mechanism, followed by UV-vis and Infra-red spectroscopy, involves removal of water from the Ni²⁺ cations and full coordination of two out of three of the phosphonate tetrahedra forming three crystallographically distinct Ni and P atoms. No structural distortion takes place on dehydration of Ni and Co STA-12 prepared using the methylated bisphosphonate, and the solids give a higher N₂ uptake as a result. Dehydrated Ni and Co STA-12 were tested for adsorption performance for fuel related gases and probe molecules. Investigations were undertaken at low temperature with H₂, CO and CO₂, and ambient temperature with CO₂, CH₄, CH₃CN, CH₃OH and large hydrocarbons. Due to the presence of lower crystallinity, Co STA-12 has an inferior adsorption performance to Ni STA-12, although it has similar adsorption enthalpies for CO₂ at ambient temperature (-30 to -35 kJ mol⁻¹). Ni STA-12 adsorbs similar amounts of CO₂ and N₂ at low temperature, indicating the adsorption mechanisms are similar. Also, it adsorbs 10 × more CO₂ than CH₄ at low pressure, meaning it could be used for separation applications. Ni STA-12 adsorbs 2 mmol g⁻¹ H₂ with an enthalpy of -7.5 kJ mol⁻¹, the uptake being due to adsorption on only one-third of the Ni²⁺ cations. The uptake for CO is 6 mmol g⁻¹, with adsorption enthalpies ranging from -24 to -14 kJ mol⁻¹. This uptake is due to adsorption on all the Ni²⁺, meaning the adsorption enthalpies are high enough to allow the structure to relax. This is also observed for adsorption of CH₃CN and CH₃OH, where there is a return to rhombohedral symmetry after uptake. The adsorption sites in dehydrated Ni and Co STA-12 were investigated via Infra-red spectroscopic analysis of adsorbed probe molecules (H₂, CO, CO₂, CH₃CN and CH₃OH). The results indicate the adsorption sites at both low and ambient temperature are the metal cations and the P=O groups. The metal cation sites are also characterised as Lewis acids with reasonable strength. STA-12 was shown to have acidic activity for the liquid phase selective oxidations of 1-hexene and cyclohexene, although there is evidence active sites are coordinated by products and/or solvents during the reaction. STA-12 also demonstrates basic activity for the Knoevenagel condensation of ethyl cyanoacetate and benzaldehyde. Modification of STA-12 by adsorption of diamine molecules causes a slight increase in the basicity, and the highest conversions are where water and diamine molecules are both present.