Total scattering can be used to study crystalline materials, whose structure presents a periodic arrangement of atoms, as well as disordered materials, such as liquids, glasses or nanomaterials. This thesis work reports three experimental case studies in which different analysis methods were chosen as appropriate on a case-by-case basis. This study demonstrates that total scattering combined with modelling and complementary experimental techniques can guide the understanding of the structure of complex nanostructures. X-ray and neutron total scattering data were collected on multi-walled carbon nanotubes continuously filled with iron and analysed using the program PDFgui for refinement of the pair distribution function and molecular dynamics simulations using the program DL_Poly_4. The analyses show that the iron core is mainly composed of ��-Fe and confirms the dependence of the local ordering on the orientation of the crystallographic axes of iron with respect to the nanowire axis. Prussian blue (Fe4[Fe(CN)6]3 · ��H2O) was synthesised in bulk and nanoparticulate phases using deuterated chemicals; the amount of D2O and H2O in the pores and vacancies, as well as polyvinylpyrrolidone remaining in the nanoparticle samples, were estimated, using an ad hoc modelling procedure of the first few peaks in the neutron PDF function. Models of the structure were refined using the programs PDFgui and RMCProfile. In the last case, a 50Å supercell of the bulk structure with randomly distributed stoichiometric vacancies and D2O and H2O molecules occupying both the pores and the vacancies was used as starting atomic configuration. The CaO/CaCO3 family of materials consists of a series of samples that have undergone carbonation and/or calcination. The X-ray and neutron pair distribution function data were compared to the theoretical PDF of the CaO and CaCO3 phase, generated using the program GULP, that produces PDF functions based on the spectrum of phonon frequencies of the material. The analysis shows that the carbonation is almost completed already after 2 minutes of carbonation and the structure remains stable under further carbonation.

Understanding the structure of matter in the solid state could be considered as being one of ‘the big questions’ in chemistry. Whereas the structural behaviour of molecules in the gas phase is relatively well-understood, this is not the case for the condensed phase due to the complexity of short and long-range intermolecular interactions. The purpose of the work in this thesis is to examine the structural response of solid molecular materials to stimuli of extreme pressure and temperature. L-alanine crystallises as a zwitterion in the space group P212121. Neutron powder diffraction and X-ray single crystal diffraction data show that the a and caxes are very similar in length. The a-axis is more compressible than the c-axis, and at ca. 2 GPa the cell becomes metrically tetragonal, however the underlying symmetry is still orthorhombic. The structure remains in a compressed form of the ambient phase up to 9.87 GPa. Previous Raman and energy dispersive powder diffraction studies have interpreted changes in spectra at ca. 2 and 9 GPa as phase transitions. The diffraction data and DFT calculations described here suggest that these are in fact due to changes in conformation of the ammonium group. L-alanine shows remarkable resistance to the effects of pressure but something must happen to the structure if pressure continues to be increased. Neutron powder diffraction has been used to obtain high-pressure data for L-alanine up to 15.46 GPa. These are the highest-pressure diffraction data reported for any amino acid. Above ca. 15 GPa, L-alanine undergoes a reversible transition to an amorphous phase through volume collapse of the crystal, driven by the need to minimise the PV term in the Gibbs free energy equation, as opposed to relieving destabilising contacts. It is currently the only amino acid known to undergo a transition of this type. The co-crystal of methylpyridine and pentachlorophenol (MP-PCP) forms in the space group P-1. When the phenolic proton is deuterated (MP-PCP-d) it exhibits isotopic polymorphism, crystallising in the space group Cc. Structures of the two other combinations of isotope and space group, i.e MP-PCP in Cc and MP-PCP-d in P-1 have not yet been determined. We demonstrate that these polymorphs can be obtained using high-pressure and low-temperature conditions predicted by thermodynamics. The use of in-situ crystallisation at pressure has driven MP-PCP to pack with Cc symmetry, minimising the PV term in the Gibbs free energy equation. Low-temperature crystallisation causes MP-PCP-d to form in P-1 due to this phase being favoured by vibrational enthalpic and entropic contributions. Aniline is a liquid under ambient conditions but freezes at 267 K in the monoclinic space group P21/c. It can also be frozen by pressure (ca. 0.8 GPa) in the orthorhombic space group Pna21. Neutron powder diffraction shows that on decompression the orthorhombic form transforms to the monoclinic phase at 0.3 GPa, owing to the monoclinic packing being less dense. PIXEL calculations provide an insight into the intermolecular energies of the orthorhombic crystal up to 7.301 GPa. They show that dispersive forces are more dominant than the hydrogen bonds, one of which becomes destabilising at higher pressure. Thermodynamic calculations estimating the relative stabilities of the two polymorphs prove inconclusive owing to improper treatment of dispersion interactions by Density Functional Theory calculations. The structural behaviour of cyclohexane in the crystalline (P21/c) and plastic phases (Fm3m) has been studied using neutron total scattering data and Reverse Monte Carlo (RMC) modelling. Atomistic models show that the molecules exhibit correlated motion as they prepare to undergo transformation on heating. Inclusion of I(t) data in the RMC refinements is shown to be important as when it is not accounted for, the RMC method is incapable of distinguishing the form of the disorder in the plastic phase. Molecular motion in this phase is shown to be correlated through the avoidance of short intermolecular D···D contacts. The ordered and disordered solid phases of oxalyl chloride (space groups P21/c and Pbca respectively) have been studied by neutron total scattering and modelled using a Reverse Monte Carlo approach. Atomistic models show that on heating, the atoms vibrate out of the plane of the molecule until 245 K where they show approximately isotropic vibration owing to reduced steric restriction. This may provide the molecules with the freedom they require to rotate and undergo the solidsolid transition. The onset of disorder has also been partially predicted by molecular dynamics simulations. RMC modelling does not provide satisfactory atomic configurations of the disordered solid phase due to an unrealistic distribution of intermolecular chlorine-chlorine contacts. This study presents an example of a flexible, 3-atom-type system that may be too complex for analysis by the RMC method.

The goal of this dissertation is to study the photophysics of suspensions of colloidal C₆₀ particles to determine if their nonlinear optical (NLO) response is superior in any way to benchmark NLO materials such as molecular solutions of C₆₀ and carbon black suspensions (CBS). C₆₀ in molecular form is known to exhibit strong reverse saturable absorption (RSA) and it is posited that colloidal particles composed of many C₆₀ molecules would maintain some degree of RSA behavior upon association, although some quenching is to be expected. CBS is known to have an NLO response that is dominated by nonlinear scattering resulting from a phase change due to heating of the carbon black particles by absorbed energy. Colloidal C₆₀ particles that are many nanometers in diameter are similar to CBS, so it is posited that they would also have a nonlinear scattering mechanism contributing to their NLO response. Three samples of C₆₀ colloids are characterized by several techniques, along with two carbon black suspensions and one molecular solution of C₆₀. Transmission electron microscopy is used to determine morphology. Femtosecond pump-probe spectroscopy is used to determine the absorption spectrum and the relaxation kinetics of the first excited singlet state. Nanosecond laser flash photolysis is used to determine the absorption spectrum and the relaxation kinetics of the first excited triplet state. Z-scan is used to determine triplet-triplet absorption cross-sections. An experiment is performed to determine the percentage of the input energy that is transmitted, scattered, or absorbed by each sample. Computer modeling is performed to compare the experimental results to theory. Results show that all materials that exhibit nonlinear scattering have a constant extinction coefficient in the nonlinear regime, implying a characteristic size for the scattering centers that is independent of input energy. Quenching processes in C₆₀ colloids are found to be morphology dependent, with more crystalline structures resulting in stronger quenching and less RSA. C₆₀ colloids with stronger RSA are found to result in less nonlinear scattering than strongly quenched colloids. Highly crystalline C₆₀ colloids were shown to have a stronger NLO response than the benchmark materials at medium to high energies.

This thesis explores the thermal expansion and high pressure behavior of some materials with the ReO₃ structure type. This structure is simple and has, in principle, all of the features necessary for negative thermal expansion (NTE) arising from the transverse thermal motion of the bridging anions and the coupled rotation of rigid units; however, ReO₃ itself only exhibits mild NTE across a narrow temperature range at low temperatures. ReO₃ is metallic because of a delocalized d-electron, and this may contribute to the lack of NTE in this material. The materials examined in this thesis are all based on d⁰ metal ions so that the observed thermal expansion behavior should arise from vibrational, rather than electronic, effects. In Chapter 2, the thermal expansion of scandium fluoride, ScF₃, is examined using a combination of in situ synchrotron X-ray and neutron variable temperature diffraction. ScF₃ retains the cubic ReO₃ structure across the entire temperature range examined (10-1600 K) and exhibits pronounced negative thermal expansion at low temperatures. The magnitude of NTE in this material is comparable to that of cubic ZrW₂O₈, which is perhaps the most widely studied NTE material, at room temperature and below. This is the first report of NTE in an ReO₃ type structure across a wide temperature range. Chapter 3 presents a comparison between titanium oxyfluoride, TiOF₂, and a vacancy containing titanium hydroxyoxyfluoride, Tiₓ(O/OH/F)₃. TiOF₂ was originally reported to adopt the cubic ReO₃ structure type under ambient conditions, therefore the initial goal for this study was to examine the thermal expansion of this material and determine if it displayed interesting behavior such as NTE. During the course of the study, it was discovered that the original synthetic method resulted in Tiₓ(O/OH/F)₃, which does adopt the cubic ReO₃ structure type. The chemical composition of the hydroxyoxyfluoride is highly dependent upon synthesis conditions and subsequent heat treatments. This material readily pyrohydrolyizes at low temperatures (~350 K). It was also observed that TiOF₂ does not adopt the cubic ReO₃ structure; at room temperature it adopts a rhombohedrally distorted variant of the ReO₃ structure. Positive thermal expansion was observed for TiOF₂ from 120 K through decomposition into TiO₂. At ~400 K, TiOF₂ undergoes a structural phase transition from rhombohedral to cubic symmetry. High pressure diffraction studies revealed a cubic to rhombohedral phase transition for Tiₓ(O/OH/F)₃ between 0.5-1 GPa. No phase transitions were observed for TiOF₂ on compression. In Chapter 4, an in situ variable pressure{temperature diffraction experiment examining the effects of pressure on the coefficients of thermal expansion (CTE) for ScF₃ and TaO₂F is presented. In the manufacture and use of composites, which is a possible application for low and NTE materials, stresses may be experienced. Pressure was observed to have a negligible effect on cubic ScF₃'s CTE; however, for TaO₂F the application of modest pressures, such as those that might be experienced in the manufacture or use of composites, has a major effect on its CTE. This effect is associated with a pressure-induced phase transition from cubic to rhombohedral symmetry upon compression. TaO₂F was prepared from the direct reaction of Ta₂O₅ with TaF₅ and from the digestion of Ta₂O₅ in hot hydro uoric acid. The effects of pressure on the two samples of TaO₂F were qualitatively similar. The slightly different properties for the samples are likely due to differences in their thermal history leading to differing arrangements of oxide and uoride in these disordered materials. In Chapter 5, the local structures of TiOF₂ and TaO₂F are examined using pair distribution functions (PDFs) obtained from X-ray total scattering experiments. In these materials, the anions (O/F) are disordered over the available anion positions. While traditional X-ray diffraction provides detailed information about the average structures of these materials, it is not suffcient to fully understand their thermal expansion. Fits of simple structural models to the low r portions of PDFs for these materials indicate the presence of geometrically distinct M{X{M (M = Ti, Ta; X = O, F) linkages, and a simple analysis of the TaO₂F variable temperature PDFs indicates that these distinct links respond differently to temperature.

Over the years `short-range order' (SRO), whereby the local atomic arrangement differs from that of a random distribution, has been used to explain physical phenomena such as thermodynamic discontinuities, increased strength, anomalous electrical resistivity and magnetic variations in a host of alloys. However, due mainly to experimental difficulties and the complexity of the calculations required for the analysis of diffuse scattering, such work has been largely abandoned and hence quantification and assessment of SRO is notably sparse in the literature. The recent development of reverse Monte-Carlo (RMC) methods for the analysis of total scattering data has opened a promising route for the assessment of a material's local environment and has already provided important insights into a host of complex chemical systems, including liquids, network glasses, nano-materials, functional oxides and metal organic frameworks. The work presented in this thesis focuses on the development of a new methodology for the analysis of local structural effects in metallic systems using total scattering, and the first systematic application to the study of alloys. The simulation of total scattering data from a range of model structures is used to show that the information content of total scattering functions, in particular the pair distribution function (PDF), is sufficiently high to allow the assessment of different types and degrees of short-range order. This is supported by a demonstration of how such orders can be quantified from large box models, produced by fitting total scattering data using the RMC algorithm, with the mathematical analyses outlined. This culminates in a proposed methodology for the analysis of SRO in alloys. Having developed this analytical methodology it is subsequently applied to a number of interesting alloy systems. To demonstrate the efficacy of this methodology it was first applied to the study of a sample of Cu$_{3}$Au - the classically cited case example of a system demonstrating SRO prior to an ordering transition. This experiment provides new insight into this well characterised transition, and also demonstrates the significance of data processing errors on the generation of artefacts in large box modelling. The technique is also applied to the study of the industrially important family of nickel superalloys, assessing ordering in the gamma-phase alloy Ni-Cr and the sublattice orderings occurring in L1$_{2}$ alloys. Next, the use of the technique for the analysis of local strains exhibited in a lattice is presented. A series of models is used to demonstrate how the PDF is expected to change under variations in local strain caused by increased concentration of atomic substitution and variation in atomic radii. This is subsequently used to study the characteristic high-entropy alloy (HEA) CrMnFeCoNi. Through analysis of the PDF, it is demonstrated that the level of local strain exhibited in this alloy is not significantly different from those of other related compositionally simpler alloys. This result is highly significant as it challenges one of the core principles of the field - that the lattices of HEAs are necessarily highly strained. Finally, the energetics of ordering reactions are briefly considered and used to justify some of the observed transformations presented in the earlier work. Together, the body of work in this thesis shows how the total scattering technique can be used to provide valuable insight into a host of interesting local phenomena occurring in alloy systems. It is hoped that this will open up a new field of study into these effects, and ultimately guide the creation of new alloys based on these structure-property relationships.

Using current technology, it is now possible to probe material at atomic length scales, increasing our fundamental understanding of material behavior and properties. Metastable β titanium alloys are a subset of titanium alloys with huge potential for the aerospace sector. However, they exhibit atomic transformations which, even after 60 years of research, are still disputed. For example, these alloys are strengthened using the ω phase, but the mechanism by which this phase forms and its stability are still in question. The aim of this PhD project was to investigate the strengthening of metastable Ti-15wt.%Mo by understanding the stability and transformation pathways which make the metastable β titanium alloy class unique. Athermal ω shares the same composition as the β matrix and is formed by rapid cooling from the β phase field. The classical theory of athermal ω formation is based upon a diffusion-less mechanism in which consecutive pairs of {111}β planes collapse together. However, latest high-resolution electron microscope observations have suggested chemical alterations occur as well, which give reason to challenge this classical formation mechanism. Two novel methods were explored to determine the nature of the ω phase: 1) electron imaging of thin material at different collection angles and 2) total X-ray scattering analysis of large volumes of material. Complementary techniques are invaluable since thin foil artefacts were identified. In particular, a new B2 structured phase in the Ti-15wt.%Mo alloy was observed only in thin electron transparent material. Experimental data from the two new methods were compared to simulations. It was found that a frozen phonon description of the ω structure provided a best fit in both scenarios. The results are therefore consistent with the classical theory of ω formation but the collapse of the {111}β planes towards the ω phase is not considered complete.

The local structure, atomic and magnetic structure correlated over a small length scale, of a material has a strong impact on material properties. Pair distribution function (PDF) analysis is a strong tool to investigate local structure and magnetism of this nature. This work outlines extensions to current one dimensional magnetic pair distribution functions (1D-mPDF) and the fitting of structures with symmetry breaking local atomic distortions. 1DmPDF analysis has been used to study local magnetic structure, but requires a rotational averaging of the correlations so directional information is lost, as in powder diffraction experiments. Three dimensional difference magnetic pair distribution function (3D-∆mPDF) analysis does not require this rotational averaging and preserves directional information. This is a useful tool in analyzing experimental data like single crystal neutron diffraction and studying locally anisoptropic magnetic structures. Here we present a technique and software tools to calculate the 3D-∆mPDF pattern of a given structure and give a brief analysis of the local magnetic structure of MnTe. Another problem in PDF analysis is the modeling of structures with symmetry breaking local atomic distortions. Symmetry-adapted distortion modes have been used for structural refinement in Rietveld refinement for at least 10 years; more more recently, this has also been applied to PDF data. We present here a detailed discussion of the use of symmetry-adapted modes for structural refinement using PDF data. We also outline new open-sourced software tools to apply this technique and show two analyses using symmetry-adapted structural modes.

Šiame darbe yra aptariama sklaidos matavimo sistema sukurta plačioje spektro srityje reikalingiems matavimams atlikti. Joje naudojami parametriniai šviesos generatoriai bei harmonikų generatoriai, kaupinami nanosekundinės trukmės impulsais, ir apibendrinami sklaidos tyrimai, atlikti įvairių tipų optinėse dangose ir netiesiniuose optiniuose kristaluose, naudojant derinamojo bangos ilgio lazerinius impulsus. Pirmą kartą buvo ištirti naujų netiesinėje optikoje perspektyvių LiInS2 ir LiInSe2 kristalų sklaidos nuostoliai infraraudonojoje srityje. Taip pat parodyta, kad koherentinės sklaidos tomografijos metodas, anksčiau taikytas puslaidininkinių kristalų tūriniams defektams tirti, yra tinkamas ir netiesinėje optikoje naudojamų kristalų kokybės tyrimams. / This work describes the system for the light scattering measurements in a wide spectral range, which uses the light parametric oscillators and harmonic generators pumped with a nanosecond pulses and summarizes the research in various types of coatings on optical components and inside nonlinear optical crystals. The total scattering losses for the first time were characterized in the infrared region for a new promising in nonlinear optics LiInS2 and LiInSe2 crystals. It was shown that the laser scattering tomography, previously used for investigation of volume defects in semiconductor crystals, can be applied in the nonlinear optical quality control.

Les matériaux poreux silicatés ont été mis à profit pour encapsuler différents types de molécules, clusters ou nano-objets fonctionnels, donnant lieu à des nanocomposites hybrides organiques-inorganiques à propriétés physiques, chimiques ou biologiques remarquables. Élucider l'organisation structurale à l'échelle moléculaire de tels nanocomposites est indispensable pour l'analyse et la compréhension des propriétés macroscopiques qui en découlent. Ainsi, les techniques de diffusion totale associées à la fois à l'analyse Debye et la Fonction de Distribution de Paires (PDF) sont des méthodes de choix pour la caractérisation des propriétés structurales de matériaux hybrides nano-structurés. Le principal objectif de ce travail consiste à l'utilisation des approches basées sur la diffusion totale de rayons X pour l'analyse structurale complète de molécules photoactives confinées dans des matrices silicatées amorphes avec différentes tailles de pores, afin d'étudier l'influence de l'organisation structurale sur les propriétés optiques et d'explorer également les limites de ces approches d'analyse. Nous avons étudié deux systèmes photoactifs. L'analyse structurale du premier complexe confiné, Na2[Fe(CN)5NO].2H2O (SNP), a été entreprise par une approche multi-échelle combinant la RMN du solide et l'analyse PDF. Cette approche a permis l'identification de la nature des espèces incorporées, l'arrangement des cations et des anions ainsi que la distinction des différentes phases existantes : molécules isolées et nanoparticules. Les analyses Debye et PDF sur le deuxième composé étudié, [NdCl2(H2O)6]Cl, montrent que l'organisation structurale du complexe confiné est différente de celle du matériau massif cristallin. De plus, les cations Nd3+ changent de coordination de 8 à 9 durant le processus d'imprégnation et adoptent ainsi un arrangement structural très similaire à celui en solution aqueuse. Cette modification structurale est en accord avec le changement des propriétés luminescentes de ce complexe / Silica xerogels are versatile host materials for the inclusion of molecules, clusters, or nano-objects yielding host-guest compounds with unique physical, chemical or biological properties. The knowledge of the structural organization of the guest within the host is crucial for the understanding of its properties. Total scattering methods, based on Debye function analysis (DFA) and Pair Distribution Function (PDF), have become powerful tools for structural characterization of nanostructured hybrid materials. The aim of this work is to use the X-ray total scattering method to obtain structural information on photoactive molecules embedded into amorphous silica hosts with different pore sizes, to correlate their structure with the optical properties, and to explore the limitations of the chosen method. Two different photoactive complexes have been investigated. In the first example, the combined PDF and NMR study on Na2[Fe(CN)5NO].2H2O (SNP) embedded into silica matrices allows to extract the nature of the inserted species: quasi-free isolated molecules can be distinguished from nanoparticles and in the former case a model for the arrangement of cation-anion can be proposed from the PDF analysis. In the second example, a luminescent Nd3+ complex, the PDF and DFA analysis reveal that the structural organization of the embedded Nd3+ complexes is different from that of the crystalline material. Furthermore, the Nd3+ cations change the coordination from 8 to 9 during the wet-impregnation doping and adopt very similar structural arrangement as in aqueous solution, which is in agreement with the observed change in the luminescence properties

Le travail présenté dans cette thèse concerne la mise en oeuvre numérique de techniques temporelles pour des applications en compatibilité électromagnétique (CEM) impulsionnelle, essentiellement pour des études en chambre réverbérante à brassage de modes (CRBM). Prenant le contre-pied des approches fréquentielles, adaptées par nature aux études de cavités résonantes, l’idée directrice de ce mémoire a été d’étudier des moyens temporels originaux d’investigation de CRBM en vue de proposer de nouveaux paradigmes pour la caractérisation d’équipements. Originellement développé en acoustique, le processus de retournement temporel (RT) récemment appliqué aux ondes électromagnétiques permet une focalisation spatiale et temporelle de ces dernières d’autant meilleur que le milieu de propagation est réverbérant. Les chambres réverbérantes (CR) sont ainsi des endroits idéaux pour l’application du processus de RT. Après une nécessaire étude des nombreux paramètres qui gouvernent ce dernier couplée à la définition de méthodologies numériques spécifiques, les applications du RT en CRBM sont exposées. En particulier, l’intérêt d’une focalisation sélective pour des tests en susceptibilité rayonnée est démontré. L’importance des coefficients d’absorption et de diffraction des équipements en CRBM justifie leur caractérisation précise et efficace. À cette fin, la mise en oeuvre d’un calcul temporel de section efficace totale de diffraction (TSCS en anglais) est détaillée. L’application de cette nouvelle technique à différentes formes de brasseurs de modes permet au final de confronter ces résultats avec ceux obtenus à l’aide de tests normatifs CEM. / The work presented in this thesis concerns the use of time techniques for impulsive ElectroMagnetic Compatibility (EMC) applications, mainly for Modes Stirred Reverberation Chamber (MSRC) studies. Contrary to approaches from frequency domain, obviously well-fitted for studies in resonant cavities, the main idea of this thesis was to study an original time method for MSRC investigation to propose new paradigms for equipment characterization. Originally developed in acoustics, the Time Reversal (TR) process recently applied to electromagnetic waves allows focusing it both in time and space. The process quality is even higher if the propagation environment is reverberant. Thus, the Reverberation Chambers (RC) are an ideal locations for TR implementation. After a study of parameters involved in the TR process coupled with the definition of specific numerical methods, the applications of TR in MSRC are exposed. In particular, the interest of selective focusing for radiated susceptibility tests is demonstrated. The importance of absorption and diffraction coefficients for MSRC equipment justifies their accurate and efficient characterization. To this end, the implementation of a temporal calculation of the Total Scattering Cross Section (TSCS) in RC is detailed. The application of this new technique to different forms of stirrers allows finally to face these results with those obtained from standard EMC test.