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Ferroelectric and ferromagnetic materials have been extensively studied for potential applications in sensors, actuators and transducers. Highly electrostrictive (1-x)Pb(Mg_1/3Nb_2/3)-xPbTiO₃ (PMN-xPT) and highly magnetostrictive Fe-xat.%Ga are two such novel materials. Both materials systems have chemical disorders and structural inhomogeneity on a microscale, giving rise to an interesting diversity of crystal structures and novel macroscopic physical properties, which are dependent on thermal and electrical histories of the crystals. In this thesis, I have to investigated phase transformations in these two systems under thermal and field (electric/magnetic) histories, using x-ray and neutron scattering techniques. In PMN-xPT crystals, x-ray and neutron diffractions were performed along the different crystallographic orientations and for different thermal and electrical histories. Various intermediate monoclinic (M) phases that structurally “bridge” the rhombohedral (R) and tetragonal (T) ones across a morphtropic phase boundary (MPB) have been observed. Systematic investigations of (001) and (110) electric (E) field-temperature phase diagrams of PMN-xPT crystals have demonstrated that the phase stability of PMN-xPT crystals is quite fragile: depending not only on modest changes in E (≤ 0.5kV/cm), but also on the direction along which E is applied. Structurally bridging monoclinic Mc or orthorhombic (O) phases were found to be associated with the T phase, whereas the monoclinic Ma or Mb phases bridged the Cubic (C) and R ones. In addition, neutron inelastic scattering was performed on PMN-0.32PT to study the dynamic origin of the MPB. Data were obtained between 100 and 600 K under various E applied along the cubic [001] direction. The lowest frequency zone-center, transverse optic phonon was strongly damped and softened over a wide temperature range, but started to recover on cooling into the T phase at the Curie temperature (TC). Comparisons of my findings with prior ones for PMN and PMN-0.60PT suggest that the temperature dependence and energy scales of the soft mode dynamics in PMN-xPT are independent of PT concentration below the MPB, and that the MPB may be defined in composition space x when TC matches the temperature at which the soft mode frequency begins to recover. High-resolution x-ray studies then showed that the C–T phase boundary shifted to higher temperatures under E by an expected amount within the MPB region: suggesting an unusual instability within the apparently cubic phase at the MPB. In Fe-xat.%Ga alloys, the addition of Ga atoms into the b.c.c. α-Fe phase also results in diversity of crystal structures and structural inhomogeneity, which are likely the source of its unusual magneto-elastic properties. I have carefully investigated decomposition of Fe-xat.%Ga alloys subjected to different thermal treatments by x-ray and neutron diffraction for 12 < x < 25. Quenching was found to suppress the formation of a DO₃ structure in favor of a high-temperature disordered bcc (A2) one. By contrast, annealing produced a two-phase mixture of A2 + DO₃ for 14 < x < 20 and a fully DO₃ phase for x = 25. A splitting of the (2 0 0) and (0 0 2) Bragg peaks observed along the respective transverse directions indicated that Fe-xat.%Ga –crystals' are composed of several crystal grain orientations (or texture structures), which are slightly tilted with respect to each other. In order to investigate the local structural distortions and heterogeneities, neutron diffuse scattering was performed on Fe-x%Ga alloys for different thermal conditions. Diffuse scattering around a (100) superlattice reflection was found for 14 < x < 22 in the furnace-cooled condition, indicative of short-range ordered DO₃ nanoprecipitates in an A2 matrix. This diffuse intensity had an asymmetric radial contour and an off-centering. Analysis (x=19) revealed two broad peaks with c/a–1.2: indicating that the DO₃-like nanoprecipitates are not cubic, but rather of lower symmetry with a large elastic strain. The strongest diffuse scattering was observed for x=19, which correspondingly had maximum magnetostriction: indicating a structural origin for enhanced magnetostriction. / Ph. D.

The viscoelastic behavior of concrete, nearly completely attributable to changes in properties in the cement paste, is an ongoing area of research with the objective of avoiding unpredictable response and potentially failure of concrete structures. This research explores the elastic and viscoelastic response in cement paste beams using relaxation testing, with and without strain reversals in the load history. It was seen that strain reversal imparts significant changes in mechanical response, retarding load relaxation. Companion beams were tested for chemical composition at varying depths in the beam section and the results were compared to those of control specimens not subject to stress. Results indicate significant variations in composition implying that stress accelerates the hydration process. The reasons behind the acceleration are discussed and incorporated into a preliminary solidification-dissolution model for beam relaxation. The model, though in need of improvement through further research, shows promise in potentially predicting relaxation in cement paste and by extension, in concrete structures. / Ph. D.

No / Caffeine/oxalic acid 2:1 cocrystal exhibited superior stability to humidity over caffeine, but compressional behavior is not studied yet. To compare compressional properties of caffeine/oxalic acid 2:1 cocrystal obtained by different cocrystallization techniques. Cocrystal was obtained by solvent precipitation and ultrasound assisted solution cocrystallization (USSC) and characterized by X-ray powder diffraction and scanning electron microscopy. Compaction study was carried out at different compaction forces. Compact crushing strength, thickness and elastic recovery were determined. Compaction was in order, caffeine > solvent precipitation cocrystal > USSC cocrystal. Caffeine exhibited sticking and lamination, where solvent precipitation compacts showed advantage. Caffeine and solvent precipitation compacts showed sudden drop in compactability, higher elastic recovery with severe lamination at 20,000 N. This was due to overcompaction. Crystal habit of two cocrystal products was same, but USSC cocrystals were difficult to compact. Uniform needle shaped USSC cocrystals must be difficult to orient in different direction and fracture during compression. Elastic recovery of USSC cocrystals was also more compared to other powders indicating less fracture and poor bonding between particles resulting in poor compaction. Cocrystal formation did not improve compressional property of caffeine. Cocrystals exposed to different crystallization environments in two techniques may have resulted in generation of different surface properties presenting different compressional properties.

The hydride oxides LiLnEuH2−xO2 (Ln=La, Ce, Pr, Nd and Sm) were synthesized by reaction of the lanthanide sesquioxides with europium monoxide, europium dihydride and lithium hydride under inert conditions at 750 °C as black powders. They crystallize in the tetragonal K2NiF4-type structure (space group: I4/mmm) with a mixed Ln3+/Eu2+ occupation. The crystal structures of the europium representatives LiLaEuH2−xO2 and LiLaEuD2−xO2 were analyzed by powder neutron diffraction data at short wavelengths (λ=70 pm). Hydrogen (deuterium) and oxygen atoms occupy distinct crystallographic sites with considerable vacancy concentrations on the hydrogen positions (a=363.80(8) pm, c=1323.3(3) pm, c/a=3.637 for LiLaEuH1.26(4)O2 and a=363.43(5) pm, c=1321.6(2) pm, c/a=3.636 for LiLaEuD1.41(2)O2). Moving from the mixed Ln/Eu occupation in LiLnEuH2O2 to Ln=Eu2+, we obtained the mixed-anionic phase LiEu2H3O, which crystallizes in the same structure type with a=370.04(2) pm, c=1317.32(8) pm and c/a=3.560.

Growing environmental concerns, coupled with increasing regulatory restrictions, are requiring industries to develop non-lead-based compositions of ferroelectric and piezoelectric materials. These materials—now widely used in sensors, actuators, and transducers—are for the most part lead-based compounds such as Pb(Zr,Ti)O₃ (PZT). Indeed, PZT represents the dominant market share for use in these technologies. Moreover, next generation compounds, which include Pb(Mg_1/3Nb_2/3)O₃-xat%PbTiO₃ (PMN-x%PT) crystals with ultrahigh piezo-/electromechanical properties, are also Pb-based systems and thus are problematic for meeting more restrictive environmental standards. As alternative, Pb-free ferroelectrics such as NBT-derived single crystals represent viable next-generation materials for use in ferro-/piezoelectric applications. Development of these types of NBT-based crystals has made important advancements in the last decade. In fact, the performances of NBT-based materials are beginning to approach the properties of the widely used commercial PZT ceramic material. Nonetheless, additional studies are needed before it being able to compete with PMN-x%PT and PZN-x%PT crystals in next-generation applications. As a new type of piezoelectric material, much remains to be learned about Pb-free piezoelectric crystals. For instance, in addition to enhancing our understanding the nature of the piezoelectric third-rank tensor coefficients such as d₃₃ and d₁₅, a thorough knowledge of the Curie temperature, leakage current, and electromechanical properties is also essential for increasing the applications potential of these crystals. As detailed herein, multiple dopants may have to be incorporated into NBT to modify its microstructure and properties to meet these specific requirements, which may further complicate its chemical structure-property relationships. This study, therefore, was designed to investigate the heterogeneous structure of NBT-based single crystals, using x-ray diffraction, transmission electron microscopy, and neutron inelastic scattering, with the goal of investigating the mechanism coupling of morphotropic phase boundary (MPB) and the maximum property responses in A-site disordered perovskite Pb-free piezoelectric systems. Using the framework of polar nanoregions and adaptive phase theory, I sought to determine how the nanostructure of these single crystals change with temperature and composition—and how these factors impact its properties. Diffuse scattering, domain morphology, and phonon dispersions were used to investigate both the static and dynamic properties of these heterogeneous structures. / Ph. D. / Growing environmental concerns, coupled with increasing regulatory restrictions, are requiring industries to develop non-lead-based compositions of ferroelectric and piezoelectric materials. These materials—now widely used in sensors, actuators, and transducers—are for the most part lead-based compounds such as Pb(Zr,Ti)O₃ (PZT). Indeed, PZT represents the dominant market share for use in these technologies. Moreover, next generation compounds, which include Pb(Mg_1/3Nb_2/3)O₃-xat%PbTiO₃ (PMN-x%PT) crystals with ultrahigh piezo- /electromechanical properties, are also Pb-based systems and thus are problematic for meeting more restrictive environmental standards. As alternative, Pb-free ferroelectrics such as (Na_1/2Bi_1/2)TiO₃ (NBT) -derived single crystals represent viable next-generation materials for use in ferro-/piezoelectric applications. Development of these types of NBT-based crystals has made important advancements in the last decade. In fact, the performances of NBT-based materials are beginning to approach the properties of the widely used commercial PZT ceramic material. Nonetheless, additional studies are needed before it being able to compete with PMN-x%PT and PZN-x%PT crystals in next-generation applications. As a new type of piezoelectric material, much remains to be learned about Pb-free piezoelectric single crystals. In addition to enhancing our understanding the nature of the piezoelectric properties, increasing the applications potential of these crystals is also essential. And these specific requirements from different applications further push the researchers to find a more effective model to lead the piezoelectric single crystals growth as well as developments. This study, therefore, was designed to investigate the unique microstructure of NBTbased single crystals, using x-ray diffraction, transmission electron microscopy, and neutron inelastic scattering, with the goal of investigating the mechanism coupling between the chemical compositions and the maximum property responses in these specific Pb-free piezoelectric systems. Using the framework of an advanced microstructure description model, I sought to determine how the nanostructure of these single crystals change with temperature and composition—and how these factors impact its properties. The results from different experiment methods also successfully supported each other and brought new perspectives to the Pb-free material researches.

The interplay between different self-organized electronically ordered states and their relation to unconventional electronic properties like superconductivity constitutes one of the most exciting challenges of modern condensed matter physics. In the present thesis this issue is thoroughly investigated for the prototypical layered material 1T-TaS2 both experimentally and theoretically. At first the static charge density wave order in 1T-TaS2 is investigated as a function of pressure and temperature by means of X-ray diffraction. These data indeed reveal that the superconductivity in this material coexists with an inhomogeneous charge density wave on a macroscopic scale in real space. This result is fundamentally different from a previously proposed separation of superconducting and insulating regions in real space. Furthermore, the X-ray diffraction data uncover the important role of interlayer correlations in 1T-TaS2. Based on the detailed insights into the charge density wave structure obtained by the X-ray diffraction experiments, density functional theory models are deduced in order to describe the electronic structure of 1T-TaS2 in the second part of this thesis. As opposed to most previous studies, these calculations take the three-dimensional character of the charge density wave into account. Indeed the electronic structure calculations uncover complex orbital textures, which are interwoven with the charge density wave order and cause dramatic differences in the electronic structure depending on the alignment of the orbitals between neighboring layers. Furthermore, it is demonstrated that these orbital-mediated effects provide a route to drive semiconductor-to-metal transitions with technologically pertinent gaps and on ultrafast timescales. These results are particularly relevant for the ongoing development of novel, miniaturized and ultrafast devices based on layered transition metal dichalcogenides. The discovery of orbital textures also helps to explain a number of long-standing puzzles concerning the electronic self-organization in 1T-TaS2 : the ultrafast response to optical excitations, the high sensitivity to pressure as well as a mysterious commensurate phase that is commonly thought to be a special phase a so-called “Mott phase” and that is not found in any other isostructural modification.

The thesis reports improvements in the characterization techniques for stress and texture in crystalline materials by x-ray and neutron powder diffraction. Furthermore, advances are made in texture evolution modelling and validation against experimental observations. In the beginning, the fundamental assumption of diffraction strain analysis is numerically examined and verified, namely, that the lattice parameter value determined from fitting the diffraction pattern is equal to the average lattice parameter within the gauge volume. Next, the task of shear strain determination from powder diffraction measurements is addressed. A method is developed and implemented for the complete 2D strain tensor determination from the multi-directional energy-dispersive x-ray diffraction patterns. The method not only offers a way to evaluate the shear strain, but also provides a better overall strain averaging approach. Rotation and translation of sample and/or detectors in powder diffraction mode can effectively increase the pole figure coverage and thus the accuracy of texture determination. However, the movements also introduce uncertainties and aberrations into data analysis due to the changes in the diffraction volume and transmitted intensity. In order to overcome these problems, accurate <strong>single exposure</strong> texture characterization techniques are proposed based on several different powder diffraction setups. Numerical analyses are carried out to prove that any simple texture in cubic polycrystals can be effectively determined using single exposure Debye-Scherrer diffraction pattern analysis. Several experiments are reported on collecting Debye-Scherrer diffraction patterns, multi-directional energy-dispersive x-ray diffraction patterns and multi-directional TOF neutron setup. Efficient data processing procedures of the diffraction patterns for ODF determination are presented. Crystal plasticity finite element models are developed to model the texture evolution in polycrystalline engineering samples during manufacturing. In the present thesis, quantitative measures extracted from orientation distribution function are employed to make precise comparison between the model and experiment. Unlike the simple uni-axial compression and tension considered in the literature, in the present thesis the complex texture evolution during linear friction welding is modelled as a sequence of different shear deformations.

Human dental tissues are fascinating nano-structured hierarchical materials that combine organic and mineral phases in an intricate and ingenious way to obtain remarkable combinations of mechanical strength, thermal endurance, wear resistance and chemical stability. Attempts to imitate and emulate this performance have been made since time immemorial, in order to provide replacement (e.g. in dental prosthodontics) or to develop artificial materials with similar characteristics (e.g. light armour). The key objectives of the present project are to understand the structure-property relationships that underlie the integrity of natural materials, human dental tissues in particular, and the multi-scale architecture of mineralized tissues and its evolution under thermal treatment and mechanical loading. The final objective is to derive ideas for designing and manufacturing novel artificial materials serving biomimetic purposes. The objectives are achieved using the combination of a range of characterization techniques, with particular attention paid to the synchrotron X-ray scattering (Small- and Wide-Angle X-ray Scattering, SAXS and WAXS) and imaging techniques (Micro Computed Tomography), as well as microscopy techniques such as Environmental Scanning Electron Microscopy (ESEM), Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM). Mechanical properties were characterized by nanoindentation and photoelasticity; and thermal analysis was carried out via thermogravimetric analysis (TGA). Experimental observations were critically examined and matched by advanced numerical simulation of the tissue under thermal-mechanical loading. SAXS and WAXS provided the initial basis for elucidating the structure-property relationships in human dentine and enamel through in situ experimentation. Four principal types of experiment were used to examine the thermal and mechanical behaviour of the hierarchical structure of human dental tissue and contributed to the Chapters of this thesis: (i) In situ elastic strain evolution under loading within the hydroxyapatite (HAp) in both dentine and enamel. An improved multi-scale Eshelby inclusion model was proposed taking into account the two-level hierarchical structure, and was validated against the experimental strain evaluation data. The achieved agreement indicates that the multi-scale model accurately reflects the structural arrangement of human dental tissue and its response to applied forces. (ii) The morphology of the dentine-enamel junction (DEJ) was examined by a range of techniques, including X-ray imaging and diffraction. The transition of mechanical properties across the DEJ was evaluated by the high resolution mapping and in situ compression measurement, followed by a brief description of the thermal behaviour of DEJ. The results show that DEJ is a narrow band of material with graded structure and mechanical properties, rather than a discrete interface. (iii) Further investigation regarding the thermo-mechanical structure-property relationships in human dental tissues was carried out by nanoindentation mapping of the nano-mechanical properties in ex situ thermally treated dental tissues. (iv) In order to understand the details of the thermal behaviour, in situ heat treatment was carried out on both human dental tissues and synthetic HAp crystallites. For the first time the in situ ultrastructural alteration of natural and synthetic HAp crystallites was captured in these experiments. The results presented in this thesis contribute to the fundamental understanding of the structure-property integrity mechanisms of natural materials, human dental tissues in particular. These results were reported in several first author publications in peer-reviewed journals, conference proceedings, and a book chapter.