Pressboard, a high density cellulose-based material used for insulation in high voltage power transformers, exhibits stress relaxation during compressive loading. Investigating the micro-mechanical mechanisms responsible for the relaxation can lead to modifications of the production process to control the behaviour of the material. This investigation can be done using Synchrotron X-ray micro Computed Tomography which provides sufficient temporal and spatial resolutions to capture the stress relaxation process. In the present thesis, a compression rig for in-situ mechanical loading during X-ray micro Computed Tomography was designed and constructed. Local tomography scans with sub-micrometre resolution were obtained at the TOMCAT beamline at the Swiss Light Source, Paul Scherrer Institut, Switzerland. Several fibre segmentation techniques are analysed, together with Optical Flow and Digital Volume Correlation (DVC), methods used for estimating displacement, strain and velocity vector fields. Suitability of the tested methods is evaluated, and it is found that segmentation of individual fibres in a cellulose material of such a high density is probably not possible using currently available segmentation techniques. The movements during relaxation are measurable at the used resolution, and can be estimated using Optical Flow. Further work into correction of image shift due to rig movement between scans, as well as image artefact reduction should allow for measurement and comparisons of displacement during relaxation as well as DVC-computed strain measurements during compression, recreating earlier results.

Doctor of Philosophy / Department of Chemistry / Mark D. Hollingsworth / Urea inclusion compounds (UICs) are classic examples of nanoporous, host:guest materials in which the linear channels of the honeycomb structure of the urea host can include various types of long-chain compounds (the guests). By using synchrotron X-ray radiation sources, a deeper understanding of these materials is made possible through detailed structural studies. In particular, this dissertation describes a series of structural phase transitions that occur upon cooling two related UICs containing alkanedione guest molecules. UICs may be classified as either commensurate or incommensurate structures, depending on whether the repeat lengths of the host (c[subscript h]) and guest (c[subscript g]) along the channel axis are related by a small whole number ratio. Crystals of 2,8-nonanedione/urea and 2,11-dodecanedione/urea, which are incommensurate structures at room temperature, undergo "lock-in" phase transitions below room temperature to generate commensurate structures in which the guest repeat lengths are elongated. Upon nucleation and growth of these elongated, commensurate phases, other molecules in the same channels are compressed to give successively shorter guest repeat lengths. Further lock-in phase transitions give a multitude of commensurate and incommensurate phases during cooling. The crystal structures of two of these commensurate phases have been determined using synchrotron sources. The "self-compression" observed in these 1-D crystals serves as a paradigm for understanding solid-state reactions in three-dimensional crystals.

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.

This PhD project is focused on three lead-free ferroelectric solid solutions, which are specifically Na0.5Bi0.5TiO3-KNbO3(NBT-KN), Na0.5Bi0.5TiO3-NaNbO3(NBT-NN) and Na0.5Bi0.5TiO3-BaTiO3(NBT-BT), to evaluate the effects of composition, electric field and temperature on structural and electrical properties. Novel observations of both reversible and irreversible electric field-induced phase switching were made in both NBT-KN and NBT-NN ceramics. The NBT-KN solid solution is the primary focus of this thesis. All compositions were observed to be cubic in the as-sintered, unpoled state. However, a well-defined ferroelectric hysteresis P-E loop was obtained for compositions with low KN contents, indicating that an irreversible phase transition from a weak-polar relaxor ferroelectric (RF) to a long-range ordered metastable ferroelectric (FE) state had occurred during the measurement procedure. Both the unpoled and poled ceramic powders were examined using high resolution synchrotron XRD. For the poled state, a rhombohedral R3c structure was identified for compositions with low KN content, confirming the occurrence of the irreversible electric field-induced structural transformation from cubic to rhombohedral. In contrast, a cubic structure was retained for high KN contents, giving rise to reversible phase switching evidenced by constricted P-E hysteresis loops. Similar behaviour was observed for NBT-NN system. An 'in-situ' electric field poling experiment was conducted using high energy synchrotron XRD. In certain NBT-KN compositions the structural transformation, from cubic to mixed phase cubic+rhombohedral and finally single phase rhombohedral, occurred progressively with increasing cycles of a bipolar electric field. Similar behaviour was observed for NBT-NN compositions having low NN contents. Furthermore, the distributions of domain orientation and lattice strain over a range of orientations relative to the poling direction were determined for NBT-KN, NBT-NN and NBT-BT ceramics exhibiting the rhombohedral phase. By combining the structural information with the results of dielectric and ferroelectric measurements, a phase diagram was constructed to illustrate the influence of temperature and composition on the stability of the metastable ferroelectric and relaxor ferroelectric states for the NBT-KN system. Furthermore, the phase transition temperatures obtained from dielectric measurements were correlated with the ferroelectric and thermal depolarisation characteristics for each of the NBT-KN, NBT-NN and NBT-BT systems.

The development of a non-invasive method of visualizing gene expression in larger animals could revolutionize some aspects of gene research by opening up a wider variety of animal systems to explore; some of which may be better models of human systems. Presently, most gene expression studies employ Green Fluorescent Protein (GFP) transfected into the genome of the animal system. For larger animals, an x-ray equivalent of GFP would be desirable due to the high penetrating power of x-rays. A model gene modification system is to use the Sodium (Na) Iodide Symporter (NIS) which will cause the accumulation of iodine in cells which express the NIS. To non-invasively observe the dilute iodine accumulated by the cancer cells transfected with NIS in the head of small animals, such as a rat, two synchrotron-based imaging methods were studied: K-Edge Subtraction (KES) imaging and Fluorescence Subtraction Imaging (FSI).<p> KES needs wide monochromatic x-ray beams at two energies bracketing the K-edge of the contrast agent existing or injected in the tissues. The monochromatic beam in the synchrotron facility normally is prepared by a double crystal monochromator. The appearance of the azimuthal angle (tilt error) in the double crystal monochromator creates intensity variations across the imaging field. This misalignment was studied through another two synchrotron-based imaging methods, Diffraction Enhanced Imaging (DEI) and Multi-Image Radiography (MIR), which show this problem clearly in their processed images. The detailed analysis of the effect of the tilt error, how it affects the resulting images, and how to quantify such an error were presented in the thesis. A post processing method was implemented and the artifacts caused by the improper experimental settings were discussed.<p> With the wide monochromatic beam prepared by the double crystal monochromator, a sequence of KES experiments were done and the detection limit of KES was quantified at a projected amount of 17.5mM-cm iodine in a physical model of a rat head with a radiation dose of 2.65mGy. With the raster scan of the object relative to the monochromatic pencil beam, FSI was studied to obtain higher Signal to Noise Ratio (SNR) for local area and better detection limit compared to KES. The detection limit of FSI was measured as a projected amount of 2.5mM-cm iodine in the same physical rat head with a tolerable radiation dose of 24mGy. According to the comparison of these two imaging techniques with references to imaging time and area, radiation dose, spatial resolution, and SNR, it was concluded that these two imaging techniques can be used complementarily in imaging dilute contrast material. Due to the short imaging time and large imaging area, KES is used first to provide a global view of the object, locate the area of interest, do the preliminary diagnosis, and decide whether the further FSI is necessary. Due to its high SNR for the dilute sample, FSI can be used when the area of interest is known. The combination of these two imaging techniques will be very promising and powerful. To facilitate the comparison of KES and FSI, a quality factor was developed to evaluate the performance of the imaging system.<p> The measured detection limits in our experiments are far beyond the thyroidal iodine concentration of a rat (around 1mM). To further improve the performance of KES, a bent Laue crystal monochromator was designed to do the simultaneous iodine KES imaging which overcomes the artifacts in the iodine image caused by the temporal difference for a single set of images. The designed monochromator can provide two separated x-ray beams bracketing the K-edge of iodine at the same time with a very high spatial resolution which is only depends on the source size, a very high energy resolution which can almost compete with that of the double crystal monochromator, and an acceptable photon flux.

The marginal glass-forming alloys have attracted much attention due to unique products of devitrification with a very high number density of nuclei up to 10^23 m^-3. Among these alloy systems, utmost interest is given to Al-RE and Al-TM-RE alloys with excellent lightweight mechanical (fracture strength close to 1 GPa) and chemical properties attributed to the presence of an extremely high density of nanocrystals embedded in an amorphous matrix. Classical nucleation theory fails in explaining this abnormal nucleation behavior, several other mechanisms have been proposed / however, there is still no agreement on the exact nucleation mechanism. Al-Tb system was investigated in liquid and solid amorphous states with a collective study of ab-initio MD and RMC simulations and state of art X-rays and e-beam techniques. Regions of pure Al clusters in the solid and liquid states were detected with the sizes extending up to 1-2 nm length. Al clusters interconnecting regions lead to formation of RE rich MRO structure which gave rise to the pre-peak in S(Q)-Q data in liquid and solid states. Specimens having MRO were crystallized within a controlled atmosphere and temperature and investigated using a combined study of TEM, HRTEM, SEM, XRD and DSC. HRTEM investigations and JMA results indicated different mechanism of nucleation. Therefore the kinetics of highly populated nuclei formation was found too complicated to be explained by well-known JMA approach. Mechanical tests were applied to determine the effects of morphology and populations of nanocrystals embedded in amorphous matrix. The tensile tests and the subsequent fracture surface analysis indicated brittle type of failure and the formation of shear bands, respectively. Relatively high hardness and tensile strength were detected by nanocrystallization.

The development of a non-invasive method of visualizing gene expression in larger animals could revolutionize some aspects of gene research by opening up a wider variety of animal systems to explore; some of which may be better models of human systems. Presently, most gene expression studies employ Green Fluorescent Protein (GFP) transfected into the genome of the animal system. For larger animals, an x-ray equivalent of GFP would be desirable due to the high penetrating power of x-rays. A model gene modification system is to use the Sodium (Na) Iodide Symporter (NIS) which will cause the accumulation of iodine in cells which express the NIS. To non-invasively observe the dilute iodine accumulated by the cancer cells transfected with NIS in the head of small animals, such as a rat, two synchrotron-based imaging methods were studied: K-Edge Subtraction (KES) imaging and Fluorescence Subtraction Imaging (FSI).<p> KES needs wide monochromatic x-ray beams at two energies bracketing the K-edge of the contrast agent existing or injected in the tissues. The monochromatic beam in the synchrotron facility normally is prepared by a double crystal monochromator. The appearance of the azimuthal angle (tilt error) in the double crystal monochromator creates intensity variations across the imaging field. This misalignment was studied through another two synchrotron-based imaging methods, Diffraction Enhanced Imaging (DEI) and Multi-Image Radiography (MIR), which show this problem clearly in their processed images. The detailed analysis of the effect of the tilt error, how it affects the resulting images, and how to quantify such an error were presented in the thesis. A post processing method was implemented and the artifacts caused by the improper experimental settings were discussed.<p> With the wide monochromatic beam prepared by the double crystal monochromator, a sequence of KES experiments were done and the detection limit of KES was quantified at a projected amount of 17.5mM-cm iodine in a physical model of a rat head with a radiation dose of 2.65mGy. With the raster scan of the object relative to the monochromatic pencil beam, FSI was studied to obtain higher Signal to Noise Ratio (SNR) for local area and better detection limit compared to KES. The detection limit of FSI was measured as a projected amount of 2.5mM-cm iodine in the same physical rat head with a tolerable radiation dose of 24mGy. According to the comparison of these two imaging techniques with references to imaging time and area, radiation dose, spatial resolution, and SNR, it was concluded that these two imaging techniques can be used complementarily in imaging dilute contrast material. Due to the short imaging time and large imaging area, KES is used first to provide a global view of the object, locate the area of interest, do the preliminary diagnosis, and decide whether the further FSI is necessary. Due to its high SNR for the dilute sample, FSI can be used when the area of interest is known. The combination of these two imaging techniques will be very promising and powerful. To facilitate the comparison of KES and FSI, a quality factor was developed to evaluate the performance of the imaging system.<p> The measured detection limits in our experiments are far beyond the thyroidal iodine concentration of a rat (around 1mM). To further improve the performance of KES, a bent Laue crystal monochromator was designed to do the simultaneous iodine KES imaging which overcomes the artifacts in the iodine image caused by the temporal difference for a single set of images. The designed monochromator can provide two separated x-ray beams bracketing the K-edge of iodine at the same time with a very high spatial resolution which is only depends on the source size, a very high energy resolution which can almost compete with that of the double crystal monochromator, and an acceptable photon flux.

This research aims to model the microstructure development of Si-containing bainitic free-machining steel, including allotriomorphic ferrite, idiomorphic ferrite, pearlite, Widmanstatten ferrite, bainite and martensite. The effect of recalescence has been included to give a better estimation of the cooling curve under natural cooling conditions. A model for estimating retained austenite size distribution in the carbide-free bainitic microstructure has been developed. Manganese sulphide particles are used in the free-machining steel to break chips during machining; its effect on the prior austenite grain size has been investigated, taking account of the sulphide shape. The theories of all the major solid state phase transformations involved in steel are reviewed in chapter 2. The theory of the simultaneous transformation model is presented in chapter 3.uu A recalescence model dealing with the heat of reaction has been developed in chapter 5 for bar-shaped products. The model is based on the integration of a heat transfer model, considering latent heat generation, into the simultaneous transformation framework. It has been found that latent heat can greatly affect the transformation, especially in the case of pearlite and Widmanstatten ferrite. Chapter 6 presents the model for estimating the size distribution of retained austenite regions. The model builds on the random division of an austenite grain by bainite sheaves, which means the sizes of the two new compartments generated by the division of an austenite grain by a bainite sheaf are allocated randomly. The next compartment to be divided is also chosen at random. Good agreement between prediction and experiment has been achieved for high carbon carbide-free bainitic microstructures. The transition temperature from upper to lower bainite is modelled in chapter 7. The model compares the time required for decarburising a supersaturated bainitic ferrite platelet and that for cementite precipitation within the ferrite platelet. Manganese, silicon and chromium are considered in the model. It is suggested that carbon and manganese favour lower bainite, whereas silicon promotes upper bainite. The effect of manganese sulphide particles on austenite grain boundary motion has been studied in chapter 8. These rod-shaped particles span many austenite grains; the result shows that the long rod-shaped particles are more effective in pinning the austenite grain boundary than spheres of the same volume, or even strings of identical spheres with the same total volume. Experimental work is presented in chapters 9 and 10. In situ synchrotron X-ray study of the bainite transformation reveals that the distribution of carbon in the residual austenite becomes heterogeneous as transformation progresses. Low carbon regions transform preferentially into martensite during cooling after isothermal bainite transformation. The partitioning of carbon was found to lag behind the bainite transformation; more time is needed as the transformation temperature is reduced. Tetragonality was not observed in either the bainitic ferrite or martensite, because the carbon content of the alloy is relatively low, and the Zener ordering temperature is below the bainite and martensite transformation temperature. No significant difference was observed in the kinetics of bainite transformation between the high sulphur and low sulphur steel.

The thesis first introduces the topic of nuclear energy and provides a brief section on plant familiarisation, after which zirconium nuclear fuel cladding is explained, and an in-depth literature review is presented on the in-service degradation of this component from hydriding. The concept of synchrotron X-ray diffraction is elucidated, and examples of its use are given, relevant to the topic of this work. The experimental section discusses an initial quantification of the Zircaloy-4 material used throughout the present work, and documents in minutia the process of collecting and analysing in-situ synchrotron X-ray diffraction data. The experimental campaign discussed within involved a series of consecutive thermal cycles designed to investigate the redistribution of hydrogen as a function of thermal and concentration gradients; the kinetics of precipitation during isothermal dwells at reactor relevant temperatures; and the evolution of strain in the matrix and hydride during these dwells. As an alternative style thesis, these three topics are separated into three independent proposed manuscripts, produced in a format ready for publication. The diffusion and redistribution paper observes localised enrichment and depletion that occurs as a function of time and temperature, investigating the flux of hydrogen that results from concentration and thermal gradients, and introduces the concept of hydrogen trapping. The second manuscript documents evidence of the rate limiting kinetics for hydride precipitation seen at elevated temperatures, and describes a model for nucleation, developed to support the experimentally produced results. The final manuscript investigates the nature of the strains that evolve in the matrix and hydride phases during precipitation and growth, highlighting slow-strain rate relaxation in both phases and examining the constraining effect that the matrix has on the hydride precipitates. Lastly, the themes from each of the three manuscripts are drawn together in a final conclusion, after which further experimental analysis that is to be performed as part of this experimental campaign is outlined.

Foreign object damage (FOD) refers to the damage that generally takes place in aero engine fans and compressor blades, due to the ingestion of hard particles/debris during aeroplane take-off, taxiing, or landing. Such damage can reduce the fatigue life expectancy of the turbine engine components by 50%. Residual stresses and small microcracks induced by the high speed FOD impacts are two root causes that result in premature failure of these components. One way to mitigate the FOD related fatigue failure is to induce deep compressive residual stress into the surface. Among the available techniques that can induce such compressive residual stress, laser shock peening (LSP) has been found to be beneficial in improving the fatigue strength. In this study aerofoil-shaped Ti-6Al-4V leading edge specimens were laser shock peened. Subsequently, FOD was introduced onto the leading edge specimen through ballistic impacts of a cube edge at angles of 0° and 45° to the leading edge. The effect of foreign object damage (FOD) on the pre-existing compressive residual stress field associated with the laser shock peening (LSP), and its change upon solely low cycle fatigue (LCF) as well as combined low and high cycle fatigue cycling has been studied. The residual stress distribution and their redistribution upon fatigue cycling were mapped around the FOD notch, using synchrotron X-ray radiation and the contour method. The results suggest that under both impact angles, the FOD event superimposed a significant additional residual stress on top of the pre-existing stress associated with the LSP process. It has been observed that the FOD notch created by 45° impact was asymmetric in shape, and had differential notch depth between the entry and exit side. However, FOD damage that is created at 0° impact appeared as a sharp V notch. A higher amount of residual stresses were produced under 0° impact condition than at 45°. It has been found even though the FOD induced residual stresses relax, residual stresses due to LSP treatment remain highly stable even in the worst condition where a 7 mm long crack was grown from a 45° notch. The plastic zone sizes ahead of a crack tip was estimated for both 0° and 45° FOD impact, and the fatigue crack growth rates are predicted utilizing the measured residual stress distribution.