京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20189号 / 理博第4274号 / 新制||理||1614(附属図書館) / 京都大学大学院理学研究科地球惑星科学専攻 / (主査)准教授 三宅 亮, 教授 平島 崇男, 教授 山 明 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

<p>Alzheimer’s disease (AD) is a progressive neurodegenerative disease affecting more than 6 million individuals in the United States and more than 50 million worldwide. Currently, there exists no cure for AD and there are very few treatments to limit disease progression. Understanding the mechanisms through which AD develops and the risk factors associated with disease onset and progression is imperative in diagnosis and treatment of AD. Metal dysregulation has been implicated in disease pathogenesis through a number of mechanisms. Toxic heavy metals, such as lead (Pb) and mercury (Hg) are known to have deleterious effects on the central nervous system (CNS) and have been shown to increase AD pathology in animal models. However, there are significant knowledge gaps on how these metals deposit in human and animal brains at the microscopic scale, how they interact with essential metals in brain, and the relation of heavy metal exposure and AD. In this project, we aimed to investigate the distribution of heavy metals and their interactions with essential elements in transgenic mouse and human brain tissue models. We report, for the first time, Pb distribution and its co-deposition with Se in mouse brains following subchronic Pb exposure, Hg distribution and its co-deposition with Se in post-mortem AD and no cognitive impairment (NCI) brains, and the association of Pb, Hg, and other metals in these brains. All the data were obtained using synchrotron x-ray fluorescence (XRF), a powerful technique that allows for localization and quantification of multiple biological elements, as well as heavy metals, with a high spatial resolution and low detection limit. The work will shed light on the role essential metals, especially Se, play in neurotoxicity of Pb and Hg, and pave the way for potential future directions on heavy metal exposure and neurodegeneration.</p>

Inkjet printing is a versatile manufacturing method with applications beyond its traditional application in graphics and text printing, particularly in structural and functional materials. This thesis aims to enhance the understanding of DOD inkjet printing processes by investigating the behaviour of solvent mixtures and nanoparticle suspensions to identify the key parameters affecting drop ejection, drying and stacking processes. Drop ejection and flight were investigated with two modes of inkjet printheads, using a range of fluids formulated from solvent mixtures and characterised by the dimensionless Z number. The printable range was found to be 1.17 smaller or equal to Z smaller or equal to 36.76 for a 10 pl (21.5 micro metre diameter) shear-mode Dimatix printhead. However, with an 80 micro metre diameter squeeze-mode MicroFab printhead, the range was found to be narrower with 4.02 smaller or equal to Z smaller or equal to 16.2. However, both printheads were found to show a printable range of Weber number with 0.4 &lt;We &lt;20. Weber number is determined by the drop velocity and hence the actuating pulse. When designing inks for future printing work, not only the fluid properties, but also the pulse voltages need to be considered. The drop stacking and solidification processes of drops containing nano ZrO2 particles were investigated to enhance the understanding of drop drying and drop/drop interactions. In-situ synchrotron X-ray radiography provides a promising method to track the time-evolved solid segregation within printed drops during drying. Both the initial contact angle and substrate temperature during printing strongly influence the drying process and the final dried deposit shape. The drops were first pinned and then there was a slight sliding of the three-phase contact line. Drops were deformed by the stacking of overprinted drops when printed on Kapton tapes and silicon wafer surfaces, but not on glass slides due to the small contact angle of water on glass slides. Crack-like defects were found at the edge of the final dried stacking structures. The coffee stain effects within a single inkjet printed droplet and the 3D structures before and after sintering were investigated to find out the influence of ink properties, printing parameters and substrate temperature on inkjet printed structures. It was found coffee staining was more obvious at high substrate temperatures. When adding 25 vol% ethylene glycol (EG) or 5 wt% polyethylene glycol (PEG), the coffee stain effect is reduced or eliminated under room temperature drying. X-ray tomography has been demonstrated as a valuable tool for the characterization of 3D printed objects and defects that form during their manufacture. Defects were characterised as microvoids or large-scale crack-like defects. The majority of the microvoids revealed are associated with mechanisms and processes within a single drop, e.g. segregation during dryings such as the formation of coffee stains or coffee rings. The size or distribution of microvoids can be controlled by changing the ink formulation, with higher PEG content inks showing lower concentrations of microvoids.

Magma-crust interaction in magma reservoirs and conduits is a crucial process during magma evolution and ascent. This interaction is recorded by crustal xenoliths that frequently show partial melting, inflation and disintegration textures. Frothy xenoliths are widespread in volcanic deposits from all types of geological settings and indicate crustal gas liberation. To unravel the observed phenomena of frothy xenolith formation we experimentally simulated the behaviour of crustal lithologies in volcanic conduits. We subjected various sedimentary lithologies to elevated temperature (maximum 916 °C) and pressure (maximum 160 MPa) in closed-system autoclaves. Experimental conditions were held constant between 24h and 5 days. Controlled decompression to atmospheric pressure then simulated xenolith ascent. Pressure release was a function of temperature decline in our setup. Temperature lapse rate proceeded exponentially; the mean rate during the first 30 minutes was 17.8 ˚C/min and the mean decompression rate during the same interval was 3.0 MPa/min, eventually reaching room temperature after approximately 5.5 hours of slow cooling. The experimental products have been analysed for internal textures by synchrotron X-ray μ-CT at a resolution of 3.4 – 9 microns/pixel. This method permits visualisation and quantification of vesicle volumes, -networks and-connectivity in 3D without destroying the sample. Experimental products closely reproduced textures of natural frothy xenoliths in 3D and define anevolutionary sequence from partial melting to gas exsolution and bubble nucleation that eventually leads to the development of three-dimensional bubble networks. Experimental P-T-t conditions and especially rock lithology proved decisive for degassing behaviour and ensuing bubble nucleation during decompression. Progressive bubble nucleation leads to subsequent bubble coalescence to form interconnected bubble networks. This, in turn, enables efficient gas liberation and release. Our results attest to significant potential of even very common crustal rock types to release volatiles and develop interconnected bubble networks upon heating and decompression in magmatic systems. Crustal volatile input from xenoliths affects magma rheology and may drive magmas to sudden explosive eruptions. Our experiments offer insight into the mechanism of how such crustal volatile liberation is accomplished.

Most urinary tract infections in humans and dogs are caused by uropathogenic strains of , and increasing antimicrobial resistance among these pathogens has created a need for a novel approach to therapy. Bacterial iron uptake and metabolism are potential targets for novel antimicrobial therapy, as iron is a limiting factor in . growth during infection. As a trivalent metal of similar atomic size to iron (III), gallium can interact with a wide variety of biomolecules that normally contain or interact with iron. Gallium compounds disrupt bacterial iron metabolism, are known to accumulate at sites of infection and inflammation in mammals, exert antimicrobial activity against multiple bacterial pathogens in vitro, and may be good candidates as novel antimicrobial drugs. We assessed the suitability of orally administered gallium maltolate as a potential new antimicrobial therapy for urinary tract infections by evaluating its distribution into the bladder, its activity against uropathogenic . in vitro, and its pharmacokinetics and efficacy in a mouse cystitis model. Using a novel application of synchrotron-based analytical methods, we confirmed the distribution of gallium to the bladder mucosa and characterized the relationship between iron and gallium distribution in the bladder. In vitro experiments with human and canine uropathogenic . isolates demonstrated that gallium maltolate exerts antimicrobial effects in a time-dependent, bacteriostatic manner. Minimum inhibitory concentrations ranged from 0.144 µmol/mL to >9.20 µmol/mL with a median of 1.15 µmol/mL. Isolates resistant to ampicillin, ciprofloxacin, or with decreased susceptibility to cephalothin were susceptible to the antimicrobial activity of gallium maltolate, suggesting that resistance to conventional antimicrobials does not predict resistance to gallium maltolate. Pharmacokinetic studies in healthy mice and in a mouse model of urinary tract infection confirmed that gallium is absorbed into systemic circulation after oral administration of gallium maltolate. Gallium is slowly eliminated from the body, with a trend toward longer terminal half-lives in blood and bladder for infected mice relative to healthy mice. This study did not reveal any statistically significant effect of infection status on maximum blood gallium concentrations (4.46 nmol/mL, 95% confidence interval 2.75 nmol/mL – 6.18 nmol/mL and 4.80 nmol/mL, 95% confidence interval 2.53 nmol/mL – 7.06 nmol/mL in healthy and infected mice, respectively) or total gallium exposure in blood and kidney as represented by area under the concentration vs. time curves. Gallium exposure in the bladder was significantly greater for mice with urinary tract infections than for healthy mice. The investigation of gallium distribution within tissues represented a novel application of synchrotron-based analytical techniques to antimicrobial pharmacokinetics. Prior to analysing tissue samples, a library of x-ray absorption spectra was assembled for gallium compounds in both the hard and soft x-ray ranges. The suitability of hard x-ray fluorescence imaging and scanning and transmission x-ray microscopy for localizing and speciating trace elements in tissues was subsequently assessed. Of these methods, only hard x-ray microprobe analysis was well-suited to the analysis and was successfully used for this application. This approach confirmed that gallium arrives at the bladder mucosa after oral administration of gallium maltolate. Furthermore, comparison of iron and gallium distribution within the bladder mucosa indicated that these elements are similarly but not identically distributed and that they do not significantly inhibit one another’s distribution. This finding suggests that gallium may be distributed in part via pathways that do not involve iron. Despite the favorable distribution characteristics of gallium and the persistence of gallium in target tissues following the oral administration of gallium maltolate, its efficacy in a mouse model of urinary tract infection was disappointing. In this study, no statistically significant difference was detected between gallium maltolate, ciprofloxacin and sham treatments in their ability to eliminate bacteria in the urinary tracts. The failure of ciprofloxacin treatment to render bladder tissue culture-negative for an organism that is classified as ciprofloxacin-susceptible in vitro is consistent with observations from other research groups. The similar lack of efficacy observed for gallium maltolate may be related to the large gap between minimum inhibitory concentrations observed in vitro and gallium concentrations observed in tissues from treated mice, but may also be related to the small study size if the effect size of gallium maltolate treatment is small. Given the magnitude of the difference between tissue concentrations and minimum inhibitory concentrations, it may not be possible to increase the dose sufficiently to achieve therapeutic concentrations without causing toxicity. While the results of these experiments suggest that orally administered gallium maltolate may not be a reasonable antimicrobial drug candidate for treating urinary tract infections caused by uropathogenic . , it may be useful for other applications. Other bacterial pathogens may be more susceptible to the antimicrobial effects of gallium maltolate, and local or topical administration could produce much higher concentrations than we observed following oral administration. Continued development of the synchrotron-based analytical techniques used in these experiments could provide new and important opportunities to investigate antimicrobial distribution and metabolism within cells and tissues, particularly for metal-based drugs.

Ce travail résume les résultats d'études de la croissance in situ de nanofils (NFs) SiGe par UHV-CVD à l'aide des techniques de diffusion et de diffraction des rayons X (RX) synchrotron sur la ligne de lumière BM32 à l'ESRF.Les conditions d'élaboration de NFs Si, Ge, SiGe dans notre bâti sont d'abord présentées. Les études in situ à l'aide de RX durant la croissance sont ensuite décrites. La longueur des NFs, leur taille, leur espacement, leur facetage ainsi que l'angle conique sont déterminés en temps réel. Des changements de forme de la goutte liquide aussi ont été clairement observés dans les premiers stades de la croissance. Une phase AuGe métastable à l'interface catalyseur-substrat a été identifiée. Sa formation pourrait être décisive pour la croissance sous-eutectique de NFs de Ge.La relaxation des contraintes dans des NFs coeur-coquille de Si-Ge est ensuite présentée. La composition et la déformation ont été déterminée in situ par diffusion anomale des RX, en fonction de la quantité de Ge deposé et de la durée du recuit. L'influence de la taille des NFs et de la température de croissance de la coquille ont aussi été étudiée.Enfin, des résultats sur la courbure in situ de NFs sont présentés. La courbure est induite par le dépôt d'un second matériau sur un côté des NFs. La déformation et la contrainte ont été déterminées par une combinaison de suivi de la position d'un pic de Bragg, de simulation et d'ajustement de l'intensité, et de calculs d'élasticité classiques. La courbure induite par le dépôt de Ge à 220°C est principalement déterminée par la contrainte de désaccord de maille, qui évolue presque linéairement avec l'épaisseur du film Ge. La courbure induite par le dépôt de Ge à la température ambiante (TA) se trouve principalement déterminée par la contrainte de surface, qui évolue progressivement de la tension à la compression pour une épaisseur de Ge plus grande. Pour le suivi de courbure en temps réel, nous avons mise au point une technique de mesures stationnaires avec un détecteur 2D. Elle a permis de mettre en évidence plusieurs changements de signe lors de dépôts d'Au et Ge à TA. / This work summarizes the progress made on the BM32 beamline at the ESRF over the past 4 years since the launch of the CVD project, which was aimed at studying the in situ growth of SiGe nanowires, using synchrotron X-ray scattering techniques.Results on the growth of Si and Ge NWs are first presented. The NWs length, size, spacing, facet morphology and their tapering angle are determined in real time with X-ray techniques. Special attention was paid to the very early stage of growth where changes in the shape of the AuSi liquid droplet were clearly observed. We also found clues indicating the presence of a metastable AuGe phase at the catalyst-substrate interface, the formation of which may be crucial to the sub-eutectic growth of Ge NWs.Strain relaxation in Si-Ge core-shell NWs is presented next. The composition and strain were determined in situ as a function of the Ge overgrowth amount and of the annealing time, using anomalous X-ray scattering techniques. Their dependence on the NW size and on the shell growth temperature was also studied.Finally, results on the in situ bending of as-grown NWs are shown. The bending was induced by depositing a second material on one side of the NWs. The strain and stress were determined by a combination of Bragg peak tracking, intensity simulation plus fitting and classic elasticity calculations. The bending induced by Ge deposition at 220°C is found to be mainly driven by the misfit stress, which scales almost linearly with Ge film thickness. On the other hand, the bending induced by Ge deposition at RT is found to be mainly driven by the surface stress, which evolves gradually from tensile to compressive for larger Ge thickness. A new technique was also devised which makes it possible to follow qualitatively the bending process. The NWs were seen dancing back and forth with increasing amount of deposition as revealed by real time stationary measurements with a 2D detector.

Prussian blue (PB) and Prussian blue analogues (PBAs) are compounds with potential applications in a large variety of fields such as gas storage, poison antidotes, electrochromism, electrochemistry and molecular magnets. The compounds are easy to synthesize, cheap, environmentally friendly and have been pursued for both fundamental research and industrial purposes. Despite the multifunctionality of PB and PBAs, they have complicated compositions, which are largely dependent on the synthesis methods and storage conditions. Thus, performing investigations on such compounds with defined composition, stoichiometry and crystal structure is essential. This thesis has focused on synthesis and detailed structure characterization of copper hexacyanoferrate (CuHCF) via X-ray powder diffraction (XRPD), neutron powder diffraction (NPD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), inductively coupled plasma-optical emission spectroscopy (ICP-OES), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), Mössbauer spectroscopy, extended X-ray absorption fine structure (EXAFS), infrared (IR) and Raman techniques. In addition, kinetics of thermal dehydration process, CO2 adsorption and CO2 adsorption kinetics were investigated. Moreover, in operando synchrotron X-ray diffraction experiments were performed to gain insight into the structure-electrochemistry relationships in an aqueous CuHCF/Zn battery during operation. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Manuscript. Paper 5: Manuscript.</p>

The relationship between microstructure and mechanical properties of semicrystalline polymer materials has been a hot topic since many years in materials science and engineering. Isotactic polypropylene (iPP) is frequently used as a model material, due to its good mechanical properties and wide applications. In the past few years, numerous studies have been performed in the field of structural evolution during deformation. Previous results revealed that phase transition from crystal to mesophase happens in the crystal scale, lamellae orientation and fragmentation occurs in the lamellae scale, and even cavitation behavior exists in the larger scale. Although abundant work has been done, some problems remain under debate, for instance the relationship between lamellae deformation and cavitation behavior, the role of phase transition on the void formation, et al. In this study, well defined microstructure of iPP is obtained by annealing or adding nucleating agent. Afterward, the structural evolution under three types of mechanical load modes (including uniaxial stretching, creep, and stress relaxation) is in-situ monitored by synchrotron X-ray scattering. During uniaxial stretching, we revealed, for the first time, how lamellae deformation occurs in the time scales of elastic deformation, intra-lamellar slip, and melting-recrystallization, separated by three critical strains which were only rarely found to be influenced by annealing. Strain I (a Hencky strain value of 0.1) marks the end of elastic deformation and the onset of intra-lamellar slip. Strain II (a Hencky strain value of 0.45) signifies the start of the recrystallization process, from where the long period in the stretching direction begins to decrease from its maximum and the polymer chains in the crystal start to orient along the stretching direction. The energy required by melting arises from the friction between the fragmented lamellae. Strain III (a Hencky strain value of 0.95) denotes the end of the recrystallization process. Beyond the strain of 0.95, the long period and the crystal size remain nearly unchanged. During further stretching, the extension of the polymer chains anchored by lamellae triggers the strain hardening behavior. On the other hand, annealing significantly decreases the critical strain for voids formation and increases the voids number, but restricts the void size. For those samples annealed at a temperature lower than 90 oC, voids are formed between strain II and strain III. The voids are oriented in the stretching direction once they are formed. For those samples annealed at a temperature higher than 105 oC, voids are formed between strain I and strain II. The voids are initially oriented with their longitudinal axis perpendicular to the stretching direction and then transferred along stretching direction via voids coalescence. Additionally, the formation of voids influences neither the critical strains for lamellae deformation, nor the final long period, the orientation of polymer chains or the crystal size. β-iPP is a kind of metastable phase which can be induced only under special condition. By adjusting the morphology of N,N'-dicyclohexyl-2,6-naphthalene dicarboxamide (NJS) through self-assembly, the relative content of β-iPP (Kβ) is successfully controlled, under the condition that the weight content of NJS in the composite keeps at 0.3 wt. %. The microstructural evolution of the iPP/NJS composites with different Kβ during uniaxial stretching is studied. The results show that a higher Kβ could increase the number of the voids. However, the size of the voids is similar regardless of the NJS morphology. The β-α phase transition takes place after voids formation. During intralamellar and inter-lamellar slip, no obvious polymer chains orientation can be found for α-iPP. In the strain range of 0.1~0.6, the c-axis of the β-iPP crystal tends to orient perpendicular to the stretching direction due to lamellae twisting, which is a unique deformation mode of β-iPP lamellae. And the lamellae twisting are proposed to be responsible for the intense voids formation of the composite with higher Kβ. During creep, the evolution of the long period can be divided into four stages (primary creep, transition stage, secondary creep, and tertiary creep). This fits quite well with the macroscopic displacement and strain evolution. In primary creep, the long period along loading direction (L_p^∥) increases with time due to the stretching of amorphous phase, whereas the long period perpendicular to loading direction (L_p^⊥) decreases slightly. In secondary creep, strain increases linearly with time. Both L_p^∥ and L_p^⊥ exhibit the same tendency with strain. The increase of the long period is caused by lamellae thickening, which is a kind of cooperative motion of molecular chains with their neighbors onto the lamellae surface. The increasing rate of L_p^∥ is larger than that of L_p^⊥, indicating that the orientation of molecular chains along loading direction decreases the energy barrier for the cooperative motion. In tertiary creep, strain grows dramatically within a limited time. The lamellae are tilted and rotated, and then disaggregated. In addition, fibrillary structure is formed during lamellae breaking. The length of the fibrillary structure increases from 364 nm to 497 nm but its width stays at 102 nm as creep time increases. During stress relaxation, the local deformation behavior of the long period is affine with the macroscopic stress relaxation. However, the evolution of the crystal orientation and the void size lag behind the macroscopic stress relaxation. The decrease of the long period is mainly caused by the relaxation of the strained polymer chains in the amorphous phase. The retardation of the evolution of the crystal orientation is probably caused by the phase transition from stable α-iPP to metastable mesomorphic-iPP. By phase transition, the highly oriented α-iPP is transferred to weakly oriented mesomorphic-iPP. Due to the fact that the void is confined by the network of the strained polymer chains where lamellae blocks serve as the physical anchoring points, the phase transition contributes greatly to the viscoplastic deformation of the network. Consequently, the evolution of the voids size shows a similar trend with that of the phase transition. With this thesis, we gained a deeper insight into the relationship between structure and properties of semicrystalline polymers. The current study will not only benefit the understanding of polymer materials science but also serve as guidance for the processing of semicrystalline polymers for engineering applications.:1 Introduction 1 1.1 Isotactic polypropylene (iPP) 1 1.1.1 Chain structure of PP 1 1.1.2 Crystal forms of iPP 2 1.1.3 Lamellae of iPP 4 1.1.4 The morphology of the supra-structure of iPP 4 1.2 Structural evolution during deformation 5 1.2.1 Deformation process of semicrystalline polymers 5 1.2.2 Cavitation behavior of semicrystalline polymers 7 1.3 Synchrotron X-ray scattering 9 1.3.1 X-ray and its sources 9 1.3.2 The interaction between X-rays and objects 11 1.3.3 Wide angle X-ray scattering 12 1.3.4 Small angle X-ray scattering 13 2 Motivation and objectives 15 3 Samples preparation and basic characterization 17 3.1 Materials and samples preparation 17 3.1.1 Preparation of iPP films with single layer of spherulites and transcrystalline regions 17 3.1.2 Preparation of iPP plates crystallized with different thermal histories 17 3.1.3 Preparation of iPP/NJS plates with different morphologies of NJS 18 3.1.4 Preparation of microinjection molded iPP/NJS sample 18 3.2 Characterization 18 3.2.1 Differential scanning calorimetry (DSC) 18 3.2.2 Dynamic mechanical analysis (DMA) 19 3.2.3 Scanning electron microscopy (SEM) 19 3.2.4 Polarized optical microscopy (POM) 20 3.2.5 Rheology test 20 3.2.6 Gel Permeation Chromatography (GPC) 21 3.2.7 In situ synchrotron X-ray scattering measurements 21 3.2.8 X-ray scattering pattern processing and calculation 24 4 Microstructure characterization in a single iPP spherulite by synchrotron microfocus wide angle X-ray scattering 29 4.1 Introduction 30 4.2 The nucleation efficiency of the carbon fiber on iPP 31 4.3 Morphology of iPP spherulites and transcrystalline region 32 4.4 Defining of the position of the carbon fiber 33 4.5 Microstructure studies of the spherulite 34 4.5.1 Crystallinity in the spherulite 35 4.5.2 The ratio between “daughter” lamellae and “mother” lamellae in the spherulite 36 4.5.3 The orientation of the crystal axis in the spherulite 37 4.6 Conclusion 39 5 Influence of annealing on the mechanical αc-relaxation of iPP: a study from the intermediate phase perspective 41 5.1 Introduction 42 5.2 Crystal form of water cooled and annealed iPP 44 5.3 Microstructure of iPP with different thermal history 45 5.4 Melting behavior of iPP with different thermal history 50 5.5 Mechanical relaxation behavior of iPP with different thermal history 52 5.6 Conclusion 57 6 Critical strains for lamellae deformation and cavitation during uniaxial stretching of annealed iPP 59 6.1 Introduction 60 6.2 The true stress-strain curves of iPP uniaxial stretched at 75 oC 61 6.3 In Situ SAXS and WAXS Results 63 6.3.1 Synchronize mechanical test and in-situ SAXS/WAXS measurement 66 6.4 Lamellae deformation 67 6.4.1 The evolution of the long period 67 6.4.2 The evolution of the crystal size 69 6.4.3 The orientation of the c-axis of the crystal 71 6.4.4 The evolution of the crystallinity 72 6.5 Cavitation behavior 74 6.5.1 The onset strain of the voids formation and the voids direction transition 74 6.5.2 The evolution of the voids size 75 6.5.3 The scattering invariant (Q) of the voids 76 6.5.4 The morphology of voids 77 6.6 Final discussion 79 6.7 Conclusion 82 7 Accelerating shear-induced crystallization and enhancing crystal orientation of iPP by controlling the morphology of N,N'-dicyclohexyl-2,6-naphthalene dicarboxamide 83 7.1 Introduction 84 7.2 The self-assembly process of N,N'-dicyclohexyl-2,6-naphthalene dicarboxamide 85 7.3 Rheological behavior 88 7.3.1 Frequency sweep test 88 7.3.2 Strain sweep test 88 7.3.3 Steady-state shear test 89 7.4 Shear-induced crystallization 91 7.4.1 Crystallization kinetics studied by rheological method 91 7.4.2 In-situ SAXS measurement 93 7.4.3 Microstructure of iPP after shear-induced crystallization 96 7.4.4 The morphology of the sample 98 7.4.5 The crystallization mechanism 99 7.5 Conclusion 100 8 Influence of nucleating agent self-assembly on structural evolution of iPP during uniaxial stretching 101 8.1 Introduction 102 8.2 The morphology of the NJS in the compression molded iPP 103 8.3 Microstructure of iPP with different NJS morphologies 104 8.4 In-situ SAXS results 105 8.4.1 Cavitation behavior 107 8.4.2 Evolution of the long period 110 8.5 In-situ WAXS results 111 8.5.1 The β-α phase transition behavior 112 8.5.2 The orientation of the crystal 115 8.6 Conclusion 117 9 Microstructural evolution of iPP during creep: an in-situ study by synchrotron SAXS 119 9.1 Introduction 120 9.2 The creep curve 121 9.3 In-situ SAXS results 123 9.3.1 Evolution of long period and domain thickness 125 9.3.2 Lamellae tilting and rotation 128 9.3.3 Lamellae orientation and fibrillary structure formation 129 9.4 Conclusions 132 10 Microstructural evolution of iPP during stress relaxation 133 10.1 Introduction 134 10.1.1 The structural evolution during stress relaxation at 60 oC 135 10.1.2 The structural evolution during stress relaxation at 90 oC 140 10.2 Conclusion 145 11 Conclusion and outlook 146 12 References 148 13 Appendix 158 13.1 List of symbols and abbreviations 158 13.2 List of figures and tables 163 13.3 List of publications 171 14 Acknowledgements 173 15 Eidesstattliche Erklärung 175

No description available.

Zirconium alloys are widely used in the nuclear industry because of their high strength, good corrosion resistance and low neutron absorption cross-section. However, zirconium has strong affinity for hydrogen, which may lead to hydrogen concentration build-up over time during a corrosion reaction when exposed to water. Hydrogen stays in solution at higher temperature but precipitates as zirconium hydrides at ambient temperatures. The formation of zirconium hydrides is considered to be a major cause of embrittlement, in particular as a key step in the mechanism of delayed hydride cracking. Despite the fact that zirconium hydrides have been studied for several decades, the basic nature and mechanisms of hydride formation, transformation and exact structure are not yet fully understood. In order to find the answer to some of these problems, the precipitation and dissolution of hydrides in commercial grade Zr powder were monitored in real time with high resolution synchrotron and neutron radiations, and the whole pattern crystal structure analysis, using Rietveld and Pawley refinements, were performed. For the first time all commonly reported zirconium hydride phases and complete reversible transformation between two different Zr-hydride phases were recorded with a single setup and their phase transformation type have been analyzed. In addition, the preparation route of controversial γ-zirconium hydride (ZrH), its crystal structure and formation mechanisms are also discussed. / <p>Note: The papers are not included in the fulltext online.</p><p>Paper II and III in thesis as manuscript, paper II with title "The phase transformation between the δ and ε Zr hydrides"</p>