Synthetic Retinoids

Chapter one is split into three sections, providing general overviews of synthetic retinoids and their biology, Pd-catalysed C-C bond forming reactions and transition metal-catalysed borylation of aromatic and vinylic C-H bonds, respectively. Chapter two details the application of sequential Ir-catalysed aromatic C-H borylations, Pd-catalysed C-C bond forming reactions and Rh-catalysed vinylic C-H borylations for the stereo-controlled synthesis of stilbene-based TTNPB retinoids. Chapter three details the application of Ir-catalysed aromatic C-H borylations, Sonogashira cross-couplings and Suzuki-Miyaura cross-couplings for the synthesis of tolan-, and biaryl-based retinoids. Chapter four details the development and applications of new RhI catalyst precursors for the dehydrogenative borylation of unactivated olefins. The dehydrogenative borylation reactions were utilised in one-pot, single solvent syntheses of 2-arylindenes from indene and arylhalides through C-H borylation and subsequent Suzuki-Miyaura cross-couplings

External proton beam analysis of plasma facing materials for magnetic confinement fusion applications

Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Nuclear Science and Engineering, 2009.Cataloged from PDF version of thesis.Includes bibliographical references (p. 135-137).A 1.7MV tandem accelerator was reconstructed and refurbished for this thesis and for surface science applications at the Cambridge laboratory for accelerator study of surfaces (CLASS). At CLASS, an external proton beam set-up was designed and constructed to perform in-air ion beam analysis on plasma facing divertor tiles from the Alcator C-Mod tokamak. A Particle Induced Gamma Emission (PIGE) technique was developed for boron depth profiling. In addition, Particle Induced X-ray Emission (PIXE) was implemented and used for a comprehensive study of poloidal tungsten migration in the C-Mod divertor. A novel PIGE technique was developed for measuring depth profiles of boron deposition on C-Mod tile surfaces. Boron (B) is regularly deposited on C-Mod tiles to improve plasma performance. This technique is therefore useful for studying the interaction of B with plasma facing components (PFC) to develop a better understanding of the effects of B in Alcator C-Mod. The technique involves taking multiple PIGE yield measurements of a single sample while changing the beams path-length through the air to vary the energy of the beam incident on the sample. A numerical code was written to deconvolve boron depth profiles from these gamma yields by exploiting the sharply peaked cross section of the '0B(p, ay)7Be resonance reaction. Simulations demonstrate that this code converges to the expected results. Preliminary measurements of C-Mod tiles were performed using the external proton beam to induce 429keV gamma emission from the 10B(p, ay)7Be reaction which was measured, using a Sodium Iodide (Nal) scintillation detector.(cont.) These preliminary results verified the feasibility of this technique. An external PIXE ion beam analysis study was conducted to measure campaign integrated, poloidal tungsten (W) migration patterns in the C-Mod divertor. Eroded W from a toroidally continuous row of W tiles near the outer divertor strike point was used as a tracer to map W erosion and redeposition onto a set of Mo and W tiles that covered the poloidal extent of the C-Mod lower divertor which were removed following the 2008 experimental campaign. These tiles were examined for W using external Particle Induced X-ray emission (X-PIXE) analysis; a highly W sensitive ion beam analysis (IBA) technique in which a characteristic x-ray emission is induced from a material surface as it is exposed to an external proton beam, produced by the electrostatic tandem accelerator. With a set of systematic high spacial resolution measurements (~ 3mm resolution), complete poloidal profiles of W redeposition have been constructed. These profiles indicate W transport and redeposition of up to 1.5 x 102 atoms/m 2 (14nm of equivalent W thickness) in several regions including the outer divertor, the inner divertor, and inside the private flux region. In addition to the W results, PIXE allowed for indirect measurements of spatially resolved boron profiles and direct measurements of titanium, chromium, and iron. A comprehensive description and explanation these PIGE and PIXE studies and their results are presented.by Harold Salvadore Barnard.S.M

A new mini-triaxial cell for combined high-pressure and high-temperature in situ synchrotron X-ray microtomography experiments up to 400°C and 24 MPa.

A new experimental triaxial cell for in situ synchrotron X-ray micro-computed tomography aimed at imaging small samples of (6 mm × 19 mm) at high temperatures (up to 400°C) and pressures (up to 24 MPa confining) is presented. The system has flow-through capabilities, independent axial and radial pressure control, and has been developed and tested at the 8.3.2. beamline at the Advanced Light Source. The characteristics of this new experimental rig are described, along with the challenges, mainly concerning the combination of X-ray transparency with vessel strength at high temperature, and solutions found during the development stage. An experiment involving oil shale pyrolysis under subsurface conditions, highlighting the importance of a device able to operate in this pressure and temperature range, is also introduced. The availability of this cell enables an unprecedented range of experiments in the Earth Sciences, with a special focus on subsurface geothermal processes

On the reduced damage tolerance of fine-grained nuclear graphite at elevated temperatures using in situ 4D tomographic imaging

Fine-grained nuclear graphite is one of the key structural materials for high temperature gas-cooled reactors as well as several Generation IV nuclear fission reactor designs. However, its deformation and fracture behaviours at elevated temperatures are not well understood. In light of this, the current study focused on investigating the flexural strength and fracture toughness of two fine-grained graphite (SNG623 and T220) using real-time X-ray computed micro-tomography imaging at room temperature, 750°C and 1100°C. Specifically, nonlinear-elastic fracture mechanics-based JR(Δa) R-curves at these temperatures were presented with evolution of damage and failure micro-mechanisms, local strain distributions and J-integral fracture analysis, purveying notable findings. Compared to the coarser-grained Gilsocarbon nuclear graphites used in the current UK Advanced Gas-cooled Reactors (AGRs), these modern fine-grained graphites display deficient fracture resistance in the form of far less stable crack growth prior to catastrophic fracture and reduced failure strain at 1100 °C. Moreover, their elevation in strength and toughness at high temperatures is remarkably lower than that of Gilsocarbon graphite. Based on in situ high-temperature Raman spectroscopy mapping, we believe that one of the major causes of this behaviour can be attributed to the smaller magnitude of ‘frozen-in’ residual stress relaxed at elevated temperatures compared with Gilsocarbon graphite

Initial results of tests of depth markers as a surface diagnostic for fusion devices

The Accelerator-Based In Situ Materials Surveillance (AIMS) diagnostic was developed to perform in situ ion beam analysis (IBA) on Alcator C-Mod in August 2012 to study divertor surfaces between shots. These results were limited to studying low-Z surface properties, because the Coulomb barrier precludes nuclear reactions between high-Z elements and the ∼1 MeV AIMS deuteron beam. In order to measure the high-Z erosion, a technique using deuteron-induced gamma emission and a low-Z depth marker is being developed. To determine the depth of the marker while eliminating some uncertainty due to beam and detector parameters, the energy dependence of the ratio of two gamma yields produced from the same depth marker will be used to determine the ion beam energy loss in the surface, and thus the thickness of the high-Z surface. This paper presents the results of initial trials of using an implanted depth marker layer with a deuteron beam and the method of ratios. First tests of a lithium depth marker proved unsuccessful due to the production of conflicting gamma peaks, among other issues. However, successful trials with a boron depth marker show that it is possible to measure the depth of the marker layer with the method of gamma yield ratios.United States. Department of Energy. (grant number DE-FG02-94ER54235, cooperative agreement number DEFC02-99ER54512

Damage tolerance of nuclear graphite at elevated temperatures

Nuclear-grade graphite is a critically important high-temperature structural material for current and potentially next generation of fission reactors worldwide. It is imperative to understand its damage-tolerant behaviour and to discern the mechanisms of damage evolution under in-service conditions. Here we perform in situ mechanical testing with synchrotron X-ray computed micro-tomography at temperatures between ambient and 1,000 °C on a nuclear-grade Gilsocarbon graphite.We find that both the strength and fracture toughness of this graphite are improved at elevated temperature. Whereas this behaviour is consistent with observations of the closure of microcracks formed parallel to the covalent-sp2-bonded graphene layers at higher temperatures, which accommodate the more than tenfold larger thermal expansion perpendicular to these layers, we attribute the elevation in strength and toughness primarily to changes in the residual stress state at 800–1,000 °C, specifically to the reduction in significant levels of residual tensile stresses in the graphite that are ‘frozen-in’ following processing

X-ray Micro-Tomography of Ablative Heat Shield Materials

X-ray micro-tomography is a non-destructive characterization technique that allows imaging of materials structures with voxel sizes in the micrometer range. This level of resolution makes the technique very attractive for imaging porous ablators used in hypersonic entry systems. Besides providing a high fidelity description of the material architecture, micro-tomography enables computations of bulk material properties and simulations of micro-scale phenomena. This presentation provides an overview of a collaborative effort between NASA Ames Research Center and Lawrence Berkeley National Laboratory, aimed at developing micro-tomography experiments and simulations for porous ablative materials. Measurements are carried using x-rays from the Advanced Light Source at Berkeley Lab on different classes of ablative materials used in NASA entry systems. Challenges, strengths and limitations of the technique for imaging materials such as lightweight carbon-phenolic systems and woven textiles are discussed. Computational tools developed to perform numerical simulations based on micro-tomography are described. These enable computations of material properties such as permeability, thermal and radiative conductivity, tortuosity and other parameters that are used in ablator response models. Finally, we present the design of environmental cells that enable imaging materials under simulated operational conditions, such as high temperature, mechanical loads and oxidizing atmospheres.Keywords: Micro-tomography, Porous media, Ablatio

X-Ray Micro-Tomography Applied to Nasa's Materials Research: Heat Shields, Parachutes and Asteroids

X-ray micro-tomography is used to support the research on materials carried out at NASA Ames Research Center. The technique is applied to a variety of applications, including the ability to characterize heat shield materials for planetary entry, to study the Earth- impacting asteroids, and to improve broadcloths of spacecraft parachutes. From micro-tomography images, relevant morphological and transport properties are determined and validated against experimental data