Tomography of crystal defects in the electron microscope was first attempted in 2005 by the author and colleagues. This thesis further develops the technique, using a variety of samples and methods. Use of a more optimised, commercial tomographic reconstruction program on the original GaN weak beam dark-field (WBDF) tilt series gave a finer reconstruction with lower background, line width 10-20 nm. Four WBDF tilt series were obtained of a microcrack surrounded by dislocations in a sample of indented silicon, tilt axes parallel to g = 220, 220, 400 and 040. Moiré fringes in the defect impaired alignment and reconstruction. The effect on reconstruction of moiré fringe motion with tilt was simulated, resulting in an array of rods, not a flat plane. Dislocations in a TiAl alloy were reconstructed from WBDF images with no thickness contours, giving an exceptionally clear reconstruction. The effect of misalignment of the tilt axis with systematic row g(ng) was assessed by simulating tilt series with diffraction condition variation across the tilt range of Δn = 0, 1 and 2. Misalignment changed the inclination of the reconstructed dislocation with the foil surfaces, and elongated the reconstruction in the foil normal direction; this may explain elongation additional to the missing wedge effect in experiments. Tomography from annular dark-field (ADF) STEM dislocation images was also attempted. A tilt series was obtained from the GaN sample; the reconstructed dislocations had a core of bright intensity of comparable width to WBDF reconstructions, with a surrounding region of low intensity to 60 nm width. An ADF STEM reconstruction was obtained from the Si sample at the same microcrack as for WBDF; here automatic specimen drift correction in tomography acquisition software succeeded, a significant improvement. The microcrack surfaces in Si reconstructed as faint planes and dislocations were recovered as less fragmented lines than from the WBDF reconstruction. ADF STEM tomography was also carried out on the TiAl sample, using a detector inner angle (βin) that included the first order Bragg spots (in other series βin had been 4-6θ B). Extinctions occurred which were dependent on tilt; this produced only weak lines in the reconstruction. Bragg scattering in the ADF STEM image was estimated by summing simulated dark-field dislocation images from all Bragg beams at a zone axis; a double line was produced. It was hypothised that choosing the inner detector angle to omit these first Bragg peaks may preclude most dynamical image features. Additional thermal diffuse scattering (TDS) intensity due to dilatation around an edge dislocation was estimated and found to be insignificant. The Huang scattering cross section was estimated and found to be 9Å, ten times thinner than experimental ADF STEM dislocation images. The remaining intensity may be from changes to TDS from Bloch wave transitions at the dislocation; assessing this as a function of tilt is for further work. On simple assessment, only three possible axial channeling orientations were found over the tilt range for GaN; if this is typical, dechanneling contrast probably does not apply to defect tomography.

This Ph.D. thesis reports the discovery and study of several morphologies of ABC triblock copolymer assemblies in block selective solvents. One block copolymer self-assembled into helices (mostly double and some triple helices), and the other block copolymer formed a mixture of structures resembling hamburgers and striped cylinders. The helices, biomimmetic structures which are unusual from block copolymer self assembly, were prepared from the triblock copolymer poly(n-butyl methacrylate)-block-poly(2-cinnamoyloxyethyl methacrylate)-block-poly(tert-butyl acrylate) (PBMA-b-PCEMA-b-PtBA). They were formed spontaneously in several binary solvent mixtures including dichloromethane/methanol, tetrahydrofuran (THF)/methanol, and chloroform/methanol. They were formed in the composition ranges where the mixtures were good for the PtBA block, poor for the PCEMA block, and marginal for the PBMA block. The structure was studied and established by TEM, AFM, DLS and 1H NMR and by TEM tomography. The mechanism and kinetics of helix formation was examined. The Hamburger and striped cylinder structures were produced from poly(tert-butyl acrylate)-block-poly(2-cinnamoyloxyethyl methacrylate)-block-poly(succinated glyceryl monomethacrylate) or (PtBA-b-PCEMA-b-PSGMA) in mixtures of THF, (-)-sparteine and 1- or 2-propanol. Here THF solubilized all the blocks of the copolymer, while propanol was a precipitant for the middle block (PCEMA), and the chiral amine, (-)-sparteine, complexed with PSGMA and made it insoluble. Within the Hamburger-like structure, the “filling” was made of the complexed PSGMA chains and the "buns" were made of PCEMA. The striped cylinders were made of stacking alternating PCEMA and PtBA stubs. The PtBA chains were located on the outer surfaces of both of these structures. With the hamburger structures, after PCEMA crosslinking, we were able to remove the chiral amine by dialysis and make the PSGMA chains soluble again in solvents such as N, N dimethylformamide. The hamburgers were thus separated into two halves, with each half existing as a Janus particle, which had PtBA chains on one side and PSGMA chains on the other side. The Janus particles might have interesting applications, such as in Pickering emulsion stabilization. / Thesis (Ph.D, Chemistry) -- Queen's University, 2010-04-30 18:01:06.281

Objective: We examined the three-dimensional organization of the endothelial vesicular system with TEM tomography of semi-thick sections. Materials and methods: Mouse abdominal muscle capillaries were perfused with terbium to label vesicular compartments open to the luminal surface. The tissue was prepared for TEM and semi-thick (250nm) sections were cut. Dual axis tilt series, collected from +60° to -60° at 1° increments, were acquired in regions of labeled abluminal caveolae. These tomograms were reconstructed and analyzed to reveal three-dimensional vesicular associations not evident in thin sections. Results: Reconstructed tomograms revealed free vesicles, both labeled and unlabeled, in the endothelial cytoplasm as well as transendothelial channels that spanned the luminal and abluminal membranes. A large membranous compartment connecting the luminal and abluminal surfaces was also present. Computer modeling of tomographic data and video animations provided three-dimensional perspectives to these structures. Conclusions: Uncertainties associated with other three-dimensional methods to study the capillary wall are remedied by tomographic analysis of semi-thick sections. Transendothelial channels of fused vesicles and free cytoplasmic vesicles give credence to their role as large pores in the transport of solutes across the walls of continuous capillaries.