<p> The fatigue softening behaviour of copper single crystals was investigated as a function of temperature. Copper crystals, prestrained in tension, were softened by "push-pull" cycling at constant plastic strain amplitude, in the low amplitude range, and the cyclic stress-strain curves determined at various temperatures. Transmission electron microscopy was employed to determine the detailed microstructural changes which occured during softening while X-ray and slip line observations were utilized to indicate the overall structural changes on a macroscopic scale. The results were correlated and a rationale, based on dipole production, proposed for the observed softening behaviour. </p> / Thesis / Master of Science (MSc)

<p> Polymers and block copolymers have been grafted from hard and soft polymer micro-spheres by atom transfer radical polymerization (ATRP) and ring opening polymerization (ROP). The hard and soft micro-spheres were prepared by precipitation polymerization of divinylbenzene-80 (DVB80), and of DVB80/hydroxyethylmethacrylate (HEMA), respectively, in neat acetonitrile.</p> <p> Residual vinyl groups in the hard, poly(DVB80) micro-spheres were hydrochlorinated to form benzyl chloride groups that subsequently served as ATRP initiators for poly(styrene) and poly(styrene-block-4-methylstyrene) grafts. Hydrophilic poly(HEMA) and poly(2-( dimethylamino)ethyl methacrylate) poly(DMAEMA) were also grafted from hard micro-spheres containing bromopropionates, using ATRP in the presence of CuBr/Me4Cyclam.</p> <p> Hydroxy groups in soft, poly(DVB80-co-HEMA) micro-spheres were used directly as initiators for ring opening polymerization of ε-caprolactone catalyzed by aluminum compounds. In the addition, they were reacted with α-bromopropionyl bromide to form ATRP initiators.</p> <p> Several combinations of ATRP-ATRP and ROP-ATRP with different monomers were carried out using these initiator micro-spheres. In particular, the soft micro-spheres grafted with poly(methacrylic acid), poly(methylmethacrylate), poly(methylmethacrylate-block-dimethylaminoethylmethacrylate), poly(methylmethacrylate-block-trimethylammoniumethylmethacrylate), poly(methylmethacrylate-block-HEMA), poly(methylmethacrylate-block-glycidylmethacrylate), poly(ε-caprolactone-block- methylmethacrylate), poly(ε-caprolactone-block-dimethylaminoethylmethacrylate).</p> <p> The internal morphology of these homo and block copolymer grafted microspheres was studied using electron microscopy and x-ray microspectroscopy.</p> / Thesis / Doctor of Philosophy (PhD)

Supporting videos attached / The nanoscale structure of fully dense human cortical bone is explored using advanced transmission electron microscopy (TEM) techniques. Studies of fully dense cortical bone are rare because of the sample preparation challenges. In this work, cryogenic ion milling is compared favourably with traditional ultramicrotoming methods because of the clearer imaging results and better preservation of biological structures in the ion milled samples. Ion milled samples were prepared parallel, perpendicular and at a 45 degree angle to the long axis of a human femur. The samples are cooled with liquid nitrogen while being milled to prevent heating damage to the bone structure. Bright-field and dark-field imaging show that mineral mainly occurs as 65 nm wide, 5 nm thick mineral structures, external to the collagen fibrils, and with the long axis of the mineral running parallel to the fibrils. In samples cut parallel to the long axis of the bone, the mineral structures have their c-axes aligned with the collagen fibril long axis. In these sections the mineral structures extend up to 200 nm and are grouped into stripe-like bunches, 53 nm apart. Samples cut perpendicular to the long axis of the bone show open areas roughly 45 nm in diameter. These open areas are assumed to be the location of collagen fibrils within the structure and are tangentially surrounded by 65 nm wide, 5 nm thick mineral structures. On average, there are 22 nm of mineral structures between adjoining collagen fibrils. Samples cut at 45 degrees to the long axis of the bone confirm that the open structure seen in the perpendicular section is not an artefact of sample preparation. By tilting the sample, the 45 degree sample shows the structure of both the parallel and perpendicular sections. The parallel structure strongly resembles images of embryonic bone and other mineralized tissues seen in the literature, so the perpendicular open structure is not caused by sample preparation. An examination of ultramicrotoming’s effect on mineral structure size compared with that of ion milling shows that the mineral structures in ion milled samples are twice as long as in ultramicrotomed samples, indicating that bone mineral may be damaged by the forces applied to the complex composite structure existing in fully dense cortical bone. Using energy dispersive X-ray spectroscopy (EDXS) results and a simplified model of the locations of mineral within the collagen/mineral framework, a calculation of the percentage of external mineral was performed. The result showed that 80+_ 6 % of the mineral in fully dense cortical bone must be external to the collagen fibrils to obtain the EDXS results. Finally, Z-contrast tomography, based on the use of high angle annular darkfield (HAADF) imaging, was used to prepared tomographic reconstructions of the external mineral in fully dense cortical bone. Unlike bright-field tomography, the Z-contrast technique allows examination of crystalline materials as the contrast in HAADF images is mass-thickness dependent instead of diffraction based. These reconstructions again showed the mineral tangentially surrounding 50 nm diameter cylindrical holes, assumed to be the location of collagen fibrils in all directions. This work shows the importance of mineral that is external to the collagen fibrils to the nanoscale structure of fully dense cortical bone. / Thesis / Doctor of Philosophy (PhD)

Surface plasmon resonances at the nanoscale hold great potential for applications in many areas, and the characterization of plasmonic nanostructures plays a critical role in the realization of these applications. Electron energy loss spectroscopy (EELS) has emerged as a powerful characterization tool to study the response of plasmonic nanostructures due to its high spatial-resolution and the capability to probe bright as well as dark plasmonic modes. The main limiting factor of EELS is the energy resolution. However, in this thesis, we overcome this limitation using a combination of electron monochromation and the use of the Richardson-Lucy algorithm. We show that the algorithm could be used to obtain effective energy resolutions up to 10 meV. Using EELS we analyze the resonances of planar nanostructures, and we found that the supported resonances can be described as edge and cavity or film modes, behaving as 1D and 2D modes respectively. We also demonstrate that edge modes are unaffected by the presence of bends up to the critical angle of 90◦ where the modes start self-interacting producing large energy shifts. The interaction of plasmon resonances is also studied, and we show that the coupling can be reduced to three behaviors: coupling through the edge, coupling through a corner, and non-coupling. We propose a method to control the coupling through the edge in offset nanowires, by tuning the nodal alignment and spectral overlap of the edge modes. Finally, we analyze the plasmon modes supported by Koch snowflake fractal antennas, and we demonstrate that modes present in the fractals are formed by the edge modes supported by their characteristic edges. This thesis provides a complete picture of the surface plasmon resonances supported by planar nanostructures and demonstrates the ability of EELS to probe and image a wide variety of plasmonic resonances. / Thesis / Doctor of Philosophy (PhD)

The purpose of this study was to examine changes in muscle ultrastructure and strength performance following a single bout of elbow flexor resistance exercise. Eight untrained males performed 8 sets of 8 repetitions at 80% concentric 1 RM. One arm performed only the concentric (CON) phase of the movement while the other performed only the eccentric (ECC) phase. Maximum isometric (MVC), low (LV} and high velocity (HV} concentric peak torque, and evoked contractile property measurements of the elbow flexors were made before and after the bout, and at 24, 48, 72 and 96 h. Needle biopsies were obtained from the biceps brachii prior to the exercise, immediately post-exercise from each arm (POSTCON, POST-ECC}, and 48 h post-exercise from each arm (48H-CON, 48H-ECC). Electron microscopy was used to quantify the extent of fiber disruption in each sample. The severity of disruption was classified as focal (FOC}, moderate (MOD}, or extreme (EXT}. All strength measurements decreased (P s; o. 05} below pre-exercise values immediately post-ex in both arms, but dramatic differences were observed between arms during the subsequent recovery period. MVC, LV, HV and peak twitch torque (PTT) recovered to pre-ex values by 24 h in the CON arm. In the ECC arm, HV did not recover for at least 72 h, and MVC, LV and PTT remained depressed at 96 h. ANOVA revealed a greater (P s; 0.05) number fibers were disrupted in the POST-CON, POST-ECC, 48H-CON and 48H-ECC samples compared to BASE. Significantly more fibers appeared disrupted in the POST-ECC (82%) and 48H-ECC (80%) samples compared to the POSTCON (33%) and 48H-CON (37%) samples, respectively. In addition, the POST-ECC (41%) and 48H-ECC (50%) samples contained a greater number of fibers with EXT disruption compared to the POST-CON (13%) and 48H-CON (17%) samples. Decreases in MVC at 48 h correlated (P ~ 0.05) with the extent of EXT disruption in the 48H-CON and 48H-ECC samples. These data indicate that both the CON and ECC phase of weightlifting produce myofibrillar disruption, with the greatest disruption occurring during the ECC phase. This study was supported by the Natural Sciences and Engineering Research Council of Canada. / Thesis / Master of Science (MSc)

Thesis / Master of Science (MS)

Schwertmannite, a ferric oxyhydroxysulfate mineral typically found under acidic, high sulfate and iron aqueous conditions, such as acid mine drainage environments, was studied using analytical high resolution transmission electron microscopy (HRTEM). HRTEM offers advantages over bulk techniques such as powder x-ray diffraction and pair distribution function (PDF) analysis of synchrotron data, in its ability to discern multiple phases within poorly crystalline nanominerals. Based on extensive HRTEM observations of both natural and synthetic schwertmannite samples, the authors suggest that schwertmannite should not be described as a single phase mineral with a repeating unit cell, but as a polyphasic nanomineral with crystalline areas spanning less than a few nanometers within an amorphous matrix. The few visible lattice fringes observable in both natural and synthetic schwertmannite agree well with d-spacings of goethite (and jarosite in natural samples) implying that the transformation from schwertmannite to these phases occurs as a gradual structural reordering at the nanoscale. In the synthetic study, the complete transformation from schwertmannite to goethite nanorods and nanoparticles within 24 hours at 75°C was observed, indicating a low energetic barrier to schwertmannite's phase transformation. We also found that amorphous silica can be intimately entrained within natural schwertmannite, and that high concentrations of arsenic can be held in close association of nanocrystalline regions of the mineral. / Ph. D.

The major experimental problems involved in this investigation were two in number. The first problem was that of obtaining an accurate calibration of the electron microscope to be used for making electron micrographs. This was done by comparison with a secondary standard. A Bausch and Lomb Type ILS metalloscope, which was calibrated by use of a steel grating furnished by the manufacturer, was used as the secondary standard. The second problem was the examination of yellow iron oxide pigments manufactured by three major manufacturers for the purpose of comparing individual pigment particles and also determining particle shape and dimensions. Both problems were successfully solved and the following observations were made: 1. The magnification of the RCA Type ENC electron microscope used in the investigation is 4274. 2. The particle size and structure of yellow iron oxide paint pigments made by different manufacturers are the same, i.e., 0.5 micron by 0.1 micron and rod-like in structure. / Master of Science

Yes / Previous research on the Iron Age in Britain has argued that no fishing occurred during this period in Britain. This argument has now been complicated by large assemblages of fish bones that have been excavated from Iron Age sites in the Northern Isles. Further investigation into this issue became the focus of the author's MSc dissertation research in 2016, specifically on the recently excavated fish bone assemblages from the site of Swandro on Rousay, Orkney. Analytical methods, including stable isotope analysis and scanning electron microscopy, were applied in an attempt to determine how the fish may have been utilised at the site. Results have revealed evidence that could be interpreted as fishing activity and possible consumption by humans at Swandro. This paper disseminates and further examines these results and considers how this particular project is useful as a pilot study in the application of analytical methodologies to problematic faunal remains such as fish, and why this could be important to future zooarchaeological and environmental archaeological research.

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