Mineral Liberation Analyzer (MLA) is an automated mineralogical system originally developed to characterize ore and mill feeds for the metallurgical processing industry. Its ability to quantitatively characterize solid and particulate material, including whole rock thin sections, waste rock, tailings, soil, and sediments, has led to increasing applications in other industries. The software uses back-scatter electron imagery and energy dispersive X-ray analysis to analyze each particle’s shape, size, and mineralogical information. Energy dispersive X-ray data are compared to a user-generated Mineral Reference Library consisting of known phases and corresponding EDS spectra to classify each particle. MLA is used in this study to provide quantitative assessments of mining-related environmental samples to answer questions regarding mineralogical controls on bioaccessibility, metal leaching/acid rock drainage potential, and anthropogenic influence. Six tailings samples from the New Calumet Mine in Quebec, Canada, were analyzed using MLA. Gastric Pb bioaccessibility testing and total metal content performed on these samples indicated that Pb bioaccessibility in the <250 micron size fraction was not directly correlated with the total Pb concentration. This suggested that there were mineralogical and/or physical controls on bioaccessibility. MLA was used to quantify the relative proportions of cerussite, a highly bioaccessible Pb carbonate, and galena, a lower bioaccessibility Pb sulfide. Liberation and particle size were also analyzed as controls on bioaccessibility. Sample GD-VEG1 (highest bioaccessibility) has the highest ratio of cerussite to galena, the smallest particle size, and the most liberated Pb-bearing particles. The New Calumet tailings were also analyzed using static testing, a suite of laboratory tests used by environmental scientists and mine operators to operationally define acid rock drainage and metal leaching potential. Modal mineralogy obtained from MLA analysis was used to calculate neutralization potential (NP) and acid potential (AP), taking into account the presence of iron carbonate minerals and iron-bearing sulfides other than pyrite. Results are within several units of those obtained by static testing. Two Ni-impacted soil samples collected from the region of Kalgoorlie, Australia were characterized using MLA. Previous studies had focused on bioaccessibility and sequential extraction testing and minor mineralogical work. Preliminary XANES characterization conflicted with mineralogy predicted from sequential extraction and EMPA and MLA were used to quantitatively characterize major Ni-bearing phases and resolve previous discrepancies. / Thesis (Master, Geological Sciences & Geological Engineering) -- Queen's University, 2013-08-24 08:13:18.722

Semiconductor nanostructures have attracted great interest owing to their unique physical properties and potential applications in nanoscale functional devices. The enhancement of the physical properties of semiconductor nanostructures and their performance in devices requires a deeper understanding of their fundamental microstructural properties. Thus this thesis is focused on the experimental and theoretical studies of the microstructural properties of two important semiconductor nanostructures: axial heterostructured silicon nanowires with varying doping and indium nitride colloidal nanoparticles. In this thesis, axial heterostructured silicon nanowires with varying doping were synthesized on an oxide-removed Si{111} substrate using a vapour-liquid-solid approach. Their fundamental microstructural properties, including the crystalline structure, wire growth direction and morphologies, were studied using various characterization techniques. It is found that a very small fraction of the silicon nanowires crystallize in a hexagonal (wurtzite) phase, which is thermodynamically unstable in bulk silicon under ambient conditions, while a large majority of the synthesized silicon nanowires exhibit the expected diamond cubic crystalline structure. About 75% of the diamond cubic silicon nanowires synthesized grow in a single <111> direction, while the rest contain growth-related kinks, where the nanowire switches to another direction during the growth. The ~109° silicon nanowire kinks are the most commonly observed, and the growth direction before and after such ~109° kink are both <111>. The sidewalls of silicon nanowires do not change abruptly at the ~109° kink, but exhibit an elbow-shaped structure. It is also found that the nanowire sidewalls exhibit periodic nanofaceting, which is strongly doping-dependent. The nanofaceting is found to occur during the enhanced sidewall growth that arises when the diborane dopant gas is introduced. A thermodynamic model predicting the dependence of nanofacet period on the wire diameter is developed. Another semiconductor nanostructure studied in this thesis is indium nitride colloidal nanoparticles, which were grown using a solution-phase chemical method. The formation of such indium nitride colloidal nanoparticles is confirmed by studying their compositions, crystalline structures and shape using various electron microscopy techniques. The size of the indium nitride colloidal nanoparticles was controlled by varying the time of solution-phase reactions. The most probable size of the colloidal nanoparticles increases and the size distribution broadens with the increase of reaction time. The crystalline structures of the indium nitride colloidal nanoparticles are found to be particle size dependent. The observed dependence of the band gap blueshift of the indium nitride colloidal nanoparticles on the reaction time (hence the particle size) is explained by the quantum-size effect.

The objective of this study was to evaluate the biofilm removal efficacy of three root canal treatment systems: ProUltra® PiezoFlow™, traditional needle irrigation, and the GentleWave® system in an ex-vivo benchtop study. Twenty-four extracted maxillary and mandibular molars were selected. Teeth were all instrumented to a master apical file size #25 with 4% taper. Teeth were then randomly divided into four experimental groups and two control groups. The root canals were inoculated with a culture of Enterococcus faecalis and incubated for five weeks to form a biofilm. Each group was then treated with one of the different root canal treatment systems using 6% sodium hypochlorite (NaOCl) as per the respective manufacturer’s recommendation followed by a rinse with water. Following treatment, teeth were decoronated and roots were sectioned longitudinally. Three scanning electron microscope images were taken at the apical level per root half at 5000x magnification. Images were scored by four calibrated examiners blind to group membership using a four-point scoring system (<5% coverage, 5-33%, 34-66%, and >66%). Results were analyzed using mixed model ANOVA. All the experimental groups were significantly better than the positive control group in removing biofilm. Among the experimental groups, the GentleWave® 15/04 group was significantly better than the other groups. There was no significant difference between the GentleWave® and the ProUltra® PiezoFlow™. Traditional needle irrigation scored the worst in reducing E. faecalis biofilm. The GentleWave™ system was as effective at intracanal biofilm removal as the ProUltra® PiezoFlow™ and better than traditional needle irrigation using 6% NaOCl as an irrigant.

The interwall spacing of multi-walled carbon nanotubes has an effect on their physical and chemical properties. Tubes with larger interwall spacing - compared to the spacing where the carbon atoms are in their natural distance to each other - are for instance expected to be mechanically less stable. Considering the MWCNT interwall spacing’s dependence on the tube size, three interesting previous studies with slightly different conclusions can be found. All of them conclude an increase of the interwall spacing with a decreasing tube size. We describe their analysis procedure, compare them to each other and to our own measured data. In the beginning of our analyses, we determine the expected inaccuracy for measured distances out of TEM images being up to 10 % and we show the impacts of the TEM’s defocus, a powerful setting in TEM imaging. Finally, we suppose that the interwall spacings are not as strongly varying as one previous study concludes, but our analyses are relatively in harmony with the two other studies. The interwall spacings from tubes with an inner diameter larger than 5 nm are relatively constant within the whole tube. Furthermore, it appears that the middle spacings (excluding the outer- and innermost ones) show values that are most consistent with the interlayer spacings of turbostratic graphite. In underfocused images, the outer- and innermost spacings tend to have values being slightly smaller than the middle ones from the same tube.

Aerosol particles, especially in the high Arctic are still not very well represented in climate models. Particle size and number concentrations are strongly under-predicted and temporal variations of aerosol composition and size are still not very well understood, mainly due to the sparsity of observations. The main objective of this thesis is the characterization of the high Arctic summer aerosol by means of electron microscopy in order to extend the existing data set from previous expeditions by size resolved data on aerosol number, morphology and chemical composition and to gain a better understanding of the evolution of the aerosol in the atmosphere. Ambient aerosol was collected over the pack ice during the Arctic Summer Cloud and Ocean (ASCOS) campaign to the high Arctic in summer 2008. Aerosol particles were evaluated with scanning electron microscopy and subsequent digital image processing to assess particle size and morphology. More than 3900 aerosol particles from 9 sampling events were imaged with scanning electron microscopy and merged into groups of similar morphology which contributed to different degrees to the total aerosol: single particles (82%), gel particles (11%) and halo particles (7%). Single particles were observed over the whole size range with a maximum at 64 nm in diameter, gel particles appeared &gt; 45 nm with a maximum in number at 174 nm, halo particles appeared &gt; 75 nm with a maximum in number at 161 nm. The majority of particles showed the morphology of marine gels, no sea salt or otherwise crystalline particles were observed. Transmission electron microscopy enabled more subtle insights into particle morphology and allowed further subdivision of gel particles into aggregates, aggregates with film and mucus-like particles. Energy dispersive X-ray spectroscopy of individual particles revealed a gradual transition in the content of Na+/K+ and Ca2+/Mg2+ between particle morphologies. Single particles and aggregate particles preferentially contained Na+/K+ whereas aggregate with film particles and mucus-like particles mainly contained Ca2+/Mg2+ suggesting a connection between particle morphology and ion content. Back-trajectory analysis was used to identify aerosol sources and to understand the evolution of the aerosol as a function of the synoptic weather situation. Particle numbers, size and morphology changed with the days the air mass spent over the pack-ice. A morphological descriptor applied to gel particles showed a clear trend suggesting that the contour of the particles becomes sharper and more distinct with increased time spent over the pack-ice. For a very long time over the pack-ice, however, we observed a morphology comparable to freshly emitted particles suggesting aerosol sources over the inner pack-ice. Size resolved aerosol chemical composition measurements were utilized to investigate the inorganic composition of laboratory generated nascent sea spray aerosol particles and ambient aerosol samples collected during ASCOS. A significant enrichment of Ca2+ was observed in submicrometer particles in either case with a tendency for increasing Ca2+ enrichment with decreasing particle size. This has strong implications for the alkalinity of sea spray aerosol particles with consequences for the sulfur chemistry in the marine boundary layer, the hygroscopicity and thus the potential of sea spray aerosol particles to act as cloud condensation nuclei. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.</p>

The current work is part of the EPSRC MUZIC project, which established the collaboration among several universities to carry out a multidiscipline study on the breakaway oxidation of zirconium alloys. The overall goal of the project is to further understand the mechanisms of the oxidation and breakaway process of zirconium alloys. This thesis describes the nano/micro-structural study and nano-analysis of the corroded zirconium alloys using up-to-date TEM and 3D focused ion beam (FIB) slicing and reconstruction techniques. The work mainly focused on the characterization of ZIRLO. The oxide morphology in general comprises an inner columnar layer and an outer equiaxed layer, except for a post-second transition oxide grown on a Zr-Nb-Ti test alloy with a very poor corrosion resistance, which exhibits generally only equiaxed grains throughout the whole oxide scale. Detailed investigation reveals oxides in a slower oxidation stage exhibit better developed columnar grain structure. All the oxides, independent of different corrosion stages and alloy types, contain predominantly monoclinic oxide and a small amount of tetragonal oxide. Defects at different length scales were examined. In stead of a sudden burst of crack nucleation at the kinetic transition, a gradual introduction of cracks parallel to the metal/oxide interface throughout the pre-transition stage is found, suggesting no direction correlation between the formation of cracks and the transition. Besides cracks, the oxide also contains different forms of nano-porosity: isolated pores of 1-3 nm or interconnected pores at grain boundaries. The density of interconnected porosity, especially those along the oxide growth direction, increases towards the oxide surface, evolving over time. It is suggested that the kinetic transition is related to the development of an interconnected porosity down to the metal/oxide interface, providing easy pathways for the transportation of oxidation species. The metal-oxide interface has a wavy morphology both in the micrometer and nanometer scale. The roughness develops to a maximum just before the first kinetic transition. An intermediate suboxide layer with complex 3D morphology between the bulk oxide and the metal substrate is found. Quantitative EELS analysis shows the composition of this layer to be 40-50 at. % oxygen. The suboxide appears to develop in thickness with increasing oxidation time for the pre-transition oxides, while is very thin or absent in the post-, and post-second transition oxides. In the suboxide region, multiple phases including &alpha;-Zr, &omega;-Zr, tetragonal oxide and a phase with an unidentified structure were found, suggesting different structures can coexist in the suboxide layer. Second-phase particles (SSPs) of &beta;-Nb and hexagonal Zr(Fe,Nb)₂ types were found in ZIRLO samples and FCC Zr(Fe,Cr)₂ was the predominant type in Zircaloy-4. The SPPs showed delayed oxidation compared to surrounding Zr. In ZIRLO, those containing high Fe contents were found to be oxidized and transform into an amorphous state much earlier than &beta;-Nb. Hydrides of different types (&gamma;, &sigma; and &epsilon;) were observed in the metal and metal/oxide region for both Zircaloy-4 and ZIRLO samples. A higher density of hydrides was seen in post-transition oxides of ZIRLO than in pre-transition oxides.

This thesis considers the theory and calculations of image formation mechanisms for various modes of three-dimensional imaging in aberration-corrected scanning transmission electron microscopy. Discrete tomography is used to determine and refine the three-dimensional structure of molecular nanowire bundles. The structure determination is expedited by the use of annular dark-field imaging, an incoherent imaging mode which provides directly interpretable images. The development of spherical aberration correctors and the subsequent reduction in probe sizes, including the depth of field, has made optical depth sectioning a feasible technique. The localisation in three dimensions of substitutional impurity atoms in zone-axis imaging is discussed. Both the channelling of the probe and the pre-focussing effect of the atomic column play an important role in determining the depth response of the impurity atom. Interband scattering within a sample is shown to be influential in imaging crystals containing dislocations and optical depth sectioning is explored as a possible option for overcoming surface relaxation effects in the imaging of screw dislocations end-on. The possibility of extending the optical depth sectioning approach using aberration-corrected scanning confocal electron microscopy is discussed. The coherent and incoherent imaging modes, involving elastically and inelastically scattered electrons respectively, are investigated.

Canola (Brassica napus) contributes $19.3 billion dollars to the Canadian economy each year as a result of its oil- and protein-rich seeds. These economically important seed products are produced in highest concentration in the embryo. Embryo development is supported nutritionally and structurally by the maternal subregions, which include the inner (ISC) and outer distal seed coat (OSC), the chalazal seed coat (CZSC), and the chalazal proliferating tissue (CPT). Research on the maternal seed subregions is limited to the SC as a result of its accessibility; the embedded CZSC and CPT subregions have yet to be characterized in canola. Using light and transmission electron microscopy, I found the CZSC and CPT to be anatomically distinct and experience profound changes throughout seed development. To understand these changes at the RNA level, laser microdissection and RNA sequencing were used to profile these subregions spatially and temporally from the ovule to mature green stage of seed development. Employing vigorous bioinformatics analyses, I found that the maternal subregions are transcriptomically distinct and possess unique RNA populations. From here I began to elucidate the biological processes operating within the maternal subregions. As a whole, the maternal subregions appear to have a critical role in transporting nutrients to the filial subregions as well as in coping with oxidative stress produced during these energy-rich processes. Additionally, using CanEnrich, I was able to generate predictive transcriptional circuits regulating the biological processes occurring within the maternal seed. This research has produced the most comprehensive dataset on the canola seed to date and will provide a valuable resource for research on seed development as well as seed improvement. / October 2016

Tomographic electron holography combines tomography, the reconstruction of three-dimensionally resolved data from multiple measurements with different specimen orientations, with electron holography, an interferometrical method for measuring the complex wave function inside a transmission electron microscope (TEM). Due to multiple scattering and free wave propagation conventional, ray projection based, tomography does perform badly when approaching atomic resolution. This is remedied by incorporating propagation effects into the projection while maintaining linearity in the object potential. Using the Rytov approach an approximation is derived, where the logarithm of the complex wave is linear in the potential. The ray projection becomes a convolution with a Fresnel propagation kernel, which is considerably more computationally expensive. A framework for such calculations has been implemented in Python. So has a multislice electron scattering algorithm, optimised for large fields of view and high numbers of atoms for simulations of scattering at nanoparticles. The Rytov approximation gives a remarkable increase in resolution and signal quality over the conventional approach in the tested system of a tungsten disulfide nanotube. The response to noise seems to be similar as in conventional tomography, so rather benign. This comes at the downside of much longer calculation time per iteration. / Tomographische Elektronenholographie kombiniert Tomographie, die Rekonstruktion dreidimensional aufgelößter Daten aus einem Satz von mehreren Messungen bei verschiedenen Objektorientierungen, mit Elektronenholographie, eine interferrometrische Messung der komplexen Elektronenwelle im Transmissionselektronenmikroskop (TEM). Wegen Mehrfachstreuung und Propagationseffekten erzeugt konventionelle, auf einer Strahlprojektion basierende, Tomography ernste Probleme bei Hochauflösung hin zu atomarer Auflösung. Diese sollen durch ein Modell, welches Fresnel-Propagation beinhaltet, aber weiterhin linear im Potential des Objektes ist, vermindert werden. Mit dem Rytov-Ansatz wird eine Näherung abgeleitet, wobei der Logarithmus der komplexen Welle linear im Potential ist. Die Strahlen-Projektion ist dann eine Faltung mit dem Fresnel-Propagations-Faltungskernel welche rechentechnisch wesentlich aufwendiger ist. Ein Programm-Paket für solche Rechnungen wurde in Python implementiert. Weiterhin wurde ein Multislice Algorithmus für große Gesichtsfelder und Objekte mit vielen Atomen wie Nanopartikel optimiert. Die Rytov-Näherung verbessert sowohl die Auflösung als auch die Signalqualität immens gegenüber konventioneller Tomographie, zumindest in dem getesteten System eines Wolframdisulfid-Nanoröhrchens. Das Rauschverhalten scheint ähnlich der konventionallen Tomographie zu sein, also eher gutmütig. Im Gegenzug braucht die Tomographie basierend auf der Rytov-Näherung wesentlich mehr Rechenzeit pro Iteration.

No description available.