Ultrafast electron diffraction is a novel pump-probe technique which aims to determine transient structures during photoinduced chemical reactions and other structural transitions. This technique provides structural information at the atomic level of inspection by using an electron pulse as a diffractive probe. The atomic motions of interest happen on the 100 fs = 10^(−13) s time scale. To observe these atomic motions, a probe which matches this time scale is required. In this thesis, I describe the development of an electron diffractometer which is capable of 200 fs temporal resolution while maintaining high signal level per electron pulse. This was made possible by the construction of an ultra-compact photoactivated 60 keV femtosecond electron gun. Traditional electron pulse characterization methods are unsuitable for high number density femtosecond electron pulses such as the pulses produced by this electron gun. I developed two techniques based on the laser ponderomotive force to reliably determine the duration of femtosecond electron pulses into the sub-100 fs range. These techniques produce a direct cross-correlation trace between the electron pulse and a laser pulse. The results of these measurements confirmed the temporal resolution of the newly developed femtosecond electron diffractometer. This cross-correlation technique was also used to calibrate a method for the determination of the temporal overlap of electron and laser pulses. These techniques provide the pulse diagnostics necessary to utilize the temporal resolution provided by femtosecond electron pulses. Owing to their high charge-to-mass ratio, electrons are a sensitive probe for electric fields. I used femtosecond electron pulses in an electron deflectometry experiment to directly observe the transient charge distributions produced during femtosecond laser ablation of a silicon (100) surface. We found an electric field strength of 3.5 × 10^6 V/m produced by the emission of 5.3 × 10^11 electrons/cm^2 just 3 ps after an excitation pulse of 5.6 J/cm^2 . This observation allowed us to rule out Coulomb explosion as the mechanism for ablation under the conditions present in this experiment.

VO2-based films are thermochromic and exhibit high or low infrared transmittance when the temperature is below or above a critical temperature. The thermochromic switching is passive and reversible, and therefore VO2 based films are promising for energy-efficient window appli­cations. However the practicaluse of VO2 for energy-efficient windows has long been hampered by low luminous transmittance and low solar energy transmittance modulation. The main goal of this dissertation work is to address these issues. The first half of the work proposes the concept of nanothermochromics for simultaneous improvement of luminous transmittance and modulation of solar energy throughput. nanoth­ermochromics considers VO2 nanoparticle composite layers, whose optical properties were modeled by effective medium theories. Calculations on VO2 spheroids have shown that VO2 nanoparticles, especially nanospheres, can offer dramatically improved luminous transmittance and solar transmittance modulation that are not possible for films. Calculations done on coreshell nanoparticles showed comparable improvements and offer an opportunity to reduce the material costs. It was also found that the composite of In2O3:Sn (ITO) and VO2 can yield moderately high luminous transmittance, solar transmittance modulation and low-emittance properties. In the second half of the dissertation work, Mg-doped VO2 films were sputter deposited. Their band gaps and Mg-content were investigated by means of optical absorption measurement and Rutherford backscattering spectrometry, respectively. The band gaps of VO2 were found to increase by ∼3.9±0.5 eV per unit of atom ratio Mg/(Mg+V) for 0<Mg/(Mg+V)<0.21. Computations based on effective medium theory were done to estimate the performance of Mg­-doped VO2 films and nanoparticle composite layers. The results suggest that moderately doped VO2 films with 0<Mg/(Mg+V)<0.06 perform better than un-doped films and that the perfor­mance can be further enhanced with one layer of antireflection coating. The best results were achieved by un-doped VO2 nanospheres, closely followed by the VO2 nanospheres with low Mg-content. Furthermore, the an experimental study on sputter deposited VO2 nanorods has identified the geometry of the oxygen gas inlet, the type of substrate, the substrate temperature and the layer thickness as important factors that influence the growth morphology. Taken as a whole, nanothermochromics offered by VO2 nanoparticles was shown to be the best solution for VO2 based thermochromic energy-efficient window coatings.

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

Chemical detection, including analysis of gases and liquids, is a large field in environmental research and industry. It requires sensitive, rapid, and inexpensive chemical sensors. Many industrial materials such as coatings and adhesives readily absorb chemical analytes, which may result in changes of their chemical, mechanical, and optical properties. This uptake of volatile organic compounds either from the gas phase or from an aqueous solution into a thin film is frequently accompanied by a change in material refractive index and film thickness. While the undesired swelling of thin film coatings and their refractive index changes affect their use in harsh environments, the sensitivity of some polymers to solvent vapours can also be exploited for sensing applications. In this project, a method is reported for real-time monitoring of vapour uptake by simultaneous detection of the refractive index, n, and thickness, d, of thin transparent films with a precision of 10-4 for refractive index and 100 nm for thickness. The setup combines a total internal reflection refractometer with an interferometric imaging method. Two setups using 1550 nm and 635 nm measurement wavelengths were developed, with a detection rate of 1 second per measurement. Two processing methods using a fast Fourier transform algorithm to calculate n and d are applied to the experimental results and compared. Both methods could extract n and d simultaneously from each image captured by the refractometer. The results show that the setup is capable of monitoring film RI and thickness change in real-time. The partitioning of volatile organic compound vapours into polydimethylsiloxane (PDMS) and PDMS-polydiphenylsiloxane (PDPS) copolymers is described. The system is also suited for characterization of other solid and liquid films like SU-8 photoresist and crude oil. It shows great potential in commercial applications of thin film characterization. / Thesis (Master, Electrical & Computer Engineering) -- Queen's University, 2013-09-19 22:21:38.836

The depletion of fossil fuels together with growing environmental concerns have created incitement for developing a more energy-efficient and environmentally-friendly vehicle fleet. The development towards cleaner heavy-duty vehicles started already in the 80’s with the introduction of emission legislations. Initially, engine optimization was enough for reaching the legislated levels of emissions. However, at present engine optimization is not enough but exhaust aftertreatment has become an essential part of heavy-duty vehicles, in order to meet the emission standards. Today, the total emissions are targeted which means that there is an interest in decreasing the idling emissions as well as the emissions during operation. To reduce the overall emissions several states in the USA have introduced idling legislations. Due to the limitations in idling time alternative solutions for power generation during rests are requested. A possible alternative is a fuel cell auxiliary power unit, combining a fuel cell with a fuel reformer (FC-APU).  The focus of this thesis is the development of the fuel reformer for an FC-APU, in which the hydrogen to the fuel cell is generated from diesel in a high-temperature catalytic process. The produced hydrogen can also be used in other heavy-duty vehicle applications i.e. selective catalytic reduction of NOx (HC-SCR), where addition of hydrogen is essential for reaching high conversion at low temperatures. The effect of using hydrogen from a fuel reformer in HC-SCR is included in this work. The catalytic material development is focused on developing promoted materials with lower rhodium content but with catalytic activity comparable to that of materials with higher rhodium content. This includes evaluation and extensive characterization of both fresh and aged promoted materials. The work also includes reactor design where a micro reactor with multiple air inlets is evaluated. This work has contributed to increased knowledge of catalytic materials suitable for reforming of diesel. By changing the support material from the traditionally used alumina to ceria-zirconia, increased H2 yield was achieved. In addition, the ceria-zirconia supported material was less prone to coke. By promoting the material with cobalt or lanthanum it was possible to decrease the rhodium content by 2/3 with enhanced catalytic performance. It was also discovered that promotion with lanthanum decreased the tendency for coking even further. Additionally, the lanthanum-promoted material had higher thermal stability as well as a stable highly dispersed rhodium phase. Furthermore, the work has contributed to an increased knowledge concerning the fuel reformer’s effect on HC-SCR. The work displays clear evidence of benefits with using hydrogen-rich gas from a fuel reformer instead of pure hydrogen. The benefits are derived from the content of low molecular weight hydrocarbons present in the hydrogen-rich gas, which are strong reducing agents increasing the NOx reduction. This finding proves that fuel reforming in combination with HC-SCR is a viable option for NOx abatement. / <p>QC 20150202</p>

Mit wellenlängenabhängigen Messungen der Oberflächenphotospannung (Surface Photovoltage, SPV) lässt sich die Diffusionslänge von Ladungsträgern im Volumen von Siliziumproben messen. Das Ziel der Arbeit war es, mit Hilfe temperatur- und injektionsabhängiger Messungen der Diffusionslänge die Natur rekombinationsaktiver Defekte in kristallinem Silizium zu untersuchen. Im Rahmen der Arbeit wurde eine zu diesem Zwecke geeignete Messanlage sowie die nötigen Mess- und Auswerteprozeduren entwickelt. Die Möglichkeiten und Grenzen der aufgebauten Anlage wurden durch Messungen an gezielt mit Eisen, Kupfer oder Chrom verunreinigten mono- und multikristallinen Siliziumproben bewertet. Es zeigt sich, dass die SPV-Methode in einem jeweils begrenzten Temperatur- und Injektionsbereich bei Vorhandensein dominanter Defekte zur Defekt-Spektroskopie einsetzbar ist. Eine Anwendung fand das Verfahren an industriell relevantem, aufbereitetem metallurgischen Silizium (umg-Si).

Garden of Eden imagery is ubiquitous in contemporary print advertising in North America, especially in advertisements directed at women. Three telling characteristics emerge in characterizations of Eve in these advertising reconstructions. In the first place, Eve is consistently hypersexualized and over-eroticized. Secondly, such Garden of Eden images often conflate the Eve figure with that of the Serpent. Thirdly, the highly eroticized Eve-Serpent figures also commonly suffer further conflation with the Garden of Eden itself. Like Eve, nature becomes eroticized. In the Eve-Serpent-Eden conflation, woman becomes nature, nature becomes woman, and both perform a single narrative plot function, in tandem with the Serpent. The erotic and tempting Eve-Serpent-Eden character is both protagonist and antagonist, seducer and seduced. In this dissertation, I engage in an ecofeminist narratological analysis of the Genesis/Fall myth, as it is retold in contemporary fashion magazine advertisements. My analysis examines how reconstructions of this myth in advertisements construct the reader, the narrator, and the primary characters of the story (Eve, Adam, the Serpent, and Eden). I then further explore the ways in which these characterizations inform our perceptions of woman, nature, and environmentalism. Using a narratological methodology, and through a poststructuralist ecofeminist lens, I examine which plot and character elements have been kept, which have been discarded, and how certain erasures impact the narrative characterizations of the story. In addition to what is being told, I further analyze how and where it is told. How is the basic plot being storied in these reconstructions, and what are the effects of this version on the archetypal characterizations of Eve and the Garden of Eden? What are the cultural and literary contexts of the reconstructed narrative and the characters within it? How do these contexts inform how we read the characters within the story? Finally, I examine the cultural effects of these narrative reconstructions, exploring their influence on our gendered relationships with each other and with the natural world around us.

Circulating DNA is fragments of DNA which can be found in the blood of healthy as well as diseased individuals. Higher levels of these nucleic acid molecules can be found in diseased and pregnant individuals in contrast to healthy controls. The origin of circulating DNA has not been elucidated, but release of DNA after apoptosis or necrosis or active release by living cells has been hypothesized. It was concluded in this study that apoptosis or necrosis may only be a minor source of circulating DNA and that release of DNA by living cells might play a major role in the origin, while disturbance of the equilibrium between release by living cells and clearance mechanisms may cause the rise in the levels of circulating DNA observed in different conditions. Before circulating DNA can be analyzed, it has to be isolated from the blood. A number of different preanalytical conditions can have an impact on the quantity and quality of circulating DNA that can be isolated. Furthermore, the choice of isolation and quantification method may also influence the results obtained. Quantitative analysis of circulating DNA was done by real-time PCR analysis of the &Globin gene and the DNA levels obtained for healthy controls and cancer patients correlated with levels reported in the literature. Characterization of total circulating DNA may be beneficial in diagnosis and prognosis and may also contribute to determining the source and function of circulating DNA. In order for characterization to take place a method to clone total circulating DNA was developed and standardized and thirty-five clones were obtained and analyzed. It was found that the sequences contain a large amount of Alu repeats and the significance of this has not been determined yet. This is a first step towards future studies. / Thesis (M.Sc. (Biochemistry))--North-West University, Potchefstroom Campus, 2007

The current research has considered the characterization of the high strain rate constitutive response of three steels: a drawing quality steel (DDQ), a high strength low alloy steel (HSLA350), and a dual phase steel (DP600). The stress-strain response of these steels were measured at seven strain rates between 0. 003 s^-1 and 1500 s^-1 (0. 003, 0. 1, 30, 100, 500, 1000, and 1500 s^-1) and temperatures of 21, 150, and 300 ??C. In addition, the steels were tested in both the undeformed sheet condition and the as-formed tube condition, so that tube forming effects could be identified. After the experiments were performed, the parameters of the Johnson-Cook and Zerilli-Armstrong constitutive models were fit to the results. <br /><br /> In order to determine the response of the steels at strain rates of 30 and 100 s^-1, an intermediate rate tensile experiment was developed as part of this research using an instrumented falling weight impact facility (IFWI). An Instron tensile apparatus was used to perform the experiments at lower strain rates and a tensile split-Hopkinson bar was used to perform the experiments at strain rates above 500 s^-1 <br /><br /> A positive strain rate sensitivity was observed for each of the steels. It was found that, as the nominal strength of the steel increased, the strain rate sensitivity decreased. For an increase in strain rate from 0. 003 to 100 s^-1, the corresponding increase in strength at 10% strain was found to be approximately 170, 130, and 110 MPa for DDQ, HSLA350, and DP600, respectively. <br /><br /> The thermal sensitivity was obtained for each steel as well, however no correlation was seen between strength and thermal sensitivity. For a rise in temperature from 21 to 300 ??C, the loss in strength at 10% strain was found to be 200, 225, and 195 MPa for DDQ, HSLA350, and DP600, respectively for the 6 o?clock tube specimens. <br /><br /> For all of the alloys, a difference in the stress ? strain behaviour was seen between the sheet and tube specimens due to the plastic work that was imparted during forming of the tube. For the DP600, the plastic work only affected the work-hardening response. <br /><br /> It was found that both the HSLA350 and DDQ sheet specimens exhibited an upper/lower yield stress that was amplified as the strain rate increased. Consequently the actual strength at 30 and 100 s^-1 was obscured and the data at strain rates above 500 s^-1 to be unusable for constitutive modeling. This effect was not observed in any of the tube specimens or the DP600 sheet specimens <br /><br /> For each of the steels, both the Johnson-Cook and Zerilli-Armstrong models fit the experimental data well; however, the Zerilli-Armstrong fit was slightly more accurate. Numerical models of the IFWI and the TSHB tests were created to assess whether the experimental results could be reproduced using the constitutive fits. Both numerical models confirmed that the constitutive fits were applied correctly.

The doping concentration and resistivity of tin doped Gallium arsenide nanowires (GaAs NWs) have been investigated using Hall effect-, 4-probe-, transmission line-, and field effect measurements. Single nanowires were contacted using electron beam lithography followed by thermal evaporation of Au/Ti (900/100 Å). The Sn precursor (TESn) molar ratios of the investigated nanowires were 8.5·10-7, 1.7·10-6, 3.4·10-6 and 6.8·10-6 resulting in doping concentrations ranging from 4.64·1013 to 2.11·1017 cm-3 and resistivities from ~0.01 to ~1 Ωcm. The yield of the device fabrication was 2.4-7.1 % and evaluation of additional samples should be done in order to establish the validity of the results. The contact material was proved to work well with the higher doped samples but non-ohmic, highly resistive behavior was seen in the lower doped devices. A resistivity gradient along the length of the nanowires was found to be present, most likely the result of a doping gradient. The sample series with TESn molar ratio 1.7·10-6 showed more tapering than the other series possibly leading to a highly doped shell, which was indicated by 4-probe measurements.