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Thesis (Ph.D.) -- McMaster University, 2000. / Includes bibliographical references (leaves 224-249). Also available via World Wide Web.

Debris flows can be highly destructive and pose a significant threat to both life and property in those areas in which they naturally occur. Such flows can be especially hazardous when large amplitude surges form, which cause more damage than continuous flows of the same mass flux. It is therefore important to understand how these surges form and subsequently behave. The most likely explanation for their formation is the spontaneous development of roll waves - small shock-like disturbances typically observed in thin liquid films - which merge and coarsen as they travel downslope, in turn growing in amplitude and wavespeed. There have also been observations of naturally occurring debris flows which develop surges with regions of completely stationary material between them. The terminology of 'erosion-deposition' waves is introduced to describe these waves, according to the process by which they propagate steadily through a flow by eroding at the static layer ahead of the wave front and depositing a stationary layer behind it. This behaviour is particularly novel and the pulses can be even more destructive than their roll wave counterparts. A combination of experimental observations, travelling-wave solutions and numerical simulations are used here to study the behaviour of both roll waves and erosion-deposition waves in granular flows.

Historical change in the geomorphology, hydrodynamics, and surficial sediment of the tidal delta system of Tauranga Harbour are investigated with the general aim of analysing The general aims of this thesis are: firstly to analyse historical changes to inlet delta system geomorphology using historical hydrographic charts, secondly, to conduct hydrodynamic numerical modelling using historical bathymetries to access changes in peak spring flow and potential net tidal sediment transport, and thirdly, to analyse historical changes in surficial sediment and bedforms. Geomorphic change was investigated through plotting difference in bathymetry graphs and conducting cross sections taken from digisitied bathymetries obtained from historical hydrographic charts from 1852, 1879, 1901, 1927, 1954 and a modern bathymetry from 2006. Two-dimensional hydrodynamic numerical modelling was conducted to investigate the changes in peak tidal current flow and potential net sediment transport between 1852 and 2006. Changes in surficial sediment patterns were determined through completing a side scan sonar survey with associated sediment samples for ground truthing of grain size and underwater videography to gather surficial shell coverage information. This was used to produce a surficial sediment coverage map which was compared to historical studies Major geomorphological findings include that the shipping channel appears to have induced minor change in the geomorphology of the FTD but such changes are similar to those identified in the historical bathymetries of 1852, 1879, 1901, 1927, 1954 prior to dredging. Significant changes have occurred on the ETD, with the majority of the ETD showing scour of 1 m while the terminal lobe has extended seawards. This is associated with historical (since 1852) narrowing of the inlet from Panepane Point to Mt Maunganui by ~ 900 m. Hydrodynamic numerical modelling has shown a significant increase in potential net tidal sediment transport in the Cutter Channel due to dredging, while the Maunganui Roads Channel shows a reduction of net potential tidal sediment transport that is associated with the dredging of this channel. The area surrounding Panepane Point undergoes significant increases and decreases in net potential tidal sediment transport both before and after dredging Investigation of the surficial sediment patterns over the FTD and ETD from sidescan sonar and bottom samples show that between 1983 and 2007 there has been a northwards extension of the area of major shell (greater than 50 %) converge in the main ebb channel as well as reduction in major shell converge in flood tidal delta ebb shield region. The Maunganui Roads Channel changes from sitly sands to medium and fine sands.

The potential use of 3D aluminium nanorod structures as current collectors and negative electrodes for 3D Li-ion micro-batteries was studied based on the use of relatively simple and cost-effective electrochemical and sol-gel deposition techniques. Aluminium rod structures were synthesised by galvanostatic electrodeposition using commercial porous membranes as templates. It was shown that the use of a short (i.e., 50 ms long) potential pulse (i.e., -0.9 V vs. Al3+/Al) applied prior to a pulsed current electrochemical deposition gave rise to homogeneous deposits with more even rod heights.  Electrophoretic and sol-gel deposition of TiO2 on the same substrates were also studied. The use of the sol-gel technique successfully resulted in a thin coating of amorphous TiO2 on the Al nanorod current collector, but with relatively small discharge capacities due to the amorphous character of the deposits. Electrophoretic deposition was, however, successful only on 2D substrates. Anodisation of titanium was used to prepare 3D TiO2 nanotube electrodes, with a nanotube length of 9 um and wall thickness of 50 nm. The electrodes displayed high and stable discharge capacities of 460 µAh/cm2 at a 0.1 C rate upon prolonged cycling with good rate capability. The 3D aluminium nanorod structures were tested as negative electrodes for Li-ion cells and the observed capacity fading was assigned to trapping of LiAl alloy inside the aluminium electrode caused by the diffusion of lithium into the electrode, rather than to pulverisation of the aluminium rods. The capacity fading effect could, however, be eliminated by decreasing the oxidation potential limit from 3.0 to 1.0 V vs. Li+/Li. A model for the alloying and dealloying of lithium with aluminium was also proposed. Finally, a proof-of-concept for a full 3D Li-ion micro-battery with electrodes of different geometries was demonstrated. The cell comprised a positive electrode, based on LiFePO4 deposited on a carbon foam current collector, with an area gain factor an order of magnitude larger than that for the Al nanorod negative electrode. This concept facilitates the balancing of 3D Li-ion cells as the positive electrode materials generally have significant lower specific energy densities than the negative electrodes.

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Volatile organic compounds (VOCs) in the indoor air have adverse effects on the dwellers residing in a building or a vehicle. One of these effects is called sick building syndrome (SBS). SBS refers to situations in which the users of a building develop acute health effects and discomfort depending on the time they spend inside some buildings without having any specific illness. Furthermore, monitoring volatile organic compounds could lead to early diagnosis of specific illnesses through breath analysis. Among those VOCs formaldehyde, acetaldehyde can be listed. In this thesis, VOC detecting thin film sensors have been investigated. Such sensors have been manufactured using semiconducting metal oxides, ligand activated gold nanoparticles and Graphene/TiO2 mixtures. Advanced gas deposition unit, have been used to produce NiO thin films and Au nanoparticles. DC magnetron sputtering has been used to produce InSnO and VO2 thin film sensors. Graphene/TiO2 sensors have been manufactured using doctor-blading. While presenting the results, first, material characterization details are presented for each sensor, then, gas sensing results are presented. Morphologies, crystalline structures and chemical properties have been analyzed using scanning electron microscopy, X-ray diffraction and X-ray photo electron spectroscopy. Furthermore, more detailed analyses have been performed on NiO samples using extended X-ray absorption fine structure method and N2 adsorption measurements. Gas sensing measurements were focused on monitoring formaldehyde and acetaldehyde. However, responses ethanol and methane were measured in some cases to monitor selectivity. Graphene/TiO2 samples were used to monitor NO2 and NH3. For NiO thin film sensors and Au nano particles, fluctuation enhanced gas sensing is also presented in addition to conductometric measurements.

A rapid, mask-less deposition technique for writing metal tracks has been developed. The technique was based on laser-induced chemical vapour deposition. The novelty in the technique was the usage of pulsed ultrafast lasers instead of continuous wave lasers in pyrolytic dissociation of the chemical precursor. The motivation of the study was that (1) ultrafast laser pulses have smaller heat affected zones thus the deposition resolution would be higher, (2) the ultrashort pulses are absorbed in most materials (including those transparent to the continuous wave light at the same wavelength) thus the deposition would be compatible with a large range of materials, and (3) the development of higher frequency repetition rate ultrafast lasers would enable higher deposition rates. A deposition system was set-up for the study to investigate the ultrafast laser deposition of tungsten from tungsten hexacarbonyl chemical vapour precursors. A 405 nm laser diode was used for continuous wave deposition experiments that were optimized to achieve the lowest track resistivity. These results were used for comparison with the ultrafast laser track deposition. The usage of the 405 nm laser diode was itself novel and beneficial due to the low capital and running cost, high wall plug efficiency, high device lifetime, and shallower optical penetration depth in silicon substrates compared to green argon ion lasers which were commonly used by other investigators. The lowest as-deposited track resistivity achieved in the continuous wave laser experiments on silicon dioxide coated silicon was 93±27 µΩ cm (16.6 times bulk tungsten resistivity). This deposition was done with a laser output power of 350 mW, scan speed of 10 µm/s, deposition pressure of 0.5 mBar, substrate temperature of 100 °C and laser spot size of approximately 7 µm. The laser power, scan speed, deposition pressure and substrate temperature were all optimized in this study. By annealing the deposited track with hydrogen at 650 °C for 30 mins, removal of the deposition outside the laser spot was achieved and the overall track resistivity dropped to 66±7 µΩ cm (11.7 times bulk tungsten resistivity). For ultrafast laser deposition of tungsten, spot dwell experiments showed that a thin film of tungsten was first deposited followed by quasi-periodic structures perpendicular to the linear polarization of the laser beam. The wavelength of the periodic structures was approximately half the laser wavelength (λ/2) and was thought to be formed due to interference between the incident laser and scattered surface waves similar to that in laser-induced surface periodic structures. Deposition of the quasi-periodic structures was possible on stainless steel, silicon dioxide coated silicon wafers, borosilicate glass and polyimide films. The thin-films were deposited when the laser was scanned at higher laser speeds such that the number of pulses per spot was lower (η≤11,000) and using a larger focal spot diameter of 33 µm. The lowest track resistivity for the thin-film tracks on silicon dioxide coated silicon wafers was 37±4 µΩ cm (6.7 times bulk tungsten resistivity). This value was achieved without post-deposition annealing and was lower than the annealed track deposited using the continuous wave laser. The ultrafast tungsten thin-film direct write technique was tested for writing metal contacts to single layer graphene on silicon dioxide coated silicon substrates. Without the precursor, the exposure of the graphene to the laser at the deposition parameters damaged the graphene without removing it. This was evidenced by the increase in the Raman D peak of the exposed graphene compared to pristine. The damage threshold was estimated to be 53±7 mJ/cm2 for a scanning speed of 500 µm/s. The deposition threshold of thin-film tungsten on graphene at that speed was lower at 38±8 mJ/cm2. However, no graphene was found when the deposited thin-film tungsten was dissolved in 30 wt% H2O2 that was tested to have no effect on the graphene for the dissolution time of one hour. The graphene likely reacted with the deposited tungsten to form tungsten carbide which was reported to dissolve in H2O2. Tungsten carbide was also found on the tungsten tracks deposited on reduced graphene oxide samples. The contact resistance between tungsten and graphene was measured by both transfer length and four-point probe method with an average value of 4.3±0.4 kΩ µm. This value was higher than reported values using noble metals such as palladium (2.8±0.4 kΩ µm), but lower than reported values using other metals that creates carbides such as nickel (9.3±1.0 kΩ µm). This study opened many potential paths for future work. The main issue to address in the tungsten ultrafast deposition was the deposition outside the laser spot. This prevented uniform deposition in successive tracks close to one another. The ultrafast deposition technique also needs verification using other precursors to understand the precursor requirements for this process. An interesting future study would be a combination with a sulphur source for the direct write of tungsten disulphide, a transition metal dichalcogenide that has a two-dimensional structure similar to graphene. This material has a bandgap and is sought after for applications in high-end electronics, spintronics, optoelectronics, energy harvesting, flexible electronics, DNA sequencing and personalized medicine. Initial tests using sulphur micro-flakes on silicon and stainless-steel substrates exposed to the tungsten precursor and ultrafast laser pulses produced multilayer tungsten disulphide as verified in Raman measurements.

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