Robust nanostructured silver and copper fabrics with localized surface plasmon resonance property for effective visible light induced reductive catalysis

Inspired by high porosity, absorbency, wettability and hierarchical ordering on the micrometer and nanometer scale of cotton fabrics, a facile strategy is developed to coat visible light active metal nanostructures of copper and silver on cotton fabric substrates. The fabrication of nanostructured Ag and Cu onto interwoven threads of a cotton fabric by electroless deposition creates metal nanostructures that show a localized surface plasmon resonance (LSPR) effect. The micro/nanoscale hierarchical ordering of the cotton fabrics allows access to catalytically active sites to participate in heterogeneous catalysis with high efficiency. The ability of metals to absorb visible light through LSPR further enhances the catalytic reaction rates under photoexcitation conditions. Understanding the mode of electron transfer during visible light illumination in Ag@Cotton and Cu@Cotton through electrochemical measurements provides mechanistic evidence on the influence of light in promoting electron transfer during heterogeneous catalysis for the first time. The outcomes presented in this work will be helpful in designing new multifunctional fabrics with the ability to absorb visible light and thereby enhance light-activated catalytic processes.

Bioavailability aspects of hydrophobic contaminant degradation in soils

This thesis concentrates on bioavailability of organic soil contaminants in the context of bioremediation of soil contaminated with volatile or non-volatile hydrophobic pollutants. Bioavailability and biodegradation was studied from four viewpoints: (i) Improvement of bioavailability and biodegradation of volatile hydrocarbons in contained bioremediation systems at laboratory - and pilot-scale. (ii) Improvement of bioavailability of non-volatile, hydrophobic compounds in such systems. (iii) Biodegradation of a non-volatile hydrophobic compound in soil organic matter in microcosms. (iiii) Bioavailability of nitrogen in an open, full-scale bioremediation system. It was demonstrated that volatility of organic compounds can be controlled by amending the soil with adsorbents. The sorbed hydrocarbons were shown to be available to soil microbiota. As the result, biodegradation of the volatile hydrocarbons was greatly favored at the expense of volatilization. PAH compounds were shown to be mobilized and their bioavailability improved by a hydrophobic, non-toxic additive, vegetable oil. Bioavailability of the PAHs was recorded as an increased toxicity of the soil. In spite of the increased bioavailability, biodegradation of the PAHs decreased. In microcosms simulating boreal forest organic surface soil, PAH-compound (pyrene) was shown to be removed from soil biologically. Therefore hydrophobicity of the substrate does not necessarily mean low availability and biodegradation in organic soil. Finally, in this thesis it was demonstrated that an unsuitable source of nitrogen or its overdose resulted in wasteful spending of this nutrient and even harmful effects on soil microbes. Such events may inhibit rather than promote the bioremediation process in soil.

X-Ray Spectroscopic Studies of the Surface Species in Co-Mo-Al2O3 Hydrodesulphurization Catalysts

Octahedrally coordinated CoII and MoIV species are present on the surfaces of sulfided Co-Mo-Al2O3 catalysts used for hydrodesulfurization. They were characterized by XPE, EXAFS and XANES data. An excess of sulfur in the surface species can be explained in terms of the presence of S[stack 22 ] ions. Disulfide bridges could play a role in the hydrodesulfurization.

Exact, self-similar, time-dependent free surface flows under gravity

A class of exact, self-similar, time-dependent solutions describing free surface flows under gravity is found which extends the self-propagating class of solutions discovered earlier by Freeman (1972) to those which decay with time.

Investigation of surface activity and photoinduced diffusion of metals in solution deposited amorphous films of As2S3

Surface activity of solution deposited (SD) amorphous films of As2S3 has been investigated. Silver and copper are readily deposited on such films from appropriate aqueous ionic solutions. The metals diffuse into the films upon irradiation with energetic photons. Structure and properties of SD films have been investigated using electron microscopy, optical spectroscopy and differential scanning calorimetry. The amorphous films tend to crystallize upon metal diffusion. The stability of amorphous films, the deposition of metals on their active surfaces and the photo-induced diffusion may all be attributed to the presence or production of charged defects in amorphous chalcogenide films.

Two-Mode Structure of Alfvén Surface Waves

The Alfvén surface waves propagating along a viscous conducting fluid-vacuum interface have been studied. It is found that besides the "ordinary" Alfvén surface waves, modified by viscosity effects, the interface can support a second mode which is the over-damped solution of the dispersion equation. The possibility of observation of a two-mode structure of Alfvén surface waves in the laboratory and in the solar coronal plasmas is discussed.

A note on the existence of Alfven surface waves

The Alfven surface waves can arise due to the discontinuity in the Alfven speed across the interface along which these waves propagate. This note studies the relationship between v A1 and v A2 which is required for the existence of Alfven surface waves in low-beta plasma.

A comparison of stocking methods for beef production in northern Australia: pasture and soil surface condition responses

Historical stocking methods of continuous, season-long grazing of pastures with little account of growing conditions have caused some degradation within grazed landscapes in northern Australia. Alternative stocking methods have been implemented to address this degradation and raise the productivity and profitability of the principal livestock, cattle. Because information comparing stocking methods is limited, an evaluation was undertaken to quantify the effects of stocking methods on pastures, soils and grazing capacity. The approach was to monitor existing stocking methods on nine commercial beef properties in north and south Queensland. Environments included native and exotic pastures and eucalypt (lighter soil) and brigalow (heavier soil) land types. Breeding and growing cattle were grazed under each method. The owners/managers, formally trained in pasture and grazing management, made all management decisions affecting the study sites. Three stocking methods were compared: continuous (with rest), extensive rotation and intensive rotation (commonly referred to as 'cell grazing'). There were two or three stocking methods examined on each property: in total 21 methods (seven continuous, six extensive rotations and eight intensive rotations) were monitored over 74 paddocks, between 2006 and 2009. Pasture and soil surface measurements were made in the autumns of 2006, 2007 and 2009, while the paddock grazing was analysed from property records for the period from 2006 to 2009. The first 2 years had drought conditions (rainfall average 3.4 decile) but were followed by 2 years of above-average rainfall. There were no consistent differences between stocking methods across all sites over the 4 years for herbage mass, plant species composition, total and litter cover, or landscape function analysis (LFA) indices. There were large responses to rainfall in the last 2 years with mean herbage mass in the autumn increasing from 1970 kg DM ha(-1) in 2006-07 to 3830 kg DM ha(-1) in 2009. Over the same period, ground and litter cover and LFA indices increased. Across all sites and 4 years, mean grazing capacity was similar for the three stocking methods. There were, however, significant differences in grazing capacity between stocking methods at four sites but these differences were not consistent between stocking methods or sites. Both the continuous and intensive rotation methods supported the highest average annual grazing capacity at different sites. The results suggest that cattle producers can obtain similar ecological responses and carry similar numbers of livestock under any of the three stocking methods.

On the non-existence of hydrodynamic solution of surface plasmons at the bimetallic interface

It is shown that for an abrupt bimetallic interface a hydrodynamic solution for interface plasmons does not exist. It appears that this result is valid irrespective of the choice of of the additional boundary condition, thereby suggesting a careful look at the use of usual hydrodynamic equations for a bimetallic interface.

Study of surface acidity of oxide catalysts by photoacoustic spectroscopy

Photoacoustic spectroscopy has been employed to estimate quantitatively the acid sites on oxide catalysts. The technique involves the measurement of the ratio of intensities of absorption bands due to conjugate bases and acids of indicators adsorbed on the catalyst surface as a function of the amount of added n-butylamine. Basic sites in sodium-impregnated alumina samples have been examined by adsorbing phenolphthalein on these surfaces.

Effect of surface resistance on gas absorption accompanied by a chemical reaction in a gas - liquid contactor

An analysis of gas absorption accompanied by chemical reaction in the presence of interfacial resistance is presented. The analysis indicates that the effect of interfacial resistance on interphase mass transfer is significantly higher in presence of a reaction compared to the pure absorption case. For fixed values of surface resistance and contact time, the difference between the amount of gas transferred across the interface with and without surface resistance increases as the value of reaction velocity increases. For ranges of contact time and surface resistance of practical relevance, the influence of surface resistance is too high to be neglected while designing gas-liquid contactors.

Feasibility of assimilating ASCAT surface winds into a Limited Area Model

Sea-surface wind observations of previous generation scatterometers have been successfully assimilated into Numerical Weather Prediction (NWP) models. Impact studies conducted with these assimilation implementations have shown a distinct improvement to model analysis and forecast accuracies. The Advanced Scatterometer (ASCAT), flown on Metop-A, offers an improved sea-surface wind accuracy and better data coverage when compared to the previous generation scatterometers. Five individual case studies are carried out. The effect of including ASCAT data into High Resolution Limited Area Model (HIRLAM) assimilation system (4D-Var) is tested to be neutral-positive for situations with general flow direction from the Atlantic Ocean. For northerly flow regimes the effect is negative. This is later discussed to be caused by problems involving modeling northern flows, and also due to the lack of a suitable verification method. Suggestions and an example of an improved verification method is presented later on. A closer examination of a polar low evolution is also shown. It is found that the ASCAT assimilation scheme improves forecast of the initial evolution of the polar low, but the model advects the strong low pressure centre too fast eastward. Finally, the flaws of the implementation are found small and implementing the ASCAT assimilation scheme into the operational HIRLAM suite is feasible, but longer time period validation is still required.

Surface treatments for pistons and their effect on engine performance

Surface treatment alters the frictional behaviour of pistons in I.C. engines and can be used to improve engine performance. Surface treatments applied to aluminium alloy pistons of a high speed diesel engine and their effect on the engine performance are described. Certain piston surface treatments improve engine performance and also reduce the run-in period.

Surface explosive instability for high frequency waves

High frequency three-wave nonlinear 'explosive' interaction of the surface modes of a semi-infinite beam-plasma system under no external field is investigated. The conditions that favour nonlinear instability, keep the plasma linearly stable. The beam runs parallel to the surface. If at least one of the three wave vectors of the surface modes is parallel to the beam, explosive interaction at the surface takes place after it has happened in the plasma bulk, provided the bulk waves propagate almost perpendicular to the surface and are of short wavelength. On the other hand if the bulk modes have long wavelength and propagate almost parallel to the surface, the surface modes can 'explode' first.