A novel nonintrusive soot diagnostics methodology was developed, validated and applied for in-situ determination of temperature, volume fraction and refractive index of soot aggregates formed inside flames by using near-infrared emission spectrometry. Research was conducted in three main parts, first one addressing development and validation of a comprehensive &quot / direct&quot / model for simulation of line-of-sight radiative emission from axisymmetric sooty flames by coupling sub-models for radiative transfer, radiative properties and optical constants. Radiative property estimation for soot agglomerates was investigated by experimentally validating discrete dipole approximation against microwave measurements and using it as reference to assess applicability of simpler Rayleigh-Debye-Gans approximation for fractal aggregates (RDG-FA). Comparisons between predictions of two methods for soot-like model aggregates demonstrated that radiative property predictions of RDG-FA are acceptably accurate for relatively small soot aggregates encountered in small-scale flames. Part two concerns experimental investigation of an axisymmetric ethylene/air diffusion flame by Fourier Transform Near-Infrared spectroscopy. Measurement of line-of-sight emission intensity spectra was performed along with analyses on calibration, noise, uncertainty and reproducibility. A noise characterization approach was introduced to account for spatial fluctuations which were found to dominate over spectral noise. Final part focuses on development, evaluation and application of an inversion methodology that inputs spectral emission intensity measurements from optically thin flames, removes noise, identifies soot refractive index from spectral gradients and retrieves soot temperature and volume fraction fields by tomographic reconstruction. Validation with simulated data and favorable application to measurements indicate that proposed methodology is a promising option for nonintrusive soot diagnostics in flames.

This dissertation describes the assessment and use of carbon optically transparent electrodes (C-OTEs) based on pyrolyzed photoresist films (PPFs) as a platform for spectroelectrochemical investigations. C-OTEs are examined for use in UV-Vis spectroelectrochemistry and electrogenerated chemiluminescence and compared to non-transparent glassy carbon (GC) and the conventional transparent electrode indium tin oxide (ITO). Chapter 1 provides a general overview of transparent electrodes, carbon electrodes, and spectroelectrochemistry. Chapter 2 details a UV-Vis spectroelectrochemical investigation of electrogenerated graphitic oxides (EGO) on the surface of the C-OTE in the presence of KCl. X-ray photoelectron spectroscopy and time of flight secondary ion mass spectroscopy are used to determine EGO composition. Several supporting electrolytes are investigated to determine the mechanism of EGO formation. Chapter 3 details experiments to electrochemically access the exciton emission from self-assembled double-walled tubular J-aggregates via electrogenerated chemiluminescence (ECL). Optimization of ECL intensity with respect to the coreactant concentration and the supporting electrolyte pH is performed on opaque glassy carbon electrodes. ECL and fluorescence spectra are compared, and C-OTEs are utilized to determine the source of disagreement between the spectra. Chapter 4 describes the preparation and characterization (i.e. transparency, thickness, sheet resistance, rms roughness, and electroactive surface area) of C-OTEs and explores C-OTEs for general use in ECL under a variety of conditions. Simultaneous cyclic voltammograms and ECL transients are obtained for three thicknesses of PPFs and compared to non-transparent GC and the conventional transparent electrode ITO in both front face and transmission electrode cell geometries. Despite positive potential shifts in oxidation and ECL peaks, attributed to the internal resistance of the PPFs that result from their nanoscale thickness, the PPFs display similar ECL activity to GC, including the low oxidation potential observed for amine coreactants on hydrophobic electrodes. Overall, C-OTEs are promising electrodes for spectroelectrochemical applications because they yield higher ECL than ITO in both oxidative-reductive and reductive-oxidative ECL modes, are more stable in alkaline solutions, display a wide potential window of stability, and have tunable transparency for more efficient detection of light in the transmission cell geometry. Future directions for this research are discussed in Chapter 5, which outlines several approaches to designing and improving spectroelectrochemical sensors. / text

Solution deposition of thin film photovoltaic materials leads to large variations in the morphological and chemical compositions of the film. In order to improve device functionality, it is important to understand how morphology and chemical composition affects charge generation, separation, and collection. This PhD work will first study bulk methods in order to characterize materials in solution and films. The results are then correlated with microscopy studies examining morphology. Other methods used in this PhD work will directly couple spectra and microscopy. Microscopic regions of such films and devices can be illuminated using scanning confocal microscopy or near-field scanning optical microscopy (NSOM), which allows for one to directly probe regions of the film at or below the optical diffraction limit. By scanning the sample over a fixed laser spot we can simultaneously create image maps of the topographical, electrical and optical properties. This technique, known as laser beam induced current (LBIC) allows one to directly probe a local area of a device with 100-300nm resolution. Along with bulk device efficiency studies, near field and confocal data of inorganic and organic materials are investigated. These include devices fabricated with a blend of P3HT (poly[3-hexylthiophene]) and perylene diimide derivatives, and Cu(InxGa1-x)Se2 [CIGS] nanoparticle devices. Finally, we use a new device architecture, a lateral organic photovoltaic (LOPV) in order to spatially resolve transport in functional organic devices. / text

published_or_final_version / abstract / toc / Civil Engineering / Doctoral / Doctor of Philosophy

Soil structure influences many chemical, biological and physical processes and it is well established that organic carbon acts as a soil binding agent. However, the precise location of organic matter and carbon in relation to structural features within intact samples is unknown. The sensitivity of organic carbon to decomposition is dependent not only upon its intrinsic chemical recalcitrance, but also its location within the soil structure. Soil structure provides organic carbon with chemical and physical protection, the extent of which varies between structural units. Furthermore soil structure is transient, and is sensitive to both environmental changes and physical disturbance, therefore it is difficult to determine and quantify the impact of this dynamic entity upon the storage of organic carbon. To date the majority of research that has advanced our understanding of the role soil structure plays in the storage of organic carbon, has relied upon some form of fractionation technique to separate aggregates from the bulk soil. However this approach has its disadvantages as much of the soil structure is destroyed; clearly when studying the impact of soil structure upon organic carbon-storage it is advantageous to implement any method that minimises disturbance to the soil structure. This study entails removing intact soil samples (through the use of kubiena tins) from long-term agricultural experimental fields at Rothamsted Research, (Hertfordshire, UK) with the aim of comparing and evaluating the location of organic matter and it’s associated organic carbon, in soils with contrasting organic carbon contents and a well documented land-use history. Thin sections will be analysed by integrating conventional micromorphology, image analysis and sub-microscopy combined with microscale chemical analysis scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS). In doing so a new alternative method for analysing the distribution of organic matter and organic carbon is proposed. It was found that agricultural soils, which are the same in all aspects except total-OC content, differ in total organic matter, water release characteristics, aggregate stability and pore size distribution; therefore these differences could be attributed to the relationship between OC and soil structure. The water release curve, aggregate stability and pore size distribution also differed between soils with similar OC-contents but from different land-uses. The analysis of organic matter within intact soil samples provided evidence for the redistribution of organic matter as it is decomposed within the soil structure, for instance, less decomposed organ and tissue forms were located in or near to soil pores while more decomposed amorphous forms were located within the soil matrix. Since the same pattern of redistribution was observed in both agricultural and grassland soil this is likely to be directed by soil macro and micro fauna. It is concluded that since the location of different forms of organic matter is consistent across all soil, organic matter location is not responsible for creating differences in aggregate stability between treatments. Instead the results indicate that the amount and strength of organic carbon bonds and its hydrophobic properties are responsible. Micromorphology results demonstrated an absence of defined aggregation between treatments. Despite the difficulties in the interpretation of aggregation, the results contradict theories of aggregation, which state that aggregates are formed around “fresh” organic matter and it is argued that OM will undergo substantial decomposition before it acts as core for aggregation. Initial SEM-EDS analysis, has shown that in the soil matrix adjacent to organic matter (plant/organ) fragments there is a heightened concentration of C, indicating that these fragments are acting as a source of organic carbon. Interestingly BC, which represent one of the most recalcitrant C forms is also acting as a source of C, although these initial results suggest to a lesser extent than more labile C-sources. This source of organic carbon could stimulate microbial activity thereby enhancing soil structural stability. Alternatively, the release of liable carbon into soil pores may represent one route by which labile carbon enters sub-soil horizons.

No description available.

The quality of asphalt depends on quality and type of components. The e main characteristic of asphalt is the composition – binder content and aggregate graduation. There are developed many methods for the evaluation of asphalt content. This work analyzes the methods of asphalt content determination. Also there are compared to methods: solvent extraction and ignition method. For the evaluation of these methods the researches of 50 samples have been made. The samples were taken from the asphalt pavement and others were made in laboratory. When results of research were analyzed by principles of statistics. The conclusions and recommendations are presented at the end of the research paper.

A new class of polymer coated lanthanide fluoride nanoparticle aggregates (NPAs) was developed as potential MRI contrast agents. The NPA synthesis has been perfected to control the size distribution and optimize relaxivities. Polyacrylic acid was used as a stabilizing polymer, and was conjugated to folic acid to improve targeting to SK-BR-3 breast cancer cells. Terbium was incorporated in the synthesis to study the passive and active targeting properties of NPAs. Through a series of microscopy experiments, a significant difference in uptake between NPAs with and without targeting moieties occurs after 48 hours of incubation. The relaxivity of the optimized nanoparticles was measured to be 56 s-1(mg/ml)-1 using a 1.5 T scanner, which may be compared to that of the commercially available Gd3+-DTPA [R1 = 7 s-1(mg/ml)-1]. Abdominal perfusion studies in rats also demonstrated that the NPAs provide better contrast of the vasculature than Gd3+-DTPA does at the same mass concentration.

The work presented here report findings in (1) infrared detectors based on p-GaAs/AlGaAs heterojunctions, (2) J and H aggregate sensitized heterojunctions for solar cell and photon detection applications, (3) heterojunctions sensitized with quantum dots as low cost solar energy conversion devices and near infrared photodetectors. (1)A GaAs/AlGaAs based structure with a graded AlGaAs barrier is found to demonstrate a photovoltaic responsivity of ~ 30mA/W (~ 450mV/W) at the wavelength of 1.8 mm at 300K. Additionally the graded barrier has enhanced the photoconductive response at 78 K, showing a responsivity of ~ 80mA/W with a D*=1.4×108 Jones under 1V bias at 2.7 mm wavelength. This is an approximately 25 times improvement compared to the flat barrier detector structure, probably due to the improved carrier transport, and low recapture rate in the graded barrier structure. However, these graded barrier devices did not indicate a photoresponse with photoconductive mode at 300K due to high shot noise. Additionally, two generation-recombination noise components and a 1/f noise component were identified. A series of GaAs/AlGaAs multilayer hetero-junction structures were tested as thermal detectors. A superlattice structure containing 57% Al fraction in the barrier and 3 × 1018 cm-3 p-doped GaAs emitter showed the highest responsivity as a thermal detector with a TCR of ~ 4% K-1, at 300K. (2)The photovoltaic properties of heterojunctions with J-/ H- aggregated dye films sandwiched between n– and p-type semiconductors were investigated for potential application as solar cells and IR detectors. Films of cationic dye Rhodamine-B-thiocyanate adsorbed on Cu2O substrate are found to form organized dye layers by self-assembled J- aggregation, resulting in large red-shifts in the photo -response. Additionally, cells sensitized with a pentamethine cyanine dye exhibited a broad spectral response originating from J- and H-aggregates. The photocurrent is produced by exciton transport over relatively long distances with significant hole-mobility as well as direct sensitized injection at the first interface. (3) A ZnO/PbS-QD/Dye heterostructure had enhanced efficiency compared to ZnO/Dye heterostructure as a solar cell. Furthermore, a ZnO/PbS-QD structure has demonstrated UV and NIR responses with 4×105V/W (390 nm) and 5.5×105 V/W (750 nm) under 1V bias at 300K.

The ocean is the most extended biome present on our planet. Recent decades have seen a dramatic increase in the number and gravity of threats impacting the ocean, including discharge of pollutants, cultural eutrophication and spread of alien species. It is essential therefore to understand how different impacts may affect the marine realm, its life forms and biogeochemical cycles. The marine nitrogen cycle is of particular importance because nitrogen is the limiting factor in the ocean and a better understanding of its reaction mechanisms and regulation is indispensable. Furthermore, new nitrogen pathways have continuously been described. The scope of this project was to better constrain cause-effect mechanisms of microbially mediated nitrogen pathways, and how these can be affected by biotic and abiotic factors. This thesis demonstrates that meiofauna, the most abundant animal group inhabiting the world’s seafloors, considerably alters nitrogen cycling by enhancing nitrogen loss from the system. In contrast, larger fauna such as the polychaete Marenzelleria spp. enhance nitrogen retention, when they invade eutrophic Baltic Sea sediments. Sediment anoxia, caused by nutrient excess, has negative consequences for ecosystem processes such as nitrogen removal because it stops nitrification, which in turn limits both denitrification and anammox. This was the case of Himmerfjärden and Byfjord, two estuarine systems affected by anthropogenic activities, such as treated sewage discharges. When Byfjord was artificially oxygenated, nitrate reduction mechanisms started just one month after pumping. However, the balance between denitrification and nitrate ammonification did not favor either nitrogen removal or its retention. Anoxia is also present in aggregates of the filamentous cyanobacteria Nodularia spumigena. This thesis shows that even in fully oxic waters, millimetric aggregates can host anaerobic nitrogen processes, with clear implications for the pelagic compartment. While the thesis contributed to our knowledge on marine nitrogen cycling, more data need to be collected and experiments performed in order to understand key processes and regulation mechanisms of element cycles in the ocean. In this way, stakeholders may follow and take decisions in order to limit the continuous flow of human metabolites and impacts on the marine environment. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 2: Manuscript.</p>