Le projet de cette thèse consistait à élaborer de nouveaux matériaux donneurs d’électrons pour les cellules solaires organiques. Cette technologie photovoltaïque émergente en plein essor a d’ores et déjà atteint la limite d’efficacité lui permettant d’être industrialisée et commercialisée à grande échelle. Le faible coût de production des dispositifs photovoltaïques organiques les rendent compétitives vis-à-vis des technologies inorganiques déjà bien implantées. Mais leur plus gros avantage est surement leur légèreté et leurs propriétés mécaniques qui les rendent très souples. Elles devraient donc certainement avoir un rôle majeur à jouer dans le futur en complément des cellules solaires classiques, avec une utilisation pour des applications spécifiques. Nous avons ainsi développé des polymères en utilisant des chromophores réputés pour leurs propriétés photophysiques : les porphyrines, les BODIPY et les dicétopyrrolopyrroles. Ces différentes unités absorbent intensément la lumière, ce qui les rend adéquates pour être utilisées pour la conversion de l’énergie solaire en électricité. En concevant un design original et adapté à cette application, nous avons ainsi obtenu plusieurs nouveaux polymères prometteurs. Nous avons ensuite pu étudier leurs propriétés électrochimiques et électroniques, ainsi que leurs caractéristiques photophysiques. Pour cela nous avons utilisé de nombreux outils (caméra streak, absorption transitoire femtoseconde, etc.) afin de comprendre en détails leur propriétés d’absorption et de luminescence. Ces informations nous ont permis de pouvoir ensuite comprendre leur comportement une fois intégrés dans la couche active des dispositifs photovoltaïques. En effet, le mécanisme de fonctionnement pour la création d’un courant électrique met en jeu des transferts d’électrons ultrarapides (∼50 fs) vers un accepteur d’électron. Il est alors crucial de pouvoir comprendre et contrôler les paramètres pouvant influencer l’efficacité de ces transferts et la stabilisation des charges qui en résultent, pour pouvoir finalement mener à des rendements de conversion de l’énergie lumineuse élevés.

Forest fires can have a great impact on the relationship between soil organic matter (SOM) and soilbulk density (SBD). SOM will reduce with increased fire intensity, which ultimately leads to more compaction of the soil. The compaction rate might increase to the limit of where root growth will be absent thus leading to actions to restore the soil. This study investigates changes in the relationship between SOM and SBD in spodosol and histosol in Seglingsberg, located in South-central Sweden, where a forest fire occurred summer 2014.  In addition, changes of pH values in the two types of soilwere examined in order to receive information about the chemical states of the different soil types.A total of 29 samples at depths of 0-17 cm were received from one day of fieldwork and these were later analysed concerning the pH, the SBD and the SOM content. The results showed an increase of pH-values in the fire-exposed area compared to pH values measured at the reference site (pH ~5). More importantly, the results from the SBD and SOM analyses indicated that there was in fact an inversely proportional relationship between the two soil parameters. In addition, high pH values were measured at the same subareas of which the highest SBD- and the lowest SOM values were obtained.Statistical analyses were applied on the results in order to conclude if the soil property changes caused by the fire were significantly different from normal conditions or not. The results from the statistical analyses revealed that 25% of the fire-exposed sites had changed significantly. However, more samples should have been taken while in field, since lack of data is thought to have had a great impact on the final results.Although there were no strong statistical evidence for the hypothesis, it is clear that the forest firein Västmanland year 2014 affected both the SOM, SBD and pH values in the soils. / Under sommaren år 2014 utbröt en omfattande skogsbrand i Västmanlands län, vilket medföljdedramatiska konsekvenser för framförallt ett flertal skogsbolag, men även för boende i området. Med skogsbränder följer negativa såväl som positiva konsekvenser, där de positiva framförallt gäller med avseende på arter som har evolverat i samband med bränder. Förutom ovannämnda konsekvenser så finns det risk för att markförhållandena ändras till följd av en skogsbrand. I denna studie undersöktes hur  markegenskaper  i  torv-  samt  podsoljordar  hade  förändrats  med  avseende  på  pH,  halten  avorganiskt material samt packningsgrad. Fältstudien genomfördes i ett drabbat brandområde strax norrom Seglingsberg, Surahammars kommun. Totalt togs 29 stycken jordprover inom fem stycken transekter i området. Av dessa kunde 25 stycken användas till alla tre analyserna. Resultaten från jordprovsanalyserna användes därefter till att genomföra statistiska undersökningar. Detta för att se hur stor spridningen var mellan och inom de fem transekterna samt för att kunna avgöra om jordproverna visade sig vara signifikant förändrade från ursprungsförhållanden.Resultaten från jordprovsanalyserna visade att det fanns mest organiskt material kvar i de östra delarna av området, medan det var kraftigt reducerat ju längre nordväst jordproverna hade hämtats. I samband med att markens organiska material hade reducerats kunde man även bevittna att jordtäcket hade blivit mer kompakterat. Resultaten från pH-analysen pekar också på att förändringarna varit som störst i de nordvästliga delarna. pH-analysen bevisade att markkemin ser annorlunda ut än innanbranden, då värdena ibland låg 2 enheter för högt än vad man vanligen brukar observera i podsol- ochtorvjordar. Då pH-skalan är logaritmisk innebär detta en minskad försurning med 100 gånger. Resultaten från alla jordprovsanalyser tyder att branden varit som mest intensiv i den nordvästra delen av undersökningsområdet, i området bestående av ungskog.Även om resultaten från jordprovsanalyserna pekade på att branden orsakat tydliga mark- förändringar, visade majoriteten av de statistiska undersökningarna inte på signifikanta förändringar. Det är därför inte möjligt att generalisera resultaten och således applicera dessa på hela brandområdet i Västmanland.Eftersom att naturligt förekommande skogsbränder är relativt få till antalet i Sverige, finns därmed få studier tillgängliga inom ämnesområdet. Det finns en upplaga av studier inom kontrollerade och anlagda brandfält, men i och med att dessa förhållanden är fixerade, så påverkas markegenskaperna sällan avsevärt. Forskningsrapporter indikerar på ett mer extremt klimat i framtiden, som förmodas leda till en ökad omfattning samt ett ökat antal naturligt förekommande skogsbränder. Om denna prognos stämmer är det viktigt att undersöka markförhållandena, då en skogsbrand kan ha direktavgörande effekt på återväxten.

Midlatitudinal hydrated sulfates on Mars may influence brine pH, atmospheric humidity, and collectively water activity. These factors affect the habitability of the planetary subsurface and the preservation of relict biomolecules. Regolith at grain sizes smaller than gravel, constituting the bulk of the Martian subsurface at regional scales, may be a primary repository of chemical alteration, mechanical alteration, and biosignatures. The Mars Odyssey Gamma Ray Spectrometer with hundreds of kilometers of lateral resolution and compositional sensitivity to decimeter depth provides unique insight into this component of the regolith, which we call soil. Advancing the globally compelling association between H2O and S established by our previous work, we characterize latitudinal variations in the association between H and S, as well as in the hydration state of soil. Represented by H2O:S molar ratios, the hydration state of candidate sulfates increases with latitude in the northern hemisphere. In contrast, hydration states generally decrease with latitude in the south. Furthermore, we observe that H2O concentration may affect the degree of sulfate hydration more than S concentration. Limited H2O availability in soil-atmosphere exchange and in subsurface recharge could explain such control exerted by H2O on salt hydration. Differences in soil thickness, ground ice table depths, atmospheric circulation, and insolation may contribute to hemispheric differences in the progression of hydration with latitude. Our observations support chemical association of H2O with S in the southern hemisphere as suggested by Karunatillake et al. (2014), including the possibility of Fe sulfates as a key mineral group.

Soil compaction is a widely spread problem in agricultural soils that has negative agronomic and environmental impacts. The former may lead to poor crop growth and yield, whereas the latter may lead to poor hydraulic properties of soils, and high risk to flooding, soil erosion and degradation. Therefore, the elimination of soil compaction must be done on regular bases. One of the main parameters to quantify soil compaction is soil bulk density (BD). Mapping of within field variation in soil BD will be a main requirement for within field management of soil compaction. The aim of this research was to develop a new approach for the measurement of soil BD as an indicator of soil compaction. The research relies on the fusion of data from visible and near infrared spectroscopy (vis-NIRS), to measure soil gravimetric moisture content (ω), with frequency domain reflectometry (FDR) data to measure soil volumetric moisture content (θv). The values of the estimated ω and θv, for the same undisturbed soil samples were collected from selected locations, textures, soil moisture contents and land use systems to derive soil BD. A total of 1013 samples were collected from 32 sites in the England and Wales. Two calibration techniques for vis-NIRS were evaluated, namely, partial least squares regression (PLSR) and artificial neural networks (ANN). ThetaProbe calibration was performed using the general formula (GF), soil specific calibration (SSC), the output voltage (OV) and artificial neural networks (ANN). ANN analyses for both ω and θv properties were based either on a single input variable or multiple input variables (data fusion). Effects of texture, moisture content, and land use on the prediction accuracy on ω, θv and BD were evaluated to arrive at the best experimental conditions for the measurement of BD with the proposed new system. A prototype was developed and tested under laboratory conditions and implemented in-situ for mapping of ω, θv and BD. When using the entire dataset (general data set), results proved that high measurement accuracy can be obtained for ω and θv with PLSR and the best performing traditional calibration method of the ThetaProbe with R2 values of 0.91 and 0.97, and root mean square error of prediction (RMSEp) of 0.027 g g-1 and 0.019 cm3 cm-3, respectively. However, the ANN – data fusion method resulted in improved accuracy (R2 = 0.98 and RMSEp = 0.014 g g-1 and 0.015 cm3 cm-3, respectively). This data fusion approach gave the best accuracy for BD assessment when only vis-NIRS spectra and ThetaProbe V were used as an input data (R2 = 0.81 and RMSEp = 0.095 g cm-3). The moisture level (L) impact on BD prediction revealed that the accuracy improved with soil moisture increasing, with RMSEp values of 0.081, 0.068 and 0.061 g cm-3, for average ω of 0.11, 0.20 and 0.28 g g-1, respectively. The influence of soil texture was discussed in relation with the clay content in %. It was found that clay positively affected vis-NIRS accuracy for ω measurement and no obvious impact on the dielectric sensor readings was observed, hence, no clear influence of the soil textures on the accuracy of BD prediction. But, RMSEp values of BD assessment ranged from 0.046 to 0.115 g cm-3. The land use effect of BD prediction showed measurement of grassland soils are more accurate compared to arable land soils, with RMSEp values of 0.083 and 0.097 g cm-3, respectively. The prototype measuring system showed moderate accuracy during the laboratory test and encouraging precision of measuring soil BD in the field test, with RMSEp of 0.077 and 0.104 g cm-3 of measurement for arable land and grassland soils, respectively. Further development of the prototype measuring system expected to improve prediction accuracy of soil BD. It can be concluded that BD can be measured accurately by combining the vis-NIRS and FDR techniques based on an ANN-data fusion approach.

Assignment of a receivable arising from a business relation, bulk assignment, factoring The thesis deals with several selected questionable issues related to the assignment of a receivable arising from a business relation. I have chosen this theme because the Czech legal theory doesn't offer satisfactory answers to all of the questions that arise from this topic. The thesis seeks to analyse the selected issues and to offer reasonable solutions to the problems relating to the selected issues. The method of the thesis is based on a comprehensive analysis of the relevant Czech case law as well as the relevant literature. The realized legal conclusions are afterwards put into a broader context and critically evaluated. The thesis is composed of ten chapters. Chapter One defines aims of the thesis. Chapter Two is introductory and explains the basic concept of the assignment of a receivable under the Czech commercial law. Chapter Three contains a basic overview of the receivables which are generally assignable under the Czech commercial law including the assignment of future receivables. It also deals with the topic of another assignment of a future receivable before its origin which is in my opinion allowable. Chapter Four describes cases of prohibitions of an assignment of a receivable. The chapter is...

Numerical models will be developed for the prediction of silencer transmission loss under the operating conditions present in gas turbine exhausts. In these systems the large diameter ducts and high operating temperatures produce a challenging acoustic environment due to the unverified behaviour of fibrous materials at high temperatures and the existence of complex sound fields. To understand the behaviour of fibrous materials at high temperatures their bulk acoustic properties are measured using a modified impedance tube which can heat material samples up to a temperature of 500 C. It will be demonstrated that the high temperature material properties can be extrapolated from room temperature measurements given knowledge of the temperature dependant flow resistivity. Finite element numerical models using point collocation and mode matching techniques to predict the transmission loss of silencers are developed and successfully validated. Dissipative silencer designs with various cross-sectional designs are explored numerically and experimentally according to common industry standards. It is demonstrated that transmission loss may be optimised by the arrangement of the fibrous material across the cross-section. The accurate numerical models allow for effe cient silencers to be designed reducing silencer size and cost. A new hybrid silencer is presented combining dissipative and reactive elements with the aim of increasing the low frequency attenuation of large silencers while maintaining an effective broadband spectrum. Measurements and predictions show this innovative design to be successfull. Application of the hybrid silencer allows for more flexible noise control solutions when design is limited by low frequency noise.

Approved for public release, distribution is unlimited / A study of the performance of the Coupled Ocean Atmosphere Mesoscale Prediction System (COAMPS) was performed based on collected METOC properties affecting radar propagation during the Roughness and Evaporation Duct (RED) experiment conducted off the windward coast of Oahu, HI. The measured refractivity influencing parameters (SST, air temperature, humidity, and wind speed) were compared to COAMPS predicted values. Using the NPS bulk evaporation duct model, profiles of the modified refractivity were computed from the buoy data and compared to profiles computed from the COAMPS data. The profiles were obtained concurrently with S-Band propagation measurements along a 26-km path. The radar propagation predictions created by APM from the modified refractivity profiles, derived from the measured METOC values and COAMPS modeled values, were compared to the in situ measured propagation losses. The mean RMS error of the prop loss predictions derived from the COAMPS forecasted METOC values was <4 dB compared to a mean RMS error of <3 dB from the in situ measurement derived prop loss predictions. Significantly larger errors occurred at the COAMPS analysis times. Overall, the results are very promising for this trade wind region, where the air is cooler than the relatively warm sea surface. / Lieutenant, United States Navy

Master of Science / Department of Grain Science and Industry / Leland McKinney / The current forage handling equipment in the cellulosic ethanol industry is severely limited by the low bulk densities of baled and ground biomass. Low bulk densities contribute to flowability problems and lack of maximizing trailer capacities. By pelleting we can increase the bulk density and flowability characteristics of forages. The objectives of this research were to evaluate (1) the energy requirements of grinding sorghum stalks, corn stover, wheat straw and big bluestem through two different screen sizes, (2) the energy requirements of pelleting forages from the two grind sizes, and (3) the physical properties of our various end products. The two screen types were found to have significantly different energy consumptions from each other (P<.0001). The majority of the four forage types were also found to have significantly different energy consumptions for grinding from each other (P<.0001). The exception was big bluestem vs. corn (P=.2329). All of the 1/8” vs. 1/8” and 1/8” vs. 3/8” grinds were significantly different from each other (Most P<.0001 and all at least P<.05). 3/8” sorghum was significant against all other 3/8” forage types. No other comparisons were significant for 3/8” vs. 3/8” (All 3/8” sorghum P<.0001). Production rate through the 3/8” screen was almost 3 times that of the 1/8” screen (Average of 400 lb/hr vs. 150 lb/hr). The two screen types were found to have significantly different energy consumptions for pelleting from each other (P<.0001). The four forage types were also found to have significantly different energy consumptions from each other (P<.0001) while the big blue vs. wheat did not. (P=.1192). Particle length for the 1/8” grind ranged from .06 inches to .07 inches, while the 3/8” grind ranged from .08 inches to .12 inches. Pelleting increased bulk density from 6.24 lb/ft3 to 9.99 lb/ft3 for biomass grinds to 31.17 lb/ft3 to 43.77 lb/ft3 for pelleted biomass. Pellet quality ranged from 93% to 98%. A cost analysis indicated that it would take roughly $20 extra per ton for the transportation, pre-processing and storage of pelleted cellulosic biomass than whole corn. This cost is still almost half that of the cost for baled biomass.

Master of Science / Department of Chemical Engineering / James H. Edgar / Boron nitride is a purely synthetic material that has been known for over 150 years but only recently has sparked interest as a semiconductor material due to its potential in ultraviolet lasing and neutron detection. Thin-layer hexagonal boron nitride (hBN) is probably most attractive as a complementary material to graphene during its intense research endeavors. But for hBN to be successful in the realm of semiconductor technology, methods for growing large single crystals are critical, and its properties need to be accurately determined. In this study, hBN crystals were grown from metal solvents. The effects of soak temperature, soak time, source materials and their proportions on hBN crystal size and properties were investigated. The largest crystals of hBN measured five millimeters across and about 30 micrometers thick by precipitation from BN powder dissolved in a nickel-chromium solvent at 1700°C. High temperatures promoted outward growth of the crystal along the a-axis, whereas low temperatures promoted growth along the c-axis. Crystal growth at high temperatures also caused bulk hBN to adopt a triangular habit rather than a hexagonal one. A previously unreported method of synthesizing hBN was proven successful by substituting BN powder with elemental boron and a nitrogen ambient. XRD and Raman spectroscopy confirmed hBN from solution growth to be highly crystalline, with an 8.0 cm[superscript]-1 FWHM of the Raman peak being the narrowest reported. Photoluminescence spectra exhibited peaks mid-gap and near the band edge, suggesting impurities and defects in the hBN samples. However, high-purity reactants and post-growth annealing showed promise for synthesizing semiconductor-grade hBN. Several etchants were explored for defect-selective etching of hBN. A molten eutectic mixture of KOH/NaOH was the most effective defect-selective etchant of hBN at temperatures of 430-450°C for about one minute. The two prevalent hexagonal etch pit morphologies observed were deep, pointed-bottom pits and shallow, flat-bottom pits. TEM and SAED confirmed basal plane twists and dislocations in hBN crystals, but due to the highly anisotropic nature of hBN, their existence may be inevitable no matter the growth technique.

Bayou St. John, an urban water body extending south from Lake Pontchartrain, has two anthropogenic structures that regulate flow from the Lake . The City of New Orleans has plans to remove the inner control structure to improve water quality. Field and numerical methods used in this study show removing this structure increased water elevations throughout the Bayou but resulted in lower water elevation signal amplitudes that caused a lower tidal flow exchange from north to south. Bulk Richardson numbers showed mixing was inversely related to flow and the Bayou generally remains stratified. Resuspension of contaminated sediment could negatively impact the local ecology but predicted shear stress values did not reach a critical value (0.1 N/m2) for resuspension. Removal of the waterfall structure will benefit Bayou St. John by decreasing energy losses from the Lake, however a more pronounced tidal signal from Lake Pontchartrain is required to flush the Bayou.